JPH01774A - Flexible light receiving element and its manufacturing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to improvements in a flexible light-receiving element and a method for manufacturing the same.

(b) Conventional technology Light-receiving elements that input light and output electricity include photoconductive elements, photodiodes, solar cells, e)) lannostars,
Photocyrisk etc. are known.

Semiconductors having photovoltaic properties are used in these light-receiving elements, and among them, those using amorphous silicon are inexpensive and widely used as solar cells or optical sensors.

For example, in solar cells, p-type, i-type, and n-type amorphous silicon are sequentially deposited in thin films on a metal substrate that also serves as a metal back electrode layer, and a transparent electrode layer is laminated.
Alternatively, a transparent electrode layer, p
A structure in which valvus crystalline silicon, i-type valvate silicon, and n-type valvate silicon are sequentially deposited, and a metal back electrode layer made of aluminum or the like is further laminated has been put into practical use.

The base plate, which also serves as the metal back electrode layer, is made of foil or thin plate made of stainless steel, aluminum, copper, etc., and the transparent electrode layer is made of, for example, tin oxide, indium oxide, or a solid solution of both (ITO). ) etc.

In the former case, which uses a metal substrate, the electric resistance of the substrate is sufficiently low, so that a large output can be obtained from a substrate of a certain area.

In addition, in the latter case where a glass plate is used as a substrate, since the substrate has insulating properties, it is possible to obtain more than twice the voltage by arranging multiple semiconductors adjacent to each other and connecting them in series with a conductor. It's easy.

By the way, solar cells using such amorphous silicon (referred to as amorphous silicon solar cells) are currently being developed to reduce material costs, be lighter, thinner, etc., as well as improve production processes and In order to facilitate handling during transportation and reduce production costs and transportation costs,
It has been proposed to use a flexible substrate.

For example, a flexible film using a heat-resistant plastic film such as a polyimide film as a substrate, and laminating a metal electrode layer such as a stainless steel foil or film, an amorphous silicon layer, and a transparent electrode layer on this substrate. Amorphous silicon solar cells have been proposed (for example, JP-A-54-149489, JP-A-55-4994, JP-A-56-16).
9372, JP-A-55-29154, JP-A-57-103839, etc.), these types have features compared to conventional linot-type ones in terms of weight reduction, thinner thickness, etc. , a wide range of applications and uses are expected.

This type of amorphous silicon solar cell is lightweight, thin, and has low material cost, and is highly flexible, so it can be rolled into a roll and processed continuously to reduce production and transportation costs. This is very advantageous in reducing

Furthermore, since it can be formed into any shape, it is expected to have a wide range of applications and uses.

(C) Problems to be Solved by the Invention However, to date, amorphous silicon solar cells using heat-resistant plastic films such as polyimide films as substrates have not met these expectations. However, it has not been put into practical use due to the following problems.

In other words, there are problems such as curling of the substrate film when heating the substrate film during manufacturing, and curling of the product due to the difference in thermal expansion coefficient between the substrate film and the amorphous silicon layer. It has become.

Moreover, the occurrence of such curling is not only a problem in terms of handling, but also an essential problem in that the occurrence of curling causes a reduction in the photoelectric conversion rate.

Furthermore, when such curling becomes extreme, cracks occur in the amorphous silicon layer, resulting in a disconnection state.

By the way, at higher temperatures than polyimide film (250 ~
If an aromatic polyimide film with a high initial Young's modulus at 350°C is used for the substrate, the initial Young's modulus at high temperatures will be improved, but the heat shrinkage rate at 300°C will be lower than that of conventional products. is 0.5%, whereas that of aromatic polyimide film is less than 0.7%, which is about an order of magnitude higher than the thermal shrinkage rate of the semiconductor layer, so it is not possible to prevent curling of the product. .

In addition, a drawback of conventional rigid solar cells using a positive plate, a metal plate, etc. as a substrate is that the (surface) shape is flat, so that the applications are limited.

That is, for example, in order for light-receiving elements (solar cells) to be widely used in the automobile field, they must be used integrally with roof parts (for example, sunroofs, etc.) or bodies, or by being attached to them. However, these parts of the car need to have a moderately convex curved shape in terms of strength and air resistance, and flat solar cells cannot be directly installed in these parts. Therefore, a method is being adopted in which solar cells are manufactured using tempered glass that has been preformed into a curved surface as a substrate.

However, the sunroof and panel made of tempered glass are
Since they are significantly heavier than plastic ones, fundamental solutions are needed to reduce the weight of automobiles.

On the other hand, the above-mentioned flexible light receiving element (solar cell) can be applied to an extremely gently curved body, but the radius is 5 cm.
When applied to the following spherical surfaces, cracks occur in the amorphous silicon layer or internal wire breaks occur, which means that the shape of the setting part is restricted, and therefore the use and application are limited. In this respect, we still have some luck.

The present invention has been made in consideration of the above-mentioned circumstances associated with a flexible light-receiving element whose substrate is made of plastic having heat resistance and electrical insulation properties, and a method for manufacturing the same. The present invention is characterized by providing a flexible light-receiving element that can prevent the occurrence of damage or can be suitably mounted on a portion having a curved or curved surface shape, and a method for manufacturing the same.

(d) Means for Solving the Problems In order to achieve the above object, the flexible light receiving element according to the present invention comprises a transparent electrode layer, a photovoltaic semiconductor layer, and a back electrode layer. The element is interposed between a plastic substrate having heat resistance, flexibility and electrical insulation, and an electrical insulation layer having heat shrinkage characteristics equivalent to that of the substrate and flexibility. The internal stress of the plastic substrate caused by temperature changes is offset by the internal stress of the electrically insulating layer, thereby preventing the flexible light-receiving element from curling.

Such a flexible light-receiving element of the present invention can be manufactured by a method for manufacturing a flexible light-receiving element according to the present invention, which includes, for example, the following process.

That is, the method for manufacturing a flexible light-receiving element according to the present invention includes a step (A) of forming a transparent plastic substrate having heat resistance, flexibility, and electrical insulation on the surface of a support; and the above steps. Step (B) of laminating a transparent electrode layer on the surface of the substrate formed in step (A), and forming a photovoltaic semiconductor layer on the surface of the transparent electrode layer formed in step (B) above. a step (C) of forming a back electrode layer on the surface of the semiconductor layer formed in the above step (C); and a step (D) of forming a back electrode layer on the surface of the back electrode layer formed in the above step (D). Step (E) of forming an electrical insulating layer having heat shrinkage characteristics equivalent to those of the above substrate, and having heat resistance and flexibility; A flexible light-receiving element according to the present invention can be obtained through a step (F) of peeling off a laminate consisting of a substrate, a transparent electrode layer, a semiconductor layer, a back electrode layer, and an electrically insulating layer from a support.

In the present invention, the flexible light-receiving element refers to a light-receiving element that inputs light and outputs electricity, and includes all types of flexible light-receiving elements.Specifically, it includes photoconductive elements, photodiodes, Examples include solar cells, phototransistors, and photothyristors.

Furthermore, the light referred to here includes not only visible light but also infrared and ultraviolet rays.

The flexible light-receiving element and other manufacturing methods according to the present invention will be described in detail as follows.

In the present invention, first, a step (A) of forming a heat-resistant, flexible, and electrically insulating transparent plastic substrate on the surface of a support is carried out.

The support used in the present invention is to be peeled off in the step (F) described later, and from the viewpoint of removability in this step (F), the support may be glass, reinforced FF glass, stainless steel, It is preferable to use a plate or foil made of aluminum or iron.

The support used in this step (A) includes a glass plate,
Metal plates or foils such as stainless steel or aluminum are used, but among these, glass plates are recommended because they allow evaluation of charge conversion elements in intermediate processes, especially the photoelectric properties of semiconductors.

In addition, stainless steel plates or foils are most suitable for carrying out each process continuously.

Furthermore, the plastic constituting the substrate used in the present invention is not particularly limited as long as it is transparent, has heat resistance, flexibility, and electrical insulation properties, and typical examples include: , polyimide, polyether sulfone, polysulfone, polyetherimide, 4-methylpentene terephthalate, and the like.

Among these, repeating units represented by the following general formula (1) or (II), or (1) and (t
A polyimide film whose main component is polyimide having the repeating unit represented by r) is particularly recommended in terms of heat resistance and light transmittance.

That is, this polyimide film has a film thickness of 50±5 μm.
Visible light (500 nm) for polyimide film of
It has a transmittance of 70% or more and a yellow index of 40 or less.

In the present invention, the term "main component" is meant to include cases where the whole consists of only the above general formula (1) and V/ or (II).

And/or such a polyimide film substrate can be formed as a colorless and transparent polyimide film substrate having excellent heat resistance, flexibility, and electrical insulation on the surface of a support by, for example, the following process. be done.

That is, such a polyimide film substrate is obtained by a reaction between a biphenyltetracarboxylic dianhydride represented by the general formula NV) and an aromatic diamino compound represented by the general formulas (V) and (Vl). .

As the biphenyltetracarboxylic dianhydride, the following 3.3', 4.4''-biphenyltetracarboxylic dianhydride and 2.3.3', 4'-biphenyltetracarboxylic dianhydride are used. Examples include:

Further, among the aromatic diamino compounds having an amino group at the meta position, the following are representative examples of the aromatic dinuclear diamine represented by the general formula (V).

3.3'-Diamino non-7enyl ether 3.3'-Diamino diphenyl sulfone 3.3'-Diamino diphenyl thioether 313'-diamino:) phenylmethane 3
．． Representative examples of 3'-diaminobenzophenone and aromatic tetranuclear diamine include the following.

4.4'-No(3-7minophenoxy)diphenylsulfone CH.

4.4'-di(3-amino/7enoxy)diphenylpropane CF.

4.4'-No(3-7mi/phenoxy)nophenylhexafluoropropane The above aromatic dinuclear noamine and aromatic tetranuclear diamine may be used alone or in appropriate combinations. good.

In the polyimide thus obtained, the higher the content of the polyimide represented by the repeating unit represented by the above general formula (1) and/or the repeating unit represented by the above general formula (II), the more the polyimide obtained is obtained. The colorless transparency of polyimide increases.

Other aromatic tetracarboxylic dianhydrides mentioned above include
Pyromellitic dianhydride, 3.3', 4.4'-benzophenonetetracarboxylic dianhydride, 4.4'-oxycyphthalic dianhydride, 4.4'-bis(3,4-)
carboxyphenoxy)-7enylsulfone dianhydride,
2,2-bis(3,4-nocarpoxyphenyl)hexafluoropropane dianhydride, 2.3.6.7-su7talenetetracarboxylic dianhydride, 1.2.5.6-su 7talentetracarboxylic dianhydride, 1.4.5.8
-S7talentetracarboxylic dianhydride, which can be used alone or in combination.

In addition, other diamino compounds include 4゜4'-diaminodiphenyl ether, 3.4'-noaminonophenyl ether, 4.4'-noami/nophenyl sulfone, 4.4''-noaminophenylmethane, 4.
4'-diaminoben'/ 7 x non, 4.4'-
Noamino-7enylpropane, paraphenylenediamine, metaphenylenediamine, benzuzine, 3.3'
-Tmethylbentunone, 4,4'-noamino di-7enyl thioether, 3,3'-:, tmethoxy-4,4'
-diaminocy7enylmethane, 3,3'-trimethyl-4
, 4'-diaminonophenylmethane, 2,2-bis(
4-7minophenyl)furopane, 2,2-bis[4-
Examples include (4-7minophenoxy)phenyl]-hexafluoropropane and 1,3-bis(7minophenoxy)benzene, which can be used alone or in combination.

The other side of the polyimide film used in the present invention is one in which the substrate is formed of a polyimide film whose main component is polyimide having a repeating unit represented by the general formula:

In the present invention, the substrate is required to have a certain level of transparency in order to transmit light irradiated from the substrate side to the semiconductor, and this required transparency is expressed by the above general formula (I). and/or a repeating unit represented by the above general formula (I[), or the above general formula (I[[)
It is desirable that the polyimide represented by the repeating unit represented by is contained in an amount of 70 mol% or more, most preferably 95 mol% or more.

In the colorless and transparent polyimide film used in the present invention, the polyimide film represented by the repeating unit represented by the above general formula (I) and/or the repeating unit represented by the above general formula (n) is composed of the above aromatic A polyimide precursor solution is prepared by polymerizing a group tetracarboxylic dianhydride and a diamino compound in an organic polar solvent at a temperature of 80°C or less, and this polyimide precursor solution is used to cast onto the surface of a support. A molded body of a desired shape is formed by a method such as roll coating, and the molded body is heated with an organic polar solvent in air or in an inert gas at a temperature of 50 to 350°C under normal pressure or reduced pressure. It is obtained by evaporating the polyimide precursor and simultaneously dehydrating and ring-closing the polyimide precursor.

Alternatively, instead of the above method, the polyimide precursor can be obtained by using a benzene solution of birinone and acetic anhydride, etc., and removing the solvent and imidizing it to form a polyimide.

Furthermore, a polyimide film represented by the repeating unit represented by the above general formula (III) is disclosed in Japanese Patent Application Laid-Open No. 62-185.
It is suitably produced by the method disclosed in Japanese Patent No. 715.

The above-mentioned growth polar solvents include trimethylformamide,
Dimethylacetamide, noblime, cresol, 7-ethyl halide, etc. are suitable, and dimethylacetamide is particularly preferred because it is a good solvent and has an extremely low boiling point. These organic polar solvents may be used alone or
Alternatively, there is no problem even if two or more of these are used in combination.

As organic polar solvents, the boiling points of the organic polar solvents listed above are low, so decomposition products of the growth polar solvent do not remain in the polyimide during dehydration and ring closure by heating. This is advantageous in that there is no risk of coloring.

However, if a high boiling point polymerization solvent such as N-methyl-2-pyrrolidone is used, and after synthesizing the polyimide precursor, the resulting polyimide precursor is dissolved in the above-mentioned suitable solvent by solvent substitution. The above disadvantages can be eliminated.

In this case, the suitable solvent exemplified above is a diluting solvent.

In producing the above polyimide film, the polymerization solvent and the diluting solvent may be of different types, and the polyimide precursor produced may be dissolved in the diluting solvent by solvent substitution.

When using the suitable organic polar solvents listed above, add solvents such as ethanol, toluene, benzene, xylene, nooxane, tetrahydrofuran, nitrobenzene, etc. to this solvent within a range that does not impair the colorless transparency of the polyimide film. These may be used alone or in combination of two or more.

When producing the above colorless and transparent polyimide film, the logarithmic viscosity of the polyimide precursor solution (measured at 30°C at a concentration of 0.5 g/100n+1 in N-methyl-2-pyrrolidone solvent) is 0.3 to 5.0. The logarithmic viscosity of the polyimide precursor solution is preferably adjusted within the range of 0.4 to 2.0.

If the logarithmic viscosity is too low, the resulting polyimide film will have low mechanical strength, which is not preferable. On the other hand, if the logarithmic viscosity is too high, it is not preferable because it becomes difficult to cast the polyimide precursor solution into an appropriate shape, making the work difficult.

Furthermore, from the viewpoint of workability, it is desirable to set the concentration of the polyimide precursor solution to 5 to 30% by weight, preferably 15 to 25% by weight.

Note that the above-mentioned logarithmic viscosity is calculated by the following formula, and the viscosity in the formula is measured by a capillary viscometer.

To obtain a polyimide film with excellent colorless transparency using a polyimide precursor solution, the polyimide precursor solution is cast onto a mirror surface such as a glass plate or stainless steel plate to a certain thickness, and then heated at 100 to 350°C. This is carried out by gradually heating at a high temperature to cause dehydration and ring closure, and then imidizing the polyimide precursor. In forming a polyimide film from a polyimide precursor solution, the removal of the Pl-containing polar solvent and the heating for imidization of the polyimide precursor may be performed continuously, or these steps may be performed under reduced pressure or in an inert atmosphere. It may be done in an atmosphere. Furthermore, the properties of the resulting polyimide film can be improved by finally heating it to around 400° C. for a short time.

Another method for forming a polyimide film is to cast the above polyimide precursor solution onto a glass plate or the like.
A film is formed by heating and drying at 150°C for 30 to 120 minutes, and this film is immersed in a solution of pyrinone and acetic anhydride in benzene, etc. to remove the solvent and imidize the film to form a polyimide film. A colorless and transparent polyimide film can also be obtained by this method.

The thickness of the polyimide film obtained in this way is preferably set to about 5 to 150 μm. If the thickness exceeds 150 μm, the light transmittance will deteriorate and the flexibility will be suppressed, making it difficult to wind into a roll, which will cause problems in productivity. If the temperature is less than 250", sufficient mechanical strength cannot be obtained and the temperature (250") when depositing the amorphous silicon RI film is
C to 350 C), and the substrate may be deformed by this thermal stress, which is not preferable. This polyimide film is colorless and transparent and is not colored yellow or yellowish brown as in the past, so it is relatively r! !
Even if it is a film, it is extremely colorless and transparent.

When polyimide is produced by imidizing a polyimide precursor solution as described above, the resulting polyimide has a logarithmic viscosity (0.58/2 in 97 wt% sulfuric acid) from the viewpoint of properties.
d1 concentration at 30″C) from 0.3 to 5.0
It is preferable to set it within the range of . Most preferred is 0
．． 4 to 4.0.

The polyimide film obtained in this manner is completely different from conventional films, and is colorless and transparent, and has extremely high transparency.

In particular, aromatic dinuclear diamines and aromatic tetranuclear noamines represented by general formulas (V) and (V[) have excellent colorless transparency and are most suitable for the substrate used in the present invention.
In this example, X and X2 are S02. The polyimide film obtained using this material not only has excellent colorless transparency, but also excellent heat resistance and low heat shrinkage.

In the present invention, the next step (B) is to laminate a transparent electrode layer on the surface of the substrate formed in the above step (A).
Implement.

In this step (B), a transparent electrode layer is formed on the substrate by a method such as sputtering, vapor deposition, or printing.

The thickness of the transparent electrode layer is not particularly limited, but
Specifically, approximately 300 to 7,000 people, especially considering the balance between sheet resistance and visible light transmittance, 200
A range of approximately 0 to 5,000 people is desirable.

If the thickness of the transparent electrode layer becomes too thin, the desired conductivity (surface resistance of 1000 Ω/hole or less) cannot be obtained, which is undesirable (on the other hand, if it becomes too thick, the transparency of the transparent electrode layer may decrease). This is not desirable because it occurs.

In addition, when forming multiple cells on one substrate,
For example, unnecessary portions of the transparent electrode are removed by a technique such as 7-etching.

The transparent electrode layer may be made of a known material, such as tin oxide, indium oxide, or a solid solution of both (ITO).

In the present invention, a step (C) of forming a photovoltaic semiconductor layer on the surface of the transparent electrode layer on the substrate formed in the step (B) is performed.

The semiconductor constituting the semiconductor layer is not particularly limited as long as it has photovoltaic properties, and examples include germanium (Ge) for infrared rays, selenium (Se), innoum antimony (InSb), Cadmium sulfide (CdS), cadmium selenide (CdS e) for radiation and visible light
, silicon (Si) for visible light, and the like.

Furthermore, cadmium chloride (CdC12), copper chloride (CuCf'2), and silver salts can be freely used as active impurities in these semiconductors.

For example, when forming a semiconductor layer with silicon, it is possible to form a pn junction by diffusing active impurities into single crystal silicon, but it is possible to form a p-n junction by diffusing active impurities into single crystal silicon. Sequentially depositing the silicon layer and the n-type crystalline silicon layer is advantageous in making the semiconductor layer thinner.

In addition, sputtering method, glow discharge method, photo-CVD method, and ion blating method are methods for sequentially depositing the p-type valve crystalline silicon layer, the i-type valve crystalline silicon layer, and the 1-type valve crystalline silicon layer. Various methods such as

For example, if we take the case of adopting the glow discharge method as an example and explain it specifically, the temperature will be around 250℃ (200~350℃).
Hold the substrate with a transparent electrode formed on a holder heated to 'C), and apply 5,000p of silane and hydrogen diluted to about 10 mol% with hydrogen at a vacuum level of about 0.2 Torr.
A mixture of diborane diluted to about pm [B2H6/(S
+04+BzHa) = 0.1 to 0.6 mol%, preferably about 0.3 mol% 1 is introduced at a total flow rate of 11003 CC, and in that atmosphere, the holder is used as one electrode,
A high frequency power of 13.56 MHz and about 10 layers is applied between the counter electrode and the p-type crystalline silicon layer doped with boron to a thickness of 200 layers on the transparent electrode layer.

Subsequently, only hydrogen diluted silane was supplied at a total flow rate of 11003C.
Under the atmosphere introduced in step C, an undoped i-type crystalline silicon layer was deposited to a thickness of 4,500 nm in the same manner as above, and further treated with hydrogen-diluted silane and hydrogen for 5.5 hours. OOO
A mixture of 7 osphin (PH3) diluted to ppm [P
Hy/(S iH−10P H3)=0.

1 to 0.6 mol %, preferably 0.3 mol %] at a total flow rate of 100 CCM, a layer of n-type crystalline silicon doped with phosphorus is similarly deposited to a thickness of 500 nm. let

By the way, for convenience, the explanation has been given using an example of p-1-n type amorphous silicon as a photovoltaic element, but in addition to amorphous silicon, the first layer contains p-type amorphous silicon carbide with a film composition of 5ixC,
Indicated by x, x=0.6-0.95, preferably x=0
．． 8 and doped with diborane B2H6 etc. can also be used.

In this case, the carbonization source used is a saturated hydrocarbon such as methane or ethane, or a saturated hydrocarbon such as ethylene or propylene.

The molar ratio of silane (SiH, ) or disilane (SizHs) used as the raw material gas and the above-mentioned hydrocarbons is determined as follows.

That is, for example, to produce a film with the film composition Sio, aCo, z, the molar ratio of SiH, and CI (, O, a to 0.2 (also,
5i211s and CH, 0.4 vs. 0.2), SiH,
and C2H, then 0.8 vs. 0.1.5i2H, and C2H,
Then, the number of Si atoms in the raw material gas and C
The molar ratio is determined by the number of atoms.

In the present invention, a step (D) is performed in which a back electrode layer is further laminated on the semiconductor layer thus obtained.

This back electrode layer may be made of tin oxide, indium oxide, or a solid solution of both (ITO), etc., like the transparent electrode layer laminated between the substrate and the semiconductor layer. It may be made of metal such as nickel, titanium, chromium, iron, stainless steel, nickel-chromium, or the like.

In this case, the back electrode layer is formed by a printing method, a sputtering method, a vapor deposition method, or the like. For example, in the case of a vapor deposition method, it is carried out in a vacuum of 10 -4 to I Torr under the condition that the temperature of the vapor deposition source is near the melting point of the material used.

The thickness of the back ring Wi layer is not particularly limited, but it must be thick enough to have the required conductivity without significantly reducing the flexibility of the entire flexible light receiving element.
For example, in the case of aluminum electrodes, approximately 0.1 μm is considered appropriate.

In this way, a transparent electrode layer is formed on a transparent plastic substrate having heat resistance, flexibility, and electrical insulation as a support.
Semiconductor layer and back surface consisting of p-type, 1-type, and n-type crystalline silicon layers! A light receiving element (solar cell) is formed by stacking pole layers.

In this case, if the support is made of a glass plate such as tempered glass, the characteristics of the light-receiving element can be evaluated by allowing light to enter from the support plate side at this stage.

What is particularly important in the present invention is that a flexible electrical insulating layer is further laminated on the back electrode layer laminated in this manner [step (E)].

This electrically insulating layer must have electrically insulating properties, heat resistance, and flexibility, as well as heat shrinkage characteristics equivalent to those of the substrate. As will be described later, this electrical insulating layer is used to generate stress that curls in a direction that cancels the curl caused by the difference in thermal shrinkage between the substrate and the semiconductor layer due to the difference in thermal shrinkage between this and the semiconductor layer. .

That is, for example, if the semiconductor layer is composed of a p-type-1-n-type crystalline silicon layer, curling of the flexible light-receiving element or the semiconductor layer caused by the difference in thermal shrinkage rate may occur. If the radius of curvature becomes smaller than 4On+m, cracks will occur in the semiconductor layer, so the coefficient of thermal expansion of the substrate is C1, the coefficient of thermal expansion of the electrically insulating layer is C2, and the sum of the thickness of the substrate and the thickness of the electrically insulating layer is b (+nm), ΔT is the temperature difference between the amorphous silicon deposition temperature and room temperature, and ΔT2 is the temperature difference between the electrical insulating layer formation temperature and room temperature.

Most preferably, the substrate and the electrical insulating layer are made of exactly the same material and have the same shape and size (same thickness).

For example, a solution of the same polyimide precursor as used for forming the substrate is cast onto the back electrode layer to the same thickness to form a film, and the film is dried with hot air to complete the imidization reaction. It is possible to form an electrically insulating layer that has electrically insulating properties, heat resistance, and flexibility, and also has heat shrinkage characteristics equivalent to those of the substrate.

The laminate thus laminated on the support is peeled off from the support in the final step (F).

In this step (F), if the laminate laminated on the support obtained as described above is immersed together with the support in water at room temperature for about 1 hour, the laminate will naturally peel off from the support and the transparent electrode A flexible light-receiving element having a sandwich structure in which the semiconductor layer, the semiconductor layer, and the back electrode layer are sandwiched between the substrate on the transparent electrode side and the electrically insulating layer on the back side is obtained.

The thus obtained flexible light receiving element is prevented from curling by the electrically insulating layer.

Furthermore, the present invention improves the method for manufacturing the flexible light-receiving element described above, thereby making it possible to suitably mount this kind of flexible light-receiving element even in a portion having a curved or curved surface shape. It is.

That is, for example, in order for light receiving elements (solar cells, etc.) to be widely used in the automobile field, roof parts such as sunroofs! 9) and the body, etc., but these parts of the car need to have a moderately convex curved shape in consideration of strength and air resistance, etc. When the above-mentioned flexible light-receiving element is applied to a curved or curved area, cracks may occur in the amorphous silicon layer or internal wire breakage may occur.
The flexible light-receiving element described above is limited by the shape of the area to which it is applied, which limits its uses and applications.

Therefore, the present invention improves the method for manufacturing a flexible light-receiving element as described above, and uses a support body that is used in the manufacturing process such that its surface has a shape similar to that of the application area of the flexible light-receiving element. It is characterized by being formed into a curved or curved surface corresponding to the above.

That is, a transparent electrode layer, a semiconductor layer, and a back electrode layer are sequentially laminated on a transparent plastic substrate on a support formed in a curved or curved shape, and then a part of the back electrode layer is removed ( When attaching the electrode terminal, the electrical insulation layer is laminated,
With this configuration, the electrical insulating layer absorbs and alleviates the difference in thermal shrinkage between the substrate made of transparent molecules and the semiconductor layer, thereby preventing the flexible light receiving element from curling.
A flexible light-receiving element with even better charge conversion efficiency can be obtained.

That is, the surface of the support is formed into a curved or curved surface shape corresponding to the shape of the surface on which the flexible light-receiving element (solar cell, etc.) is installed and applied after fabrication, and the surface of the support is coated with a liquid or heat-softening material. A transparent plastic substrate having a desired shape is formed by coating and curing the resin, and then, in the same manner as in the above invention, a transparent electrode layer, a semiconductor layer, a back electrode layer and an electrical By forming a laminate made of insulating layers and peeling this laminate from a support, a flexible light-receiving element (such as a solar cell) that is substantially compatible with the installation surface is formed.

In this case, the support, the substrate, the transparent electrode layer, the semiconductor layer, the back electrode layer, and the electrical insulating layer are the same as those in the above invention, and the formation method and other conditions for these are all in accordance with the above invention. It is similar to

This electrically insulating layer has electrically insulating properties, heat resistance, and flexibility, and due to the difference in heat loss 1a between this electrically insulating layer and the semiconductor layer, the thermal shrinkage rate between the substrate and the semiconductor layer increases. Since the purpose is to generate stress that causes curling in a direction that cancels the curling caused by the difference in This goal can be achieved in the same way.

As this electrical insulating layer, the same material as that explained in the above invention is used.

Next, peeling is performed from the interface between the support body and the substrate formed in the above-mentioned curved or curved shape to obtain a flexible light-receiving element formed in the curved or curved shape.

As for this peeling method, the above-mentioned M formed on the support
A method such as immersing the T-layer body in water or alcohol is employed. In this way, when this laminate is immersed for a certain period of time, water and the like permeate the above-mentioned interface, and the flexible light-receiving element peels off from the support.

The obtained flexible light-receiving element reproduces the surface shape of the support, and can be formed into a curved or curved surface shape to perfectly adapt to attachment to the intended support member.

In the structure formed in this way, light is incident from the substrate side.

Incidentally, the surface shape of the support must be adapted to the transparency or non-transparency of the substrate formed thereon, since the side of light incidence on the solar cell after fabrication changes.

For example, when light enters from a convex side such as a sunroof, a transparent substrate is formed on the support by using transparent Lennon as the material for the plastic substrate formed on the support, and then the plastic substrate is formed on the support. Form a transparent electrode layer, p
Each layer of amorphous silicon is deposited, and a back electrode layer and an electrical insulating layer are further formed thereon. In this case, since light is allowed to enter from the side of the transparent plastic substrate, the surface to which the liquid (or heat-softening) resin for the support is coated needs to be gate-shaped.

The method for manufacturing a flexible light receiving element of the present invention is suitably applied to such cases.

Also, depending on the application site of the flexible photodetector, it is possible to make the light enter from the opposite side of the substrate, increase the strength of the substrate, or make the electrical resistance of the substrate sufficiently low to achieve high output from a substrate with a constant area. You may need to obtain

As a method for manufacturing such a flexible light-receiving element, the method described below is most suitable.

That is, the method for manufacturing a flexible light-receiving element according to the present invention includes the following steps: (A) forming a plastic substrate having heat resistance, flexibility, and electrical insulation on the surface of a support; step (CB) of laminating a back electrode layer on the surface of the substrate formed in step (B), and step (C) of forming a photovoltaic semiconductor layer on the surface of the back electrode layer formed in step (B). ), a step (D) of forming a transparent electrode layer on the surface of the semiconductor layer formed in the above step (C), and a heat shrinkage equivalent to the above substrate on the surface of the transparent electrode layer formed in the above step CD). a step (E) of forming an electrically insulating layer having properties and flexibility, a substrate obtained through the steps (A) to (E), a back electrode layer, a semiconductor layer, a transparent electrode layer, and Step of peeling off the laminate consisting of electrically insulating layers from the support (
F) The method for manufacturing a flexible photoelectric conversion element, characterized in that the surface of the support is formed into a curved or curved surface corresponding to the shape of the application site of the flexible photoelectric conversion element. It is something to do.

The method for manufacturing a flexible light-receiving element according to the present invention is the same as described above except for the following points.

The differences from the method for manufacturing a flexible light receiving element described above are as follows.

That is, in the method of the present invention, a back electrode layer is laminated to impart conductivity to the substrate, and since light is not incident from the substrate side, the substrate does not necessarily have to be transparent ( It may also be made of opaque plastic.

Examples of this plastic include those made of the same materials as mentioned above.

On the other hand, in this case, since light is incident from the edge side of the electrical conductor, the electrical insulating layer must be made of transparent Lennon.

In addition, the flexible light receiving element obtained by the method of the present invention has a back electrode layer formed on a substrate, and a semiconductor layer, a transparent electrode layer, and an electrical insulating layer are sequentially laminated thereon. The structure is different from that of the flexible light-receiving element.

In the flexible light-receiving element manufactured according to the present invention, since light is incident on the side opposite to the substrate side, the surface of the support coated with liquid or heat-softening resin must have a convex shape.

The completed flexible photoelectric conversion element having a curved or curved surface shape is peeled off from the support by the above method and used by being attached to an intended installation location corresponding to the shape.

As for this bonding method, the flexible light-receiving element may be attached directly to the roof or body of the vehicle using adhesive or other fixing means, or alternatively, the flexible light-receiving element may be attached to the roof or body of the vehicle. It is also possible to attach a protective plate such as an electrical insulator to the roof or body of the vehicle using adhesive or other fixing means.

(e) Function As described above, according to the present invention, there is provided a flexible light-receiving element having a sandwich structure in which a light-receiving element consisting of a transparent electrode layer, a semiconductor layer, and a back electrode layer is sandwiched between a substrate and an electrically insulating layer. In other words, when a substrate and a semiconductor layer with significantly different coefficients of thermal expansion are bonded together at high temperature via a transparent electrode layer and cooled to room temperature, the laminate attempts to curl toward the substrate with a higher coefficient of thermal expansion. While heat shrinkage force is generated internally,
By bonding an electrically insulating layer with a coefficient of thermal expansion that is almost the same as that of the substrate to a semiconductor layer through a back electrode layer at high temperature, the light-receiving element is curled toward the electrically insulating layer that has a larger coefficient of thermal expansion when cooled to room temperature. A thermal contraction force is generated internally. As a result of these thermal contraction forces trying to curl the flexible light-receiving element in opposite directions canceling each other out, the apparent heat-shrinkage force trying to curl the flexible light-receiving element decreases. This has the effect of preventing curling of the flexible light-receiving element.

In addition, by using a support whose surface is curved or formed into a curved surface corresponding to the shape of the application site of the flexible light-receiving element, it is difficult to install the photoelectric conversion element. It has the ability to be suitably installed and applied to curved or curved application areas.

(f) Examples Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.

Example 1 Using N,N-trimethylacetamide as a solvent, 3
, 3'-diaminodiphenylsulfone mo12 was reacted with 1 mo1 of 3.3'4.4'-biphenyltetracarboxylic dianhydride to obtain a solution of a polyimide precursor. This solution was spin-coated on a support made of a glass plate to form a film, this film was dried with hot air, and further heated at a temperature of 300°C for 1 hour to complete the imidization reaction.
A substrate made of a polyimide film having a thickness of 50μ+6 was formed on the above support.

The light transmittance (wavelength: 500 nm) of this film was 85%.

Next, a transparent electrode layer made of ITO with a thickness of 600 nm was provided on the surface of the polyimide film substrate with the support still attached by a sputtering method, and the substrate with the transparent electrode layer was coated with an internal electrode type high frequency (1 3.5 6MHz
) held in a heated holder inside a glow discharge device;
After maintaining the temperature at around 250°C, silane diluted with hydrogen to 10 mol % and diborane diluted with hydrogen to 5,000 ppm were mixed [B2H a/ (S iH , 18
2H s) = 0, 3 mol%] and introduced this into a 100SCCM glow discharge device as the total flow rate, and the vacuum degree was 0.
, 200 p-type crystalline silicon layers doped with boron were formed on the substrate by applying a high frequency power of 10 W in an atmosphere of 2 Torr.

Subsequently, only the above hydrogen-diluted silane was introduced, and a similar reaction was carried out to deposit a non-doped I-type valvous silicon thin film with a thickness of 4500 nm on the p-type valvate silicon layer.
Furthermore, hydrogen-diluted silane and 7-osphin (PH:l) diluted with hydrogen to 5,000 ppm were mixed [PHs/(Si
H4 + PH3) = 0.5 mol% 1, and a residual flow fi100 secM was conducted in the glow discharge device to form an n-type valvular silicon r4 film of 500A, which was thinly doped with phosphorus.

That is, IT is placed on a colorless and transparent polyimide film substrate.
A photoconductive semiconductor layer consisting of a p-type-1-n type amorphous silicon thin film was formed via an O conductive thin film.

Next, this is held in a vacuum evaporation apparatus, and a 0.1 μm thick film is deposited on an 'n-type valve silicon thin film using a normal evaporation method.
aluminum back electrode layers were laminated.

The charge conversion efficiency of the semi-finished photodetector thus obtained is A.
The result of measurement using a solar simulator with M = 1 and 100 mW/cn2 was 4.1%. In this case, the light was applied through a glass support plate.

Next, with the support plate still attached, a polyimide precursor solution similar to the polyimide precursor solution for the substrate is cast over the entire surface of the back electrode layer to a thickness similar to that of the substrate to form a film. An electrical insulating layer was formed by drying with hot air and then heating at 200° C. for 5 hours to completely imidize.

Furthermore, when this was immersed in water at room temperature for about 1 hour, the flexible light-receiving element consisting of the substrate, transparent electrode layer, semiconductor layer, back electrode layer, and electrical insulating layer peeled off from the support plate.

The light-receiving element thus obtained had a completely flat appearance and no curling occurred.

The photoelectric conversion efficiency was 4.1%, which agreed with the intermediate value measured through the glass plate.

In addition, this light receiving element is flexible and has a radius of curvature of 4cI11
No decrease in charge conversion efficiency was observed even when the battery was bent.

Example 2 Next to the photoelectric conversion element semi-finished product in which an aluminum back electrode layer was attached on the n-type crystalline silicon thin film of Example 1, an epoxy resin having the following blending ratio was applied to the back electrode layer side using an applicator. It was coated to a thickness of 50μIII.

Compounding ratio Bisthraenol A type epoxy resin 60 parts (Yuka Shell Epoxy Co., Ltd., Ebiko Co., Ltd.) 828) 1.6-hexanesiol noglycidyl ether 12 parts (Itamoto Yakuhin Co., Ltd. SR-16H) Flexible epoxy titn 8 (Itamoto Pharmaceutical Co., Ltd., SR-PTMG) Aromatic amine 20 parts (Itamoto Pharmaceutical Co., Ltd., SDA-07) Next, this was preliminarily dried with hot air at a temperature of 90°C for 2 hours. , furthermore, temperature 1
After heating for 3 hours to harden the epoxy layer while drying with hot air at 50°C, it was immersed in water at room temperature for 1 hour to peel off the light receiving element from the glass support plate. .

The obtained TL conversion element was completely flat in appearance and had no curls.

Further, this charge conversion efficiency was 4.0%, which was the same as the value measured in the middle through the glass plate.

Furthermore, this light-receiving element is flexible, and no decrease in charge conversion efficiency was observed even when it was bent to a radius of curvature of 4 am.

Comparative Example 1 A conventionally commercially available polyimide film (manufactured by Teyubon Co., Ltd., trade name: Kapton H) with a thickness of 50 μIfi was used as a substrate, and the film was heated at a temperature of 30
After drying for a minute, it was kept in a sputtering device and a back electrode layer made of stainless steel (A) having a thickness of 1000 was formed on one side.

Next, the film was held in the same glow discharge apparatus as used in Example 1 and heated to a temperature of 250"C. Since curling occurred, the film was held under tension and the phosphorus-doped film was heated to 250"C. A 500-thick n-type crystalline silicon layer, a 4,500-thick undoped p-type amorphous silicon layer doped with boron, and a 4,500-thick p-type amorphous silicon layer doped with boron. It was formed in the same order as in Example 1.

However, when the film in which the back electrode layer and the semiconductor layer were combined in this manner was taken out at room temperature, noticeable curling occurred with the polyimide film inside.

Next, the film was kept under tension in the same sputtering apparatus used in Example 1, and a transparent electrode layer of ITO having a thickness of 6° was formed on the p-type crystalline silicon layer.

The light-receiving element thus obtained was neatly curled with the substrate facing inside. When we measured the photoelectric conversion efficiency by forcibly stretching this photodetector, we found that cracks occurred in the amorphous silicon layer and the wires were broken internally, confirming that most of the cells had photovoltaic ability. could not.

For some samples that escaped disconnection, the conversion efficiency was 1.3~
It was 2.1%.

Comparative Example 2 Regarding the light-receiving element semi-finished product (semi-finished product with a glass support) in which an aluminum back electrode layer was attached on the 11 type amorphous silicon thin film of Example 1, a thickness of 7.
A 75 μm thick polyethylene terephthalate film was laminated via a 5 μrO acrylic adhesive side layer, and then immersed in water at room temperature for 1 hour and peeled off from the support to produce a light receiving element.

The light receiving element obtained in this way has a radius of curvature of 0°5 cm.
``c'' The film was forcibly curled and the charge conversion efficiency was measured, but most of the cells were disconnected.

Example 3 A film was formed on one side of a glass support by spin footing, and this film was heated at a temperature of 180°C for 1 hour to a thickness of 50°C.
A substrate made of μm polyether sulfone film was formed on the support.

Blending ratio of polyethersal7one solution Polyethersal7one 1 moNN, N-trimethylacetamide 9308 The light transmittance (wavelength 500 nm) of this film was 88%.

Hereinafter, in the same manner as in Example 1, a transparent electrode layer made of ITO with a thickness of 600 μm and a boron-doped crystalline silicon layer with a thickness of 4,500 μm were deposited on this film by sputtering. A semiconductor layer consisting of a non-doped i-type crystalline silicon layer, a 500-meter thick phosphorus-doped n-type crystalline silicon layer, and a 0.1 μm thick aluminum back electrode layer were deposited in this order.

However, the temperature for forming the semiconductor layer is 200°C, taking into account the heat resistance of the polyether sulfone film that is the substrate.
And so.

Next, a film was formed on the back electrode layer side by spin-coating the polyether sal 7one solution, and an electrically insulating layer was formed by heating and drying at a temperature of 180° C. for 1 hour.

Next, when this was immersed in water at room temperature for about 1 hour, the flexible light-receiving element peeled off from the glass plate.

b) The photodetector was completely flat in appearance and had no curls.

When charging conversion efficiency was measured in the same manner as in the above example, 3.
It was 0%.

Further, this light receiving element is flexible, and no decrease in charge conversion efficiency was observed even when it was curved to a radius of curvature of 4c+n.

Example 4 A film was formed by casting a polyimide precursor solution having the following composition on one side of a support made of a stainless steel plate, and the film was dried with hot air.
Finally, it was cured by heating at a temperature of 400'' for 1 hour to form an electrically insulating layer made of polyimide film with a thickness of 50 μm and low light transmittance.

Polyimide precursor solution blended pyromellitic anhydride 1+aoll
'(or 218g), t, 4'-diaminodiphenyl ether 1+
oo1 (or 200g) N,N'-trimethylacetamide 1670g As in the above example, it was first kept in a sputtering apparatus and a back electrode layer made of a 1°000 stainless steel thin film was formed on the electrical insulation layer made of polyimide film. .

Furthermore, at a temperature of 250 °C, an n-type valky crystalline silicon layer doped with phosphorus of 500 μm, a thickness of 4,500 μm, and a boron-doped layer of 1-type valky crystalline silicon, doped with 200 μm of boron, at a temperature of 250 °C. A semiconductor layer was formed by depositing the 1) crystalline silicon layers in this order.

Even when this was taken out into the air at room temperature, the electrical insulating layer was in close contact with the support plate made of stainless steel X4 and did not peel off.

Next, 600 people of ITO were processed using the sputtering method in the same manner as above.
1) After forming a transparent electrode layer on the crystalline silicon layer, a light-transmitting polyimide precursor solution having the following composition was cast onto the transparent electrode layer using a spin cord to form a film. Hot air drying and heating were performed to form a substrate made of a light-transmitting polyimide film with a thickness of 50 μm.

Light-transparent polyimide precursor solution formulation 3.3゛-noaminodiphenylsulfone 1 moj!
(or 248g) 3,3°,・1,4′-biphenyltetracarboxylic dianhydride 1 mol (or 294g) N,
N'-dimethylacetamide (8) 2170 g per 1 moNl2 Next, the light receiving element with the support was immersed in water at room temperature for about 1 hour, and the light receiving element peeled off from the support.

The light-receiving element thus obtained had a completely flat appearance with no curling.

This charging conversion efficiency was 2.3%.

Further, this light receiving element is flexible, and no decrease in charge conversion efficiency was observed even when it was curved to a radius of curvature of 4c+n.

Example 5 The following solution was cast and coated on the concave side of a curved tempered glass with a thickness of 5 mm, which had been prepared in advance to match the external shape of a sunroof of a passenger car, to form a film. was dried with hot air, and further heated at a temperature of 300°C for 1 hour to complete the imidization reaction.
A substrate made of polyimide film was formed.

(Solution: Using N,N-trimethylacetamide as a solvent, 3,3'4,4°-biphenyl ether tetracarboxylic dianhydride was added to 1 m01 of 4,4゛-bis(3-7minophenoxy)biphenyl. IIIlO
Q. A solution of the polyimide precursor was obtained by the reaction. This solution was spin-coated onto a support made of a glass plate to form a film, and this film was dried with hot air and further heated to 300°C for 1 hour.
The imidization reaction was completed by heating for a period of time, and a substrate made of a polyimide film having a thickness of 50 μm was formed on the support. ) Light transmission of this film! (Ripple effect 500nn
) was 85%.

Next, a light receiving element with a support was obtained in the same manner as in Example 1.

Furthermore, when this was immersed in water at room temperature for about 1 hour, the curved charge conversion element consisting of the substrate, transparent electrode layer, semiconductor layer, back electrode layer, and electrical insulating layer peeled off from the support plate.

This curved flexible photoelectric conversion element could be completely attached to the concave side of a transparent reinforced plastic sunroof panel with a transparent adhesive through the substrate side of the element.

The charge conversion efficiency of this device was 4.1%, consistent with intermediate measurements through a tempered glass plate support.

In addition, this photoelectric conversion element is flexible and has a radius of curvature of 4 cm.
No decrease in charge conversion efficiency was observed even when the battery was bent.

Example 6 A polyimide precursor solution having the following composition was cast on the concave side of a curved stainless steel plate with a thickness of l + o + n, which had been previously produced by drawing to match the outer shape of a passenger car hood, to form a film. The film was formed, dried with hot air, and finally cured by heating at a temperature of 400'C for 1 hour to form an electrically insulating layer made of a polyimide film with I7 size and 50μIl+ and low light transmittance.

Pyromellitic anhydride II1101 containing polyimide precursor solution
(or 218g) 4,4゛-noami/nophenyl ether 1+noN(
or 200g) N,N'-no,/tylacetamide 1670g
As in the above embodiment, first keep it in the sputtering equipment,
A back electrode layer made of a 1°,000 stainless steel thin film was formed on the electrically insulating layer made of polyimide film.

In addition, under the same conditions as in Example 1, a p-type crystalline silicon layer doped with boron to a thickness of 300 mm, and a non-J'-type i-type crystalline silicon layer doped with a thickness of 4.500 mm. Two hundred phosphorus-doped 11 type amorphous silicon layers were deposited in this order to form a semiconductor layer.

Even when this was taken out into the air at room temperature, the electrical insulating layer was in close contact with the stainless steel support plate and did not peel off.

Next, 600 people of ITO were processed using the sputtering method in the same manner as above.
After forming a transparent electrode layer on p-type crystalline silicon ICi, a transparent electrode layer consisting of a transparent polyimide @precursor iB of the following composition was formed.
After casting e onto the transparent electrode layer using a spin cord to form a film, it was dried with hot air*2 and heated to a thickness of 50 μI.
A substrate made of a light-transmissive polyimide film of ff was formed.

Light-transparent polyimide precursor solution formulation 3.3°-yami7diphenylsul7one 1a+ol(
or 248g) 3.3', 4.4'- and phenyltetracarboxylic dianhydride 1+ao1 (or 294.
)N,N'-trimethylacetamide (A) 2170g for 1+noZ Next, the photoelectric conversion element with the support was immersed in ethanol at room temperature for about 1 hour, and the curved photoelectric conversion element peeled off from the support. .

The substrate side of this curved flexible photoelectric conversion element could be completely pasted onto the curved hood of a passenger car using adhesive.

This charging conversion efficiency was 3.3%.

In addition, this charge conversion element is flexible and has a radius of curvature of 4c+a.
No decrease in charge conversion efficiency was observed even when the battery was bent.

(FI) Effects of the Invention A transparent plastic substrate having flexibility and electrical insulation, a transparent electrode layer laminated on the substrate, and the transparent mold f
A photovoltaic semiconductor layer and a back electrode layer are laminated on the f1 layer, and an electrical insulating layer is further layered on the upper surface of this layer and has heat shrinkage characteristics equivalent to those of the above substrate and has flexibility. A transparent plastic substrate with heat resistance, flexibility, and electrical insulation is provided on the light incident side, while an electrical insulation layer with heat shrinkage characteristics equivalent to that of this substrate is provided on the back electrode layer side. Therefore, after a photodetector made of amorphous silicon or the like is formed on a substrate at high temperature, when it is returned to room temperature, the internal stress generated due to the severe difference in thermal shrinkage characteristics between the substrate and the photodetector can be absorbed by electricity. The insulating layer can be reduced or eliminated, and as a result, it is possible to prevent curling of the flexible light-receiving element as a product.

Further, since the flexible light receiving element of the present invention is prevented from curling as described above, it has the effect of having good charge conversion efficiency and high reliability.

In the flexible light-receiving element of the present invention, by using a substrate made of a polyimide film whose main component is polyimide having a repeating unit represented by the general formula, heat resistance, flexibility and electrical insulation properties are achieved. This has the effect of providing a flexible light-receiving element with excellent light transmittance and charge conversion efficiency.

Furthermore, in the flexible light-receiving element of the present invention, by using a substrate made of a polyimide film mainly composed of polyimide having a repeating unit represented by the general formula, heat resistance, flexibility and This has the effect of providing a flexible light-receiving element with excellent electrical insulation, good optical transparency, and good charge conversion efficiency.

Further, in the flexible light-receiving element of the present invention, by using a substrate made of polyether sulfon film, it has excellent flexibility and electrical insulation, and has good light transmittance and charging. This has the effect of providing a flexible light receiving element with good conversion efficiency.

In the flexible light receiving element of the present invention, by using an electric insulating layer made of the same material and the same thickness as the substrate, no curling occurs, and as a result, charge conversion efficiency is improved. This has the effect of significantly improving reliability.

In the method for manufacturing a flexible light-receiving element of the present invention, a step (A) of forming a transparent plastic substrate having heat resistance, flexibility, and electrical insulation on the surface of a support; A step (B) of laminating a transparent electrode layer on the surface of the formed substrate, a step (C) of forming a photovoltaic semiconductor layer on the surface of the transparent electrode layer formed in the above step (B). , a step (D) of forming a back electrode layer on the surface of the semiconductor layer formed in the above step (C), a step (D) of forming a back electrode layer on the surface of the back electrode layer formed in the above step (D), and a step (D) of forming a heat shrinkable layer equivalent to the above substrate on the surface of the back electrode layer formed in the above step (D). step (E) of forming an electrically insulating layer having heat resistance and flexibility, a substrate obtained through the steps (A) to (E), a transparent electrode layer, "[" According to the method consisting of step (F) of peeling off the laminate consisting of the conductor layer, the back electrode layer and the electrical insulating layer from the support, flexible light receiving with excellent characteristics can be achieved without using special techniques or equipment. This has the effect that elements can be manufactured continuously at low cost.

In the method for manufacturing a flexible light-receiving element of the present invention, by using a support made of glass such as tempered glass, stainless steel aluminum, or iron plate or foil, the support is strong and easy to handle. Moreover, it is extremely easy to remove from the laminate (light receiving element) consisting of the substrate, the transparent 71 pole layer, the semiconductor layer, the back electrode layer, and the electrical insulating layer, which has the effect of improving productivity.

Furthermore, in the method for manufacturing a flexible light-receiving element of the present invention, by using a substrate made of a polyimide film whose main component is polyimide having a repeating unit represented by the general formula, heat resistance and flexibility can be improved. This has the effect of providing a flexible light-receiving element that has excellent properties and electrical insulation properties, good light transmittance, and good charge conversion efficiency.

In the method for manufacturing a flexible light-receiving element of the present invention, by using a substrate made of a polyimide film mainly composed of polyimide having repeating units represented by the general formula, heat resistance and flexibility can be improved. This has the effect of providing a flexible light-receiving element that has excellent properties and electrical insulation properties, good light transmittance, and good charge conversion efficiency.

What about the flexible light receiving element of the present invention? ! ! ! By using a substrate made of polyether sulfone film, a flexible substrate with excellent flexibility and electrical insulation properties, good light transmittance, and good photoelectric conversion efficiency can be obtained. This has the effect of providing a polarized photodetector.

In the method for manufacturing a flexible light-receiving element of the present invention, by using an electrical insulating layer made of the same material as the substrate and made of the same 17 pieces, no curling occurs, and as a result, , the charging conversion efficiency is extremely high, and the reliability is significantly improved.

In the method for manufacturing a flexible photoelectric conversion element according to the present invention, the support surface is curved or formed into a curved surface corresponding to the shape of the applied part surface of the obtained flexible light receiving element. By using this method, curling does not occur and it is extremely easy to attach the replica to irregularly shaped surfaces such as curved surfaces of the application site, and the workability of the installation is greatly improved. It has a wide range of effects.

In the method for manufacturing a flexible photoelectric conversion element of the present invention, the support formed into a curved or curved surface is reinforced with a plate or foil made of glass, stainless steel, aluminum, or iron such as lath. By using a material, the support is strong, and it is extremely easy to remove from the laminate (light receiving element) consisting of the substrate, transparent electrode layer, semiconductor layer, back electrode layer, and electrical insulating layer, improving productivity. It has an effect.

Further, in the method of manufacturing a flexible photoelectric conversion element using a support formed into a curved or curved surface according to the present invention, the substrate is a polyimide film mainly composed of polyimide having repeating units represented by the general formula. By using a material made of It has.

In the method for manufacturing a flexible photoelectric conversion element using a curved support formed into a curved or curved surface according to the present invention, the substrate is mainly composed of polyimide having a repeating unit represented by the general formula: By using a material made of polyimide film, it has excellent heat resistance, flexibility, and electrical insulation.
Moreover, it has the effect of providing a flexible light-receiving element with good light transmittance and good charge conversion efficiency. - In the method of manufacturing a flexible charge conversion element using a support formed into a curved or curved surface according to the present invention, the flexible This has the effect of providing a flexible light-receiving element that has excellent properties and electrical insulation properties, good light transmittance, and good charge conversion efficiency.

In the method of manufacturing a flexible charge conversion element using a support formed into a curved or curved surface according to the present invention, the electrical insulating layer is made of the same material as the substrate and has the same 1r'f.

By using a material made of the same material, no curling occurs, resulting in extremely high charge conversion efficiency and significantly improved reliability.

In the method for manufacturing a flexible photoelectric conversion element of the present invention, a step (A) of forming a plastic substrate having heat resistance, flexibility, and electrical insulation on the surface of a support; A step (B) of laminating a back electrode layer 7M on the surface of the formed substrate, a step (B) of forming a photovoltaic semiconductor layer on the surface of the back electrode layer formed in the above step (B). C), a step (D) of forming a transparent electrode layer on the surface of the semiconductor layer formed in the above step (C), a step (D) of forming a transparent electrode layer on the surface of the transparent electrode layer formed in the above step (D), a layer equivalent to the above substrate; Step (E) of forming a heat-shrinkable, flexible and transparent electrical insulating layer; the substrate obtained through the above steps (A) to (E); a back electrode layer; a semiconductor layer; transparent In the method comprising a step (F) of peeling off the laminate consisting of the electrode layer and the electrical insulating layer from the support, the surface of the support is curved in accordance with the shape of the application area surface of the flexible light receiving element. By using a material with a curved surface, curling does not occur, and it is extremely easy to attach it to irregularly shaped surfaces such as curved surfaces at the application site in a replica manner, and the workability of the installation is significantly improved. For example, it has an effect that can be used in a wide range of fields such as automobiles.

Furthermore, according to this method, since the miss resistance on the substrate surface is sufficiently low, it has the effect of relatively easily obtaining a large output from a substrate of a fixed area.

In this method for manufacturing a flexible charge conversion element, the support is strong by using a support made of a plate or foil made of plastic, such as tempered glass, stainless steel, aluminum, or iron. Moreover, it is extremely easy to remove from the laminate (light-receiving element) consisting of the substrate, transparent electrode layer, semiconductor layer, back electrode layer, and electrically insulating layer, which has the effect of improving productivity.

In addition, in this method for manufacturing a flexible photoelectric conversion element, by using a substrate made of a polyimide film whose main component is polyimide having a repeating unit represented by the general formula, heat resistance and flexibility can be improved. This has the effect of providing a flexible light-receiving element that has excellent electrical insulation properties, good light transmittance, and good charge conversion efficiency.

In this method for manufacturing a flexible photoelectric conversion element, by using a substrate made of a polyimide film mainly composed of polyimide having a repeating unit represented by the general formula, heat resistance, flexibility and This has the effect of providing a flexible light-receiving element with excellent electrical insulation, good optical transparency, and good charge conversion efficiency.

In this method for manufacturing a flexible photoelectric conversion element, by using a letterpress formed of a polyether sulfone film, it has excellent flexibility, electrical insulation, and resiliency.
Moreover, it has the effect of providing a flexible light-receiving element with good light transmittance and good charge conversion efficiency.

In this method of manufacturing a flexible photoelectric conversion element, by using an electrical insulating layer made of the same material and thickness as the substrate, curling does not occur at all, resulting in charge conversion. It is highly efficient and has the effect of significantly improving equal reliability.

Patent applicant: Nitto Electric Industry Co., Ltd.

Claims (23)

[Claims] (1) A flexible and electrically insulating transparent plastic substrate, a transparent electrode layer laminated on the substrate, a photovoltaic semiconductor layer laminated on the transparent electrode layer, and a back surface. A flexible light-receiving element comprising an electrode layer and an electrically insulating layer laminated on the upper surface of the electrode layer and having heat shrinkage characteristics equivalent to those of the substrate and flexibility. (2) The board has a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・・・・・・( I
) and/or ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) [However, in formula (I), X_1 is O, SO_2,
CH_2 or CO, and in formula (II), X_2 is SO_2, C(CH_3)_2 or C(CF_3)_2
It is. 2. The flexible light-receiving element according to claim 1, which is formed of a polyimide film whose main component is polyimide having repeating units represented by the following. (3) The substrate is a general formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) [However, in general formula (III), The bonding position of the nitrogen atom is meta or distal to the ether bond. ] The flexible light-receiving element according to claim 1, which is formed of a polyimide film containing polyimide as a main component having a repeating unit represented by the following. (4) The flexible light receiving element according to claim 1, wherein the substrate is formed of a polyether sulfone film. (5) The flexible light receiving element according to any one of claims 1 to 4, wherein the electrical insulating layer is formed of the same material and the same thickness as the substrate. (6) Step of forming a transparent plastic substrate having heat resistance, flexibility and electrical insulation on the surface of the support (A
), a step (B) of laminating a transparent electrode layer on the surface of the substrate formed in the above step (A), a semiconductor having photovoltaic properties on the surface of the transparent electrode layer formed in the above step (B) A step (C) of forming a layer, a step (D) of forming a back electrode layer on the surface of the semiconductor layer formed in the above step (C), a surface of the back electrode layer formed in the above step (D). Step (E) of forming an electrical insulating layer having heat shrinkability equivalent to that of the above substrate, and having heat resistance and flexibility, obtained through the above steps (A) to (E). A method for manufacturing a flexible light-receiving element, comprising: (F) peeling off a laminate including a substrate, a transparent electrode layer, a semiconductor layer, a back electrode layer, and an electrically insulating layer from a support. (7) The method for manufacturing a flexible light-receiving element according to claim 6, wherein the support is made of glass such as tempered glass, stainless steel, aluminum, or iron plate or foil. (8) The board has a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・・・・・・( I
) and/or ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) [However, in formula (I), X_1 is O, SO_2,
CH_2 or CO, and in formula (II), X_2 is SO_2, C(CH_3)_2 or C(CF_3)_2
It is. The method for manufacturing a flexible light-receiving element according to claim 6 or 7, wherein the flexible light-receiving element is formed of a polyimide film containing polyimide as a main component having a repeating unit represented by the following. (9) The substrate is a general formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) [However, in general formula (III), The bonding position of the nitrogen atom is meta or para to the ether bond. ] The method for manufacturing a flexible light-receiving element according to claim 6 or 7, wherein the flexible light-receiving element is formed of a polyimide film containing polyimide as a main component having a repeating unit represented by the following. (10) The method for manufacturing a flexible light receiving element according to claim 6 or 7, wherein the substrate is formed of a polyether sulfone film. (11) The method for manufacturing a flexible light receiving element according to any one of claims 6 to 10, wherein the electrical insulating layer is formed of the same material and the same thickness as the substrate. (12) Manufacturing a flexible light-receiving element according to claim 6, characterized in that the surface of the support is curved or formed into a curved surface corresponding to the shape of the application site surface of the flexible light-receiving element. Method. (13) The method for manufacturing a flexible light-receiving element according to claim 12, wherein the support is formed of glass such as tempered glass, stainless steel, aluminum, or iron plate or foil. (14) The substrate has a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・・・・・・( I
) and/or ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) [However, in formula (I), X_1 is O, SO_2,
CH_2 or CO, and in general formula (II),
_2 is SO_2, C(CH_3)_2 or C(CF_3
)_2. 14. The method for manufacturing a flexible light-receiving element according to claim 12 or 13, wherein the flexible light-receiving element is formed of a polyimide film containing polyimide as a main component having a repeating unit represented by: (15) The substrate is a general formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) [However, in general formula (III), The bonding position of the atom is meta or para to the ether bond. ] The method for manufacturing a flexible light-receiving element according to claim 12 or 13, wherein the flexible light-receiving element is formed of a polyimide film containing polyimide as a main component having a repeating unit represented by the following. (16) The method for manufacturing a flexible light receiving element according to claim 12 or 13, wherein the substrate is formed of a polyether sulfone film. (17) The method for manufacturing a flexible light receiving element according to any one of claims 12 to 16, wherein the electrical insulating layer is formed of the same material and the same thickness as the substrate. (18) Step (A) of forming a heat-resistant, flexible, and electrically insulating plastic substrate on the surface of the support
, a step (B) of laminating a back electrode layer on the surface of the substrate formed in the above step (A), a semiconductor layer having photovoltaic properties on the surface of the back electrode layer formed in the above step (B) a step (C) of forming a transparent electrode layer on the surface of the semiconductor layer formed in the above step (C); a step (D) of forming a transparent electrode layer on the surface of the transparent electrode layer formed in the above step (D); Step (E) of forming a flexible and transparent electrical insulating layer having heat shrinkability equivalent to that of the above substrate, a substrate obtained through the above steps (A) to (E), and a back electrode layer. , a step (F) of peeling off a laminate consisting of a semiconductor layer, a transparent electrode layer, and an electrically insulating layer from a support; A method for manufacturing a flexible light receiving element, characterized in that the flexible light receiving element is formed into a curved or curved surface corresponding to the shape of the surface to which it is applied. (19) The method for manufacturing a flexible light-receiving element according to claim 18, wherein the support is formed of glass such as tempered glass, stainless steel, aluminum, or iron plate or foil. (20) The board has a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・・・・・・( I
) and/or ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) [However, in formula (I), X_1 is O, SO_2, C
H_2 or CO, and in general formula (II), X_2
is SO_2, C(CH_3)_2 or C(CF_3)_
It is 2. 20. The method for manufacturing a flexible light-receiving element according to claim 18, wherein the flexible light-receiving element is formed of a polyimide film containing polyimide as a main component having a repeating unit represented by: (21) The substrate is a general formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) [However, in general formula (III), The bonding position of the atom is meta or para to the ether bond]. 20. The method for manufacturing a flexible light-receiving element according to claim 18, wherein the flexible light-receiving element is formed of a polyimide film containing polyimide as a main component having a repeating unit represented by: (22) The method for manufacturing a flexible light receiving element according to claim 18 or 19, wherein the substrate is formed of a polyether sulfone film. (23) The method for manufacturing a flexible light receiving element according to any one of claims 18 to 22, wherein the electrical insulating layer is formed of the same material and the same thickness as the substrate.