JP2006013464A - Luminous element, display, and television - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin film luminous element of low-driving-voltage, and a thin film luminous element where the deterioration of color purity and luminous efficiency do not occur even if the thin film luminous element has a structure of low-driving-voltage. <P>SOLUTION: The structure of the film luminous element to solve the above problem includes at least an electron transmitting layer, a luminous layer containing a luminous substance, a first area, and a second area. The electron transmitting layer has the second area between the luminous layer and the first area, and a substance having a polycyclic condensed ring is contained in the first area, and the substance having the ploycyclic condensed ring is not contained in the second area. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a light emitting element, and more particularly to a structure of a light emitting element that is driven at a relatively low driving voltage.

  Development of a display using a self-luminous thin-film light-emitting element that emits light when an electric current flows is being actively promoted.

  These thin-film light-emitting elements emit light when an electrode is connected to a single-layer or multi-layer thin film formed using organic, inorganic, or both, and an electric current is applied. Such thin-film light emitting devices are expected to have low power consumption, space saving, visibility, and the like, and further expansion of the market is expected in the future.

Among these, a light emitting element having a multi-layer structure is capable of creating an element that emits light more efficiently than before by dividing the function for each layer (see, for example, Non-Patent Document 1). .
C. W. Tan et al., Applied Physics Letters, Vol. 51, no. 12, 913-915 (1987)

A thin-film light-emitting element having a multilayer structure sandwiches a light-emitting laminate composed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and the like between an anode and a cathode. Of these, a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer may be used depending on the element structure. In addition, the hole transport layer and the electron transport layer may also serve as a light emitting layer. In this case, a technique is used in which an electron transport layer or a hole transport layer having a high carrier transport property is doped with a dye having a high light emission efficiency. By using this method, a material having high emission efficiency but low carrier transportability can be used as the light-emitting substance (see, for example, Non-Patent Document 2).
C. W. Tan et al., Journal of Applied Physics, Vol. 65, no. 9, 3710-3716 (1989)

By the way, light emission can be obtained by passing a current through the thin-film light emitting element, and a proportional relationship is established between the luminance of the light emission and the flowing current. That is, in order to obtain a large luminance, it is necessary to pass a large current. For this reason, attempts have been made to make it easier to flow current by doping an additive into at least a part of a thin film laminated between electrodes of a light emitting element, and to lower the driving voltage. In this case, since a relatively small voltage is required to obtain the same luminance, deterioration of the thin film light emitting element is also suppressed (see Patent Document 1).
Japanese Patent Laid-Open No. 2003-77676

  In Patent Document 1, a substance having a polycyclic condensed ring such as diphenylanthracene or rubrene having a relatively good carrier transport property is used as an additive. The effect is obtained.

  However, many substances having a polycyclic fused ring that are suitably used as these additives emit light themselves. Therefore, when the energy gap of the luminescent material in the luminescent layer is larger than those additives, the energy of the excited luminescent material is transferred to the additive added to the electron transport layer, and the additive is also excited. May emit light. In addition, even if light is not emitted, the energy is transferred, which may cause a decrease in light emission efficiency.

  As described above, it is not preferable to emit light other than the light emitting material in the light emitting layer, since the color purity is deteriorated. Therefore, when using an additive, energy larger than the energy gap of the light emitting material in the light emitting layer is usually used. Additives with gaps are used. Also in Example 1 of Patent Document 1, diphenylanthracene having an energy gap larger than that of rubrene doped as a light emitting substance in the light emitting layer is used as an additive.

  However, if the light emitting material emits red light, the energy gap is small, so it is easy to select an additive that satisfies the conditions. However, if light emission from a light emitting material having a larger energy gap is required, the options are: The current situation is getting narrower. For reference, rubrene has good electron-injection and electron-transport properties by doping the electron-injection layer and the electron-transport layer in an appropriate amount, but its emission is yellow, so it has a larger energy gap. It turns out that it is not preferable to use it for a light-emitting element having a light-emitting layer using a substance (a substance exhibiting light emission of green to purple).

  Accordingly, an object of the present invention is to provide a thin film light emitting element with a low driving voltage. It is another object of the present invention to provide a thin film light emitting element that does not cause a decrease in color purity or light emission efficiency even in a thin film light emitting element having a configuration with a low driving voltage.

  One configuration of a thin-film light-emitting element for solving the above problem includes a light-emitting layer containing at least an electron transport layer and a light-emitting substance between electrodes, and the electron transport layer includes a first region closer to the electrode and the first region. The second region is closer to the light emitting layer. The first region contains a substance having a polycyclic fused ring, and the second region does not contain a substance having the polycyclic fused ring.

One structure of a thin-film light-emitting element for solving the above problem includes at least an electron transport layer, a light-emitting layer containing a light-emitting substance, a first region, and a second region between electrodes, and the electron transport The layer has the second region between the light emitting layer and the first region. The first region includes a substance having a polycyclic fused ring, and the second region does not include a substance having the polycyclic fused ring.
As another configuration, the electrode includes at least an electron transport layer, a light-emitting layer containing a light-emitting substance, a first region, and a second region, and the electron transport layer includes the light-emitting layer and the first region. The second region is provided between the regions. The concentration of the substance having a polycyclic fused ring in the first region is higher than that in the second region.
As another configuration, the electrode includes at least an electron transport layer, a light-emitting layer containing a light-emitting substance, a first region, and a second region, and the electron transport layer includes the light-emitting layer and the first region. The second region is provided between the regions. Then, a substance having a polycyclic fused ring is selectively added to the first region.

  By using the structure of the present invention, a thin film light-emitting element with a low driving voltage can be provided. Further, even in a thin film light emitting element having a configuration with a low driving voltage, it is possible to provide a thin film light emitting element capable of suppressing a decrease in color purity and light emission efficiency.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention can be implemented in many different modes, and those skilled in the art can easily understand that the modes and details can be variously changed without departing from the spirit and scope of the present invention. Is done. Therefore, the present invention is not construed as being limited to the description of this embodiment mode.

(Embodiment 1)
FIG. 1A shows an example of the structure of a thin film light emitting element of the present invention. The thin film light-emitting element in this embodiment includes an anode electrode 101 formed on an insulating surface such as a substrate 100, a hole transport layer 102, a light-emitting layer 103 having a light-emitting substance 107, an electron transport layer 10, and a cathode electrode 106. Yes. The electron transport layer 10 is divided into two layered regions, and at least one common electron transporting material is used for the two regions. Of the two regions, the first region 105 closer to the cathode electrode 106 is doped with an additive 108 for further enhancing the electron transporting property, the electron injecting property, or both of the electron transporting material. The second region 104 closer to the light emitting layer 103 is not doped with the additive 108.

  Note that the first region 105 is doped with the additive 108 at various ratios. In the present invention, the host material in the first region has an electron transporting property common to the first region and the second region. The material is considered the first region host material. The ratio of the additive 108 in the first region 105 may be 1 wt% or more. As a configuration of the first region, the additive 108 may be 100 wt%, that is, the first region may be formed of only the additive 108. To include. In the case where the first region is formed using only the additive 108, the host material refers to a material constituting the second region.

  The host material of the light emitting layer 103 is the one having the largest constituent ratio of the substances constituting the light emitting layer 103. The host material of the light emitting layer 103 may be the same material as the host material of the electron transport layer 10 as shown in FIG. 1B, or may be a different host material as shown in FIG. Further, as illustrated in FIG. 1C, the light-emitting layer 103 may have a structure in which the light-emitting layer itself includes the light-emitting substance 107 and the light-emitting layer 103 itself emits light.

As a host material that can be used for the electron transport layer 10, tris (8-quinolinolato) aluminum (abbreviation: Alq ₃ ), tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq ₃ ), bis (10− Hydroxybenzo [h] -quinolinato) beryllium (abbreviation: BeBq ₂ ), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (abbreviation: BAlq), and other metals having a quinoline skeleton or a benzoquinoline skeleton A complex or the like can be used. As the host material of the light emitting layer 103, 9,10-diphenylanthracene, 9,10-di (2-naphthyl) anthracene, 2-t-butyl-9,10-bis [2- (naphthyl) phenyl] anthracene, 2- Aromatic compounds such as t-butyl-9,10-bis [2- (phenyl) phenyl] anthracene and 4,4 ′ (2,2-diphenylvinyl) biphenyl are preferred. Alternatively, a typical metal complex such as bis (2-methyl-8-quinolinonato)-(4-hydroxy-biphenylyl) -aluminum may be used. Materials that can be used in common for the electron transport layer 10 and the light emitting layer 103 include tris (8-quinolinolato) aluminum (abbreviation: Alq ₃ ), tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq ₃ ). Bis (10-hydroxybenzo [h] -quinolinato) beryllium (abbreviation: BeBq ₂ ), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (abbreviation: BAlq), quinoline skeleton or benzo A metal complex having a quinoline skeleton or the like can be used. Etc. can be used. Further, as a light-emitting substance 107 which is added to these and becomes a luminescent center, 4-dicyanomethylene-2-methyl-6- [2- (1,1,7,7-tetramethyljulolidin-9-yl)- Ethenyl] -4H-pyran (abbreviation: DCJT), 4-dicyanomethylene-2-tert-butyl-6- [2- (1,1,7,7-tetramethyljulolidin-9-yl) ethenyl] -4H -Pyran (abbreviation: DCJTB), periflanthene, 2,5-dicyano-1,4-bis [2- (10-methoxy-1,1,7,7-tetramethyljulolidin-9-yl) ethenyl] benzene, N, N'-dimethyl quinacridone (abbreviation: DMQd), coumarin 6, coumarin 545T, tris (8-quinolinolato) aluminum (abbreviation: Alq _3), 9,9'-bianthryl, 9,10 Phenyl anthracene (abbreviation: DPA) and 9,10-bis (2-naphthyl) anthracene (abbreviation: DNA), 2,5,8,11-tetra -t- butyl perylene (abbreviation: TBP), and the like. Examples of a material that can form the light-emitting layer 103 using only the light-emitting substance 107 include tris (8-quinolinolato) aluminum (abbreviation: Alq ₃ ), 9,10-bis (2-naphthyl) anthracene (abbreviation: DNA), And bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (abbreviation: BAlq).

  As the additive 108 doped in the first region of the electron transport layer, a substance having a polycyclic fused ring may be used, and among them, a substance having a higher electron injection property or electron transport property than the host material in the first region. Select. Moreover, it is preferable that the substance is preferably a material having both high electron injecting property and electron transporting property. Note that a material having a high electron-injection property can be said to be a material having a lower LUMO level than the main constituent material of the first region. Specifically, rubrene, 9,10-diphenylanthracene, pentacene, perylene, and derivatives thereof can be used.

  In the thin film light emitting element of the present invention having such a structure, the electron injection property and / or the electron transport property are improved by the additive 108 doped in the first region. A thin film light emitting element with a low voltage is obtained.

  In addition, since the second region 104 in which the additive 108 is not doped is formed in the electron transport layer, the distance between the light-emitting substance 107 and the additive 108 in the light-emitting layer 103 is at least the film of the second region 104. It will be more than the thickness. Since the efficiency of energy transfer between excited species is supposed to decrease in proportion to the sixth power of the distance, it is considered that energy transfer from the excited luminescent substance 107 to the additive 108 is greatly suppressed. As a result, light emission from the additive 108 can be greatly reduced.

Even when light emission from the additive 108 does not occur, energy transfer occurs from the excited light-emitting substance 107 to the additive 108, and the light-emitting substance 107 that should have emitted light is deactivated, and light emission occurs. In some cases, the current efficiency is reduced. Also in this case, by using the light-emitting element having the structure of the present invention, energy transfer from the light-emitting substance 107 to the additive 108 is significantly reduced, so that a reduction in light emission efficiency can be suppressed. As a result, the thin film light emitting device of the present invention can greatly reduce light emission other than light emission from the target light emitting material 107, so that it is a thin film light emitting device having very good color purity.

  Note that the thickness of the second region 104 is 5 nm or more, preferably 10 nm or more as a distance that can sufficiently suppress the energy transfer between excited species.

  In addition, since the structure of the thin film light emitting device of the present invention can greatly reduce the energy transfer between excited species, the energy gap of the additive 108 doped in the first region of the electron transport layer is reduced. Even if it is smaller than the energy gap of the light emitting substance 107, it can be used without causing deterioration of color purity or light emission efficiency. In addition, the difference in the selection of the additive to be added to the electron transport layer is not caused by the size of the energy gap of the light emitting material doped in the light emitting layer, and more electron injecting property, electron transporting property or both. Can be used as the additive 108 regardless of the emission color.

  In addition, when light emitted from the light-emitting substance 107 is phosphorescence, energy transfer to the additive 108 may occur even when the energy gap of the additive 108 is smaller than that of the light-emitting substance 107. . Even in such a case, by adopting the structure of the thin film light emitting element of the present invention, energy transfer from the light emitting substance 107 to the additive 108 is suppressed, and it is possible to suppress a decrease in color purity and a decrease in light emission efficiency. .

  Note that the hole injection layer 109 is formed over the anode electrode 101 in FIG. 1B; however, the hole injection layer 109 may be formed in this manner, or FIGS. It does not have to be formed as in C). Further, an electron injecting layer 113 may be provided as in FIG. Furthermore, both a hole injection layer and an electron injection layer may be provided.

  The structures of the light-emitting elements described in this embodiment can be combined as appropriate.

  FIG. 2 shows an example of a conventional thin film light emitting device. The thin film light emitting element of FIG. 2 does not have a structure corresponding to the second region in the present invention, and the distance between the additive in the electron transport layer 110 and the light emitting substance in the light emitting layer 103 is short. For this reason, energy moves from the excited luminescent material 112 to the additive 111 contained in the electron transport layer, and part of the energy is emitted. Therefore, the light emitted to the outside becomes light in which the light emitted from the light emitting substance 107 and the light emitted from the additive 111 are mixed, and the color purity is deteriorated. Further, even if the additive 111 whose energy is transferred from the light emitting substance 112 does not emit light, the light emitting efficiency is lowered.

(Embodiment 2)
In this embodiment mode, a method for manufacturing a display device of the present invention will be described with reference to FIGS. Note that although an example in which an active matrix display device is formed is described in this embodiment mode, it is needless to say that the thin film light emitting element of the present invention can be applied to a passive matrix display device.

  First, after the first base insulating layer 51a and the second base insulating layer 51b are formed over the substrate 50, a semiconductor layer is further formed over the second base insulating layer 51b. (Fig. 3 (A))

  As the material of the substrate 50, light-transmitting glass, quartz, plastic (polyimide, acrylic, polyethylene terephthalate, polycarbonate, polyacrylate, polyethersulfone, or the like) can be used. These substrates may be used after being polished by CMP or the like, if necessary. In this embodiment, a glass substrate is used.

  The first base insulating layer 51a and the second base insulating layer 51b prevent an element such as an alkali metal or an alkaline earth metal in the substrate 50 that adversely affects the characteristics of the semiconductor film from diffusing into the semiconductor layer. Provided for this purpose. As a material, silicon oxide, silicon nitride, silicon oxide containing nitrogen, silicon nitride containing oxygen, or the like can be used. In this embodiment mode, the first base insulating layer 51a is formed using silicon nitride, and the second base insulating layer 51b is formed using silicon oxide. In this embodiment mode, the base insulating layer is formed of the first base insulating layer 51a and the second base insulating layer 51b. However, the base insulating layer may be formed of a single layer or a multilayer of two or more layers. It doesn't matter. In addition, it is not necessary to provide a base insulating layer as long as the diffusion of impurities from the substrate does not matter.

  The semiconductor layer formed subsequently is obtained by laser crystallization of an amorphous silicon film in this embodiment mode. An amorphous silicon film is formed to a thickness of 25 to 100 nm (preferably 30 to 60 nm) over the second base insulating layer 51b. As a manufacturing method, a known method such as a sputtering method, a low pressure CVD method or a plasma CVD method can be used. Then, hydrogen treatment is performed at 500 ° C. for 1 hour.

  Subsequently, the amorphous silicon film is crystallized using a laser irradiation apparatus to form a crystalline silicon film. In the laser crystallization of this embodiment, an excimer laser is used, and a laser beam oscillated is processed into a linear beam spot using an optical system and irradiated to an amorphous silicon film to form a crystalline silicon film. Used as a semiconductor layer.

  Other crystallization methods for the amorphous silicon film include a method for crystallization only by heat treatment and a method for heat treatment using a catalyst element that promotes crystallization. Examples of elements that promote crystallization include nickel, iron, palladium, tin, lead, cobalt, platinum, gold, gold, etc. Compared to the case where crystallization is performed only by heat treatment by using such elements, Since crystallization is performed at a low temperature for a short time, there is little damage to the glass substrate. When crystallization is performed only by heat treatment, the substrate 50 may be a quartz substrate resistant to heat.

  Subsequently, in order to control the threshold value in the semiconductor layer as required, a small amount of impurity addition, so-called channel doping is performed. In order to obtain a required threshold value, N-type or P-type impurities (phosphorus, boron, etc.) are added by an ion doping method or the like.

  After that, as shown in FIG. 3A, the semiconductor layer is patterned into a predetermined shape, and an island-shaped semiconductor layer 52 is obtained. Patterning is performed by applying a photoresist to the semiconductor layer, exposing a predetermined mask shape, baking, forming a resist mask on the semiconductor layer, and etching using the mask.

Subsequently, a gate insulating layer 53 is formed so as to cover the semiconductor layer 52. The gate insulating layer 53 is formed of an insulating layer containing silicon with a film thickness of 40 to 150 nm using a plasma CVD method or a sputtering method. In this embodiment mode, silicon oxide is used.

  Next, the gate electrode 54 is formed over the gate insulating layer 53. The gate electrode 54 may be formed of an element selected from Ta, W, Ti, Mo, Al, Cu, Cr, and Nd, or an alloy material or a compound material containing the element as a main component. Alternatively, a semiconductor film typified by a polycrystalline silicon film doped with an impurity element such as phosphorus may be used. Further, an AgPdCu alloy may be used.

  Further, although the gate electrode 54 is formed as a single layer in this embodiment mode, a stacked structure of two or more layers such as tungsten in the lower layer and molybdenum in the upper layer may be used. Even in the case where the gate electrode is formed as a stacked structure, the materials described in the preceding stage may be used. Moreover, the combination may be selected as appropriate.

  The gate electrode 54 is processed by etching using a mask using a photoresist.

  Subsequently, a high concentration impurity is added to the semiconductor layer 52 using the gate electrode 54 as a mask. Thus, the thin film transistor 70 including the semiconductor layer 52, the gate insulating layer 53, and the gate electrode 54 is formed.

  Note that there is no particular limitation on the manufacturing process of the thin film transistor, and it may be changed as appropriate so that a transistor with a desired structure can be manufactured.

  In this embodiment mode, a top-gate thin film transistor using a crystalline silicon film crystallized by laser crystallization is used; however, a bottom-gate thin film transistor using an amorphous semiconductor film is used for a pixel portion. It is also possible. As the amorphous semiconductor, not only silicon but also silicon germanium can be used. When silicon germanium is used, the concentration of germanium is preferably about 0.01 to 4.5 atomic%.

  Alternatively, a microcrystalline semiconductor film (semi-amorphous semiconductor) in which crystals of 0.5 nm to 20 nm can be observed in an amorphous semiconductor may be used. Microcrystals capable of observing 0.5 nm to 20 nm crystals are also called so-called microcrystals (μc).

Semi-amorphous silicon (also referred to as SAS), which is a semi-amorphous semiconductor, can be obtained by glow discharge decomposition of a silicide gas. A typical silicide gas is SiH ₄ , and in addition, Si ₂ H ₆ , SiH ₂ Cl ₂ , SiHCl ₃ , SiCl ₄ , SiF _{4 and the} like can be used. The formation of the SAS can be facilitated by diluting the silicide gas with one or plural kinds of rare gas elements selected from hydrogen, hydrogen and helium, argon, krypton, and neon. It is preferable to dilute the silicide gas at a dilution ratio in the range of 10 times to 1000 times. The reaction generation of the film by glow discharge decomposition may be performed at a pressure in the range of 0.1 Pa to 133 Pa. The power for forming the glow discharge may be high frequency power of 1 MHz to 120 MHz, preferably 13 MHz to 60 MHz. The substrate heating temperature is preferably 300 ° C. or less, and a substrate heating temperature of 100 to 250 ° C. is suitable.

The SAS formed in this way has a Raman spectrum shifted to a lower wavenumber than 520 cm ⁻¹ , and diffraction peaks of (111) and (220), which are considered to be derived from the Si crystal lattice in X-ray diffraction, are observed. Is done. As a termination of dangling bonds (dangling bonds), hydrogen or halogen is contained at least 1 atomic% or more. As an impurity element in the film, impurities of atmospheric components such as oxygen, nitrogen, and carbon are desirably 1 × 10 ²⁰ cm ⁻¹ or less, and in particular, the oxygen concentration is 5 × 10 ¹⁹ / cm ³ or less, preferably 1 × 10 ¹⁹ / cm ³ or less. When the TFT is used, μ = 1 to 10 cm ² / Vsec.

  Further, this SAS may be further crystallized with a laser.

  Subsequently, an insulating film (hydrogenated film) 59 is formed of silicon nitride so as to cover the gate electrode 54 and the gate insulating layer 53. After the insulating film (hydrogenated film) 59 is formed, heating is performed at 480 ° C. for about 1 hour to activate the impurity element and hydrogenate the semiconductor layer 52.

  Subsequently, a first interlayer insulating layer 60 covering the insulating film (hydrogenated film) 59 is formed. As a material for forming the first interlayer insulating layer 60, silicon oxide, acrylic, polyimide, siloxane, an Iow-k material, or the like may be used. In this embodiment mode, the silicon oxide film is formed as the first interlayer insulating layer. Note that siloxane is a material which has a skeleton structure of a bond of silicon (Si) and oxygen (O) and has an organic group (for example, an alkyl group or an aryl group) containing at least hydrogen as a substituent. As a substituent which siloxane has, it may have fluorine, and may have both a group containing hydrogen and fluorine. (Fig. 3 (B))

  Next, a contact hole reaching the semiconductor layer 52 is opened. The contact hole can be formed by performing etching using a resist mask until the semiconductor layer 52 is exposed, and can be formed by either wet etching or dry etching. Note that etching may be performed once depending on conditions, or etching may be performed in a plurality of times. In addition, when etching is performed a plurality of times, both wet etching and dry etching may be used. (Figure 3 (C))

Then, a conductive layer covering the contact hole and the first interlayer insulating layer 60 is formed. The conductive layer is processed into a desired shape, and the connection portion 61a, the wiring 61b, and the like are formed. Although this wiring may be a single layer of aluminum, copper, or the like, in this embodiment mode, a multilayer structure of molybdenum, aluminum, and molybdenum is formed from the substrate side. The laminated wiring may have a structure of titanium, aluminum, titanium, titanium, titanium nitride, aluminum, titanium from the substrate side. (Fig. 3 (D))

  Thereafter, a second interlayer insulating layer 63 is formed so as to cover the connection portion 61a, the wiring 61b, and the first interlayer insulating layer 60. As a material for the second interlayer insulating layer 63, a coating film of acrylic, polyimide, siloxane or the like having self-flatness can be suitably used. In this embodiment mode, siloxane is used as the second interlayer insulating layer 63. (Figure 3 (E))

  Subsequently, an insulating layer may be formed of silicon nitride or the like on the second interlayer insulating layer 63. This is formed to prevent the second interlayer insulating layer 63 from being etched more than necessary in the subsequent etching of the pixel electrode. Therefore, when the ratio of the etching rate between the pixel electrode and the second interlayer insulating layer is large, it may not be provided. Subsequently, a contact hole that penetrates through the second interlayer insulating layer 63 and reaches the connection portion 61a is formed.

  Then, a light-transmitting conductive layer is formed so as to cover the contact hole and the second interlayer insulating layer 63 (or insulating layer), and then the light-transmitting conductive layer is processed to form an anode of the thin film light-emitting element. An electrode 64 (first electrode) is formed. Here, the anode electrode 64 (first electrode) is in electrical contact with the connecting portion 61a. As materials for the anode electrode 64 (first electrode), indium tin oxide (ITO), ITO containing silicon oxide (ITSO: Indium Tin Silicon Oxide), zinc oxide of 2 to 20% in indium oxide are used. It is preferable to use IZO (Indium Zinc Oxide) containing zinc, zinc oxide itself, GZO (gallium Zinc Oxide) containing zinc in gallium oxide, or the like. In this embodiment, ITSO is used as the anode electrode 64 (first electrode). (Fig. 4 (A))

  Next, an insulating layer made of an organic material or an inorganic material is formed so as to cover the second interlayer insulating layer 63 (or insulating layer) and the anode electrode 64 (first electrode). Subsequently, the insulating layer is processed so that a part of the anode electrode 64 (first electrode) is exposed, and the partition wall 65 is formed. As the material of the partition wall 65, a photosensitive organic material (acrylic, polyimide, or the like) is preferably used, but it may be formed of an organic material or an inorganic material that does not have photosensitivity. It is desirable that the end face of the partition wall 65 facing the first electrode has a curvature and has a tapered shape in which the curvature continuously changes. (Fig. 4 (B))

  Next, the light emitting laminate 66 that covers the anode electrode 64 (first electrode) exposed from the partition wall 65 is formed. The light emitting laminate 66 may be formed by vapor deposition or the like. In the present invention, the light emitting laminate 66 has at least an electron transport layer and a light emitting layer, and the electron transport layer is added by a substance having a polycyclic condensed ring for facilitating current flow. A first region including an object and a second region not including the additive.

  Note that the thickness of the second region is 5 nm or more, preferably 10 nm or more as a distance that can sufficiently suppress energy transfer between excited species.

  When doping an additive for facilitating current flow in the first region of the electron transport layer, it can be formed by co-evaporation with the host material of the electron transport layer. Since the material of the second region not doped with the additive and the host material of the first region doped with the additive are the same, the light emitting layer and the electron transport layer doped with the additive Rather than providing a hole blocking layer or the like with another material in between, the configuration of the present invention can be easily obtained with good tact. (Fig. 4 (C))

Examples of a substance that has a relatively high electron transport property and can be used as a host material for the electron transport layer include tris (8-quinolinolato) aluminum (abbreviation: Alq ₃ ), tris (4-methyl-8-quinolinolato) aluminum ( Abbreviations: Almq ₃ ), bis (10-hydroxybenzo [h] -quinolinato) beryllium (abbreviation: BeBq ₂ ), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (abbreviation: BAlq), etc. And metal complexes having a quinoline skeleton or a benzoquinoline skeleton. By applying the structure of the present invention, the electron transport layer can have a larger electron transport property, and the driving voltage of the thin film light emitting element can be lowered.

  Examples of the additive to be added to the electron transport layer include substances having a polycyclic fused ring such as rubrene, 9,10-diphenylanthracene, pentacene, and perylene. Among these, a substance having a higher electron injecting property or electron transporting property than the host material in the first region is selected. Moreover, it is preferable that the substance is preferably a material having both high electron injecting property and electron transporting property. Note that a material having a high electron-injection property can be said to be a material having a lower LUMO level than the main constituent material of the first region. By applying the structure of the present invention, it is possible to select these additives regardless of the energy gap of the light emitting material of the light emitting layer.

There are various materials for light-emitting substances, such as 4-dicyanomethylene-2-methyl-6- [2- (1,1,7,7-tetramethyljulolidin-9-yl) ethenyl] -4H-pyran (abbreviation). : DCJT), 4-dicyanomethylene-2-t-butyl-6- [2- (1,1,7,7-tetramethyljulolidin-9-yl) ethenyl] -4H-pyran (DCJTB), periflanthene, 2,5-dicyano-1,4-bis [2- (10-methoxy-1,1,7,7-tetramethyljulolidin-9-yl) ethenyl] benzene, N, N′-dimethylquinacridone (abbreviation: DMQd), coumarin 6, coumarin 545T, tris (8-quinolinolato) aluminum (abbreviation: Alq ₃ ), 9,9′-bianthryl, 9,10-diphenylanthracene (abbreviation: DPA), 9,10-bis (2-naphthyl) anthracene (abbreviation: DNA), 2,5,8,11-tetra-t-butylperylene (abbreviation: TBP), or the like can be used. Other substances may also be used.

  In addition to the above, the light emitting laminate 66 may be provided with layers such as an electron injection layer, a hole transport layer, and a hole injection layer.

  As a substance having a high hole-transport property, for example, 4,4′-bis [N- (1-naphthyl) -N-phenyl-amino] -biphenyl (abbreviation: NPB), 4,4′-bis [N- ( 3-methylphenyl) -N-phenyl-amino] -biphenyl (abbreviation: TPD) and 4,4 ′, 4 ″ -tris (N, N-diphenyl-amino) -triphenylamine (abbreviation: TDATA), 4 , 4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenyl-amino] -triphenylamine (abbreviation: MTDATA) and 4,4-bis (N- (4- (N, N And an aromatic amine-based compound (that is, having a benzene ring-nitrogen bond) such as -di-m-tolylamino) phenyl) -N-phenylamino) biphenyl (abbreviation: DNTPD).

In addition, examples of the substance having a high electron-injecting property include alkali metal or alkaline earth metal compounds such as lithium fluoride (LiF), cesium fluoride (CsF), and calcium fluoride (CaF ₂ ). In addition, a mixture of a substance having a high electron transport property such as Alq ₃ and an alkaline earth metal such as magnesium (Mg) may be used.

Examples of the material having a high hole injection property include metal oxides such as molybdenum oxide (MoOx), vanadium oxide (VOx), ruthenium oxide (RuOx), tungsten oxide (WOx), and manganese oxide (MnOx). Things. In addition, phthalocyanine compounds such as phthalocyanine (abbreviation: H ₂ Pc) and copper phthalocyanine (CuPC) can be given.

  The light emitting layer may be configured to perform color display by forming light emitting elements having different emission wavelength bands for each pixel. Typically, a light emitting element corresponding to each color of R (red), G (green), and B (blue) is formed. In this case as well, by providing a filter (colored layer) that transmits light in the emission wavelength band on the light emission side of the pixel, the color purity is improved and the pixel portion is mirrored (reflected). Prevention can be achieved. By providing the filter (colored layer), it is possible to omit a circularly polarizing plate that has been conventionally required, and it is possible to eliminate the loss of light emitted from the light emitting element. Furthermore, a change in color tone that occurs when the pixel portion (display screen) is viewed obliquely can be reduced.

  In addition, the light-emitting element can have a structure that emits monochromatic or white light. In the case of using a white light emitting material, color display can be made possible by providing a filter (colored layer) that transmits light of a specific wavelength on the light emission side of the pixel.

To form a light emitting layer that emits white light, for _{example, Alq 3, Alq 3, Alq} 3 doped with Nile Red which is partly red light emitting pigment, p-EtTAZ, by TPD (aromatic diamine) evaporation A white color can be obtained by sequentially laminating.

  Furthermore, a triplet excitation material containing a metal complex or the like may be used for the light emitting layer in addition to a singlet excitation light emitting material. For example, among red light emitting pixels, green light emitting pixels, and blue light emitting pixels, a red light emitting pixel having a relatively short luminance half time is formed of a triplet excitation light emitting material, and the other A singlet excited luminescent material is used. The triplet excited luminescent material has a feature that the light emission efficiency is good, so that less power is required to obtain the same luminance. That is, when applied to a red pixel, the amount of current flowing through the light emitting element can be reduced, so that reliability can be improved. As a reduction in power consumption, a red light-emitting pixel and a green light-emitting pixel may be formed using a triplet excitation light-emitting material, and a blue light-emitting pixel may be formed using a singlet excitation light-emitting material. By forming a green light-emitting element having high human visibility with a triplet excited light-emitting material, power consumption can be further reduced.

  Examples of triplet excited luminescent materials include those using a metal complex as a dopant, and metal complexes having a third transition series element platinum as the central metal and metal complexes having iridium as the central metal are known. Yes. The triplet excited light-emitting material is not limited to these compounds, and a compound having the above structure and having an element belonging to group 8 to 10 in the periodic table as a central metal can also be used.

  The substances forming the light-emitting layer listed above are examples, and functionalities such as a hole injection transport layer, a hole transport layer, an electron injection transport layer, an electron transport layer, a light emission layer, an electron block layer, and a hole block layer are included. A light emitting element can be formed by appropriately stacking each layer. Moreover, you may form the mixed layer or mixed junction which combined these each layer. The layer structure of the light-emitting laminate can be changed, and instead of having a specific electron injection region or light-emitting region, it has an electrode for this purpose or a dispersed light-emitting material. Modifications can be made without departing from the spirit of the present invention.

  A light-emitting element formed using the above materials emits light by being forward-biased. A pixel of a display device formed using a light-emitting element can be driven by a simple matrix method or an active matrix method. In any case, each pixel emits light by applying a forward bias at a specific timing, but is in a non-light emitting state for a certain period. By applying a reverse bias during this non-light emitting time, the reliability of the light emitting element can be improved. The light emitting element has a degradation mode in which the light emission intensity decreases under a constant driving condition and a degradation mode in which the non-light emitting area is enlarged in the pixel and the luminance is apparently decreased. However, alternating current that applies a bias in the forward and reverse directions. By performing a typical drive, the progress of deterioration can be slowed and the reliability of the light emitting device can be improved.

  Subsequently, a second electrode (cathode) 67 covering the light emitting laminate 66 is formed. Thus, a light emitting element 93 including the anode electrode 64 (first electrode), the light emitting laminate 66, and the second electrode (cathode) 67 can be manufactured.

Thereafter, a silicon oxide film containing nitrogen is formed as a second passivation film by a plasma CVD method. In the case of using a silicon oxide film containing nitrogen, a silicon oxynitride film manufactured from SiH ₄ , N ₂ O, NH ₃ by a plasma CVD method, or a silicon oxynitride film manufactured from SiH ₄ , N ₂ O, Alternatively, a silicon oxynitride film formed from a gas obtained by diluting SiH ₄ or N ₂ O with Ar may be formed.

Alternatively, a silicon oxynitride silicon film formed from SiH ₄ , N ₂ O, and H ₂ may be applied as the first passivation film. Needless to say, the second passivation film 905 is not limited to a single layer structure, and another insulating layer containing silicon may be used as a single layer structure or a stacked structure. Further, a multilayer film of carbon nitride film and silicon nitride film, a multilayer film of styrene polymer, a silicon nitride film, or a diamond-like carbon film may be formed instead of the silicon oxide film containing nitrogen.

  Subsequently, the display portion is sealed in order to protect the electroluminescent element from a substance that promotes deterioration such as water. In the case where the counter substrate is used for sealing, bonding is performed with an insulating sealing material so that the external connection portion is exposed. A space between the counter substrate and the element substrate may be filled with an inert gas such as dry nitrogen, or a seal material may be applied to the entire surface of the pixel portion to form the counter substrate. It is preferable to use an ultraviolet curable resin or the like for the sealing material. The sealing material may contain a desiccant and particles for keeping the gap constant. Subsequently, the display device is completed by attaching a flexible wiring board to the external connection portion.

  One example of the structure of the display device manufactured as described above will be described with reference to FIG. In addition, even if the shapes are different, parts showing similar functions are denoted by the same reference numerals, and explanations thereof are omitted. In this embodiment mode, the thin film transistor 70 having an LDD structure is connected to the light emitting element 93 through the connection portion 61a.

  FIG. 5A illustrates a structure in which the anode electrode 64 (first electrode) is formed using a light-transmitting conductive film, and light emitted from the light-emitting stack 66 is extracted to the substrate 50 side. Reference numeral 94 denotes a counter substrate, which is fixed to the substrate 50 by using a sealing material or the like after the light emitting element 93 is formed. Filling the counter substrate 94 with the light-transmitting resin 88 or the like between the elements and sealing them can prevent the light-emitting element 93 from being deteriorated by moisture. Further, it is desirable that the resin 88 has a hygroscopic property. Further, if a desiccant 89 having high translucency is dispersed in the resin 88, the influence of moisture can be further suppressed, which is a more desirable form.

  In FIG. 5B, both the anode electrode 64 (first electrode) and the second electrode 92 are formed of a light-transmitting conductive film, and light can be extracted to both the substrate 50 and the counter substrate 94. It has a possible configuration. Further, in this configuration, by providing the polarizing plate 90 outside the substrate 50 and the counter substrate 94, it is possible to prevent the screen from being seen through, and visibility is improved. A protective film 91 may be provided outside the polarizing plate 90.

  Note that either an analog video signal or a digital video signal may be used for the display device of the present invention having a display function. When a digital video signal is used, the video signal is classified into one using a voltage and one using a current. When the light emitting element emits light, the video signal input to the pixel has a constant voltage and a constant current. When the video signal has a constant voltage, the voltage applied to the light emitting element is constant. And the current flowing through the light emitting element is constant. In addition, a video signal having a constant current includes a constant voltage applied to the light emitting element and a constant current flowing in the light emitting element. A constant voltage applied to the light emitting element is constant voltage driving, and a constant current flowing through the light emitting element is constant current driving. In constant current driving, a constant current flows regardless of the resistance change of the light emitting element. Any of the above driving methods may be used for the light emitting display device and the driving method thereof of the present invention.

  The display device of the present invention formed by a method as in this embodiment mode is a display device with low driving voltage and high color purity and light emission efficiency.

(Embodiment 3)
In this embodiment, the appearance of a panel of a light-emitting device that corresponds to one embodiment of the present invention will be described with reference to FIGS. 6 is a top view of a panel in which a transistor and a light-emitting element formed over a substrate are sealed with a sealant formed between a counter substrate 4006 and FIG. 6B is a cross-sectional view of FIG. It corresponds to. The structure of the light-emitting element mounted on this panel consists of an anode electrode, a hole transport layer, a light-emitting layer having a light-emitting substance, an electron transport layer, and a cathode electrode. The electron transport layer is divided into two layered regions. The first region closer to the cathode is doped with an additive composed of a polycyclic fused ring, and the second region closer to the light emitting layer is doped with an additive composed of a polycyclic fused ring. It has no configuration.

  A sealant 4005 is provided so as to surround the pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004 which are provided over the substrate 4001. A counter substrate 4006 is provided over the pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004. Therefore, the pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004 are sealed together with the filler 4007 by the substrate 4001, the sealant 4005, and the counter substrate 4006.

  The pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004 provided over the substrate 4001 include a plurality of thin film transistors. In FIG. 6B, the thin film transistor 4008 included in the signal line driver circuit 4003 is provided. And a thin film transistor 4010 included in the pixel portion 4002.

  Reference numeral 4011 corresponds to a light-emitting element and is electrically connected to the thin film transistor 4010.

  Further, the lead wiring 4014 corresponds to a wiring of a eye when a signal or a power supply voltage is supplied to the pixel portion 4002, the signal line driver circuit 4003, and the scan line driver circuit 4004. The lead wiring 4014 is connected to the connection terminal 4016 via the lead wiring 4015a and the lead wiring 4015b. The connection terminal 4016 is electrically connected to a terminal included in a flexible printed circuit (FPC) 4018 through an anisotropic conductive film 4019.

  Note that as the filler 4007, in addition to an inert gas such as nitrogen or argon, an ultraviolet curable resin or a thermosetting resin can be used, and polyvinyl chloride, acrylic, polyimide, epoxy resin, silicon resin, polyvinyl butyral, Alternatively, ethylene vinylene acetate can be used.

  Note that the display device of the present invention includes in its category a panel in which a pixel portion having a light-emitting element is formed and a module in which an IC is mounted on the panel.

The panel and module configured as in this embodiment are panels and modules that have low driving voltage and good color purity and luminous efficiency.

(Embodiment 4)
As an electronic device of the present invention on which a module whose example is shown in Embodiment 3 is mounted, a video camera, a digital camera, a goggle-type display (head-mounted display), a navigation system, a sound reproduction device (car audio component, etc.) A recording medium such as a computer, a game machine, a portable information terminal (mobile computer, cellular phone, portable game machine, electronic book, etc.), an image reproducing device (specifically Digital Versatile Disc (DVD)) equipped with a recording medium And a device having a display capable of reproducing and displaying the image). Specific examples of these electronic devices are shown in FIGS.

  FIG. 7A illustrates a light-emitting display device, such as a television receiver or a personal computer monitor. A housing 2001, a display portion 2003, a speaker portion 2004, and the like are included. The light-emitting display device of the present invention has low driving voltage for the display portion 2003, and has good color purity and luminous efficiency. In order to increase the contrast in the pixel portion, a polarizing plate or a circular polarizing plate may be provided. For example, a film may be provided on the sealing substrate in the order of a 1 / 4λ plate, a 1 / 2λ plate, and a polarizing plate. Further, an antireflection film may be provided on the polarizing plate.

  FIG. 7B illustrates a mobile phone, which includes a main body 2101, a housing 2102, a display portion 2103, a voice input portion 2104, a voice output portion 2105, operation keys 2106, an antenna 2108, and the like. In the cellular phone of the present invention, the driving voltage of the display portion 2103 is small, and color purity and light emission efficiency are good.

  FIG. 7C illustrates a computer, which includes a main body 2201, a housing 2202, a display portion 2203, a keyboard 2204, an external connection port 2205, a pointing mouse 2206, and the like. The computer of the present invention has a low driving voltage for the display portion 2203 and good color purity and light emission efficiency. FIG. 7C illustrates a notebook computer, but the present invention can also be applied to a desktop computer in which a hard disk and a display portion are integrated.

  FIG. 7D illustrates a mobile computer, which includes a main body 2301, a display portion 2302, a switch 2303, operation keys 2304, an infrared port 2305, and the like. In the mobile computer of the present invention, the driving voltage of the display portion 2302 is small, and color purity and light emission efficiency are good.

  FIG. 7E illustrates a portable game machine which includes a housing 2401, a display portion 2402, speaker portions 2403, operation keys 2404, a recording medium insertion portion 2405, and the like. In the portable game machine of the present invention, the driving voltage of the display portion 2402 is small, and color purity and light emission efficiency are good.

As described above, the applicable range of the present invention is so wide that it can be used for electronic devices in various fields.
(Embodiment 5)

  FIG. 8 shows an example of bottom emission, double side emission, and top emission. The structure in which the creation process is described in Embodiment Mode 2 corresponds to the structure in FIG. 8A and 8B, the first interlayer insulating layer in FIG. 8C is formed of a self-planar material, and the wiring of the thin film transistor and the first electrode of the light-emitting element are formed over the same insulating layer. This is the configuration when formed. FIG. 8A illustrates a structure of bottom emission in which only the first electrode of the light-emitting element is formed using a light-transmitting material and light is emitted toward the lower portion of the light-emitting device, and FIG. A material containing Li is formed thinly (to the extent that it has translucency) under the electrode, and a translucent material such as ITO, ITSO, or IZO is formed as the second electrode in FIG. 8B. Thus, it is possible to obtain a light-emitting display device that emits light from both sides. In addition, although it is non-translucent when formed with a thick film such as aluminum or silver, it becomes translucent when it is thinned. Therefore, the second electrode is formed with a thin film having translucency such as aluminum or silver. When formed, double-sided light emission can be achieved.

  By the way, since ITO and ITSO which are transparent electrodes used in the case of double-sided light emission or top-surface light emission are difficult to form by vapor deposition, film formation by sputtering is performed. When the second electrode 904 is formed by a sputtering method, the surface of the electron injection layer or the interface between the electron injection layer and the electron transport layer may be damaged by sputtering, which may adversely affect the characteristics of the light-emitting element. There is. In order to prevent this, a material which is not easily damaged by sputtering is preferably provided at a position closest to the second electrode 904. As a material that is not easily damaged by sputtering and can be used for the light-emitting stack 903, molybdenum oxide (MoOx) can be given. However, since MoOx is a suitable material for the hole injection layer, the second electrode 904 needs to be used as an anode in order to be in contact with the second electrode 904. In this way, an element having the cathode as the first electrode and the anode as the second electrode is called a reversely stacked element.

  Therefore, in the case of this reverse stacked element, the first electrode is formed as the cathode electrode 106 on the insulating surface such as the substrate 100 or the insulating film formed on the substrate 100 as shown in FIG. A layer (substantially), an electron transport layer 10, a light emitting layer 103, a hole transport layer 102, a hole injection layer 109 (MoOx), and an anode electrode 101 (second electrode) are formed. In the case of an active matrix display device, a thin film transistor for driving a pixel needs to be an N-channel type.

  MoOx is formed by vapor deposition, and x = 3 or more can be suitably used. In addition, the MoOx layer may be an organic / inorganic mixed layer by co-evaporation with an organic metal complex such as copper phthalocyanine (CuPc) or an organic substance. In the case where a reversely stacked element is used, it is preferable that the thin film transistor in the pixel portion is originally an N-type transistor using a-Si: H as a semiconductor layer because the process is simplified. In the case where the driver circuit portion is formed over the same substrate, only the driver circuit portion may be crystallized by irradiation with a laser or the like.

If the sputter damage at the time of anode formation does not become a problem, elements may be formed by reverse stacking without using MoOx. 9A to 9C are examples of reversely stacked elements corresponding to FIGS. 1A to 1C, respectively. The present invention can also be used for such a reversely stacked element, and can provide a light emitting element that functions effectively, realizes a low driving voltage, and does not cause deterioration in color purity and current efficiency.
(Embodiment 6)

  In this embodiment mode, pixel circuits and protection circuits included in the panel and module described in Embodiment Mode 3 and operations thereof will be described. Note that the cross-sectional views shown in FIGS. 3 and 4 are cross-sectional views of the driving TFT 1403 and the light emitting element 1405.

  In the pixel shown in FIG. 10A, a signal line 1410 and power supply lines 1411 and 1412 are arranged in the column direction, and a scanning line 1414 is arranged in the row direction. The pixel further includes a switching TFT 1401, a driving TFT 1403, a current control TFT 1404, a capacitor element 1402, and a light emitting element 1405.

  The pixel shown in FIG. 10C is different from the pixel shown in FIG. 10A except that the gate electrode of the driving TFT 1403 is connected to the power supply line 1412 arranged in the row direction. It is a configuration. That is, both pixels shown in FIGS. 10A and 10C show the same equivalent circuit diagram. However, in the case where the power supply line 1412 is arranged in the row direction (FIG. 10A) and in the case where the power supply line 1412 is arranged in the column direction (FIG. 10C), each power supply line has a different layer. It is formed of a conductive film. Here, attention is paid to the wiring to which the gate electrode of the driving TFT 1403 is connected, and FIGS. 10A and 10C are shown separately to show that layers for manufacturing these are different.

  10A and 10C, the driving TFT 1403 and the current control TFT 1404 are connected in series in the pixel, and the channel length L (1403) and channel width W (1403) of the driving TFT 1403 are connected. ), The channel length L (1404) and the channel width W (1404) of the current control TFT 1404 satisfy L (1403) / W (1403): L (1404) / W (1404) = 5 to 6000: 1. It is good to set to.

  Note that the driving TFT 1403 operates in a saturation region and has a role of controlling a current value flowing through the light emitting element 1405, and the current control TFT 1404 operates in a linear region and has a role of controlling supply of current to the light emitting element 1405. . Both TFTs preferably have the same conductivity type in terms of manufacturing process, and in this embodiment mode, they are formed as n-channel TFTs. The driving TFT 1403 may be a depletion type TFT as well as an enhancement type. In the present invention having the above configuration, since the current control TFT 1404 operates in a linear region, a slight change in Vgs of the current control TFT 1404 does not affect the current value of the light emitting element 1405. That is, the current value of the light emitting element 1405 can be determined by the driving TFT 1403 operating in the saturation region. With the above structure, it is possible to provide a display device in which luminance unevenness of a light-emitting element due to variation in TFT characteristics is improved and image quality is improved.

  In the pixel shown in FIGS. 10A to 10D, the switching TFT 1401 controls input of a video signal to the pixel. When the switching TFT 1401 is turned on, the video signal is input into the pixel. Then, the voltage of the video signal is held in the capacitor element 1402. Note that FIGS. 10A and 10C illustrate the structure in which the capacitor 1402 is provided; however, the present invention is not limited to this, and the capacity for holding a video signal can be covered by a gate capacity or the like. In this case, the capacitor 1402 is not necessarily provided.

  The pixel shown in FIG. 10B has the same pixel structure as that shown in FIG. 10A except that a TFT 1406 and a scanning line 1414 are added. Similarly, the pixel illustrated in FIG. 10D has the same pixel structure as that illustrated in FIG. 10C except that a TFT 1406 and a scanning line 1414 are added.

  The TFT 1406 is controlled to be turned on or off by a newly arranged scanning line 1414. When the TFT 1406 is turned on, the charge held in the capacitor element 1402 is discharged, and the current control TFT 1404 is turned off. That is, the arrangement of the TFT 1406 can forcibly create a state where no current flows through the light-emitting element 1405. Therefore, the TFT 1406 can be called an erasing TFT. 10B and 10D can improve the duty ratio because the lighting period can be started at the same time as or immediately after the start of the writing period without waiting for signal writing to all the pixels. It becomes possible.

  In the pixel illustrated in FIG. 10E, a signal line 1410, a power supply line 1411 are arranged in the column direction, and a scanning line 1414 is arranged in the row direction. Further, the pixel includes a switching TFT 1401, a driving TFT 1403, a capacitor element 1402, and a light emitting element 1405. The pixel illustrated in FIG. 10F has the same pixel structure as that illustrated in FIG. 7E except that a TFT 1406 and a scanning line 1415 are added. Note that the duty ratio of the structure in FIG. 10F can also be improved by the arrangement of the TFT 1406.

  As described above, various pixel circuits can be employed. In particular, in the case where a thin film transistor is formed using an amorphous semiconductor film, it is preferable to increase the semiconductor film of the driving TFT 1403. Therefore, it is preferable that the pixel circuit be a top emission type in which light from the electroluminescent layer is emitted from the sealing substrate side.

  Such an active matrix light-emitting device is considered to be advantageous because it can be driven at a low voltage because a TFT is provided in each pixel when the pixel density is increased.

  In this embodiment mode, an active matrix light-emitting device in which each pixel is provided with each TFT has been described; however, a passive matrix light-emitting device in which a TFT is provided for each column can also be formed. A passive matrix light-emitting device has a high aperture ratio because a TFT is not provided for each pixel. In the case of a light-emitting device in which light emission is emitted to both sides of an electroluminescent layer, transmittance using a passive matrix display device is increased.

  The display device of the present invention further including such a pixel circuit can be a display device having a low driving voltage, good color purity and light emission efficiency, and each characteristic.

  Next, the case where a diode is provided as a protection circuit in the scan line and the signal line will be described using the equivalent circuit illustrated in FIG.

  In FIG. 11, switching TFTs 1401 and 1403, a capacitor element 1402, and a light emitting element 1405 are provided in the pixel portion 1500. The signal line 1410 is provided with diodes 1561 and 1562. Similarly to the switching TFT 1401 or 1403, the diodes 1561 and 1562 are manufactured based on the above embodiment mode, and include a gate electrode, a semiconductor layer, a source electrode, a drain electrode, and the like. The diodes 1561 and 1562 operate as diodes by connecting a gate electrode and a drain electrode or a source electrode.

  Common potential lines 1554 and 1555 connected to the diode are formed in the same layer as the gate electrode. Therefore, in order to connect to the source electrode or the drain electrode of the diode, it is necessary to form a contact hole in the gate insulating layer.

  A diode provided in the scan line 1414 has a similar structure.

  Thus, according to the present invention, the protection diode provided in the input stage can be formed simultaneously. Note that the position where the protective diode is formed is not limited to this, and the protective diode can be provided between the driver circuit and the pixel.

The display device of the present invention having such a protective circuit has a low driving voltage, good color purity and light emission efficiency, and can also improve the reliability as a display device.

In Example 1, a thin film light emitting element in which a hole injection layer 109 and an electron injection layer are provided in a structure in which the host material of the light emitting layer and the host material of the first region shown in FIG. The measurement was performed. In this embodiment, t-BuDNA in which ITSO is added as the anode electrode 101 (first electrode), DNTPD is 50 nm as the hole injection layer, NPB is 10 nm as the hole transport layer, and TBP is added as the light emitting material 107 to the light emitting layer 103. Is 40 nm, the second region 104 of the electron transport layer 10 is 10 nm of Alq ₃ , and the first region 105 is 10 nm of Alq ₃ to which rubrene is added as an additive 108, and further CaF as an electron injection layer is formed thereon. A light emitting element was formed by stacking aluminum as the cathode electrode 106 (second electrode).

The amount of TBP, which is the light emitting substance 107 in the light emitting layer 103, is added at a ratio of 0.01 to 1 for t-BuDNA, which is the host material of the light emitting layer 103, and added in the first region of the electron transport layer. The amount of rubrene as the product 108 was added at a ratio of 1 to 1 for Alq ₃ which is the host material of the electron transport layer 10.

As Comparative Example 1, the first region and the second region were not provided, and instead, Alq ₃ to which rubrene was added as an additive was formed to 20 nm. In this configuration, a hole injection layer and an electron injection layer are provided in the configuration of FIG. All other configurations are the same as in the first embodiment.

In Comparative Example 2, the first region and the second region were not provided, and instead, Alq ₃ to which rubrene was not added was formed to 20 nm. All other configurations are the same as in the first embodiment.

Table 1 and FIGS. 12 and 13 show the results of measuring these thin film light emitting devices. The current efficiency shown in Table 1 is the efficiency in the case of 300 cd / m ² .

  First, since TBP is a light emitting material that emits blue light, it has a larger energy gap than rubrene that emits yellow light. Note that in the case of a substance that emits fluorescence, the energy gap can be estimated from the emission color, and it can be said that a substance that emits light having a shorter wavelength has a larger energy gap.

  Since TBP has a larger energy gap than rubrene, in Comparative Example 1, it is considered that energy transfer from TBP to rubrene causes rubrene to emit light. In the spectrum of Comparative Example 1 in FIG. 12, a change in spectral shape considered to be emitted by rubrene is observed near 560 nm. Moreover, it can be seen from Table 2 that the current efficiency of Comparative Example 1 has also deteriorated.

  In Comparative Example 2, since rubrene was not added, the spectral shape change due to the emission of rubrene did not appear. Of course, Example 1 in which rubrene was added to the second region in the electron transport layer also emitted rubrene. The resulting spectral change is not observed.

  In addition, regarding the chromaticity in Table 1, the chromaticity of Example 1 and Comparative Example 2 is almost the same, but when the chromaticity of Comparative Example 1 is seen, it turns out that it is whitish. From this result, even if the energy gap of the light emitting material added to the light emitting layer is larger than the energy gap of the additive added to the electron transport layer, such a light emitting device having the structure of the present invention can be used. It was proved that the color purity did not deteriorate.

  In addition, it can be seen from FIG. 13 that the light-emitting element of Example 1 has the same luminance at a lower voltage, and has a low driving voltage.

In Example 2, a thin film light-emitting element in which an electron injection layer was provided in the structure illustrated in FIG. 1B was manufactured and measured. In this example, ITSO is used as anode electrode 101 (first electrode), DNTPD is used as 50 nm as hole injection layer 109, NPB is used as 10 nm as hole transport layer, and light emitting layer 103 is Alq to which coumarin 6 is added as light emitting substance 107. ₃ is 40 nm, the second region 104 of the electron transport layer 10 is 10 nm of Alq ₃ , and the first region 105 is 10 nm of Alq ₃ to which rubrene is added as an additive 108, and an electron injection layer is further formed thereon. A light emitting element was formed by stacking CaF and aluminum as the cathode electrode 106 (second electrode).

The amount of coumarin 6 as the light emitting substance 107 in the light emitting layer 103 is added at a ratio of 0.005 to 1 for Alq _{3 as} the host material of the light emitting layer 103, and added in the first region of the electron transport layer. The amount of rubrene as the product 108 was added at a ratio of 1 to 1 for Alq ₃ which is the host material of the electron transport layer 10.

In Comparative Example 3, as the electron transport layer, the first region and the second region were not provided, and Alq ₃ to which rubrene was added as an additive was formed to 20 nm. In this configuration, a hole injection layer and an electron injection layer are provided in the configuration of FIG. All other configurations are the same as in the first embodiment.

In Comparative Example 4, 20 nm of Alq ₃ not added with rubrene as an additive was formed as an electron transport layer. All other configurations are the same as in the first embodiment.

The results of measuring these thin film light emitting devices are shown in Table 2, FIG. 14 and FIG. The current efficiency shown in Table 2 is the efficiency in the case of 1000 cd / m ² .

  The coumarin 6 used as the luminescent substance 107 in Example 2, Comparative Example 3 and Comparative Example 4 is a luminescent substance that emits green light, and the rubrene as an additive exhibits yellow light, so that the coumarin 6 is larger. It can be inferred that there is an energy gap. Here, when the spectrum data of FIG. 14 is seen, it turns out that the emission spectrum of Example 2, Comparative Example 3, and Comparative Example 4 is substantially the same, and the light emission from the rubrene which is an additive has not occurred.

  However, looking at the current efficiency in Table 2, the current efficiency of Comparative Example 3 is smaller than that of Example 2, and the coumarin 6 is lost due to the transfer of excitation energy from coumarin 6 to rubrene as an additive. It is believed that the current efficiency was reduced.

  Further, when comparison is made between Comparative Example 4 in which rubrene is not added and Example 2 in which rubrene is added, the light-emitting element of Example 2 is obtained at the same luminance and lower voltage from the graph of FIG. Thus, it can be seen that the light-emitting element of Example 2 having the configuration of the present invention has a low driving voltage.

In Example 3, thin-film light emission in which an electron injection layer is provided in a configuration in which the host material of the light-emitting layer illustrated in FIG. 1B is common to the host material of the first region and the material of the second region. An element was fabricated and measured. In this embodiment, ITSO is used as the anode electrode 101 (first electrode), 50 nm of DNTPD is used as the hole injection layer 109, NPB is 10 nm as the hole transport layer, and the light emitting layer 103 is bis [2,3-bis. (4-Fluorophenyl) quinoxalinato] iridium (acetylacetonate) (abbreviation: Ir (Fdpq) ₂ (acac)) is added to Alq ₃ for 30 nm, and the second region 104 serving as the electron transport layer 10 contains Alq ₃ 20 nm, the first region 105 is formed by forming 10 nm of Alq ₃ doped with rubrene as an additive 108, and further stacking CaF as an electron injection layer and aluminum as a cathode electrode 106 (second electrode). An element was formed.

The amount of Ir (Fdpq) ₂ (acac), which is the light-emitting substance 107 in the light-emitting layer 103, was added at a ratio of 0.08 to 1 for Alq ₃ that is the host material of the light-emitting layer 103, and The amount of rubrene as additive 108 in the region 1 was added at a mass ratio of 1: 1 with respect to Alq _{3 as} the host material of the electron transport layer 10.

In Comparative Example 5, 20 nm of Alq ₃ to which rubrene as an additive was not added was formed as an electron transport layer instead of the first region and the second region in Example 3. All other configurations are the same as in the first embodiment.

The results of measuring these thin film light emitting devices are shown in Table 3, FIG. 16 and FIG. The current efficiency shown in Table 3 is the efficiency in the case of 500 cd / m ² .

Ir (Fdpq) ₂ (acac) used as the luminescent material 107 in Example 3 and Comparative Example 5 is a luminescent material that emits red light, and has an energy gap smaller than that of rubrene as an additive, but Ir (Fdpq) ₂ ( Since the red light emission of acac) is phosphorescence, it is quenched by energy transfer when rubrene as an additive is present nearby. However, such quenching can be prevented by forming the second region to which rubrene is not added as in Example 3. From Table 3, it can be seen that the current efficiency of Example 3 is not decreased (rather increased) than that of Comparative Example 5, and that the configuration of Example 3 does not cause quenching due to rubrene.

  FIG. 16 shows emission spectrum data of Example 3 and Comparative Example 5. The emission spectra of Example 3 and Comparative Example 5 are almost the same, and it can be seen that no emission from the additive rubrene occurred.

  FIG. 17 shows voltage-luminance curves of Example 3 and Example 5. The light-emitting element of Example 3 has the same luminance and lower voltage than that of Comparative Example 5, and the voltage of the light-emitting element of Example 3 having the configuration of the present invention is reduced.

Since Ir (Fdpq) ₂ (acac) used in this example is a novel substance, a synthesis example is shown below.

<< Synthesis Example 1 >>
In this synthesis example, bis {2,3-bis (4-fluorophenyl) quinoxalinato} acetylacetonate iridium (III) [abbreviation: Ir (Fdpq) ₂ (acac)] represented by the following structural formula (1) It is a synthesis example.

<Step 1: Synthesis of Ligand (HFdpq)>
First, 3.71 g of 4,4′-difluorobenzyl and 1.71 g of o-phenylenediamine were stirred with heating in 200 mL of a solvent chloroform for 6 hours. The reaction solution was returned to room temperature, washed with 1N HCl and saturated brine, and dried over magnesium sulfate. The solvent was distilled off to obtain a ligand HFdpq [2,3-bis (4-fluorophenyl) quinoxaline] (pale yellow powder, yield 99%). The synthesis scheme and the structural formula of the ligand HFdpq are shown in the following formula (2).

<Step 2: Synthesis of binuclear complex [Ir (Fdpq) ₂ Cl] ₂ >
First, 3.61 g of ligand HFdpq (2,3-bis- (4-fluorophenyl) quinoxaline) and iridium chloride (IrCl ₃ · HCl ·) using a mixed solution of 30 ml of 2-ethoxyethanol and 10 ml of water as a solvent. 1.35 g of H ₂ O) was mixed and refluxed for 17 hours under a nitrogen atmosphere to obtain a binuclear complex [Ir (Fdpq) ₂ Cl] ₂ (brown powder, yield 99%). The synthesis scheme and the structural formula of the binuclear complex [Ir (Fdpq) ₂ Cl] ₂ are shown in the following formula (3).

<Step 3: Synthesis of organometallic complex Ir (Fdpq) ₂ (acac)>
Furthermore, using 30 ml of 2-ethoxyethanol as a solvent, 2.00 g of the binuclear complex [Ir (Fdpq) ₂ Cl] ₂ obtained in Step 2 above, 0.44 ml of acetylacetone (Hacac), and 1.23 g of sodium carbonate are mixed. Then, by refluxing in a nitrogen atmosphere for 20 hours, the organometallic complex Ir (Fdpq) ₂ (acac) of the present invention represented by the structural formula (16) was obtained (red powder, yield 44%). . The synthesis scheme is shown in the following formula (4).

By the above, Ir (Fdpq) ₂ (acac) can be synthesized.

The figure showing the structure of the thin film light emitting element of this invention. The figure showing the structure of the conventional thin film light emitting element. The figure showing the creation process of the thin film light emitting element of this invention. The figure showing the creation process of the thin film light emitting element of this invention. The figure which illustrated the structure of the display apparatus. 2A and 2B are a top view and a cross-sectional view of a light-emitting device of the present invention. FIG. 10 illustrates an electronic device to which the present invention is applicable. The figure which illustrated the structure of the display apparatus. The figure showing the structure of the thin film light emitting element of this invention. FIG. 14 illustrates an example of a pixel circuit of a display device. FIG. 11 illustrates an example of a protection circuit of a display device. Spectrum data of Example 1, Comparative Example 1, and Comparative Example 2. FIG. 3 is a voltage luminance curve of Example 1, Comparative Example 1, and Comparative Example 2. FIG. Spectrum data of Example 2, Comparative Example 3, and Comparative Example 4. The voltage brightness | luminance curve of Example 2, the comparative example 3, and the comparative example 4. FIG. Spectrum data of Example 3 and Comparative Example 5. The voltage luminance curve of Example 3 and Comparative Example 5.

Claims (13)

A light emitting layer containing at least an electron transport layer and a light emitting substance between the electrodes;
The electron transport layer has a first region closer to the electrode and a second region closer to the light emitting layer,
The first region includes a substance having a polycyclic fused ring,
The light-emitting element, wherein the second region does not contain a substance having the polycyclic fused ring. Having at least an electron transporting layer between the electrodes, a light emitting layer containing a light emitting substance, a first region, and a second region;
The electron transport layer has the second region between the light emitting layer and the first region,
The first region includes a substance having a polycyclic fused ring,
The light-emitting element, wherein the second region does not contain a substance having the polycyclic fused ring. Having at least an electron transporting layer between the electrodes, a light emitting layer containing a light emitting substance, a first region, and a second region;
The electron transport layer has the second region between the light emitting layer and the first region,
The light-emitting element is characterized in that the concentration of the substance having a polycyclic fused ring in the first region is higher than that in the second region. Having at least an electron transporting layer between the electrodes, a light emitting layer containing a light emitting substance, a first region, and a second region;
The electron transport layer has the second region between the light emitting layer and the first region,
A light-emitting element, wherein a substance having a polycyclic fused ring is selectively added to the first region.   5. The light-emitting element according to claim 1, wherein the second region has a thickness of 5 nm or more.   5. The light-emitting element according to claim 1, wherein the second region has a thickness of 10 nm or more.   7. The light-emitting element according to claim 1, wherein a compound mainly constituting the first region and the second region is the same compound.   8. The light-emitting element according to claim 1, wherein compounds that mainly constitute the first region, the second region, and the light-emitting layer are the same compound.   The light-emitting element according to claim 1, wherein the light-emitting substance is a phosphorescent material.   10. The light-emitting element according to claim 1, wherein an energy gap of the substance having a polycyclic fused ring is smaller than an energy gap of the light-emitting substance.   11. The light-emitting element according to claim 1, wherein the substance having a polycyclic fused ring is one of rubrene, 9,10-diphenylanthracene, pentacene, and perylene.   12. A display device using the light-emitting element according to claim 1. A television receiver using the display device according to claim 12.

Images