JP2007059188A - Manufacturing method of organic electroluminescent element, and the organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a stable organic EL element that does not have generating leakage current in light emission drive by preventing degradation in the production efficiency and by taking countermeasures against attached foreign matters, dust and the like. <P>SOLUTION: In this manufacturing method of an organic EL element, a manufacturing device having a process of sequentially forming, on a substrate, a positive electrode layer including at least a first electrode, an organic compound layer, including a luminescent layer and a negative electrode layer including a second electrode is used, and at least one layer of the organic compound layer, including the luminescent layer, is formed by using a vapor phase deposition device. The manufacturing method is such that the vapor phase deposition device has a deposition chamber, a substrate-holding means, a mask arrangement means and a material evaporation means; the material evaporation means is arranged outside a normal line of an end edge of a deposition film forming region; and, in forming a deposition film, it is executed such that, for the positional relation between the material evaporation means and the deposition film forming region, the material deposition means is set so that at least at two positional relations hold with respect to the deposition film forming area. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an organic electroluminescence element (hereinafter also referred to as an organic EL element) used as a surface light source, a display panel or the like, and an organic EL element produced by this production method.

  In recent years, organic EL elements using organic substances have been promising for use as solid light-emitting inexpensive, large-area full-color display elements and writing light source arrays, and active research and development have been promoted. The organic EL element includes a first electrode (anode or cathode) formed on a substrate, an organic compound layer (single layer portion or multilayer portion) containing an organic light emitting material laminated thereon, that is, a light emitting layer, It is a thin film type element having a second electrode (cathode or anode) laminated on the light emitting layer. When a voltage is applied to such an organic EL element, electrons are injected from the cathode and holes are injected from the anode into the organic compound layer. It is known that light is obtained by releasing energy as light when the electrons and holes recombine in the light emitting layer and the energy level returns from the conduction band to the valence band.

  As described above, since the organic EL element is a thin film type element, when an organic EL panel in which one or a plurality of organic EL elements are formed on a substrate is used as a surface light source such as a backlight, a surface light source. It is possible to easily make a device equipped with In addition, when a display device is configured using an organic EL panel in which a predetermined number of organic EL elements as pixels are formed on a substrate as a display panel, the liquid crystal display device has high visibility and no viewing angle dependency. There are benefits that cannot be obtained. The configuration of the organic EL element will be described with reference to FIG.

  FIG. 9 is a schematic cross-sectional view showing an example of the layer structure of the organic EL element.

  In the figure, 1 indicates an organic EL element. The organic EL element 1 includes a first electrode (anode) 102, a hole transport layer 103, a light emitting layer 104, an electron injection layer 105, a second electrode (cathode) 106, a sealing layer on a substrate 101. 107 in this order.

  In the organic EL element shown in this figure, a hole injection layer (not shown) may be provided between the first electrode (anode) 102 and the light emitting layer 104 or the hole transport layer 103. Further, an electron transport layer (not shown) may be provided between the second electrode (cathode) 106 and the light emitting layer 104 or the electron injection layer 105. In the organic EL element 1 a and the organic EL element 1 b shown in this drawing, it is preferable to provide a gas barrier film (not shown) between the anode (first electrode) 102 and the substrate 101.

  The layer configuration of the organic EL element shown in this figure shows an example, but the following configuration can be given as a layer configuration of another typical organic EL element.

(1) Substrate / anode / light emitting layer / electron transport layer / cathode / sealing layer (2) Substrate / anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode / sealing layer (3) ) Substrate / anode / hole transport layer (hole injection layer) / emission layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode / sealing layer (4) substrate / anode / anode Buffer layer (hole injection layer) / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode / sealing layer In the case of an organic EL device, usually the first The electrode (anode) 102 side is the observation side, and the first electrode (anode) 102 includes ITO (mixture of tin oxide and indium oxide), IZO (mixture of zinc oxide and indium oxide), ZnO, SnO ₂ , In ₂ O _3. Etc. are known. Among them, the ITO electrode has a high light transmittance of 90% or more and a low sheet resistance value of 10Ω / □ or less, and is also used as a transparent electrode for liquid crystal displays and solar cells. Further, the IZO electrode has an advantage that a predetermined low resistance value can be obtained without heating the substrate at the time of formation, and the film surface is smoother than the ITO electrode.

In the organic EL element, since the total thickness of the organic compound layer is about 50 to 200 nm, it is known that the organic EL element is easily affected by large foreign matters exceeding 3 μm, dust, etc. adhering to the substrate. When such foreign matter, dust, or the like is present, the distance between the first electrode (anode) and the second electrode (cathode) is shortened, and a voltage in the positive direction (direction in which the element emits light) is applied to the element. A phenomenon occurs in which current flows intensively in that part. This is a leakage current. If a leakage current is generated during light emission of the device, not only the brightness (current-luminance characteristics) with respect to the flowing current is reduced, but also the anode and cathode of that portion are short-circuited, and only there. In some cases, current does not flow and the device does not emit light. In the case of an organic EL element, when a reverse voltage is applied (reverse bias), the current value is a low level of 1 × 10 ⁻⁷ A / cm ² or less, depending on the film thickness of the organic EL element. On the other hand, when a leak current is generated, a current easily flows in the reverse direction in that portion, so that the reverse bias current of the element increases and the current value is not stabilized.

  The deterioration of the reverse bias characteristic that occurs when the leak current is generated becomes a problem even when a reverse bias is applied to the element for convenience of driving or a circuit for actually driving the element. However, foreign matters and dust adhering to the first electrode (anode) are the surface condition of the first electrode (anode), the production conditions of the first electrode (anode), the cleaning of the substrate, the transfer in the process, the cleanliness of the process, etc. Depending on the lot.

  So far, measures against foreign matters and dust adhering to the first electrode (anode) have been studied. For example, when the first electrode (anode) is formed and the first electrode (anode) is processed in a process in which foreign matter, dust, etc. may be deposited, a sampling inspection is performed and a prescribed size is obtained. There is known a method in which when there is foreign matter or dust attached, it is removed and a defective product is not brought into the final process (see, for example, Patent Document 1). However, although the method described in Patent Document 1 certainly removes the substrate on which foreign matter, dust, and the like are attached, it is necessary to introduce an inspection device in the inspection process or increase the number of inspection personnel, thereby increasing costs. Become one. In addition, it is one of the causes that the yield decreases and the production efficiency decreases.

  There is known a technique for preventing the occurrence of leak current by providing a leak prevention layer that increases in resistance with a rise in temperature between the first electrode (anode) and the second electrode (cathode) (for example, patents). See reference 2.) However, the method described in Patent Document 2 can surely prevent the occurrence of leakage current, but since the high resistance portion becomes an insulating portion, this portion does not emit light. It becomes smaller and becomes one of the causes of a decrease in luminous efficiency. In addition, since the leak prevention layer is provided, the number of processes is increased, the production process is complicated, and this is one of the causes of a decrease in productivity.

  Moisture and oxygen will reach the organic layer from the pinholes in the protective layer generated by the attached foreign matter and dust, etc., and in order to prevent the occurrence of non-light emitting areas called dark spots or dark areas, A method of providing a protective layer thicker than the above is known (see, for example, Patent Document 2). However, although the method described in Patent Document 3 can certainly prevent the generation of pinholes in the protective layer, the first electrode (anode) and the second electrode (cathode) due to adhered foreign matter, dust, etc. It is impossible to prevent the occurrence of leakage current due to the short circuit.

As described above, in the methods described in Patent Documents 1 to 3, none of the measures against attached foreign matter, dust, etc. is sufficient. Under such circumstances, measures against attached foreign matter, dust, etc. are taken without reducing the production efficiency, and a method for manufacturing a stable organic EL element free of leakage current during light emission driving, and development of an organic EL element have been developed. It is desired.
JP 2002-75660 A JP 2004-95388 A JP 2004-362912 A

  The present invention has been made in view of the above circumstances, and its purpose is to take measures against adhering foreign matter, dust, and the like without reducing production efficiency, and to achieve stable organicity without leakage current during light emission driving. It is providing the manufacturing method of an EL element, and the organic EL element produced by this manufacturing method.

  The above object of the present invention has been achieved by the following constitution.

(1) Using a manufacturing apparatus including a step of sequentially forming an anode layer including at least a first electrode, an organic compound layer including a light emitting layer, and a cathode layer including a second electrode on a substrate, the light emitting layer In the method for producing an organic electroluminescent element, wherein at least one layer of the organic compound layer containing is formed using a vapor deposition apparatus,
The vapor deposition apparatus includes a vapor deposition chamber that is depressurized by a depressurization unit, a substrate holding unit for a substrate, a mask arrangement unit for a mask that regulates a deposition film formation region with respect to the substrate, and a raw material evaporation unit that evaporates the raw material. Have
The raw material evaporation means is disposed outside the normal line of the edge of the deposited film formation region,
When forming a deposited film in the deposited film forming region by the vapor deposition apparatus,
The positional relationship between the raw material evaporation means and the deposited film formation region is as follows:
A method of manufacturing an organic electroluminescence element, wherein the raw material evaporation means is in at least two positional relationships with respect to the deposited film formation region.

  (2) The method for manufacturing an organic electroluminescence element according to (1), wherein when forming the deposited film, either the raw material evaporation means or the substrate is moved.

  (3) When forming the deposited film, the positional relationship between the raw material evaporation means and the deposited film forming region is such that the center of the raw material vaporizing means and the nearest vapor deposition point of the deposited film forming region are O, and the farthest vapor deposition point is P. The angle between the line connecting the center of the raw material evaporation means and the nearest vapor deposition point O and the normal line of the nearest vapor deposition point O, and connecting the center of the raw material evaporation means and the farthest vapor deposition point P. The manufacturing method of an organic electroluminescent element according to (1) or (2) above, wherein an angle formed between the line and a normal line of the farthest vapor deposition point P is greater than 0 ° and not greater than 75 ° Method.

  (4) At the time of forming the deposited film, the raw material evaporation means having at least two positional relations with respect to the deposited film formation area includes all vapor deposition points in the deposited film formation area and the center of each raw material evaporation means. The method for producing an organic electroluminescent element according to any one of (1) to (3), wherein the intersection angle with the connecting line has a positional relationship of 45 ° to 180 °. .

  (5) When forming the deposited film, the positional relationship between the raw material evaporation means and the deposited film forming area, which are in a plurality of positional relations with respect to the deposited film forming area, is the center of the raw material evaporation means and the deposited film forming area Where the most recent vapor deposition point is O and the farthest vapor deposition point is P, the angle formed by the line connecting the center of the raw material evaporation means and the recent vapor deposition point O and the normal line of the recent vapor deposition point O, and the raw material The angle formed between the line connecting the center of the evaporation means and the farthest vapor deposition point P and the normal line of the farthest vapor deposition point P is greater than 0 ° and less than or equal to 75 °, with respect to the deposited film formation region Two of the raw material evaporation means at arbitrary positions among the plural raw material evaporation means are intersections of lines connecting the centers of the respective raw material evaporation means and arbitrary evaporation points of the deposited film forming region. In any one of the above (1) to (3), the crossing angle at has a positional relationship of 45 ° to 180 ° Method of manufacturing an organic electroluminescent device mounting.

  (6) The method for manufacturing an organic electroluminescent element according to any one of (1) to (5), wherein the substrate is a single wafer.

  (7) The method for producing an organic electroluminescent element according to any one of (1) to (6), wherein the substrate is a strip-shaped plastic film.

  (8) The method for manufacturing an organic electroluminescent element according to any one of (1) to (7), wherein the substrate holding means is a flat plate having holding means.

  (9) The method for manufacturing an organic electroluminescent element according to any one of (1) to (7), wherein the substrate holding means is a backup roll.

  (10) In any one of the above (1) to (7), the substrate holding means is two support rolls and an auxiliary plate disposed between the support rolls. The manufacturing method of organic electroluminescent element of this.

  (11) An organic electroluminescence device produced by the method for producing an organic electroluminescence device according to any one of (1) to (10).

  Provided is a method for manufacturing a stable organic EL element that is free from leakage current during light emission driving, and an organic EL element manufactured by this manufacturing method, taking measures against adhering foreign matter, dust, etc. without reducing production efficiency It was possible to manufacture high quality organic EL elements.

  Embodiments of the present invention will be described with reference to FIGS. 1 to 8, but the present invention is not limited thereto.

  FIG. 1 is a schematic view of a method for producing an organic EL element using a single-wafer sheet-like substrate.

  In the figure, 2 indicates a manufacturing apparatus. Reference numeral 201 denotes a supply unit that supplies the sheet-like substrate 201a to the process. 202 is a substrate cleaning for cleaning the surface of the sheet-like substrate 201a before the first electrode is vapor-deposited on the surface of the sheet-like substrate 201a supplied from the supply unit 201. A processing device is shown. Reference numeral 203 denotes a first electrode forming vapor deposition apparatus for forming a first electrode on the single-wafer sheet-like substrate 201a after the cleaning process. Reference numeral 204 denotes a hole transport layer forming vapor deposition apparatus for forming a hole transport layer on the first electrode of the sheet-like substrate 201b on which the first electrode is formed. Reference numeral 205 denotes a light emitting layer forming vapor deposition apparatus that forms a light emitting layer on the hole transport layer of the single wafer sheet substrate 201c on which the hole transport layer is formed. Reference numeral 206 denotes an electron injection layer forming vapor deposition apparatus for forming an electron injection layer on the light emitting layer of the single wafer sheet substrate 201d on which the light emitting layer is formed. Reference numeral 207 denotes a second electrode forming vapor deposition apparatus for forming a second electrode on the electron injection layer of the single wafer sheet substrate 201e on which the electron injection layer is formed. Reference numeral 208 denotes a sealing layer forming vapor deposition apparatus for forming a sealing layer on the second electrode of the single-wafer sheet-like substrate 201f on which the second electrode is formed. The organic EL element 4 is completed by forming the sealing layer. Reference numeral 209 denotes a collection unit for collecting the organic EL element 4. The first electrode formation vapor deposition apparatus 203 to the sealing layer formation vapor deposition apparatus 208 all have the same configuration, and these configurations will be described in detail with reference to FIGS.

  FIG. 2 is a schematic view of a method for producing an organic EL element using a strip-shaped plastic film substrate.

  In the figure, 3 indicates a manufacturing apparatus. Reference numeral 301 denotes a supply unit that supplies the strip-shaped plastic film substrate 5 to the process. Reference numeral 302 denotes a substrate cleaning apparatus for cleaning the surface of the strip-shaped plastic film substrate 5 in order to improve the vapor deposition property before the first electrode is deposited on the surface of the strip-shaped plastic film substrate 5 supplied from the supply unit 301. Indicates. Reference numeral 303a denotes a first accumulator unit. Reference numeral 304 denotes a first electrode forming vapor deposition apparatus for forming the first electrode 5a on the surface of the belt-like sheet-like substrate 5 after the cleaning process. Reference numeral 303b denotes a second accumulator unit. Reference numeral 305 denotes a hole transport layer forming vapor deposition apparatus for forming a hole transport layer on the first electrode 5 a formed on the belt-like plastic film substrate 5. Reference numeral 303c denotes a third accumulator unit. Reference numeral 306 denotes a light emitting layer forming vapor deposition apparatus for forming a light emitting layer on the hole transport layer 5b formed on the belt-like plastic film substrate 5. Reference numeral 303d denotes a fourth accumulator unit. Reference numeral 307 denotes an electron injection layer forming vapor deposition apparatus for forming an electron injection layer on the light emitting layer 5c formed on the belt-like plastic film substrate 5. Reference numeral 303e denotes a fifth accumulator unit.

  Reference numeral 308 denotes a second electrode forming vapor deposition apparatus for forming a second electrode on the electron injection layer 5d formed on the belt-like plastic film substrate 5. Reference numeral 303f denotes a sixth accumulator unit. Reference numeral 309 denotes a sealing layer forming vapor deposition apparatus for forming a sealing layer on the second electrode 5e formed on the belt-like plastic film substrate 5. 303g shows a 7th accumulator part. Reference numeral 310 denotes a collection unit that winds the belt-shaped plastic film substrate 5 on which a sealing layer (not shown) is formed around a winding core and collects it as a roll. The band-shaped plastic film substrate 5 on which the sealing layer 5f is formed is cut into a prescribed size to form a sheet, whereby an organic EL element is produced.

  The manufacturing apparatus 3 shown in this figure supplies a strip-shaped plastic film substrate 5 from a roll-shaped strip-shaped plastic film substrate 501 wound around a winding core, and a first electrode, a hole transport layer, a light emitting layer, an electron injection layer, a second This is a so-called roll-to-roll method in which an electrode and a sealing layer are sequentially formed and finally wound up and collected in a roll shape. The first accumulator unit 303a to the seventh accumulator unit 303g are arranged to correct a difference in transport speed generated in each vapor deposition apparatus. The first electrode formation vapor deposition apparatus 304 to the sealing layer formation vapor deposition apparatus 309 all have the same configuration, and the first electrode formation vapor deposition apparatus 203 to the sealing layer formation vapor phase shown in FIG. The same as the deposition device 208.

In the drawing, the manufacturing apparatus that continuously performs the process from the first electrode to the formation of the sealing layer is shown, but the process may be divided in consideration of the installation location of the manufacturing apparatus, ease of management, and the like. For example, after the light emitting layer is formed, it is once stored as a take-up roll, and then again using the roll-shaped strip plastic film substrate 5 on which the light emitting layer is formed, the electron injection layer, the second electrode, the sealing A method of forming a stop layer sequentially and finally winding up and collecting it in a roll form is mentioned. When storing a belt-shaped plastic film substrate on which at least one of the first electrode, the hole transport layer, the light emitting layer, the electron injection layer, the second electrode, the sealing layer, etc. is stored, the performance deterioration of each layer is prevented. Therefore, it is preferable to store under reduced pressure conditions of 10 ⁻⁵ to 10 Pa.

As the substrate cleaning apparatus shown in FIGS. 1 and 2, it is preferable to use, for example, a low-pressure mercury lamp, an excimer lamp, a plasma cleaning apparatus, or the like. Examples of the conditions for the substrate cleaning treatment using the low-pressure mercury lamp include conditions for performing substrate cleaning by irradiating a low-pressure mercury lamp with a wavelength of 184.2 nm at an irradiation intensity of 5 to ²⁰ mW / cm ² and a distance of 5 to 15 mm. For example, atmospheric pressure plasma is preferably used as a condition for the substrate cleaning process by the plasma cleaning apparatus. Examples of the cleaning conditions include conditions in which a gas containing 1 to 5% by volume of oxygen is used as the argon gas, and the substrate cleaning process is performed at a frequency of 100 KHz to 150 MHz, a voltage of 10 V to 10 KV, and an irradiation distance of 5 to 20 mm.

  Each step of manufacturing each layer constituting the organic EL element using the manufacturing apparatus shown in FIG. 1 and FIG. 2 takes into consideration the maintenance of the performance of the light emitting layer, the prevention of failure defects due to the adhesion of foreign matter, and the like. It is preferable that the measured cleanliness is Class 3 to Class 5 in accordance with JISB 9920 or lower.

  FIG. 3 is a schematic flow diagram showing step by step until a passive organic EL element is manufactured by the manufacturing apparatus shown in FIG.

  S1 shows the state of the strip-shaped plastic film substrate 5 supplied from the supply part 301 (refer FIG. 2). The surface of the belt-shaped plastic film substrate 5 is in a state in which a mark 5g indicating a deposited film forming region is attached. The interval between the deposited film formation regions can be appropriately changed according to the manufacturing apparatus. After the surface of the belt-shaped plastic film substrate 5 is cleaned by the substrate cleaning processing device 302 (see FIG. 2), it is sent to the first electrode forming vapor deposition device 304 (see FIG. 2). The arrows in the figure indicate the transport direction of the strip-shaped plastic film substrate 5.

  S2 shows a state in which the first electrode 5a in a state of being patterned in the deposited film formation region is formed by the first electrode forming vapor deposition apparatus 304 (see FIG. 2). The place painted in stripes indicates the first electrode. The first electrode forming vapor deposition apparatus 304 (see FIG. 2) detects the mark 5g attached to the belt-shaped plastic film substrate 5 to detect the first electrode forming raw material through the mask in the deposited film forming region. Vapor deposition is performed to form the first electrode 5a. After the first electrode 5a is formed, it is sent to a hole transport layer forming vapor deposition apparatus 305 (see FIG. 2).

  S3 shows a state in which the hole transport layer 5b is formed on the first electrode 5b. In the hole transport layer forming vapor deposition apparatus 305 (see FIG. 2), by detecting the mark 5g attached to the strip-shaped plastic film substrate 5, the first electrode 5a is removed except for the end of the first electrode 5a. The hole transport layer forming raw material is deposited on the formed region through a mask to form the hole transport layer 5b. After the hole transport layer 5b is formed, it is sent to the light emitting layer forming vapor deposition apparatus 306 (see FIG. 2).

  S4 shows a state in which a light emitting layer is formed on the hole transport layer 5c in accordance with the pattern of the first electrode 5a. In the light emitting layer forming vapor deposition apparatus 306 (see FIG. 2), the mask 5g is matched with the pattern of the first electrode 5a on the hole transport layer 5b by detecting the mark 5g attached to the belt-shaped plastic film substrate 5. The material for forming the light emitting layer is vapor-deposited through the step to form the light emitting layer 5c. After the light emitting layer 5c is formed, it is sent to an electron injection layer forming vapor deposition apparatus 307 (see FIG. 2).

  S5 shows a state in which the electron injection layer 5d is formed in the region where the hole transport layer 5b is formed including the region where the light emitting layer 5c is formed. In the electron injection layer forming vapor deposition apparatus 307 (see FIG. 2), the hole transport layer 5b including the formation region of the light emitting layer 5c is formed by detecting the mark 5g attached to the belt-shaped plastic film substrate 5. The material for forming the electron injection layer is deposited on the exposed region through a mask to form the electron injection layer 5d. After the electron injection layer 5d is formed, it is sent to the second electrode formation vapor deposition apparatus 308 (see FIG. 2).

  S6 shows a state in which the second electrode patterned in a state orthogonal to the first electrode 5b is formed on the electron injection layer 5e. In the second electrode forming vapor deposition apparatus 308 (see FIG. 2), the second electrode forming raw material is deposited on the electron injection layer 5d by detecting the mark 5g attached to the belt-shaped plastic film substrate 5. As a result, the second electrode 5e is formed. After the second electrode 5e is formed, it is sent to a sealing layer forming vapor deposition apparatus 309 (see FIG. 2).

  S7 shows a state in which the sealing layer is formed on the formation region of the electron injection layer 5d including the second electrode 5e except for the end portion of the second electrode 5e. The sealing layer forming vapor deposition apparatus 309 (see FIG. 2) includes the second electrode 5e except for the end portion of the second electrode 5e by detecting the mark 5g attached to the strip-shaped plastic film substrate 5. The sealing layer forming raw material is deposited on the formation region of the electron injection layer 5d to form the sealing layer 5f. The production of the passive organic EL element is completed when the sealing layer 5f is formed. After the sealing layer 5f is formed, it is wound around the winding core by the recovery unit 310 (see FIG. 2) and stored as a roll.

  FIG. 4 is a schematic view of the hole transport layer forming vapor deposition apparatus shown in FIG. FIG. 4A is an enlarged schematic view of the hole transport layer forming vapor deposition apparatus shown in FIG. FIG. 4B is a schematic block diagram showing the relationship between each part and each means constituting the hole transport layer forming vapor deposition apparatus. Since the first electrode formation vapor deposition apparatus 203 to the sealing layer formation vapor deposition apparatus 208 shown in FIG. 1 have the same configuration, the hole transport layer formation vapor deposition apparatus 204 will be described as a representative. To do.

  In the figure, the vapor deposition apparatus 204 has a vapor deposition chamber 204a, a substrate holding means 204b, a mask placement means 204c, a raw material evaporation means 204d, and a control means 204e. The material evaporation means 204d is placed outside the normal line of the edge of the deposited film formation region.

Reference numeral 204a1 denotes an exhaust port disposed in the vapor deposition chamber 204a, which is connected to an exhaust means (not shown) that is a decompression means, so that the vapor deposition chamber 204a has a set degree of vacuum via the main valve 204a2. . The degree of vacuum in the vapor deposition chamber 204a can be appropriately set as necessary. Reference numeral 204a3 denotes a vacuum degree meter which is a measuring means for measuring the vacuum degree of the vapor deposition chamber 204a. There is no limitation in particular as a vacuum measuring meter, For example, an ionization vacuum gauge and a Pirani vacuum gauge are mentioned. Reference numeral 204a4 denotes an inert gas inlet, and an inert gas such as N ₂ , Ar, Ne, or He is introduced as an atmospheric gas through the gas inlet valve 204a5 as necessary.

  The substrate holding unit 204b includes a substrate holding member 204b1, a temperature measuring unit 204b2, and a temperature control mechanism 204b3, and the temperature can be controlled by the temperature control mechanism 204b3. A plurality of substrates 201a held by the substrate holding member 204b1 (substrates processed by the substrate cleaning processing device 202 and the first charge removing device 203a as shown in FIG. 1) may be arranged. It can be placed at any position. The substrate holding member 204b1 is not particularly limited as long as the planarity of the substrate can be held and held, and examples thereof include stainless steel and aluminum.

  The temperature measuring means 204b2 measures the temperature of the substrate 201a disposed on the substrate holding member 204b1, and feeds back the result to the control means 204e. By controlling the temperature control mechanism 204b3 that circulates the heat medium to the substrate holding member 204b1 according to the fed back information, the temperature of the substrate can be kept constant while the raw material is deposited on the substrate. Yes. The temperature measuring unit 204b2 is not particularly limited, and examples thereof include a thermocouple and a temperature sensor.

  Reference numeral 204b4 denotes a rotating means for rotating the substrate holding member 204b1. The rotating means is not particularly limited, and may be, for example, a rotary motor or a belt via a pulley. This figure shows the case of a rotary motor. Further, the substrate holding member 204b1 may be rotated or fixed. This figure has shown the case where it rotates. When the substrate holding member 204b1 is fixed, a method of moving the raw material evaporation means 204d may be used in consideration of film formation uniformity on the substrate holding member 204b1.

  The mask placement unit 204c includes a mask placement member 204c1, a temperature measurement unit 204c4, and a temperature control mechanism 204c5. The temperature control mechanism 204c5 can control the temperature. The temperature measuring unit 204c4 is preferably the same as the temperature measuring unit 204b2 disposed on the substrate holding member 204b1.

  Reference numeral 204c3 denotes a mask arranged on the mask arrangement member 204c1. The mask placement member 204c1 is not particularly limited as long as the planarity of the mask 204c3 can be maintained and placed, and examples thereof include stainless steel, aluminum, and copper. The mask arrangement member 204c1 is attached to the substrate holding member 204b1.

  Reference numeral 204a6 denotes a shielding plate of a material deposition control means for controlling the deposition of the material (first electrode material) on the substrate 201a. The shielding plate 204a6 may be of any type, but preferably has a type that can completely prevent vapor deposition on the substrate 3 by being completely closed. Note that the shielding plate shown in this figure is of an open / close type and can be controlled to open / close. Reference numeral 204a7 denotes a driving means for the shielding plate 204a6.

  The temperature control mechanism 204b3 includes a temperature control unit (not shown) for a medium that can be heated and cooled, and a substrate holding member 204b1 for the substrate holding unit 204b and a mask arrangement member 204c1 for the mask arrangement unit 204c. Circulation means (not shown) for circulation to the medium and circulation amount control means (not shown) for the circulation amount of the medium. By circulating the medium controlled to a predetermined temperature to the substrate holding member 204b1 and the mask arrangement member 204c3 by the temperature control mechanism 204b3, the substrate 201a arranged on the substrate holding member 204b1 and the mask arranged on the mask arrangement member 204c1. It is possible to set 204c3 to a predetermined temperature.

  Examples of the medium include synthetic organic heat medium oil. Examples of the medium temperature control means include a combination of a heater and a chiller. Examples of the circulation amount control means include a combination of a flow meter and a pump.

  The raw material evaporation means 204d is disposed in the lower part of the vapor deposition chamber 204a, and measures the temperature of the raw material container 204d1 having heating means (not shown) and the raw material (first electrode raw material) 204d2 in the raw material container 204d1. The raw material temperature measuring means 204d3, the current supply section 204d4 for heating the raw material container 204d1, and the opening ratio control means lid 204d6 for controlling the opening ratio of the opening 204d5 of the raw material container 204d1. The shape of the raw material container 204d1 is not particularly limited, and examples thereof include a line type and a spot type, and the number to be arranged can be appropriately selected depending on the size of the substrate. The heating means for the raw material container 204d1 is not particularly limited, and examples thereof include a sputtering method and a resistance heating method. This figure shows the resistance heating method. The lid 204d6 may have any shape, and may not have a shape that covers all the mouths of the raw material evaporation means. The lid 204d6 is preferably a controllable movable lid in order to obtain a stable deposited film surface until the raw material 204d2 reaches a set temperature. Reference numeral 204d7 denotes a moving means for moving the lid 204d6.

  It is preferable to feed back the result of the raw material temperature measuring means 204d3 to the control means 204e, and perform control processing so as to maintain the set temperature by performing arithmetic processing on the set temperature previously input to the control means 204e. By combining these controls with the control of the movable lid 204d6, it is possible to perform control such that the lid is opened when the set temperature is reached. The number of the raw material evaporation means 204d arranged can be changed as appropriate depending on the size of the substrate.

  The relationship between each part and each means constituting the hole transport layer forming vapor deposition apparatus 204 will be described with reference to a schematic block diagram shown in FIG. Information regarding the temperature of the substrate 201a held by the substrate holding means 204b measured by the substrate temperature measuring means 204b2 is input to the CPU of the control means 204e. The information input to the control unit 204e performs a calculation process with the preset temperature previously input to the memory, and a temperature control mechanism 204b3 disposed in the substrate holding unit 204b for circulating the heat medium adjusted to a predetermined temperature. It is possible to control the circulation amount of the medium and the temperature of the medium.

  Information regarding the temperature of the mask 204c3 held by the mask placement member 204c1 measured by the mask temperature measuring means 204c4 is input to the CPU of the control means 204e. The information input to the control unit 204e performs a calculation process with a preset temperature previously input to the memory, and a temperature control mechanism 204c5 disposed in the mask disposing member 204c1 for circulating the medium adjusted to a predetermined temperature. It is possible to control and control the circulation amount of the heat medium and the temperature of the heat medium. At this time, the circulation amount of the medium by the temperature control mechanism 204c5 and the temperature of the medium are controlled in accordance with the temperature history of the substrate 3 in accordance with the temperature history of the substrate 3.

  The result of the raw material (hole transport layer forming raw material) 204d2 in the raw material container 204d1 measured by the raw material temperature measuring means 204d3 is fed back to the control means 204e, and is calculated with respect to the set temperature inputted in advance to the control means 204e. It is possible to control the temperature of the raw material (hole transport layer forming raw material) 204d2 to be constant by adjusting the current of the current supply unit 204d4 of the heating means (not shown) disposed in the raw material container 204d1a. It has become. By maintaining the temperature of the raw material (hole transport layer forming raw material) 204d2 at a specified temperature, the raw material (hole transport layer forming raw material) at a substantially constant temperature is vapor-deposited on the substrate 201a and is stabilized. Can be formed.

  Information regarding the amount of the raw material (hole transport layer forming raw material) 204d2 in the raw material container 204d1 converted according to time is input to the CPU of the control means 204e. The information inputted to the control means 204e is processed with the amount of the raw material (hole transport layer forming raw material) 204d2 in the raw material container 204d1 inputted in advance in the memory, and the moving means (attached illustration) 204d7 is operated. The opening ratio can be changed by moving the lid 204d6 of the raw material container 204d1. For example, when the amount of the raw material (hole transport layer forming raw material) 204d2 in the raw material container 204d1 is 100%, the aperture ratio is 100%, and the amount of the raw material (hole transport layer forming raw material) 204d2 in the raw material container 204d1 When it is 50%, it is set to 50%.

  By maintaining the deposition rate of the raw material (hole transport layer forming raw material) 204d2 substantially constant, a constant raw material (hole transport layer forming raw material) 204d2 is vapor-deposited on the substrate 3 and stabilized. Can be formed.

  Information about the temperature of the raw material (hole transport layer forming raw material) 204d2 in the raw material container 204d1a measured by the raw material temperature measuring means 204d3 is input to the CPU of the control means 204e. The information input to the control means 204e is processed with the raw material deposition start temperature input in advance in the memory, and the driving means 204a7 is operated to open and close the shielding plate 204a6, whereby the raw material (hole transport in the vapor deposition chamber) is operated. It is possible to prevent vapor deposition on the substrate 3 at the initial stage of heating when the concentration of the layer forming material 204d2 is unstable. For example, the difference between the raw material deposition start temperature inputted in advance and the temperature of the raw material (hole transport layer forming raw material) 204d2 in the raw material container 204d1 measured by the raw material temperature measuring means 204d3 becomes −10 to + 10 ° C. After at least 30 seconds have elapsed, it is preferable to open the shielding plate and close it when the temperature reaches 20 ° C. or higher.

  Also, the temperature measurement result of the raw material (hole transport layer forming raw material) 204d2 is fed back to the temperature control mechanism 204b3 of the substrate 3 and the temperature control mechanism 204c5 of the mask 204c3, and the timing of starting heating of the substrate 3 and the mask 4 is determined. Of course, it can also be used to decide.

  By performing the control as shown in this figure, it becomes possible to reduce the fluctuation of the temperature difference between the substrate temperature and the mask temperature. Therefore, in the vicinity of the mask and the deposited film surface due to the difference with the substrate temperature. It is possible to suppress the quality difference from the center and eliminate the non-uniform quality in the deposited film surface and obtain a stable deposited film surface. Note that the positional relationship between the raw material evaporation means 204d shown in this figure when forming a deposited film and the deposited film forming region of the substrate 3 will be described with reference to FIGS. In addition, this figure shows the case where one raw material evaporation means is placed outside the normal line of the edge of the deposited film formation region, but it is outside the normal line of the other edge of the deposited film formation region. Also preferably, a raw material evaporation means is provided.

  FIG. 5 is an enlarged schematic view of the hole transport layer forming vapor deposition apparatus shown in FIG. FIG. 5A is an enlarged schematic view of a hole transport layer forming vapor deposition apparatus when a backup roll is used as a substrate holding means. FIG. 5B is a schematic block diagram showing the relationship between each part and each means constituting the hole transport layer forming vapor deposition apparatus. The first electrode forming vapor deposition apparatus 304 to the sealing layer forming vapor deposition apparatus 310 shown in FIG. 2 have the same configuration, and therefore the hole transport layer forming vapor deposition apparatus 305 will be described as a representative. To do.

In the figure, a hole transport layer forming vapor deposition apparatus 305 has a vapor deposition chamber 305a, a substrate holding means 305b, a mask arrangement means 305c, a raw material evaporation means 305d, and a control means 305e. The material evaporation means 305d is placed outside the normal line of the edge of the deposited film formation region. Reference numeral 305a1 denotes an exhaust port disposed in the vapor deposition chamber 305a, which is connected to an exhaust means (not shown) that is a decompression means, so that the vapor deposition chamber 305a has a set degree of vacuum via a main valve 305a2. . The degree of vacuum in the vapor deposition chamber 305a can be appropriately set as necessary. Reference numeral 305a3 denotes a vacuum measuring meter which is a measuring means for measuring the vacuum degree of the vapor deposition chamber 305a. There is no limitation in particular as a vacuum measuring meter, For example, an ionization vacuum gauge and a Pirani vacuum gauge are mentioned. Reference numeral 305a4 denotes an inert gas introduction port, and an inert gas such as N ₂ , Ar, Ne, or He is introduced as an atmospheric gas via the gas introduction valve 305a4 as necessary.

  The substrate holding unit 305b includes a backup roll 305b1 serving as a substrate holding member, a temperature measuring unit 305b2, and a current supply unit for a heating body built in the backup roll 305b1. The measurement result of the temperature of the backup roll 305b1 measured by the temperature measuring unit 305b2 is fed back to the control unit 305e. By controlling the current supply amount of the current supply unit 305b3 of the heating body built in the backup roll 305b1 according to the fed back information, the temperature of the substrate is kept constant while depositing the raw material on the substrate, etc. Is possible. The temperature measuring means 305b2 is preferably a non-contact type, for example, an optical temperature sensor.

  The strip-shaped plastic film substrate 5 held by the backup roll 305b1 is in a state of being processed by the substrate cleaning processing device 302 and the first charge removing device 303a as shown in FIG. The peripheral speed of the backup roll 305b1 is preferably adjusted so as to be synchronized with the transport speed of the belt-shaped plastic film substrate 5. The backup roll 305b1 is not particularly limited as long as the flatness of the belt-shaped plastic film substrate 5 can be maintained and disposed, and examples thereof include stainless steel and aluminum.

  The mask arrangement unit 305c includes a mask arrangement member 305c1 and a temperature measurement unit 305c2, and the temperature can be controlled by a heating body (not shown) arranged on the mask arrangement member 305c1. The measurement result of the temperature of the mask 305c3 measured by the temperature measuring unit 305c2 is fed back to the control unit 305e. According to the fed back information, the current supply amount of the current supply unit 305c4 of the heating body (not shown) arranged on the mask arrangement member 305c1 is controlled, so that the temperature of the mask 305c3 is adjusted during the deposition of the raw material on the substrate. It can be held constant. The temperature measuring unit 305c2 is not particularly limited, and examples thereof include a thermocouple and a temperature sensor.

  Reference numeral 305c3 denotes a mask arranged on the mask arrangement member 305c1. The mask 305c3 is preferably matched to the curvature of the backup roll 305b1, and is arranged in a state where the first electrode formation region of the strip-shaped plastic film substrate 5 on the backup roll 305b1 is covered by the mask arrangement member 305c1. The mask arrangement member 305c1 is attached to the frame of the vapor deposition chamber 305a.

  Reference numeral 305a6 denotes a shielding plate of raw material deposition control means for controlling the deposition of the raw material (hole transport layer forming raw material) on the belt-shaped plastic film substrate 5. The shielding plate 305a6 may be of any type, but as a function, a type that can completely prevent vapor deposition on the belt-like plastic film substrate 5 by closing completely is preferable. Note that the shielding plate shown in this figure is of an open / close type and can be controlled to open / close. Reference numeral 305a7 denotes driving means for opening and closing the shielding plate 305a6.

  The raw material evaporation means 305d is disposed below the vapor deposition chamber 305a, and measures the temperature of the raw material container 305d1 having heating means (not shown) and the raw material (hole transport layer forming raw material) 305d2 in the raw material container 305d1. A raw material temperature measuring means 305d3 for heating, a current supply part 305d4 for heating the raw material container 305d1, and a cover 305d6 of an opening ratio control means for controlling the opening ratio of the opening 305d5 of the raw material container 305d1. The shape of the raw material container 305d1 is not particularly limited, and examples thereof include a line type and a spot type, and the number to be arranged can be appropriately selected depending on the size of the substrate. The heating means for the raw material container 305d1 is not particularly limited, and examples thereof include a sputtering method and a resistance heating method. This figure shows the resistance heating method. The lid 305d6 may have any shape, and may not have a shape that covers all the mouths of the raw material evaporation means. The lid 305d6 is preferably a controllable movable lid in order to obtain a stable deposited film surface until the raw material 305d2 reaches a set temperature. Reference numeral 305d7 denotes a moving means for moving the lid 305d6.

  It is preferable to feed back the result of the raw material temperature measuring means 305d3 to the control means 305e and perform control processing so as to maintain the set temperature by performing arithmetic processing on the set temperature input in advance to the control means 305e. By combining these controls with the control of the movable lid 305d6, it is possible to perform control such that the lid is opened when the set temperature is reached. The number of the raw material evaporation means 305d can be appropriately changed depending on the size of the substrate.

  Reference numeral 305a8 denotes a detection / measuring device that detects a mark 5a (see FIG. 3) previously provided on the surface of the first electrode formation region of the belt-shaped plastic film substrate 5. The information of the detection measuring device 305a8 is fed back to the control means 305e, and the calculation processing is performed on the transport speed of the belt-shaped plastic film substrate 5 inputted in advance to the control means 305e to control the opening / closing of the shielding plate 305a6. . Thereby, when the part which is not a hole transport layer formation area surface passes, it is possible to prevent vapor deposition of the hole transport layer formation material to an unnecessary part by closing shielding board 305a6.

  The relationship between each part and each means constituting the hole transport layer forming vapor deposition apparatus 305 will be described with reference to a schematic block diagram shown in FIG. Information on the temperature of the backup roll 305b1 measured by the temperature measuring means 305b2 of the backup roll 305b1 is input to the CPU of the control means 305e. The information input to the control means 305e is subjected to arithmetic processing with the preset temperature input in advance in the memory, and controls the amount of current in the current supply section of the heating body (not shown) built in the backup roll 305b1, and the backup roll It is possible to control the temperature of 305b1.

  Information on the temperature of the mask 305c3 measured by the mask temperature measuring means 305c2 is input to the CPU of the control means 305e. The information input to the control means 305e performs a calculation process with the preset temperature input in advance in the memory, and controls the amount of current in the current supply portion of the heating body (not shown) disposed in the mask placement member 305c1, The temperature of the mask 305c3 can be controlled.

  The result of the raw material (hole transport layer forming raw material) 305d2 in the raw material container 305d1 measured by the raw material temperature measuring means 305d3 is fed back to the control means 305e, and calculated with respect to the set temperature input in advance to the control means 305e. It is possible to control the temperature of the raw material (hole transport layer forming raw material) 305d2 to be constant by adjusting the current of the current supply unit 305d4 of the heating means (not shown) disposed in the raw material container 305d1a. It has become. By maintaining the temperature of the raw material (hole transport layer forming raw material) 305d2 at a specified temperature, a substantially constant temperature of the raw material (hole transport layer forming raw material) is vapor-deposited on the belt-shaped plastic film substrate 5 and stabilized. One electrode can be formed.

  Information on the amount of the raw material (hole transport layer forming raw material) 204d2 in the raw material container 305d1 converted according to time is input to the CPU of the control means 305e. The information input to the control means 305e is processed with the amount of the raw material (hole transport layer forming raw material) 305d2 in the raw material container 305d1 previously input to the memory, and the moving means (attached illustration) 305d7 is operated. The opening ratio can be changed by moving the lid 305d6 of the raw material container 305d1. For example, when the amount of the raw material (hole transport layer forming raw material) 305d2 in the raw material container 305d1 is 100%, the opening ratio is 100%, and the amount of the raw material (hole transport layer forming raw material) 305d2 in the raw material container 305d1 When it is 50%, it is set to 50%.

  By keeping the deposition rate of the raw material (hole transport layer forming raw material) 305d2 substantially constant, a constant raw material (hole transport layer forming raw material) 305d2 is vapor-deposited on the strip-shaped plastic film substrate 5 and stabilized. One electrode can be formed.

  Information on the temperature of the raw material (hole transport layer forming raw material) 305d2 in the raw material container 305d1a measured by the raw material temperature measuring means 305d3 is input to the CPU of the control means 305e. The information input to the control means 305e is processed with the raw material deposition start temperature input in advance in the memory, and the driving means 305a7 is operated to open and close the shielding plate 305a6, whereby the raw material (hole transport in the vapor deposition chamber) is operated. It is possible to prevent vapor deposition on the belt-shaped plastic film substrate 5 in the initial stage of heating, in which the concentration of the layer forming raw material (305d2) is unstable. For example, the difference between the raw material deposition start temperature inputted in advance and the temperature of the raw material (hole transport layer forming raw material) 305d2 in the raw material container 305d1 measured by the raw material temperature measuring means 305d3 becomes −10 to + 10 ° C. After at least 30 seconds have elapsed, it is preferable to open the shielding plate and close it when the temperature reaches 20 ° C. or higher.

  Further, the temperature measurement result of the raw material (hole transport layer forming raw material) 305d2 is transferred to the current supply unit of the heating body (not shown) of the backup roll 305b1 and the heating body (not shown) provided in the mask arrangement member 305c1. It is of course possible to use the feedback roll 305b1 and the mask 305c3 for heating start timing by feedback.

  Information relating to the mark 5a (see FIG. 3) previously attached to the surface of the first electrode formation area of the strip-shaped plastic film substrate 5 from the detection measuring device 305a8 is fed back to the control means 305e and previously inputted to the control means 305e. Calculation processing is performed on the conveyance speed of the belt-shaped plastic film substrate 5 to control the opening and closing of the shielding plate 305a6. Accordingly, when a portion that is not the surface of the hole transport layer forming region passes during deposition, it is possible to prevent the hole transport layer forming material from being deposited on unnecessary portions by closing the shielding plate 305a6. .

  By performing the control as shown in this figure, it becomes possible to reduce the fluctuation of the temperature difference between the substrate temperature and the mask temperature. Therefore, in the vicinity of the mask and the deposited film surface due to the difference with the substrate temperature. It is possible to suppress the quality difference from the center and eliminate the non-uniform quality in the deposited film surface and obtain a stable deposited film surface. Further, since the deposition of the hole transport layer forming material on the portion other than the hole transport layer forming region surface can be prevented, the production efficiency can be improved. In addition, this figure shows the case where one raw material evaporation means is placed outside the normal line of the edge of the deposited film formation region, but it is outside the normal line of the other edge of the deposited film formation region. Also preferably, a raw material evaporation means is provided. Incidentally, the positional relationship between the raw material evaporation means 305d shown in this figure when forming the deposited film and the deposited film forming region of the belt-like plastic film substrate 5 will be described with reference to FIGS.

  FIG. 6 is an enlarged schematic view of a vapor transport layer forming vapor deposition apparatus using two support rolls and an auxiliary plate as the substrate holding means.

The hole transport layer forming vapor deposition apparatus 305 'has a vapor deposition chamber 305'a, a substrate holding means 305'b, a mask arrangement means 305'c, and a raw material evaporation means 305'd. The raw material evaporation means 305′d is placed outside the normal line of the edge of the deposited film formation region. Reference numeral 305′a1 denotes an exhaust port disposed in the vapor deposition chamber 305′a, which is connected to an exhaust means (not shown) as a decompression means, and is a vacuum in which the vapor deposition chamber 305′a is set via the main valve 305′a2. It comes to be. The degree of vacuum in the vapor deposition chamber 305′a can be appropriately set as necessary. Reference numeral 305′a3 denotes a vacuum measuring meter which is a measuring means for measuring the vacuum degree of the vapor deposition chamber 305′a. There is no limitation in particular as a vacuum measuring meter, For example, an ionization vacuum gauge and a Pirani vacuum gauge are mentioned. Reference numeral 305′a4 denotes an inert gas inlet, and an inert gas such as N ₂ , Ar, Ne, or He is introduced as an atmospheric gas via the gas inlet valve 305′a4 as necessary.

  Substrate holding means 305'b includes two support rolls 305'b1 of the substrate holding member and an auxiliary plate 305'b2 for maintaining the flatness of the strip-shaped plastic film substrate 5 between the two support rolls 305'b1, It has temperature measuring means 305′b3 and a temperature control mechanism (attached illustration), and temperature control is possible by the temperature control mechanism (attached illustration). The strip-shaped plastic film substrate 5 held by the substrate holding means 305′b is processed by the substrate cleaning processing device 302 and the first charge removing device 303a as shown in FIG. The peripheral speed of the support roll 305 ′ b 1 is preferably adjusted so as to be synchronized with the transport speed of the belt-shaped plastic film substrate 5. The auxiliary plate 305′b2 is not particularly limited as long as the planarity of the belt-like plastic film substrate 5 can be maintained and disposed, and examples thereof include stainless steel and aluminum.

  The temperature measuring means 305'b3 measures the temperature of the auxiliary plate 305'b2, and feeds back the result to the control means (not shown). The temperature measuring means 305′b3 is not particularly limited, and examples thereof include a thermocouple and a temperature sensor.

  The mask placement unit 305′c has a mask placement member 305′c1 and a temperature measurement unit 305′c2, and temperature control is possible by a temperature control mechanism (not shown). The temperature measuring unit 305′c2 is not particularly limited, and examples thereof include a thermocouple and a temperature sensor.

  Reference numeral 305′c3 denotes a mask arranged on the mask arrangement member 305′c1. The mask 305′c3 is arranged in a state where the first electrode formation region of the strip-shaped plastic film substrate 5 on the auxiliary plate 305′b2 is covered by the mask arrangement member 305′c1. The mask arrangement member 305′c1 is attached to the frame of the vapor deposition chamber 305′a.

  Reference numeral 305′a6 denotes a shielding plate of raw material deposition control means for controlling the deposition of the raw material (hole transport layer forming raw material) on the strip-shaped plastic film substrate 5. The shielding plate 305′a6 may be of any type, but preferably has a function that can completely prevent vapor deposition on the substrate 3 by being completely closed. Note that the shielding plate shown in this figure is of an open / close type and can be controlled to open / close. 305'a7 indicates a power source for opening and closing the shielding plate 305'a6.

  The raw material evaporation means 305′d is disposed below the vapor deposition chamber 305′a, and includes a raw material container 305′d1 having a heating means (not shown) and a raw material (hole transport layer formation) in the raw material container 305′d1. Raw material) Raw material temperature measuring means 305'd3 for measuring the temperature of 305'd2, current supply unit 305'd4 for heating the raw material container 305'd1, and opening 305'd5 of the raw material container 305'd1 And an aperture ratio control means lid 305'd6 for controlling the aperture ratio. The shape of the raw material container 305′d1 is not particularly limited, and examples thereof include a line type and a spot type, and the number to be arranged can be appropriately selected depending on the size of the substrate. The heating means for the raw material container 305′d1 is not particularly limited, and examples thereof include a sputtering method and a resistance heating method. This figure shows the resistance heating method. The lid 305'd6 may have any shape, and may not have a shape that covers all the mouths of the raw material evaporation means. The lid 305'd6 is preferably a controllable movable lid (shown with an attachment) in order to obtain a stable deposited film surface until the raw material 305'd2 reaches a set temperature. Reference numeral 305′d7 denotes a current supply unit for moving means (attached) for moving the lid 305′d6. In addition, this figure shows the case where one raw material evaporation means is placed outside the normal line of the edge of the deposited film formation region, but it is outside the normal line of the other edge of the deposited film formation region. Also preferably, a raw material evaporation means is provided. The positional relationship between the raw material evaporation means 305'd when forming the deposited film and the deposited film forming region of the belt-like plastic film substrate 5 will be described with reference to FIGS.

  FIG. 7 is a schematic diagram showing the positional relationship between the raw material evaporation means and the deposited film forming region of the strip-shaped plastic film substrate when forming the deposited film.

  In the figure, reference numeral 6 denotes a substrate, and 7a denotes a raw material evaporation means arranged outside the normal line of the edge of the deposited film formation region. Reference numeral 7b denotes a raw material evaporation means arranged outside the normal line of the edge of the deposited film forming area by moving the raw material evaporation means 7a when forming the deposited film. Or the raw material evaporation means previously arrange | positioned on the outer side of the normal line of the edge of a deposited film formation area may be sufficient. When two raw material evaporation means are previously arranged outside the normal line of the edge of the deposited film formation region, a plurality of raw material evaporation means are arranged between the two raw material evaporation means as required. It doesn't matter. That is, in the present invention, when the deposited film is formed, at least two positional relations with respect to the deposited film forming region can be obtained when the deposited film is formed as shown in FIG. On the other hand, the relationship is such that the raw material evaporation means 7a and the raw material evaporation means 7b exist.

  O indicates the latest vapor deposition point (refers to the nearest vapor deposition point) of the deposited film formation region with respect to the raw material evaporation means 7a (for the raw material vaporization means 7b, the farthest vapor deposition point (refers to the farthest vapor deposition point). ). P indicates the farthest vapor deposition point (refers to the farthest vapor deposition point) of the deposited film formation region with respect to the raw material evaporation means 7a (for the raw material vaporization means 7b, the nearest vapor deposition point (refers to the nearest vapor deposition point). ).

  θ1 represents an angle formed by a line connecting the center of the raw material evaporation means 7a and the latest deposition point O and a normal line at the latest deposition point O. θ2 represents an angle formed between a line connecting the center of the raw material evaporation means 7a and the farthest vapor deposition point P and a normal line at the farthest vapor deposition point P. θ3 represents an angle formed between a line connecting the center of the raw material evaporation means 7b and the latest deposition point O and a normal line at the latest deposition point O. θ4 represents an angle formed by a line connecting the center of the raw material evaporation means 7b and the farthest vapor deposition point P and a normal line at the farthest vapor deposition point P. The angles θ1 to θ4 are larger than 0 ° and smaller than 75 ° in consideration of the uniform coverage of convex foreign matters existing in the deposited film forming region, the efficiency of the deposited film forming material, the uniform and stable formability of the deposited film, and the like. It is preferable.

When there is only one source evaporation means arranged outside the normal of the edge of the deposited film forming area and there is a convex foreign substance in the deposited film forming area, the source evaporation means side of the convex foreign substance is evaporated. The other side is not covered. That is, when forming a deposited film and there is a convex foreign material in the deposited film forming region, in order to form a deposited film evenly on the convex foreign material, the vapor deposition point and the raw material in the deposited film forming region For example, the evaporation means may be in a positional relationship of at least two. In this way, the following method can be used to bring the deposition point of the deposited film formation region and the raw material evaporation means into at least two positional relationships.
1) When one material evaporation means is arranged outside the normal line of the edge of the deposited film forming area and the deposited film is formed, the material evaporation means is placed outside the normal line of the other edge of the deposited film forming area. By moving the material evaporation means to at least two positions relative to the deposited film formation region.
2) One material evaporation means is arranged outside the normal line of the edge of the deposited film forming area, and when forming the deposited film, the substrate is moved to the outside of the normal line of the other edge of the deposited film forming area. By performing the process, the raw material evaporation means is in at least two positional relations with respect to the deposited film formation region.
3) Preliminarily disposing at least two raw material evaporation means outside the normal line of the edge of the deposited film formation region so that the raw material evaporation means has at least two positional relationships with respect to the deposited film formation region. How to do.

  In the methods described in the above 1) to 3), when forming a deposited film, the relationship between the deposited film formation region and the material evaporation means is the same as that of the material evaporation means at all the deposition points in the deposited film formation region. By forming an angle between a line connecting the vapor deposition point and the farthest vapor deposition point and the center of the raw material evaporation means and a normal line at the latest vapor deposition point and the farthest vapor deposition point to be larger than 0 ° and not larger than 75 °, the deposited film When convex foreign substances exist in the formation region, it is possible to form a deposited film evenly on the convex foreign substances.

When the vapor deposition apparatus in which the raw material evaporation means is disposed outside the normal line of the edge of the deposited film forming area and the deposited film is formed in the deposited film forming area, the raw material evaporating means and the deposited film forming area are formed. So that the material evaporation means has at least two positions relative to the deposition film formation region, and the normal of the most recent evaporation point and the farthest evaporation point of the center of each material evaporation means and the deposition film formation region The following effects were obtained by setting the angle formed between and to be greater than 0 ° and 75 ° or less.
1) It is possible to form a film so as to cover the surface of the foreign matter, dust, etc., on the foreign matter, dust, etc. existing on the electrode, and the shadow portion that is not deposited due to the shadowing phenomenon can be greatly reduced. It became possible to suppress the occurrence of leakage current.
2) An organic EL element can be manufactured without being affected by foreign matter, dust, etc. existing on the electrode, and production efficiency can be improved.
3) The occurrence of leakage current can be suppressed, the luminous efficiency of the organic EL element is improved and the lifetime is extended, and the industrial utility value can be increased.
4) The production process can be simplified without using film forming methods such as spin coating, dipping, and coating, which are considered to have good wraparound.

  FIG. 8 is a schematic diagram showing the positional relationship of the raw material evaporation means when the raw material evaporation means is in two positional relations with respect to the deposited film formation region when forming the deposited film as shown in FIG.

  In the figure, 8 indicates a belt-like plastic film substrate. Reference numeral 9 denotes a deposited film forming region of the belt-shaped plastic film substrate 8. Reference numeral 7a denotes a raw material evaporation means arranged outside the normal line of the edge (one side) of the deposited film formation region 9. Reference numeral 7b denotes the raw material evaporation means when the raw material evaporation means 7a is moved to the edge of the deposited film forming region 9 during vapor deposition. Note that the raw material evaporation means 7b also corresponds to the raw material evaporation means arranged in advance outside the normal line of the edge (opposite side) of the deposited film formation region 9. Q indicates an arbitrary vapor deposition point in the deposited film forming region 9. R represents the intersection of a line connecting the center of the raw material evaporation means 7a and the vapor deposition point Q and a line connecting the center of the raw material evaporation means 7b and the vapor deposition point Q. θ5 represents the angle of intersection R. The intersection angle θ5 is preferably 45 ° to 180 ° in consideration of the uniform coverage of convex foreign matters existing in the deposited film formation region, the efficiency of the deposited film forming material, the uniform and stable formability of the deposited film, and the like. When forming the deposited film, when the material evaporation means is in two positions relative to the deposited film formation region, the positional relationship of each material evaporation means is shown in this figure at any evaporation point in the entire area of the deposited film formation region. It is preferable to have a relationship.

As shown in this figure, when forming the deposited film, if the raw material evaporation means is in two positional relations with respect to the deposited film forming area, the positional relation of each raw material evaporation means is any vapor deposition over the entire area of the deposited film forming area. In this respect, the following effects were obtained by setting the angle of intersection between the vapor deposition point and the center of each raw material evaporation means to 45 ° to 180 °.
1) It is possible to form a film so as to cover the surface of the foreign matter, dust, etc. over the entire area of the deposited film formation with respect to the foreign matter, dust, etc. existing on the electrode. This makes it possible to eliminate the portion and suppress the occurrence of leakage current.
2) An organic EL element can be manufactured without being affected by foreign matter, dust, etc. existing on the electrode, and production efficiency can be improved.
3) The occurrence of leakage current can be suppressed, the luminous efficiency of the organic EL element is improved and the lifetime is extended, and the industrial utility value can be increased.

Further, when forming the deposited film, the relationship between the deposition point of the deposited film forming region and the raw material evaporation means is set to be arranged so that the relationship is larger than 0 ° and not larger than 75 ° as shown in FIG. The effect shown in was obtained.
1) With a small amount of vapor deposition material, it is possible to eliminate the shadow area that is not formed due to the shadowing phenomenon of foreign matter, dust, etc. in the entire area of the deposited film formation region, Savings became possible.
2) An organic EL element can be manufactured without being affected by foreign matter, dust, etc. existing on the electrode, and production efficiency can be improved.
3) The occurrence of leakage current can be suppressed, the luminous efficiency of the organic EL element is improved and the lifetime is extended, and the industrial utility value can be increased.

  Hereinafter, the substrate, the first electrode, the hole transport layer, the light emitting layer, the electron injection layer, the second electrode, the sealing means, etc. constituting the organic EL device according to the present invention will be described.

  Examples of the substrate according to the present invention include a single wafer substrate and a strip-shaped flexible substrate. Examples of the single substrate include a transparent glass plate and a sheet-like transparent resin film. Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Is mentioned. A transparent resin film is mentioned as a strip | belt-shaped flexible board | substrate, The same resin film as a single wafer board | substrate can be used.

When a transparent resin film is used as the substrate, a gas barrier film is preferably formed on the surface of the resin film as necessary. Examples of the gas barrier film include an inorganic film, an organic film, or a hybrid film of both. As a characteristic of the gas barrier film, the water vapor permeability is preferably 0.01 g / m ² · day · atm or less. Furthermore, a high barrier film having an oxygen permeability of 10 ⁻³ ml / m ² / day or less and a water vapor permeability of 10 ⁻⁵ g / m ² / day or less is preferable.

  As a material for forming the barrier film, any material may be used as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and layers made of organic materials. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times. The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma polymerization method, the atmospheric pressure plasma weighting. A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

As the first electrode, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such an electrode substance include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ .ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, the transmittance is desirably greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

  A hole injection layer (anode buffer layer) may be present between the first electrode and the light emitting layer or the hole transport layer. The hole injection layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the luminance of light emission. “The organic EL element and the forefront of industrialization (November 30, 1998, NTS) The details are described in the second volume, Chapter 2, “Electrode Materials” (pages 123 to 166) of “The Company”. Examples of the material used for the anode buffer layer (hole injection layer) include materials described in JP-A No. 2000-160328.

  The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers. The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound. Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two of those described in US Pat. No. 5,061,569. Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-3086 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, it is preferable to use these materials because a light-emitting element with higher efficiency can be obtained.

  Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. This hole transport layer may have a single layer structure composed of one or more of the above materials. A hole transport layer having a high p property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like. It is preferable to use such a hole transport layer having a high p property because an organic EL element with lower power consumption can be produced.

  In the present invention, the light emitting layer refers to a blue light emitting layer, a green light emitting layer, and a red light emitting layer. There is no restriction | limiting in particular as a lamination order in the case of laminating | stacking a light emitting layer, You may have a nonluminous intermediate | middle layer between each light emitting layer. In the present invention, it is preferable that at least one blue light emitting layer is provided at a position closest to the anode in all the light emitting layers. Also, when four or more light emitting layers are provided, for example, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting layer, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting from the order close to the anode. Layered / green light emitting layer, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting layer / green light emitting layer / red light emitting layer, etc. It is preferable for improving luminance stability. A white element can be manufactured by forming a light emitting layer in multiple layers.

  The total thickness of the light emitting layer is not particularly limited, but is usually selected in the range of 2 nm to 5 μm, preferably 2 to 200 nm in consideration of the uniformity of the film and the voltage required for light emission. Furthermore, it is preferable that it exists in the range of 10-20 nm. A film thickness of 20 nm or less is preferable because it has the effect of improving the stability of the emission color with respect to the driving current as well as the voltage surface. The film thickness of each light emitting layer is preferably selected in the range of 2 to 100 nm, and more preferably in the range of 2 to 20 nm. Although there is no restriction | limiting in particular about the film thickness relationship of each light emitting layer of blue, green, and red, It is preferable that the blue light emitting layer (the sum total when there are two or more layers) is the thickest among three light emitting layers.

  The light emitting layer includes at least three layers having different emission spectra, each having an emission maximum wavelength in the range of 430 to 480 nm, 510 to 550 nm, and 600 to 640 nm. If it is three or more layers, there will be no restriction | limiting in particular. When there are more than four layers, there may be a plurality of layers having the same emission spectrum. A layer having an emission maximum wavelength in the range of 430 to 480 nm is referred to as a blue light emitting layer, a layer in the range of 510 to 550 nm is referred to as a green light emitting layer, and a layer in the range of 600 to 640 nm is referred to as a red light emitting layer. Moreover, in the range which maintains the said maximum wavelength, you may mix a several luminescent compound in each light emitting layer. For example, the blue light emitting layer may be used by mixing a blue light emitting compound having a maximum wavelength of 430 to 480 nm and a green light emitting compound having the same wavelength of 510 to 550 nm.

  The organic light emitting material used as the material of the light emitting layer is (a) charge injection function, that is, holes can be injected from the anode or hole injection layer when an electric field is applied, and electrons are injected from the cathode or electron injection layer. (B) a transport function, that is, a function that moves injected holes and electrons by the force of an electric field, and (c) a light emission function, that is, a recombination field of electrons and holes. However, there is no particular limitation as long as it has the three functions of connecting these to light emission. For example, fluorescent whitening agents such as benzothiazole, benzimidazole, and benzoxazole, and styrylbenzene compounds can be used. Specific examples of the above-mentioned optical brightener include 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) -1,3,4-thiadiazole in the benzoxazole series, 4 , 4′-bis (5,7-t-pentyl-2-benzoxazolyl) stilbene, 4,4′-bis [5,7-di- (2-methyl-2-butyl) -2-benzoxa Zoolyl] stilbene, 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) thiophene, 2,5-bis [5-α, α-dimethylbenzyl-2-benzoxazoli Ru] thiophene, 2,5-bis [5,7-di- (2-methyl-2-butyl) -2-benzoxazolyl] -3,4-diphenylthiophene, 2,5-bis (5-methyl) -2-benzoxazolyl) thiophene, 4,4′-bis (2 -Benzoxazolyl) biphenyl, 5-methyl-2- [2- [4- (5-methyl-2-benzoxazolyl) phenyl] vinyl] benzoxazole, 2- [2- (4-chlorophenyl) vinyl Naphtho [1,2-d] oxazole and the like. Examples of the benzothiazole type include 2,2 ′-(p-phenylenedivinylene) -bisbenzothiazole, and examples of the benzimidazole type include 2- [2- [4- (2-benzimidazolyl) phenyl] vinyl] benzimidazole. 2- [2- (4-carboxyphenyl) vinyl] benzimidazole and the like. In addition, other useful compounds are listed in Chemistry of Synthetic Soybean (1971), pages 628-637 and 640.

  Specific examples of the styrylbenzene compound include 1,4-bis (2-methylstyryl) benzene, 1,4-bis (3-methylstyryl) benzene, 1,4-bis (4-methylstyryl). ) Benzene, distyrylbenzene, 1,4-bis (2-ethylstyryl) benzene, 1,4-bis (3-methylstyryl) benzene, 1,4-bis (2-methylstyryl) -2-methylbenzene, 1,4-bis (2-methylstyryl) -2-ethylbenzene and the like can be mentioned.

  Further, in addition to the above-described optical brightener and styrylbenzene compound, for example, 12-phthaloperinone, 1,4-diphenyl-1,3-butadiene, 1,1,4,4-tetraphenyl-1,3- Butadiene, naphthalimide derivatives, perylene derivatives, oxadiazole derivatives, aldazine derivatives, pyrazirine derivatives, cyclopentadiene derivatives, pyrrolopyrrole derivatives, styrylamine derivatives, coumarin compounds, international publications WO 90/13148 and Appl. Phys. Lett. , Vol 58, 18, P1982 (1991), and aromatic dimethylidin compounds. Specific examples of the aromatic dimethylidin compounds include 1,4-phenylene dimethylidin, 4,4′-phenylene dimethylidin, 2,5-xylylene dimethylidin, 2,6-naphthylene dimethylidin, 1,4-biphenylenedimethylidin, 1,4-p-terephenylenedimethylidin, 4,4′-bis (2,2-di-t-butylphenylvinyl) biphenyl, 4,4′-bis (2 , 2-diphenylvinyl) biphenyl and the like, and derivatives thereof. Specific examples of the compound represented by the general formula (I) include bis (2-methyl-8-quinolinolato) (p-phenylphenolate) aluminum (III), bis (2-methyl-8-quinolinolato). ) (1-naphtholate) aluminum (III) and the like.

  In addition, a compound in which the above-described organic light-emitting material is used as a host and the host is doped with a strong fluorescent dye from blue to green, for example, coumarin-based or the same fluorescent dye as the host, is also suitable as the organic light-emitting material. When the above-described compound is used as the organic light-emitting material, blue to green light emission (the emission color varies depending on the type of dopant) can be obtained with high efficiency. Specific examples of the host that is the material of the compound include organic light-emitting materials having a distyrylarylene skeleton (particularly preferably, 4,4′-bis (2,2-diphenylvinyl) biphenyl). Specific examples of the dopant of the material are diphenylaminovinylarylene (particularly preferably, for example, N, N-diphenylaminobiphenylbenzene and 4,4′-bis [2- [4- (N, N-di- -P-tolyl) phenyl] vinyl] biphenyl).

  The light emitting layer preferably contains a known host compound and a known phosphorescent compound (also referred to as a phosphorescent compound) in order to increase the light emission efficiency of the light emitting layer.

  The host compound is a compound contained in the light-emitting layer, the mass ratio in the layer is 20% or more, and the phosphorescence quantum yield of phosphorescence emission is 0.1 at room temperature (25 ° C.). Is defined as less than a compound. The phosphorescence quantum yield is preferably less than 0.01. A plurality of host compounds may be used in combination. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of phosphorescent compounds, it is possible to mix different light emission, thereby obtaining an arbitrary emission color. White light emission is possible by adjusting the kind of phosphorescent compound and the amount of doping, and can also be applied to illumination and backlight.

  As these host compounds, compounds having a hole transporting ability and an electron transporting ability, preventing emission light from being increased in wavelength, and having a high Tg (glass transition temperature) are preferable. Known host compounds include, for example, JP-A Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, and 2002-334786. Gazette, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645 2002-338579, 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227 2002-231453, 2003-3165, 2002-234888, 2003-27048, 2002-255934, 2002-260861, 2002-280183, Examples thereof include compounds described in 2002-299060, 2002-302516, 2002-305083, 2002-305084, 2002-308837 and the like.

  In the case of having a plurality of light emitting layers, it is preferable that 50% by mass or more of the host compound in each layer is the same compound because it is easy to obtain a uniform film property over the entire organic layer. It is more preferable that the light emission energy is 2.9 eV or more because it is advantageous in efficiently suppressing energy transfer from the dopant and obtaining high luminance. Phosphorescence emission energy means the peak energy of the 0-0 band of phosphorescence emission when the photoluminescence of a deposited film of 100 nm is measured on a substrate with a host compound.

  The host compound has a phosphorescence emission energy of 2.9 eV or more and a Tg of 90 ° C. or more in consideration of deterioration of the organic EL device over time (decrease in luminance and film properties), market needs as a light source, and the like. Preferably there is. That is, in order to satisfy both luminance and durability, it is preferable that phosphorescence emission energy is 2.9 eV or more and Tg is 90 ° C. or more. Tg is more preferably 100 ° C. or higher.

  A phosphorescent compound (phosphorescent compound) is a compound in which light emission from an excited triplet is observed, is a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 25. The compound is 0.01 or more at ° C. When used in combination with the host compound described above, an organic EL device with higher luminous efficiency can be obtained.

  The phosphorescent compound according to the present invention preferably has a phosphorescence quantum yield of 0.1 or more. The phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 version, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum yield used in the present invention only needs to achieve the phosphorescence quantum yield in any solvent.

  There are two types of light emission of the phosphorescent compound in principle. One is the recombination of the carrier on the host compound to which the carrier is transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent compound. The energy transfer type, in which light emission from the phosphorescent compound is obtained by moving to the phosphorescent compound, and the other is that the phosphorescent compound becomes a carrier trap, resulting in recombination of the carriers on the phosphorescent compound and from the phosphorescent compound. Although it is a carrier trap type in which light emission can be obtained, in any case, it is a condition that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL device. The phosphorescent compound is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex compound), rare earth Of these, iridium compounds are the most preferred.

  In the present invention, the phosphorescence emission maximum wavelength of the phosphorescent compound is not particularly limited, and can be obtained in principle by selecting a central metal, a ligand, a ligand substituent, and the like. The emission wavelength can be changed.

  The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with the total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.

The white element referred to in the present invention means that the chromaticity in the CIE1931 color system at 1000 cd / m ² is X = 0.33 ± 0.07 when the front luminance at 2 ° C. viewing angle is measured by the above method. It is in the region of Y = 0.33 ± 0.07.

  The electron injection layer is made of a material having a function of transporting electrons and is included in the electron transport layer in a broad sense. The electron injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of the light emission. “Organic EL element and its forefront of industrialization (NST 30, November 30, 1998) Issue) ”, Chapter 2, Chapter 2,“ Electrode Materials ”(pages 123-166). The details of the electron injection layer (cathode buffer layer) are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

  In addition, as an electron transport material (also serving as a hole blocking material) used for the electron transport layer adjacent to the light emitting layer side, it is sufficient if it has a function of transmitting electrons injected from the cathode to the light emitting layer. As a material, any one of conventionally known compounds can be selected and used. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodisides. Examples include methane and anthrone derivatives, oxadiazole derivatives and the like. Furthermore, in the above oxadiazole derivatives, thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group can also be used as the electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  Also, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum. Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. Distyrylpyrazine derivatives can also be used as electron transport materials, and inorganic semiconductors such as n-type-Si and n-type-SiC are also used as electron transport materials in the same manner as the hole injection layer and hole transport layer. I can do it. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  An electron transport layer having a high n property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like. It is preferable to use such an electron transport layer having a high n property because an element with lower power consumption can be manufactured.

As the second electrode, a material having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, aluminum and the like. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the first electrode (anode) or the second electrode (cathode) of the organic EL element is transparent or translucent, the emission luminance is advantageously improved.

  Moreover, after producing the metal with a thickness of 1 to 20 nm on the second electrode, the conductive transparent material mentioned in the description of the first electrode is produced thereon, so that a transparent or translucent second electrode ( A cathode) can be manufactured, and by applying this, an element in which both the first electrode (anode) and the second electrode (cathode) are transmissive can be manufactured.

As a sealing means, it is a means for preventing the performance deterioration by the penetration | invasion of the water | moisture content or oxygen to an organic EL element, for example, the method of adhere | attaching a sealing member, an electrode, and a support base | substrate with an adhesive agent is mentioned. it can. The sealing member may be disposed so as to cover the display area of the organic EL element, and may be concave or flat. Further, transparency and electrical insulation are not particularly limited. Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum. In the present invention, a polymer film and a metal film can be preferably used because the element can be thinned. Furthermore, the polymer film preferably has an oxygen permeability of 10 ⁻³ ml / m ² / day or less and a water vapor permeability of 10 ⁻⁵ g / m ² / day or less. For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

  Specific examples of the adhesive include photocuring and thermosetting adhesives having a reactive vinyl group of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylate. be able to. Moreover, the heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  In addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print it like screen printing.

  In addition, it is also preferable to coat the electrode and the organic layer on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and form an inorganic or organic layer in contact with the support substrate to form a sealing film. it can. In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of the element such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can. Furthermore, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials. The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

  In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil is injected in the gas phase and the liquid phase. Is preferred. A vacuum can also be used. Moreover, a hygroscopic compound can also be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (eg, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide), sulfates (eg, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.). Metal halides (eg, calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide, etc.), perchloric acids (eg, barium perchlorate, In particular, anhydrous salts are preferably used in sulfates, metal halides and perchloric acids.

  The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100. In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

  The organic EL device of the present invention preferably uses the following method in combination in order to efficiently extract light generated in the light emitting layer. The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1), and only about 15% to 20% of the light generated in the light emitting layer can be extracted. It is generally said that there is no. This is because the light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the element, or the transparent electrode or light emitting layer and the transparent substrate This is because the light undergoes total reflection between them, the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the side of the device.

  As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435). A method for improving efficiency by providing a substrate with a light condensing property (JP-A-63-314795). A method of forming a reflective surface on the side surface of an element (Japanese Patent Laid-Open No. 1-220394). A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between a substrate and a light emitter (Japanese Patent Laid-Open No. 62-172691). A method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter (Japanese Patent Laid-Open No. 2001-202827). There is a method of forming a diffraction grating between any one of the substrate, the transparent electrode layer, and the light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951).

  In the present invention, these methods can be used in combination with an organic EL element. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, a transparent electrode layer, A method of forming a diffraction grating between any layers of the light emitting layer (including between the substrate and the outside) can be suitably used. In the present invention, by combining these means, it is possible to obtain an element having higher luminance or durability.

  When a low refractive index medium is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower. . Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less. The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate. The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency. This method is generated from the light emitting layer by utilizing the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Of the light, the light that cannot go out due to total reflection between layers, etc. is diffracted by introducing a diffraction grating into any layer or medium (inside a transparent substrate or transparent electrode) , Trying to extract light out. The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. The light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.

  As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated. At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium. The arrangement of the diffraction grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.

  Furthermore, the organic EL device of the present invention is processed so as to provide, for example, a structure on the microlens array on the light extraction side of the substrate in order to efficiently extract light generated in the light emitting layer, or so-called condensing. By combining with the sheet, the luminance in the specific direction can be increased by collecting light in a specific direction, for example, in the front direction with respect to the element light emitting surface. As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used. As the shape of the prism sheet, for example, the substrate may be formed with a triangle stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded, and the pitch is randomly changed. The shape may be other shapes. Moreover, in order to control the light emission angle from a light emitting element, you may use a light-diffusion plate and a film together with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

  Hereinafter, although an example is given and the concrete effect of the present invention is shown, the mode of the present invention is not limited to this.

Example 1
FIG. 3 is a flow chart showing an organic EL element having a size of one dot of 2 mm × 2 mm and a total of 70 dots (light emitting area) of 7 dots × 10 dots, using the manufacturing apparatus shown in FIG. It produced according to.

(Preparation of substrate)
A soda-lime glass having a thickness of 1.1 mm, a width of 40 mm, and a length of 60 mm was prepared as a substrate. In addition, the surface of the soda-lime glass used was a silica-coated glass for protection from acid and alkali.

(Formation of the first electrode)
The prepared glass substrate was cleaned by irradiation at a distance of 12 mm with an irradiation intensity of 15 mW / cm ² using a low-pressure mercury lamp having a wavelength of 184.2 nm. Thereafter, using the first electrode forming vapor deposition apparatus shown in FIG. 4 and using indium tin oxide (ITO) under a vacuum of 5 × 10 ⁻⁴ Pa, the deposited film forming region ( In the first electrode formation region, a patterned first electrode having a width of 2 mm, a length of 50 mm, an interval of 2 mm, a thickness of 150 nm, and 7 rows was formed. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region).

(Formation of hole transport layer)
N, N′-diphenyl-N is used as a material for forming a hole transport layer in a vapor transport layer forming vapor deposition apparatus under a vacuum of 5 × 10 ⁻⁴ Pa using a glass substrate on which a first electrode is formed. , N′-m-tolyl 4,4′-diamino-1,1′-biphenyl (hereinafter referred to as TPD), except for one end of the first electrode formed on the glass substrate. On top of this, vapor deposition (vapor deposition) was performed.

  Two raw material evaporation containers are arranged with respect to the normal line of the edge of the deposited film forming area as shown in Table 1, and when forming the deposited film formation, the evaporation points (of the raw material evaporation container and the deposited film forming area ( The relationship between the latest deposition point and the farthest deposition point) is as shown in FIG. When depositing the hole transport layer forming material, the line connecting the nearest deposition point of the deposited film forming region of the source evaporation means and the center of the source evaporation container containing the hole transport layer forming material, The angle θ1 (θ3) formed with the normal line, the angle between the line connecting the farthest vapor deposition point in the deposited film formation region and the center of the source evaporation container, and the normal line at the farthest vapor deposition point, The hole transport layer was formed as shown in 1-1 and changed to 1-1 to 1-15. The thickness of the hole transport layer was 50 nm.

<Production of organic EL element>
Each glass substrate No. 1 on which a hole transport layer is formed. 1-1 to 1-15, and a light emitting layer, an electron transport layer, a second electrode layer, and a sealing layer are sequentially laminated by the method shown below to produce an organic EL element. 101-115.

(Formation of light emitting layer)
Each glass substrate No. 1 on which a hole transport layer is formed. 1-1 to 1-15, Alq ₃ is used as a light emitting layer forming material on the hole transport layer, and vapor deposition is performed with a light emitting layer forming vapor deposition apparatus under a vacuum of 5 × 10 ⁻⁴ Pa. did. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region). The thickness of the light emitting layer was 50 nm.

(Formation of electron transport layer)
Using a glass substrate on which a light emitting layer is formed, using LiF as a material for forming an electron transport layer in a region where a hole transport layer is formed including the light emitting layer, under a vacuum of 5 × 10 ⁻⁴ Pa LiF was deposited using an electron transport layer forming vapor deposition apparatus. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region). The thickness of the electron transport layer was 0.5 nm.

(Formation of second electrode)
Using a glass substrate on which an electron transport layer is formed, using Al as the second electrode forming material in a direction perpendicular to the first electrode on the electron transport layer, and under a vacuum of 5 × 10 ⁻⁴ Pa Then, Al was vapor-deposited by a second electrode forming vapor deposition apparatus. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region). The formed second electrode had a width of 2 mm, a length of 35 mm, an interval of 2 mm, a thickness of 150 nm, and a 10-row pattern.

(Formation of sealing layer)
A glass substrate on which the second electrode is formed is used, and SiOx is used as a sealing layer forming material in a region where the second electrode is formed except for an end portion of the second electrode, and 5 × 10 ⁻⁴ Pa. SiOx was vapor-deposited with a sealing layer forming vapor deposition apparatus under vacuum. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region). The thickness of the sealing layer was 300 nm.

(Evaluation)
Each prepared document No. Table 2 shows the results of the leak current characteristics tested by the test method shown below and evaluated according to the evaluation rank shown below.

Test Method for Leakage Current Characteristics Using a constant voltage power source, a reverse voltage (reverse bias) was applied at 5 V for 5 seconds, and the current flowing through the device at that time was measured. Measurement was performed for all 70 dots (light emitting region), and the maximum current value was defined as a leakage current.

Evaluation ranks of leakage current ◎: 1 less than ^{× 10- 8 A ○: 1 ×} 10- 8 A or more and less than ^{1 × 10- 6 A △: 1} × 10- 6 A or more, 1 × 10- ⁴ A less ×: 1 × 10- ⁴ A more

  The effectiveness of the present invention was confirmed.

Example 2
FIG. 3 is a flow chart showing an organic EL element having a size of one dot of 2 mm × 2 mm and a total of 70 dots (light emitting area) of 7 dots × 10 dots, using the manufacturing apparatus shown in FIG. It produced according to.

(Preparation of substrate)
A soda-lime glass having a thickness of 1.1 mm, a width of 40 mm, and a length of 60 mm was prepared as a substrate. In addition, the surface of the soda-lime glass used was a silica-coated glass for protection from acid and alkali.

(Formation of the first electrode)
The prepared glass substrate was irradiated with a low pressure mercury lamp having a wavelength of 184.2 nm, irradiated at a distance of 12 mm at an irradiation intensity of 15 mW / cm ² , and washed with a plate. Then, the first electrode forming vapor deposition apparatus shown in FIG. Using indium tin oxide (ITO) under a vacuum of 5 × 10 ⁻⁴ Pa, the deposited film formation region (first electrode formation region) of the prepared glass substrate has a width of 2 mm, a length of 50 mm, and an interval of 2 mm. A patterned first electrode having a thickness of 150 nm and 7 rows was formed.

  One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region).

(Formation of hole transport layer)
Using a glass substrate on which the first electrode is formed, using TPD as a hole transport layer forming material in a hole transport layer forming vapor deposition apparatus under a vacuum of 5 × 10 ⁻⁴ Pa, and on the glass substrate Vapor deposition (vapor phase deposition) was performed on the first electrode except for one end portion of the first electrode formed in (1). As shown in Table 1, one source evaporation container is arranged with respect to the normal line of the edge of the deposited film formation region. When forming the deposited film formation, the source evaporation container is moved to move the source evaporation container. The relationship between the deposition point of the deposited film formation region (the latest deposition point and the farthest deposition point) is as shown in FIG. The position of the deposited film formation area when depositing the hole transport layer forming material is the center of the raw material evaporation container containing the hole transport layer forming material. , The angle θ1 (θ3) formed by the normal line at the latest vapor deposition point, the line connecting the farthest vapor deposition point in the deposited film formation region and the center of the source evaporation vessel, and the normal line at the farthest vapor deposition point As shown in Table 3, the hole transport layer was formed by changing the angle θ2 (θ4) formed with 2-1 to 2-15. The thickness of the hole transport layer was 50 nm.

<Production of organic EL element>
Each glass substrate No. 1 on which a hole transport layer is formed. 2-1 to 2-15 are used, and a light emitting layer, an electron transport layer, a second electrode layer, and a sealing layer are sequentially laminated by the method shown below to produce an organic EL element. 201-215.

(Formation of light emitting layer)
Each glass substrate No. 1 on which a hole transport layer is formed. 2-1 to 2-15 are used, aligned with the pattern of the first electrode on the hole transport layer, Alq ₃ is used as a light emitting layer forming material, and light is emitted under a vacuum of 5 × 10 ⁻⁴ Pa. Vapor deposition was performed with a layer-forming vapor deposition apparatus. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region). The thickness of the light emitting layer was 50 nm.

(Formation of electron transport layer)
Using a glass substrate on which a light emitting layer is formed, using LiF as a material for forming an electron transport layer in a region where a hole transport layer is formed including the light emitting layer, under a vacuum of 5 × 10 ⁻⁴ Pa LiF was deposited using an electron transport layer forming vapor deposition apparatus. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region). The thickness of the electron transport layer was 0.5 nm.

(Formation of second electrode)
Using a glass substrate on which an electron transport layer is formed, using Al as the second electrode forming material in a direction perpendicular to the first electrode on the electron transport layer, and under a vacuum of 5 × 10 ⁻⁴ Pa Then, Al was vapor-deposited by a second electrode forming vapor deposition apparatus. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region). The formed second electrode had a width of 2 mm, a length of 35 mm, an interval of 2 mm, a thickness of 150 nm, and a 10-row pattern.

(Formation of sealing layer)
A glass substrate on which the second electrode is formed is used, and SiOx is used as a sealing layer forming material in a region where the second electrode is formed except for an end portion of the second electrode, and 5 × 10 ⁻⁴ Pa. SiOx was vapor-deposited with a sealing layer forming vapor deposition apparatus under vacuum. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region). The thickness of the sealing layer was 300 nm.

(Evaluation)
Each prepared sample No. Table 4 shows the results of the leakage current characteristics tested by the same test method as in Example 1 and evaluated according to the same evaluation rank as in Example 1.

  The effectiveness of the present invention was confirmed.

Example 3
FIG. 3 is a flow chart showing an organic EL element having a size of one dot of 2 mm × 2 mm and a total of 70 dots (light emitting area) of 7 dots × 10 dots, using the manufacturing apparatus shown in FIG. It produced according to.

(Preparation of substrate)
As a substrate, soda lime having a thickness of 1.1 mm, a width of 40 mm, and a length of 60 mm was prepared. In addition, the surface of the soda-lime glass used was a silica-coated glass for protection from acid and alkali.

(Formation of the first electrode)
The prepared glass substrate was subjected to plate cleaning using a low pressure mercury lamp with a wavelength of 184.2 nm, irradiation intensity of 15 mW / cm ² and distance of 12 mm, and then the first electrode forming vapor deposition apparatus shown in FIG. Two raw material evaporation containers in which ITO was put when forming a deposited film were placed so as to be in the position shown in FIG. 8, and indium tin oxide (ITO) was applied under a vacuum of 5 × 10 ⁻⁴ Pa. Were used to form a patterned first electrode having a width of 2 mm, a length of 50 mm, an interval of 2 mm, a thickness of 150 nm, and seven rows in a deposited film formation region (first electrode formation region) of the prepared glass substrate. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region).

(Formation of hole transport layer)
Using a glass substrate on which the first electrode is formed, except for one end of the first electrode formed on the glass substrate, TPD is used as a hole transport layer forming material in the deposited film formation region. Evaporation (vapor phase deposition) was performed in a hole transport layer forming vapor deposition apparatus in which two raw material evaporation containers were arranged at a position as shown in FIG. 8 under a vacuum of × 10 ⁻⁴ Pa. The raw material evaporation container has a line connecting the center of one raw material evaporation container and the vapor deposition point of the deposited film formation region (first electrode formation region), and the other single raw material evaporation container and the deposited film formation region ( A line connecting the vapor deposition point of the first electrode forming region) and the intersection angle θ5 of the intersection are changed as shown in Table 5 to form a hole transport layer. 3-1 to 3-10.

  Further, the relationship between the raw material evaporation container containing the hole transport layer forming material and the deposited film formation region when vapor-depositing the hole transport layer forming material is as shown in FIG. The positional relationship between the deposited film forming region and the vapor deposition point (nearest vapor deposition point, farthest vapor deposition point) is an angle θ1 (θ3) formed by a line connecting the center of the raw material evaporation container and a normal line at the latest vapor deposition point. The angle θ2 (θ4) formed between the line connecting the farthest vapor deposition point in the deposited film formation region and the center of the raw material evaporation vessel and the normal at the farthest vapor deposition point was 50 °. The thickness of the hole transport layer was 50 nm.

<Production of organic EL element>
Each glass substrate No. 1 on which a hole transport layer is formed. 3-1 to 3-9 were used, and the organic EL device was prepared by sequentially laminating the light emitting layer, the electron transport layer, the second electrode layer, and the sealing layer by the method shown below. 301 to 309.

(Formation of light emitting layer)
Using each glass substrate on which the hole transport layer is formed, aligning with the pattern of the first electrode on the hole transport layer, using Alq ₃ as the light emitting layer forming material, and a vacuum of 5 × 10 ⁻⁴ Pa Below, it vapor-deposited with the light emitting layer formation vapor deposition apparatus. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region). The thickness of the light emitting layer was 50 nm.

(Formation of electron transport layer)
Using a glass substrate on which a light emitting layer is formed, using LiF as a material for forming an electron transport layer in a region where a hole transport layer is formed including the light emitting layer, under a vacuum of 5 × 10 ⁻⁴ Pa LiF was deposited using an electron transport layer forming vapor deposition apparatus. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region). The thickness of the electron transport layer was 0.5 nm.

(Formation of second electrode)
Using a glass substrate on which an electron transport layer is formed, using Al as the second electrode forming material on the light emitting layer in a direction orthogonal to the first electrode, under a vacuum of 5 × 10 ⁻⁴ Pa Al was vapor-deposited by a second electrode forming vapor deposition apparatus. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region). The formed second electrode had a width of 2 mm, a length of 35 mm, an interval of 2 mm, a thickness of 150 nm, and a 10-row pattern.

(Formation of sealing layer)
Using the glass substrate on which the second electrode is formed, and using the SiOx as the sealing layer forming material in the region where the electron transport layer is formed except for the end of the second electrode, 5 × 10 ⁻⁴ Pa SiOx was vapor-deposited with a sealing layer forming vapor deposition apparatus under vacuum. One raw material evaporation container was placed inside the normal line of the edge of the deposited film formation region (approximately the center of the deposited film formation region). The thickness of the sealing layer was 300 nm.

(Evaluation)
Each prepared sample No. Table 6 shows the results of the leakage current characteristics tested by the same test method as in Example 1 and evaluated according to the same evaluation rank as in Example 1.

  The effectiveness of the present invention was confirmed.

Example 4
FIG. 3 shows a flow chart of an organic EL element having a size of one dot of 2 mm × 2 mm and 7 dots × 10 dots and a total of 70 dots (light emitting area) using the manufacturing apparatus shown in FIG. It produced according to.

(Preparation of belt-like support)
A polyethylene terephthalate film (a film made by Teijin-Dyupon Co., Ltd., hereinafter referred to as a winding roll shape around a winding core having a thickness of 100 μm, a width of 100 mm, and a length of 30 m, previously marked with a transparent gas barrier layer and a deposited film forming region. (Abbreviated as PET).

(Formation of a transparent gas barrier layer)
On the prepared PET, a transparent gas barrier layer having a thickness of about 90 nm was formed by an atmospheric pressure plasma discharge treatment method. As a result of measuring the water vapor transmission rate by a method based on JISk-7129B, it was 10 ⁻³ g / m ² / day or less. As a result of measuring the oxygen transmission rate by a method based on JISk-7126B, it was 10 ⁻³ g / m ² / day or less.

(Formation of the first electrode)
The prepared PET was irradiated with a low pressure mercury lamp with a wavelength of 184.2 nm and irradiated at a distance of 12 mm with an irradiation intensity of 15 mW / cm ² , and then the first electrode forming vapor deposition apparatus shown in FIG. 5 was used. The raw material evaporation container containing ITO was placed outside the normal line of the deposited film formation region, and indium tin oxide (ITO) was used under a vacuum of 5 × 10 ⁻⁴ Pa, and the deposited film of the prepared PET substrate In the formation region (first electrode formation region), a patterned first electrode having a width of 2 mm, a length of 60 mm, an interval of 2 mm, a thickness of 150 nm, and 7 rows was formed. The formation position of the first electrode was controlled by the control means by detecting the mark attached to the PET substrate.

  It should be noted that the positional relationship between the raw material evaporation container in which ITO is deposited when depositing ITO and the vapor deposition point (most recent vapor deposition point, farthest vapor deposition point) of the deposited film formation region is a line connecting the center of the raw material vaporization container. The distance between the center of the source vapor deposition container and each deposition point (most recent deposition point, the farthest deposition point) in the deposited film forming region is substantially equal (approximately the center of the deposited film forming region) inside the normal line at the most recently deposited point. One was arranged.

(Formation of hole transport layer)
Using a PET substrate on which the first electrode is formed, except for one end of the first electrode formed on the PET substrate, TPD is used as a hole transport layer forming material in the deposited film formation region. Vapor deposition (vapor phase deposition) was performed with a hole transport layer forming vapor deposition apparatus under a vacuum of × 10 ⁻⁴ Pa. The positional relationship between the raw material evaporation container and the deposited film forming region is as shown in FIG. 7, and a line connecting the center of the raw material evaporation container containing the hole transport layer forming material by transporting and moving the PET base material. And the angle θ1 between the normal line at the vapor deposition point (most recent vapor deposition point and the farthest vapor deposition point), the line connecting the recent vapor deposition point in the deposited film formation region and the center of the raw material evaporation vessel, and the normal line at the recent vapor deposition point Table 7 shows the angle θ1 (θ3) formed between the line, the line connecting the farthest vapor deposition point in the deposited film formation region and the center of the source evaporation container, and the normal θ at the farthest vapor deposition point. The hole transport layer is formed by changing the arrangement as shown in FIG. 4-1 to 4-12. The thickness of the hole transport layer was 50 nm.

<Production of organic EL element>
Each PET substrate No. with a hole transport layer formed thereon 4-1 to 4-12 are used, and a light emitting layer, an electron transport layer, a second electrode layer, and a sealing layer are sequentially laminated by the method shown below to produce an organic EL element. 401 to 412.

(Formation of light emitting layer)
Using each PET substrate on which the hole transport layer is formed, aligning with the pattern of the first electrode on the hole transport layer, using Alq ₃ as the light emitting layer forming material, and a vacuum of 5 × 10 ⁻⁴ Pa It vapor-deposited with the light emitting layer forming vapor deposition apparatus under. The positional relationship between the source evaporation container and the deposition point (most recent evaporation point, farthest evaporation point) of the deposited film formation region is located between the line connecting the center of the source evaporation container and the normal line at the latest evaporation point. One unit was arranged so that the distance between the center of the raw material vapor deposition vessel and each vapor deposition point (most recent vapor deposition point, farthest vapor deposition point) in the deposited film formation region was substantially equal (approximately the center of the deposited film formation region). The thickness of the light emitting layer was 50 nm.

(Formation of electron transport layer)
Using a PET substrate on which a light emitting layer is formed, using LiF as a material for forming an electron transport layer in a region where a hole transport layer is formed including the light emitting layer, under a vacuum of 5 × 10 ⁻⁴ Pa LiF was deposited using an electron transport layer forming vapor deposition apparatus. The positional relationship between the source evaporation container and the deposition point (most recent evaporation point, farthest evaporation point) of the deposited film formation region is located between the line connecting the center of the source evaporation container and the normal line at the latest evaporation point. One unit was arranged so that the distance between the center of the raw material vapor deposition vessel and each vapor deposition point (most recent vapor deposition point, farthest vapor deposition point) in the deposited film formation region was substantially equal (approximately the center of the deposited film formation region). The thickness of the electron transport layer was 0.5 nm.

(Formation of second electrode)
Using a PET substrate on which an electron transport layer is formed, using Al as the second electrode forming material in a direction perpendicular to the first electrode on the electron transport layer, and under a vacuum of 5 × 10 ⁻⁴ Pa Then, Al was vapor-deposited by a second electrode forming vapor deposition apparatus. The positional relationship between the source evaporation container and the deposition point (most recent evaporation point, farthest evaporation point) of the deposited film formation region is located between the line connecting the center of the source evaporation container and the normal line at the latest evaporation point. One unit was arranged so that the distance between the center of the raw material vapor deposition vessel and each vapor deposition point (most recent vapor deposition point, farthest vapor deposition point) in the deposited film formation region was substantially equal (approximately the center of the deposited film formation region). The formed second electrode had a width of 2 mm, a length of 50 mm, an interval of 2 mm, a thickness of 150 nm, and a 10-row pattern.

(Formation of sealing layer)
When using the PET substrate on which the second electrode is formed and using SiOx as a sealing layer forming material in the region where the electron transport layer is formed except for the end of the second electrode, and forming the deposited film, the SiOx the raw material evaporating vessel arranged two so that such a position shown in FIG. 8 placed, was deposited SiOx with a sealing layer formed vapor deposition apparatus at a vacuum of 5 × 10 ^-4 Pa. The positional relationship between the source evaporation container and the deposition point (most recent evaporation point, farthest evaporation point) of the deposited film formation region is located between the line connecting the center of the source evaporation container and the normal line at the latest evaporation point. One unit was arranged so that the distance between the center of the raw material vapor deposition vessel and each vapor deposition point (most recent vapor deposition point, farthest vapor deposition point) in the deposited film formation region was substantially equal (approximately the center of the deposited film formation region). The thickness of the sealing layer was 300 nm.

(Evaluation)
Each prepared sample No. Table 8 shows the results of the leakage current characteristics tested by the same test method as in Example 1 and evaluated according to the same evaluation rank as in Example 1.

  The effectiveness of the present invention was confirmed.

It is a schematic diagram of the manufacturing method of the organic EL element which uses a single-wafer sheet-like board | substrate. It is a schematic diagram of the manufacturing method of the organic EL element which uses a strip | belt-shaped plastic film board | substrate. FIG. 3 is a schematic flow diagram showing step by step until a passive organic EL element is manufactured by the manufacturing apparatus shown in FIG. 2. It is the schematic of the 1st electrode formation vapor deposition apparatus shown by FIG. FIG. 3 is an enlarged schematic view of the first electrode forming vapor deposition apparatus shown in FIG. 2. It is the expansion schematic of the 1st electrode formation vapor deposition apparatus at the time of using two support rolls and an auxiliary | assistant board for the holding | maintenance means of a board | substrate. It is a schematic diagram which shows the positional relationship of a raw material evaporation means and the deposited film formation area | region of a strip | belt-shaped plastic film substrate when forming a deposited film. FIG. 8 is a schematic diagram showing the positional relationship of each raw material evaporation means when the raw material evaporation means is in two positional relationships with respect to the deposited film formation region when forming a deposited film as shown in FIG. 7. It is a schematic sectional drawing which shows an example of the laminated constitution of an organic EL element.

Explanation of symbols

1 Organic EL element 101, 3, 6 Substrate 102 First electrode (anode)
103 hole transport layer 104 light emitting layer 105 electron injection layer 106 second electrode (cathode)
107 Sealing layer 2, 3 Manufacturing apparatus 201, 301 Supply unit 201 a to 201 f Single wafer sheet substrate 202, 302 Substrate cleaning apparatus 203, 304 First electrode forming vapor deposition apparatus 204, 305, 305 ′ Hole transport layer Formation vapor deposition apparatus 204a, 305a, 305'a Deposition chamber 204b, 305b, 305'b Substrate holding means 204c, 305c, 305'c Mask arrangement means 204d, 305d, 305'd, 7a, 7b Raw material evaporation means 204d1, 305d1, 305'd1 Raw material containers 204e, 305e Control means 205, 306 Light emitting layer forming vapor deposition apparatus 206, 307 Electron injection layer forming vapor deposition apparatus 207, 308 Second electrode forming vapor deposition apparatus 208 Sealing layer forming gas Phase deposition device 209 Collection unit 5, 8 Strip plastic film substrate 9 Deposited film A region O recently deposited point (the farthest deposition point)
P Farthest deposition point (recent deposition point)
Q Deposition point R Intersection point θ1-θ4 Angle θ5 Intersection angle

Claims (11)

Using a manufacturing apparatus including a step of sequentially forming an anode layer including at least a first electrode, an organic compound layer including a light emitting layer, and a cathode layer including a second electrode on a substrate, the organic including the light emitting layer In the method of manufacturing an organic electroluminescence element in which at least one of the compound layers is formed using a vapor deposition apparatus,
The vapor deposition apparatus includes a vapor deposition chamber that is depressurized by a depressurization unit, a substrate holding unit for a substrate, a mask arrangement unit for a mask that regulates a deposition film formation region with respect to the substrate, and a raw material evaporation unit that evaporates the raw material. Have
The raw material evaporation means is disposed outside the normal line of the edge of the deposited film formation region,
When forming a deposited film in the deposited film forming region by the vapor deposition apparatus,
The positional relationship between the raw material evaporation means and the deposited film formation region is as follows:
A method of manufacturing an organic electroluminescence element, wherein the raw material evaporation means is in at least two positional relationships with respect to the deposited film formation region. 2. The method of manufacturing an organic electroluminescent element according to claim 1, wherein when forming the deposited film, either the raw material evaporation means or the substrate is moved. When forming the deposited film, the positional relationship between the raw material evaporation means and the deposited film formation region is such that the center of the raw material evaporation means and the nearest deposition point of the deposited film formation region are O, and the farthest vapor deposition point is P. An angle formed by a line connecting the center of the raw material evaporation means and the nearest vapor deposition point O and a normal line of the nearest vapor deposition point O; a line connecting the center of the raw material evaporation means and the farthest vapor deposition point P; 3. The method of manufacturing an organic electroluminescence element according to claim 1, wherein an angle formed with the normal line of the farthest vapor deposition point P is greater than 0 ° and 75 ° or less. When forming the deposited film, the raw material evaporation means in at least two positional relations with respect to the deposited film forming region,
2. An intersection angle between intersections of all vapor deposition points in the deposited film formation region and a line connecting the centers of the raw material evaporation means has a positional relationship of 45 ° to 180 °. The manufacturing method of the organic electroluminescent element of any one of -3. When forming the deposited film, the positional relationship between the raw material evaporation means and the deposited film forming area, which are in a plurality of positional relations with respect to the deposited film forming area, is determined by the latest evaporation of the center of the raw material evaporation means and the deposited film forming area. When the point is O and the farthest vapor deposition point is P, the angle formed by the line connecting the center of the raw material evaporation means and the nearest vapor deposition point O and the normal line of the nearest vapor deposition point O, The angle formed by the line connecting the center and the farthest vapor deposition point P and the normal line of the farthest vapor deposition point P is greater than 0 ° and 75 ° or less,
Of the raw material evaporation means having a plurality of positional relations with respect to the deposited film forming region, the two raw material evaporation means at arbitrary positions may be formed by arbitrarily depositing the center of each of the raw material evaporation means and the deposited film forming region. The method for producing an organic electroluminescent element according to any one of claims 1 to 3, wherein the intersection angle at a point of intersection with a line connecting the points has a positional relationship of 45 ° to 180 °. . The method for manufacturing an organic electroluminescent element according to claim 1, wherein the substrate is a single wafer. The method for manufacturing an organic electroluminescent element according to claim 1, wherein the substrate is a strip-shaped plastic film. The method for manufacturing an organic electroluminescence element according to claim 1, wherein the substrate holding means is a flat plate having holding means. The method for manufacturing an organic electroluminescent element according to any one of claims 1 to 7, wherein the substrate holding means is a backup roll. The organic electroluminescence element according to any one of claims 1 to 7, wherein the substrate holding means is two support rolls and an auxiliary plate disposed between the support rolls. Production method. An organic electroluminescence element produced by the method for producing an organic electroluminescence element according to claim 1.

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