JP2006216891A - Manufacturing method of thin-film element structure, and functional base substance therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To constitute a peeling layer by using a new material which does not correspond to any contaminant, and to improve the practicality of a manufacturing method thereof, at the manufacturing of a thin-film element structure that uses the peeling layer. <P>SOLUTION: A method of manufacturing the thin-film element structure comprises the steps of forming a peeling layer 12 with a substance, containing at least germanium dioxide on a base substance 11, forming a thin-film element structure 13 on the peeling layer 12, making a laminate containing the peeling layer 12 immersed in a predetermined solution 21 to remove the peeling layer 12, and peeling the thin-film element structure 13 from the base substance 11. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a thin film element structure and a functional substrate for producing a thin film element structure.

  Bipolar and MOS transistors formed on the surface of single crystal silicon have good characteristics and are widely used as elements constituting electronic devices. Furthermore, at present, in order to cope with miniaturization of the element size, a transistor is fabricated on a thin film silicon fabricated through an insulating film on the silicon surface.

  The formation of these elements is based on a heat treatment process technology at a high temperature of 1000 ° C. such as a thermal oxidation method. Recently, polycrystalline silicon thin film transistors (poly-Si TFTs) or amorphous silicon thin film transistors (a-Si: H TFTs) can be fabricated at relatively low temperatures such as laser crystallization and plasma CVD. In addition, thin film transistors are expected to be applied to driving circuits for large screen direct view displays. Therefore, establishment of a large substrate processing technology is essential.

  Since the above-mentioned silicon transistor process technology is based on a high-temperature heat treatment technology, there is a problem that it cannot be applied to manufacture of a transistor formed on a substrate having no heat resistance. Although the process temperature has been lowered by new techniques such as laser crystallization and plasma CVD, 300 ° C. or more is still necessary, and it has been difficult to produce a transistor circuit on a non-heat-resistant substrate such as plastic. Further, when a transistor circuit is directly manufactured on a large-area substrate, there is a problem that an increase in the substrate size leads to an increase in manufacturing process apparatus, low accuracy, and high cost.

  In view of such a problem, Japanese Patent No. 3116085 discloses several methods for manufacturing a semiconductor thin film element by a peeling method using a peeling layer. According to this method, after the film structure constituting the semiconductor thin film element is formed via the release layer, the release layer is dissolved and removed, and the film structure is peeled off from the release layer, and then on a separate support substrate. The transfer is formed on the surface. The support substrate functions as an actual substrate of the semiconductor thin film element, but the support substrate is not exposed to a high-temperature process in manufacturing the film structure. Therefore, the support substrate can be made of an inexpensive polymer material and the like, and the manufacturing process is simplified by the transfer-type process described above, and the manufacturing process apparatus as described above is increased in size, accuracy, and cost. Etc. can be avoided.

Japanese Patent No. 3116085

  It is necessary that the release layer is chemically unstable and soluble in an acidic solution without being altered or peeled off in a high-temperature process during the formation of the film structure, and it is necessary to easily remove the release layer. From this point of view, the release layer is mainly formed using a metal material such as chromium or nickel. However, when a release layer is formed from such a metal material, when the release layer is discarded, the release layer must be treated as a contaminant, which is not preferable in terms of environmental conservation. Therefore, it is desirable that the material constituting the release layer is made of a material other than that positioned as a contaminant.

  It is an object of the present invention to improve the practicality of the manufacturing method by forming the release layer from a novel material that does not correspond to a contaminant in the production of a thin film element structure using a release layer.

In order to achieve the above object, the present invention provides:
Forming a release layer having a substance containing at least germanium oxide on a substrate;
Forming a thin film element structure on the release layer;
Removing the release layer and peeling the thin film element structure from the substrate;
It is related with the manufacturing method of the thin film element structure characterized by comprising.

  In order to achieve the above object, the inventors of the present invention can be easily dissolved when immersed in an acidic solution and the like, can be removed very easily, and do not contribute to contamination. We conducted intensive studies to find out. As a result, by allowing the release layer to contain germanium oxide, when the release layer is immersed in a predetermined solution, the germanium oxide is reduced and eluted into the solution. As a result, it has been found that the release layer can be dissolved and removed.

  That is, germanium oxide is easily reduced, and in a solution having a high hydrogen ion concentration such as an acid, germanium dissociates from oxygen and becomes GeHx and is eluted into the solution. Since germanium oxide does not fall into the category of contaminants such as metallic materials such as chromium and nickel, the thin film element structure using the release layer is formed by including the release layer in the release layer. The practicality of production can be improved. Therefore, by using the transfer formation process described above, problems such as simplification of the manufacturing process, enlargement of the manufacturing process apparatus, low accuracy, and high cost, which are the original effects of the thin film element structure using the release layer, are achieved. It can be avoided after solving practical problems.

  The release layer can be removed using a non-alkaline solution. As the non-alkaline solution, an acidic solution having a pH of less than 0.1 to 7 or neutral water can be used. The release layer can be removed by dipping in the non-alkaline solution, or can be removed by spraying the non-alkaline solution. At this time, the non-alkaline solution is preferably heated to a temperature of 10 to 90 ° C. Thereby, the etching rate for the release layer is increased, and the release layer can be removed in a shorter time.

  Moreover, the said peeling layer can be removed also by exposing to 100-300 degreeC high temperature water vapor | steam, for example. At this time, the injection pressure of the high-temperature steam is increased to about 30 MPa.

  In a preferred embodiment of the present invention, at least one through hole is formed in the laminate including at least the thin film element structure so that an upper surface of the release layer is exposed in the thickness method, and thereafter And removing the release layer. In this case, since the non-alkaline solution described above is immersed not only from the side surface portion of the release layer but also from the upper surface exposed in the through hole, the etching time of the release layer is shortened, and the release layer is removed. The operation for removing the layer can be shortened.

  In another preferred embodiment of the present invention, a coating layer is formed on the release layer so as to cover the entire release layer, and a thin film element structure is formed on the cover layer. In this case, since the release layer is covered with the coating layer in the formation process of the thin film element structure, the release layer is covered with an etching solution or the like used in the wet process in the formation process of the thin film element structure. The layer is never exposed. Accordingly, it is possible to prevent the peeling layer from being peeled off in the process of forming the thin film element structure, and to suppress a reduction in the formation yield of the thin film element structure.

  Furthermore, in still another preferred aspect of the present invention, it is preferable to apply stress to the release layer in the removal of the release layer. Preferably, the stress is applied by, for example, forming an elastic body above the release layer, deforming the elastic body, and applying a tensile stress to the release layer. As a result, the end of the release layer is slightly lifted from the base to form a minute gap between the base and the non-alkaline solution or the like is gradually immersed in the release layer through the gap. As a result, the release layer can be removed more easily. This embodiment is particularly effective when the area is extremely large with respect to the thickness of the release layer.

  The “thin film element structure” in the present invention means a structure of a part that performs basic and main functions of a target semiconductor element or the like, and a predetermined thin film circuit element or a simple mere element depending on the function of the element. It takes any form such as a single layer or a laminate of a plurality of layers.

The present invention also relates to a functional substrate used for producing the thin film element structure,
A predetermined substrate;
A release layer having a substance containing at least germanium oxide formed on the substrate;
A thin film element structure formed on the release layer;
It is characterized by comprising.

  As described above, according to the present invention, in the manufacture of a thin film element structure using a release layer, the release layer is made of a novel material that does not correspond to a contaminant, and a manufacturing method with improved practicality is provided. can do.

Details of the present invention and other features and advantages will be described below based on the best mode.
Embodiments of the method of the present invention will be described with reference to the drawings.

  FIG. 1 is a process diagram showing an example of a method for producing a thin film element structure of the present invention. In the following drawings, the same reference numerals are used for the same or similar components. First, as shown in FIG. 1 (a), a release layer 12 is formed on a predetermined substrate 11, and a film composed of a single layer or a plurality of layers necessary for forming a predetermined thin film electronic circuit element is further formed thereon. Structure 13 is formed. The release layer 12 is made of a material containing at least germanium oxide.

  Next, as shown in FIG. 1B, the laminate including the release layer 12 is immersed in a predetermined solution 21. Germanium oxide is easy to reduce, and when immersed in the solution, when the solution contains a relatively high hydrogen ion concentration, germanium dissociates from oxygen and becomes GeHx and is eluted into the solution. As a result, the release layer 12 can be easily removed from the substrate 11. Note that the release layer 12 may be formed by mixing or stacking germanium oxide or a substance containing the same and a substance that cannot be etched.

  The release layer 12 can be formed on the substrate 11 by using a known method such as a sputtering method, a plasma gas chemical reaction method, or a vacuum deposition method.

  The oxygen concentration in the release layer 12 is preferably 5-80 atomic%, and the thickness is preferably 100-10000 nm. As a result, the peelable function of the release layer 12 itself can be increased, and it can be easily peeled off by various preferable peeling means described in detail below.

  In addition, when the film structure 13 itself does not require physical support, it can be used as it is as a semiconductor element or as a circuit device using it. Moreover, the formation process of a circuit device using it as a thin film electronic circuit element can be performed continuously.

  Further, the peeled substrate 11 can be used repeatedly and can be used again to form the peeling layer 12 and the film structure 13 necessary for a predetermined electronic circuit element.

  The solution 21 is preferably composed of a non-alkaline solution. Thereby, the peeling operation of the peeling layer 12 can be simplified and shortened. As the non-alkaline solution, an acidic solution having a pH of less than 0.1 to 7, specifically, a solution of hydrochloric acid, nitric acid, phosphoric acid, acetic acid, or the like can be used. It has been experimentally confirmed that the etching rate increases as the hydrochloric acid concentration increases. Moreover, in addition to the acidic solution mentioned above, even if it uses neutral water, the peeling layer 12 can fully be peeled and removed, and it has been confirmed experimentally.

  The non-alkaline solution is preferably heated to a temperature of 10-90 ° C. Thereby, the etching rate for the release layer is increased, and the release layer can be removed in a shorter time.

  FIG. 2 is a diagram showing a modification of the manufacturing method shown in FIG. In the example shown in FIG. 2, the protective layer 14 is formed on the film structure 30 as shown in FIG. In this case, as shown in FIG. 2B, when the laminate including the release layer 12 is immersed in the solution 21 in order to release the release layer 12, the film structure 30 directly contacts the solution 21. Can be prevented and deterioration of the film structure 30 can be suppressed. In addition, mechanical handling of the membrane structure 30 can be suppressed during handling during such operations.

  FIG. 3 is a diagram showing a modification of the manufacturing method shown in FIG. In the example shown in FIG. 3, instead of immersing the release layer in a non-alkaline solution such as an acidic solution in the example shown in FIG. 1, the solution is sprayed onto the release layer. In such a case, as shown in FIG. 3A, the solution 21 comes into contact with the release layer 12 in the form of droplets or vapor. Therefore, also in this case, as shown in FIG. 3B, the peeling layer 12 can be efficiently etched and peeled off. In addition, since the contact of the solution 21 with other parts than the release layer 12 can be suppressed, damage to the film structure 13 and the like can be particularly suppressed.

  FIG. 4 is a diagram showing a modification of the manufacturing method shown in FIG. In the example shown in FIG. 4, instead of immersing the release layer in a non-alkaline solution such as an acidic solution in the example shown in FIG. 1, the laminate including the release layer is exposed to high-temperature steam. In this example, a laminate in which a base 11, a release layer 12, and a film structure 13 (a protective layer or the like can be formed if necessary) is formed in a predetermined container 22 having an isolation wall. The chamber 22 is disposed below the isolation wall, the container 22 is filled with the high temperature water vapor 22, and the peeling layer 12 is contacted with the high temperature water vapor 22 to be removed by etching.

  The temperature of the high-temperature steam 22 is preferably 100 to 300 ° C., and the pressure is preferably about 30 MPa.

  FIG. 5 is a diagram showing a modification of the manufacturing method shown in FIG. First, as shown in FIG. 5A, a germanium oxide film 12 as a release layer is formed on an insulating substrate 11, and a first cover film 15 is further formed thereon, and a thin film device is formed thereon. 13 is formed, and finally, a protective layer 14 is formed on the upper surface of the thin film device 13.

  Next, as shown in FIG. 5B, the laminate including the germanium oxide film 12 is immersed in the solution 21. The solution 21 is composed of, for example, an acidic solution, and the etching rate of the germanium oxide with respect to the acid solution is very high. Therefore, the etching proceeds rapidly from the lateral direction, and part or all of the germanium oxide is dissolved. Further, due to the presence of the protective layer 14 and the coating layer 15, the thin film device 13 is not exposed to acid solution damage. Thereby, the thin film device 13 can be peeled off from the insulating substrate 11 very easily and with a high yield.

  Next, as shown in FIG. 5C, the support base 16 is attached to the surface from which the insulating substrate 11 is removed, and the thin film device 13 is transferred and formed on the support base 16. Next, as shown in FIG. 5D, the protective layer 5 is peeled off to complete the electronic device including the thin film device 13.

  As shown in FIG. 5D, the support base 16 functions as a substrate constituting the electronic device, but as is apparent from the above description, it does not exist when the thin film device 13 is formed. It is not affected by high temperature processes. Therefore, the support base 16 can be made of any material according to the usage mode of the electronic device, and can be made of, for example, a polymer film that is inexpensive and rich in flexibility.

  FIG. 6 shows a specific example of manufacturing a MOS field effect transistor (FET) in accordance with the manufacturing method shown in FIG. As a manufacturing process of the MOSFET, formation of the crystalline silicon film 51, formation of the gate insulating film 52, formation of source / drain regions 53 and 54 by doped silicon, formation of the gate electrode 55, source electrode 56, and drain electrode 57, and This includes the formation of the interlayer insulating films 58 and 59 and the passivation film 60 and the formation of metal wirings 71 and 72 between the transistors or external circuits. FIG. 6A shows a state in which all elements constituting the transistor circuit 13 are formed on the base 11 via the release layer 20.

  In order to activate impurities for forming a crystalline film, forming a gate insulating film, forming a doped silicon region, etc., when the substrate 11 has heat resistance such as quartz, a high temperature (> 600 ° C.) heat treatment step is performed. Can be used. Furthermore, techniques capable of processing at a relatively low temperature such as laser crystallization, laser activation, and plasma CVD can also be used. Next, as shown in FIG. 6B, the protective layer 14 is adhered on the transistor circuit 13, and the laminate including the release layer 12 is removed by being immersed in a predetermined solution such as an acidic solution. Next, as shown in FIG. 6C, the peeled transistor circuit 13 is transferred and formed on another support base 16, and the protective layer 14 is removed as shown in FIG. A transistor (MOSFET) including 16 can be formed.

  In the step shown in FIG. 6, for example, the metal wirings 71 and 72 can be formed after the elements constituting the transistor circuit 13 are transferred and formed on the support base 16.

  FIG. 7 is a process diagram showing a modification of the manufacturing method shown in FIG. In the step shown in FIG. 7, the steps shown in FIGS. 7A and 7B are the same as the steps shown in FIGS. 5A and 5B, and are shown in FIGS. 7C and 7D. Different in process. In this example, as shown in FIG. 7B, after the laminate including the germanium oxide film 12 is immersed in the solution 21 and the release layer 12 is removed, as shown in FIG. The thin film device 13 is transferred and formed on a support substrate 16 having an area larger than that area. Then, as shown in FIG. 7D, an electronic device in which the protective layer 14 is removed and the thin film device 13 is transferred and formed on the large area support substrate 16 can be obtained.

  According to this example, the thin film devices are transferred and formed on the large-area support substrate. Therefore, the plurality of thin film devices are integrated by transferring and forming the plurality of thin film devices on the support substrate. Can be. Therefore, it is possible to form a semiconductor circuit or the like in which the thin film devices are integrated without requiring a highly accurate patterning technique.

  FIG. 8 is a process diagram showing another modification of the manufacturing method shown in FIG. In this example, as shown in FIG. 8A, a germanium oxide film 12 as a release layer is formed on an insulating substrate 11, and a coating layer 15 is further formed. A fine thin film device 13 is formed, and finally a protective layer 14 is formed on the upper surface of the thin film device 13.

  Next, as shown in FIG. 8B, after the laminated body including the germanium oxide film 12 is immersed in the solution 21 and the germanium oxide film 12 is removed, as shown in FIG. Each of these is transferred and formed on a corresponding support substrate 16. Thereafter, as shown in FIG. 8D, the protective layer 14 is removed, and a plurality of electronic devices having the thin film device 13 transferred and formed on the support substrate 16 can be manufactured simultaneously.

  In the example shown in FIGS. 7 and 8, since the protective layer 14 and the covering layer 15 are provided, the thin film device 13 is not exposed to the damage of the acid solution, and the insulating substrate 11 to the thin film device 13 are not exposed. Can be peeled off very easily and with good yield.

  In the manufacturing method in the example shown in FIGS. 5 to 8, the case of manufacturing a MOSFET has been described particularly with reference to FIG. 6, but other semiconductor elements such as bipolar elements, solar cell elements, and amorphous silicon TFTs have been described. It can be applied to amorphous image sensors and the like.

  FIG. 9 is a process diagram showing another example of a method for producing a thin film element structure of the present invention. First, as shown in FIG. 9A, a release layer 12 is formed on a predetermined substrate 11, and a covering layer 15, a film structure 13, and a protective layer 14 are sequentially formed on the release layer 12. Next, as shown in FIG. 9B, the laminate including the covering layer 15, the film structure 13 and the protective layer 15 is penetrated so that the upper surface of the release layer 12 is exposed in a portion where the film structure 13 does not exist. Hole 19 is formed. Thereafter, as shown in FIG. 9C, when the laminate is immersed in the solution 21 as described above, the solution 21 is immersed not only from the end of the release layer 12 but also from the upper surface thereof. . Accordingly, the etching time of the release layer is shortened, and the removal operation of the release layer can be shortened.

  FIG. 10 is a process diagram showing another example of a method for producing a thin film element structure of the present invention. First, as shown in FIG. 10A, a release layer 12 is formed on a predetermined substrate 11, a covering layer 15 is formed so as to cover the entire release layer 12, and the film structure 13 and protection are further formed. Layer 14 is formed sequentially. Next, as illustrated in FIG. 10B, the stacked body illustrated in FIG. 10A is cut in the thickness direction so that the side surface of the release layer 12 is exposed. Thereafter, as shown in FIG. 10C, when the laminate is immersed in the solution 21 as described above, the solution 21 is immersed from the side surface of the release layer 12, and as a result, the release layer 12 is removed by etching. It becomes like this.

  Next, as shown in FIG. 10D, after the film structure 13 peeled from the substrate 11 is transferred and formed on the support substrate 16, the protective layer 14 is removed as shown in FIG. A desired (thin film) element structure can be obtained.

  According to this example, since the release layer 12 is covered with the coating layer 15 in the formation process of the film structure 13, the release layer 12 is peeled off to an etching solution or the like used in the wet process in the formation process of the film structure 13. Layer 12 is not exposed. Accordingly, it is possible to prevent the peeling layer 12 from being peeled off in the process of forming the film structure 13, and to suppress a reduction in the formation yield of the film structure 13, that is, the element structure.

  FIG. 11 is an example showing a preferred embodiment of the manufacturing method shown in FIG. In the example shown in FIG. 11, as shown in FIGS. 11 (a) and 11 (b), stress is further applied on the laminate in which the substrate 11, the release layer 12, the film structure 13 and the protective layer 14 are sequentially formed. A solid-shaped elastic body 31 is formed in a circular shape. Next, as shown in FIG. 11C, the assembly including the elastic body 31 is immersed in the solution 21 and the elastic body 31 is deformed so that a tensile stress acts on the release layer 12.

  As a result, the end of the release layer 12 is slightly lifted from the base 11 to form a minute gap with the base 11 so that the solution 21 is gradually immersed in the release layer 12 through the gap. Therefore, the release layer can be removed more easily. This aspect is particularly effective when the area is extremely large with respect to the thickness of the release layer 12. Specifically, when a glass substrate having a diameter on the order of metric is used as the substrate 11, as described above, the preferable thickness of the release layer 12 is 100 to 10000 nm, and the release layer 12 is formed on the front surface of the glass substrate. Then, the thickness of the release layer 12 and the in-plane length (area) become different on the order of several digits. Therefore, in such a case, the method of this example is extremely effective.

  FIG. 12 shows a modification of the manufacturing method shown in FIG. In the example shown in FIG. 12, a balloon is used instead of the solid elastic body shown in FIG. The balloon 32 is adhered to the protective layer 14, and air is sent into the balloon 32 in this state. Then, the balloon 32 swells and exhibits a predetermined curvature, and along with this, the end portion of the protective layer 14 is also deformed outward. Accordingly, even in this case, the end of the release layer 12 slightly floats from the base 11 to form a minute gap with the base 11, and the solution 21 gradually enters the release layer 12 through the gap. So that the release layer can be removed more easily.

FIG. 13 shows an application example of the manufacturing method shown in FIG. In the example shown in FIG. 13, the release layer 12 includes a germanium oxide layer 121 and another material, specifically, a layer 122 made of a material such as SiO ₂ , SiN, Al ₂ O ₃ or the like. In this case, by immersing the release layer 12 in the solution 21 as described above, only the germanium oxide layer 121 in the release layer 12 is removed, and the layer 122 remains. Therefore, in this case, the substrate 11 becomes a supporting substrate, and the film structure 13 remains on the substrate 11 through the layer 122.

  In such an element structure, since the layer 122 is porous as a whole, the thermal conductivity and the like are low. Therefore, the element structure obtained in this way can be applied to a high-sensitivity sensor or the like.

Note that the material constituting the layer 122 needs to be composed of a material that is not etched away under the condition that the germanium oxide layer 121 is removed by etching, but the above-described SiO ₂ or the like satisfies this condition. To do.

  Further, as shown in FIG. 14, the device structure (FIG. 14A) obtained in FIG. 13 is further subjected to the same operation (FIG. 14B) to obtain the structure shown in FIG. 14C. Such an element structure in which the porous layer 122 is laminated can be obtained.

  The peeling layer 12 as shown in FIG. 13 forms a region in which the germanium oxide layer 121 or the layer 122 is uniformly formed first, and then this layer is partially etched away by photolithography or the like. Then, the layer 122 or the germanium oxide layer 121 is formed so as to be buried in this region, and then the excess portion protruding from the region can be removed by CMP or the like. Note that the germanium oxide layer 121 and the layer 122 can be formed by using a known film formation technique.

  In the example shown in FIG. 13 and FIG. 14, the case where the peeling layer 12 is composed of two types of materials (layers) has been described. However, the separation layer 12 may be composed of three or more types of materials (layers). .

  FIG. 15 shows a conceptual diagram in which the process of removing the germanium oxide film by immersing it in a hydrochloric acid aqueous solution is observed in real time. Laser light 61 is passed through the hydrochloric acid solution 21 as probe light, and the intensity of the laser light is measured using a photodetector 62. The substrate 11 on which the release layer 12 is formed is immersed in an acidic solution so as to cross the laser beam. Since the refractive index of the release layer 12 has a value different from the refractive index of the substrate 11, the transmission intensity depends on the film thickness of the release layer 12 due to the light interference effect. Therefore, the state of removal of the release layer 12 can be measured by measuring the time change of the laser light intensity.

  FIG. 16 shows the time variation of the light intensity measured when a 3 micron thick germanium oxide film 12 formed on a quartz substrate is used with a 0.1 mol% hydrochloric acid solution using the method shown in FIG. Show. After immersing the substrate 11 and the release layer 12 in the solution 21, the light intensity showed a vibration pattern in which the light intensity was particularly strong or weak. And after 2.5 seconds, it became a constant value. This indicates that the light intensity changed as the release layer 12 was removed by hydrochloric acid and the film thickness was reduced. When the light intensity becomes constant, the release layer 12 is completely removed.

  Based on the process shown in FIG. 5, a thin film element structure was fabricated. First, a germanium oxide film 12 was formed to a thickness of 2 μm on a 50 mm square glass substrate 11, and then a silicon oxide film 15 was formed to a thickness of 0.3 μm as a coating layer. Thereafter, a thin film transistor array 13 made of a polysilicon film was formed. Finally, a polyethylene film 14 was attached to the upper surface of the thin film transistor array 13 as a protective layer.

  Here, the germanium oxide film 12 was formed by sputtering using germanium as a target and a mixed gas of argon and oxygen. When a film was formed under the conditions of an argon flow rate of 40 sccm and an oxygen flow rate of 20 sccm, the etching rate of this germanium oxide with respect to hydrochloric acid at 40 ° C. was 100 μm / min. The concentration of hydrochloric acid is 0.1 mol / l. In addition, the thin film transistor array was formed based on a polysilicon film obtained by polycrystallizing amorphous silicon formed by thermal CVD using excimer laser irradiation.

  Next, as shown in FIG. 5B, the laminate obtained as described above was immersed in a hydrochloric acid solution 21 having a concentration of 0.1 mol / l at room temperature. During the immersion, the hydrochloric acid solution was sufficiently stirred. After 2 hours of immersion, the germanium oxide film 12 was almost dissolved, and the thin film transistor array 13 with the polyethylene film 14 could be peeled from the glass substrate 11.

  Next, as shown in FIG. 5 (c), a polyimide film 16 having a thickness of 100 μm as a supporting base was attached to the surface from which the glass substrate had been removed with an adhesive. Finally, as shown in FIG. 5D, the polyethylene film 14 was peeled off to complete the flexible thin film transistor substrate.

  There was almost no difference between the initial transistor characteristics on the glass substrate and the transistor characteristics after being peeled from the glass substrate and transferred onto the polyimide film substrate, and a flexible thin film transistor substrate having good characteristics could be realized.

  As described above, the present invention has been described in detail based on the embodiments of the present invention with specific examples. However, the present invention is not limited to the above contents, and all modifications and changes are made without departing from the scope of the present invention. It can be changed.

It is process drawing which shows an example of the preparation methods of the thin film element structure of this invention. It is a figure which shows the modification of the manufacturing method shown in FIG. It is a figure which shows the modification of the manufacturing method shown in FIG. It is a figure which shows the modification of the manufacturing method shown in FIG. It is a figure which shows the modification of the manufacturing method shown in FIG. A specific example of manufacturing a MOS field effect transistor (FET) according to the manufacturing method shown in FIG. It is process drawing which shows the modification of the manufacturing method shown in FIG. It is process drawing which shows the other modification of the manufacturing method shown in FIG. It is process drawing which shows the other example of the manufacturing method of the thin film element structure of this invention. It is process drawing which shows the other example of the preparation methods of the thin film element structure of this invention. It is an example which shows the preferable aspect of the manufacturing method shown in FIG. It is a modification of the manufacturing method shown in FIG. It is an application example of the manufacturing method shown in FIG. It is a modification of the manufacturing method shown in FIG. It is a conceptual diagram for observing the process which removes a germanium oxide film | membrane by immersing in hydrochloric acid aqueous solution in real time. FIG. 15 shows a change in light intensity with time when a 3 micron thick germanium oxide film formed on a quartz substrate is measured using a 0.1 mol% hydrochloric acid solution using the method shown in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Base body 12 Release layer, Germanium oxide film 13 Film structure, thin film device 14 Protective layer 15 Cover layer 16 Support base body 19 Through hole 21 Solution 22 High temperature water vapor 31 Elastic body 32 Balloon

Claims (28)

Forming a release layer having a substance containing at least germanium oxide on a substrate;
Forming a thin film element structure on the release layer;
Removing the release layer and peeling the thin film element structure from the substrate;
A method for producing a thin film element structure, comprising: Forming a release layer having a substance containing at least germanium oxide on the substrate;
Forming a thin film element structure on the release layer;
Forming at least one through hole such that an upper surface of the release layer is exposed in a thickness method of the laminate including at least the thin film element structure;
Removing the release layer and peeling the thin film element structure from the substrate;
A method for producing a thin film element structure, comprising: Forming a release layer having a substance containing at least germanium oxide on the substrate;
Forming a coating layer on the release layer so as to cover the entire release layer;
Forming a thin film element structure on the coating layer;
Removing the portion of the coating layer covering the side surface of the release layer to expose the side surface of the release layer;
Removing the release layer and peeling the thin film element structure from the substrate;
A method for producing a thin film element structure, comprising:   The method for producing a thin film element structure according to claim 1, wherein an oxygen concentration in the release layer is 5 to 80 atomic%.   The method for producing a thin film element structure according to claim 1, wherein the release layer has a thickness of 100 to 10,000 nm.   The method for producing a thin film element structure according to claim 1, wherein the release layer is removed using a non-alkaline solution.   The method according to claim 6, wherein the non-alkaline solution is an acidic solution.   The method of manufacturing a thin film element structure according to claim 6, wherein the non-alkaline solution is water.   The method for producing a thin film element structure according to any one of claims 6 to 8, wherein the release layer is removed by immersing the release layer in the non-alkaline solution.   The method for producing a thin film element structure according to any one of claims 6 to 8, wherein the release layer is removed by immersing the release layer in the non-alkaline solution heated to a predetermined temperature.   The method according to claim 10, wherein the non-alkaline solution is heated to a temperature of 10 to 90 ° C.   The method for producing a thin film element structure according to any one of claims 6 to 8, wherein the release layer is removed by spraying the non-alkaline solution onto the release layer.   The thin film element structure according to any one of claims 6 to 8, wherein the release layer is removed by exposing the release layer to high-temperature water vapor in a temperature range of 100 to 300 ° C. Manufacturing method.   The method of manufacturing a thin film element structure according to claim 13, wherein the high-temperature water vapor is ejected at a pressure of 30 MPa or more with respect to the release layer.   The method for producing a thin film element structure according to claim 1, wherein stress is applied to the release layer in removing the release layer.   16. The method of manufacturing a thin film element structure according to claim 15, wherein the stress is applied by forming an elastic body above the release layer and deforming the elastic body.   17. The method of manufacturing a thin film element structure according to claim 15, wherein the stress in applying the stress is a tensile stress.   The method for producing a thin film element structure according to claim 1, wherein the peeling layer is removed after a protective layer is provided on the thin film element structure.   19. The method according to claim 1, further comprising a step of forming a support substrate for transferring the thin film element structure on the thin film element structure after peeling the thin film element structure from the substrate. The manufacturing method of the thin film element structure as described in any one.   The method according to claim 19, wherein the support substrate includes a polymer material.   The method of manufacturing a thin film element structure according to claim 19 or 20, wherein the support substrate has an area larger than that of the thin film element structure.   The thin film element structure includes a plurality of elements, and the support substrate includes a plurality of substrate elements having a smaller area than the thin film element structure, and the plurality of elements are transferred and formed on the corresponding substrate elements, respectively. 21. A method for producing a thin film element structure according to claim 19 or 20, wherein   The release layer is made of a plurality of materials containing the germanium oxide, and has a region made of each of the plurality of materials, and only the region containing the germanium oxide of the release layer is removed, and the release layer is predetermined. The method for producing a thin film element structure according to any one of claims 1 to 22, wherein the thin film element structure is left so as to exhibit a three-dimensional structure. A predetermined substrate;
A release layer formed on the substrate and having a substance containing at least germanium oxide;
A thin film element structure formed on the release layer;
A functional substrate for producing a thin film element structure, comprising:   25. The at least one through-hole is formed in the laminated body including at least the thin film element structure in such a thickness method that an upper surface of the release layer is exposed. Functional substrate for thin film element structure fabrication.   The functional substrate for producing a thin film element structure according to claim 24, further comprising a coating layer formed on the release layer so as to cover the entire release layer.   27. The functional substrate for producing a thin film element structure according to any one of claims 24 to 26, wherein the oxygen concentration in the release layer is 5 to 80 atomic%.   The functional substrate for producing a thin film element structure according to any one of claims 24 to 27, wherein the thickness of the release layer is 100 to 10,000 nm.

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