JP2009009851A - Photoelectric conversion device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a W-type photoelectric conversion device (with photoelectric conversion elements arranged and connected like W letter of an alphabet) having high photoelectric conversion efficiency, in which adjacent cells (photoelectric conversion elements) are connected in series. <P>SOLUTION: The photoelectric conversion device is equipped with a translucent substrate 2 having a translucent conductive layer 3a formed on one main surface; a substrate 8 faced to one main surface of the translucent substrate 2 and having a conductive layer (a second translucent conductive layer 3b) formed on one main surface on the translucent substrate 2 side; and first and second photoelectric conversion elements 1a, 1b arranged between the translucent substrate 2 and the substrate 8 so as to adjacent in the lateral direction, connected in series with the translucent conductive layer 3a and the conductive layer, and the direction of current is opposite each other. The first and second photoelectric conversion elements 1a, 1b have photoelectric converters having different output current per area, and the photo acceptance area of the photoelectric conversion element 1a having the photoelectric converter in which output current per area is low is larger than that of the photoelectric conversion element 1b having the photoelectric converter in which output current per area is high. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is a photoelectric conversion device in which photoelectric conversion bodies having different spectral sensitivities are alternately connected in series. The photoelectric conversion device has a large light receiving area, high photoelectric conversion efficiency, excellent weather resistance, and can be manufactured at low cost. The present invention relates to a conversion device.

  A solar cell using a light-transmitting conductive layer as a collector electrode has a high resistance of the light-transmitting conductive layer made of an ITO layer, so that individual cells (photoelectric conversion elements) are electrically separated in one substrate. There is a configuration in which a high voltage and a low current are achieved by connecting the cells in series. Moreover, the structure which can reduce the resistance loss accompanying the enlargement of a solar cell is proposed.

  Patent Document 1 describes a dye-sensitized solar cell module (hereinafter also referred to as a W-type module) in which cells 41a and 41b of a plurality of dye-sensitized solar cells are connected in series as shown in FIG. ing. The cells 41a and the cells 41b are alternately formed in a reverse stacked structure (reverse current direction) in the horizontal direction.

  Specifically, it is produced as follows. First, two transparent glass substrates 42 in which titanium oxide layers 46 and platinum layers 44 as catalyst layers are alternately formed on the patterned light-transmitting conductive layer 43 are prepared. Next, an insulating sealing member 47 is disposed so as to seal the electrolyte layer 45 between the cells, and the two transparent glass substrates 42 are disposed so that the titanium oxide layer 46 and the platinum layer 44 face each other. Then, the insulating sealing member 47 is adhered. Next, an electrolyte solution to be the electrolyte layer 45 is injected from a through hole (not shown) formed in the transparent glass substrate 42 to seal the through hole. Thereby, a dye-sensitized solar cell module is produced.

  Patent Document 2 proposes a Z-type module using connection wirings and connection tabs of a lead structure in which the current directions of the cells are the same and the adjacent cells are electrically connected. Since this Z-type module has higher photoelectric conversion efficiency (hereinafter also referred to as conversion efficiency) of each cell than the W-type module, the photoelectric conversion efficiency of the entire module is also high.

  However, since the connection structure for electrically connecting adjacent cells is complicated, the Z-type module has poor workability at the time of manufacturing and requires many manufacturing steps, resulting in high cost. Moreover, since the area of the site | part which does not contribute to electric power generation becomes comparatively large due to a complicated connection structure, the photoelectric conversion efficiency as the whole module does not become high as expected.

On the other hand, since the W-type module is continuously connected in series between adjacent cells, the connection part between each cell is short and has a simple connection structure. Accordingly, the area of the part for separating and sealing the electrolyte layer between the adjacent cells can be extremely reduced, so that a decrease in the photoelectric conversion efficiency of the entire module can be suppressed.
International republished patent WO2002 / 052654 pamphlet JP-A-8-306399

  In the W-type module of Patent Document 1, a titanium oxide layer to which a dye serving as a photoelectric conversion unit is adsorbed is formed on a cell formed on the transparent glass substrate 42 on the incident light side and on the transparent glass substrate 42 on the opposite side to the incident light. The photoelectric conversion efficiency is different from the formed cell. That is, in the cell in which the titanium oxide layer is formed on the transparent glass substrate 42 opposite to the incident light, the incident light is attenuated by the electrolyte layer 45.

  Therefore, in the W-type module in which adjacent cells are connected in series, it is necessary to change the area of the adjacent cells so that the current of each cell becomes constant. For this reason, there is a problem in that the current is rate-limited to the cell having low photoelectric conversion efficiency, and the photoelectric conversion efficiency of the entire module is lowered.

  Accordingly, the present invention has been completed in view of the above-described conventional problems, and an object thereof is to obtain a photoelectric conversion device having high photoelectric conversion efficiency in which adjacent cells are connected in series.

  The photoelectric conversion device of the present invention includes a light-transmitting substrate having a light-transmitting conductive layer formed on one main surface, and the one light-transmitting substrate on the light-transmitting substrate side while being opposed to the one main surface. A substrate having a conductive layer formed on one main surface, and the translucent substrate and the substrate are arranged so as to be adjacent to each other in the lateral direction and connected in series by the translucent conductive layer and the conductive layer. And first and second photoelectric conversion elements having current directions opposite to each other, and the first and second photoelectric conversion elements each have a photoelectric conversion body having a different unit area output current. The light receiving area of the photoelectric conversion element having a photoelectric conversion element having a low unit area output current is larger than the light receiving area of the photoelectric conversion element having a photoelectric conversion element having a high unit area output current. .

  The photoelectric conversion device of the present invention is preferably characterized in that three or more of the first and second photoelectric conversion elements are alternately arranged.

  In the photoelectric conversion device of the present invention, preferably, the first and second photoelectric conversion elements each include a non-single-crystal semiconductor layer having a photoelectric conversion body having a lower unit area output current. It is a thing which has a type photoelectric conversion body, and the direction which has a photoelectric conversion body with a high unit area output current has a dye-sensitized photoelectric conversion body, It is characterized by the above-mentioned.

  In the photoelectric conversion device of the present invention, preferably, the photoelectric conversion element having a photoelectric conversion body having a low unit area output current is a translucent thin film photoelectric conversion body and a dye including a non-single-crystal semiconductor layer. It is a stacked photoelectric conversion element in which sensitized photoelectric conversion bodies are stacked.

  In the photoelectric conversion device of the present invention, preferably, in the stacked photoelectric conversion element, the dye-sensitized photoelectric conversion body has a spectral sensitivity with respect to the transmitted light of the thin film photoelectric conversion body. It is a feature.

  In the photoelectric conversion device of the present invention, preferably, the dye-sensitized photoelectric conversion body in the photoelectric conversion element having a photoelectric conversion body having a high unit area output current is disposed on the light-transmitting substrate side. It is characterized by being.

  In the photoelectric conversion device of the present invention, preferably, the first and second photoelectric conversion elements have the same output current.

  The photoelectric conversion device of the present invention includes a light-transmitting substrate having a light-transmitting conductive layer formed on one main surface, and a main surface on the light-transmitting substrate side that is disposed opposite to the one main surface of the light-transmitting substrate. Are disposed adjacent to each other in the lateral direction between the transparent substrate and the substrate, and are connected in series by the transparent conductive layer and the conductive layer, and the current directions are opposite to each other. 1st and 2nd photoelectric conversion element of direction, and the 1st and 2nd photoelectric conversion element has a photoelectric conversion body from which unit area output current differs, respectively, and unit area output current (A1) The light receiving area (S1) of a photoelectric conversion element having a low photoelectric conversion body is larger than the light receiving area (S2) of a photoelectric conversion element having a photoelectric conversion body having a high unit area output current (A2) (A1 <A2, S1). > S2) Therefore, the unit area output current (A1) Output current (I1 = A1 × S1) of a photoelectric conversion element having a large photoelectric conversion body and output current (I2 = A2 × S2) of a photoelectric conversion element having a high unit area output current (A2) Thus, the output currents I1 and I2 can be approximated or the same. As a result, the output current (I) of the entire photoelectric conversion device is not limited by the output current I1 of the photoelectric conversion element having the photoelectric conversion body having a low unit area output current A1, and the output current I of the entire photoelectric conversion device is reduced. Can be increased.

  Further, in the photoelectric conversion device of the present invention, preferably, three or more first and second photoelectric conversion elements are alternately arranged, and therefore, compared to a configuration in which the photoelectric conversion devices are arranged in the vertical direction, the loss of incident light is reduced. Becomes extremely small, and the conversion efficiency can be greatly increased.

  In the photoelectric conversion device of the present invention, preferably, the first and second photoelectric conversion elements each include a non-single-crystal semiconductor layer having a photoelectric conversion body having a lower unit area output current. A thin film type having a photoelectric conversion body having a photoelectric conversion body and having a photoelectric conversion body having a low unit area output current since the one having a photoelectric conversion body having a higher unit area output current has a dye-sensitized photoelectric conversion body. As for the photoelectric conversion body, the thin film photoelectric conversion body can be formed on a light-transmitting substrate (incident light side substrate) so that incident light is not dimmed by an electrolyte solution or the like, and a highly efficient photoelectric conversion element can be formed. .

  In the photoelectric conversion device of the present invention, it is preferable that the photoelectric conversion element having a photoelectric conversion body having a low unit area output current includes a light-transmitting thin film photoelectric conversion body including a non-single-crystal semiconductor layer and a dye sensitizer. Since it is a stacked photoelectric conversion element with a photosensitive photoelectric conversion layer stacked, it is a thin film type photoelectric conversion body that is a photoelectric conversion body with a low unit area output current so that incident light is not dimmed by an electrolyte solution or the like. The photoelectric conversion body can be formed on a translucent substrate (substrate on the incident light side), and a dye-sensitized photoelectric conversion body can also be formed on the counter electrode side through the electrolyte solution. It is possible to form a highly efficient photoelectric conversion element using incident light transmitted through the conversion body by a dye-sensitized photoelectric conversion body.

  In the photoelectric conversion device of the present invention, it is preferable that the stacked photoelectric conversion element has an incident light because the dye-sensitized photoelectric conversion body has spectral sensitivity to the transmitted light of the thin film photoelectric conversion body. A photoelectric conversion element capable of performing photoelectric conversion over a wide wavelength range can be formed.

  In the photoelectric conversion device of the present invention, preferably, the dye-sensitized photoelectric conversion body in the photoelectric conversion element having the photoelectric conversion body with a high unit area output current is disposed on the translucent substrate side. Since the incident light from the outside can be directly received without passing through the electrolyte layer or the like, a high output current can be obtained.

  In the photoelectric conversion device of the present invention, it is preferable that the first and second photoelectric conversion elements have the same output current. Therefore, the output current of the entire photoelectric conversion device is low in unit area output current. It is no longer limited by the output current of the photoelectric conversion element having the converter, and the output current of the entire photoelectric conversion device can be further increased.

  Hereinafter, embodiments of the photoelectric conversion device of the present invention will be described in detail. FIG. 1 is a cross-sectional view of an example of an embodiment of the photoelectric conversion device of the present invention.

  The photoelectric conversion device of the present invention includes a light-transmitting substrate 2 having a light-transmitting conductive layer 3a formed on one main surface, and a light-transmitting substrate 2 side that is disposed opposite to one main surface of the light-transmitting substrate 2. Between the substrate 8 on which a conductive layer (second translucent conductive layer 3b) is formed on one main surface and the translucent substrate 2 and the substrate 8 (one main surface of the translucent substrate 2). The first and second photoelectric conversion elements 1a and 1b are arranged so as to be adjacent to each other in the plane direction and are connected in series by the translucent conductive layer 3a and the conductive layer, and the current directions are opposite to each other. Each of the first and second photoelectric conversion elements 1a and 1b includes photoelectric conversion elements having different unit area output currents, and receives light of the photoelectric conversion element 1a having a photoelectric conversion element having a low unit area output current A1. Photoelectric conversion element 1 having a photoelectric conversion body with an area S1 having a high unit area output current A2 Is larger configuration than the light receiving area S2 of (A1 <A2, S1> S2).

  The photoelectric conversion device of FIG. 1 of the present invention has a structure in which first photoelectric conversion elements 1 a and second photoelectric conversion elements 1 b are alternately arranged adjacent to each other on a light-transmitting substrate 2.

  The first photoelectric conversion element 1a includes a first light-transmitting conductive layer 3a, a non-single-crystal semiconductor layer 5, an intermediate layer 6a, an electrolyte layer 7a, and a porous material in which a dye is adsorbed from the light-transmitting substrate 2 side. The semiconductor layer 4a, the second translucent conductive layer 3b, and the substrate 8 are laminated in this order, and the porous semiconductor layer 4a is impregnated with the electrolyte solution of the electrolyte layer 7a.

  The second photoelectric conversion element 1b includes a first translucent conductive layer 3a, a porous semiconductor layer 4b on which a dye is adsorbed, an electrolyte layer 7b, an intermediate layer 6b, and a second translucent substrate 2 from the translucent substrate 2 side. The photoconductive layer 3b and the substrate 8 are laminated in this order, and the electrolyte solution of the electrolyte layer 7b is impregnated in the porous semiconductor layer 4b that has adsorbed the dye.

  In the first photoelectric conversion element 1a, since incident light such as sunlight is transmitted through the non-single-crystal semiconductor layer 5, the intermediate layer 6a, and the electrolyte layer 7a, the non-single-crystal semiconductor layer 5, the intermediate layer 6a, and the electrolyte Since the light on the short wavelength side of sunlight (wavelength 700 nm or less) is absorbed by the layer 7a, the porous semiconductor layer 4a in which a dye having long wavelength sensitivity is adsorbed is formed.

  Since the second photoelectric conversion element 1b can use all wavelengths of incident light (wavelength 350 nm to 1100 nm) without using an electrolytic solution, the second photoelectric conversion element 1b absorbs a dye that can absorb a wide wavelength range and photoelectrically convert it. A quality semiconductor layer 4b may be formed. Moreover, since it has the porous semiconductor layer 4b which adsorb | sucked the pigment | dye which has long wavelength sensitivity (wavelength 600nm-1100nm) and short wavelength light (wavelength 600nm or less) can also be utilized, the pigment | dye which has long wavelength sensitivity Alternatively, a porous semiconductor layer 4b in which a dye having a short wavelength sensitivity is adsorbed may be formed.

  It is preferable that three or more first and second photoelectric conversion elements 1a and 1b are alternately arranged in the horizontal direction. Since the first photoelectric conversion element 1a and the second photoelectric conversion element 1b are alternately arranged in the horizontal direction, the first light-transmitting conductive layer 3a and the second light-transmitting conductive layer 3b make it easy. Can be connected in series.

Moreover, in order to generate electric power efficiently by connecting in series and performing current matching between the photoelectric conversion elements 1a and 1b, the output currents of the photoelectric conversion elements 1a and 1b are made the same. That is, the light receiving area S1 of the first photoelectric conversion element 1a having a photoelectric conversion body having a low unit area output current A1 is equal to the light receiving area S2 of the second photoelectric conversion element 1b having a photoelectric conversion body having a high unit area output current A2. Is bigger than. For example, when the short circuit current density (unit area output current) of the first photoelectric conversion element 1a is 10 mA / cm ² and the short circuit current density (unit area output current) of the second photoelectric conversion element 1b is 20 mA / cm ^2. The light receiving area of the first photoelectric conversion element 1a is made twice the light receiving area of the second photoelectric conversion element 1b (A1 × S1 = A2 × S2). In addition, the voltage of the whole photoelectric conversion apparatus becomes the sum of the voltage of each photoelectric conversion element (cell).

  Further, the first photoelectric conversion element 1a and the second photoelectric conversion element 1b are separated by an insulating sealing member 9, and the periphery of the photoelectric conversion device is also sealed by the insulating sealing member 9. ing.

  The first and second photoelectric conversion elements 1a and 1b each have a translucent thin-film photoelectric converter including a non-single-crystal semiconductor layer 5 when the photoelectric converter having a lower unit area output current is included. It is preferable that the one having a photoelectric conversion body having a high unit area output current has a dye-sensitized photoelectric conversion body. In this case, with respect to the thin film type photoelectric conversion body which is a photoelectric conversion body having a low unit area output current, the thin film type photoelectric conversion body is applied to the translucent substrate 2 (incident light side substrate) without dimming incident light with the electrolyte solution. Therefore, a highly efficient photoelectric conversion element can be formed.

  The photoelectric conversion element 1a having a photoelectric conversion body with a lower unit area output current is formed by laminating a light-transmitting thin film photoelectric conversion body including a non-single-crystal semiconductor layer 5 and a dye-sensitized photoelectric conversion body. A stacked photoelectric conversion element is preferable. In this case, with respect to the thin film type photoelectric conversion body which is a photoelectric conversion body having a low unit area output current, the thin film type photoelectric conversion body is applied to the translucent substrate 2 (incident light side substrate) without dimming incident light with the electrolyte solution. In addition, since a dye-sensitized photoelectric conversion body can be formed on the counter electrode side through the electrolyte solution, incident light transmitted through the thin-film photoelectric conversion body is converted by the dye-sensitized photoelectric conversion body. A highly efficient photoelectric conversion element can be formed.

  In the stacked photoelectric conversion element, it is preferable that the dye-sensitized photoelectric conversion body has a spectral sensitivity to the transmitted light of the thin film photoelectric conversion body. In this case, a dye-sensitized photoelectric converter for transmitted light (long wavelength light having a wavelength of 500 nm or more) of a thin film photoelectric converter made of an amorphous silicon thin film having spectral sensitivity to short wavelength light (wavelength 700 nm or less). Has a spectral sensitivity, it can photoelectrically convert light in a wide wavelength band.

  Moreover, it is preferable that the dye-sensitized photoelectric conversion body in the photoelectric conversion element 1b having the photoelectric conversion body having a higher unit area output current is disposed on the light-transmitting substrate 2 side. In this case, since the incident light from the outside can be directly received without passing through the electrolyte layer 7b or the like, a high output current can be obtained.

  Further, the first and second photoelectric conversion elements 1a and 1b may have the same output current. In this case, the output current of the entire photoelectric conversion device is not limited by the output current of the photoelectric conversion element 1a having the photoelectric conversion body having a low unit area output current, and the output current of the entire photoelectric conversion device can be further increased. it can.

  The non-single-crystal semiconductor layer 5 includes, for example, a first conductivity type (p-type) amorphous silicon semiconductor layer and an intrinsic type (i-type) amorphous silicon semiconductor layer on the first light-transmitting conductive layer 3a. , An amorphous silicon semiconductor layer having a pin junction structure in which second conductive type (n-type) amorphous silicon semiconductor layers are stacked. Here, as the first conductivity type (p-type) amorphous silicon semiconductor layer, not only amorphous silicon but also amorphous silicon carbide which is a wide band gap material may be used. Furthermore, as the second conductivity type (n-type) amorphous silicon semiconductor layer, not only amorphous silicon but also microcrystalline silicon may be used.

Instead of the non-single-crystal semiconductor layer 5, a compound semiconductor photoelectric converter such as a CIGS photoelectric converter having a Cu (In, Ga) Se ₂ layer may be used.

  The non-single-crystal semiconductor layer 5 may be any material that generates an internal electric field such as a pin junction type, a pn junction type, a Schottky junction type, or a hetero junction type. Amorphous silicon, amorphous silicon containing nanosize crystals, microcrystalline silicon, etc. are good, especially amorphous silicon with short wavelength sensitivity and amorphous containing nanosize crystals with reduced photodegradation Quality silicon system is good. Amorphous silicon-based materials include alloy-based materials such as amorphous silicon carbide and amorphous silicon nitride.

  Hereinafter, each component of the photoelectric conversion device will be described in detail.

<Translucent substrate>
In the configuration of FIG. 1, the translucent substrate 2 is a substrate that transmits sunlight or the like without loss, and is an inorganic substrate, a plastic substrate, or the like. For example, the material of the translucent substrate 2 is weather resistant resin such as fluororesin, silicon polyester resin, high weather resistance polyester resin, polyvinyl chloride resin, silicone urethane resin applied to metal roof, acrylic urethane resin, etc. Excellent in properties and particularly good. Other materials include resin sheets made of PET (polyethylene terephthalate), PEN (polyethylene naphthalate), polyimide, polycarbonate, etc., inorganic sheets made of white plate glass, soda glass, borosilicate glass, ceramics, etc., organic-inorganic hybrid sheets Etc. are good.

  The thickness of the translucent substrate 2 is preferably 0.1 μm to 6 mm, more preferably 1 μm to 4 mm. If it is less than 0.1 μm, the covering rate and the scratch strength tend to decrease, and if it exceeds 6 mm, the transmittance tends to decrease.

  In addition, the translucent substrate 2 is provided with heat shielding, heat resistance, low contamination, antibacterial, antifungal, design, high workability, antistatic, far infrared radiation, acid resistance, corrosion resistance, environmental compatibility, etc. By imparting, reliability and merchantability can be further improved.

<First translucent conductive layer>
The first translucent conductive layer 3a is formed of a tin-doped indium oxide layer (ITO layer), an impurity-doped indium oxide layer (In ₂ O ₃ layer), antimony formed by a low-temperature growth sputtering method or a low-temperature spray pyrolysis method. Doped tin oxide (SnO ₂ : Sb (ATO) layer) or the like is preferable. “SnO ₂ : Sb” means “Sb-doped SnO ₂ ”.

Further, it may be a fluorine-doped tin oxide layer (SnO ₂ : F layer) formed by a thermal CVD method or a spray vapor deposition method. In addition, an impurity-doped zinc oxide layer (ZnO layer) formed by a solution growth method, etc. But you can. Moreover, what laminated | stacked these layers may be used. The first translucent conductive layer 3a can be formed with a pattern as shown in FIG. 1 by a laser ablation method, a sand blast method, an etching method, or the like.

<Non-single crystal semiconductor layer>
The non-single-crystal semiconductor layer 5 is preferably a hydrogenated amorphous silicon semiconductor layer having a pin junction structure continuously deposited by plasma CVD. That is, the non-single-crystal semiconductor layer 5 includes the first conductive type (p-type) amorphous silicon semiconductor layer and the intrinsic type (i-type) amorphous silicon semiconductor layer from the first translucent conductive layer 3a side. A pin junction structure in which the second conductivity type (n-type) amorphous silicon semiconductor layers are sequentially stacked, but a nip junction structure that is a reverse junction may also be used. The bonding direction is more preferably the same as the bonding direction of the dye-sensitized photoelectric conversion body on the counter electrode side, that is, the current direction.

  The non-single-crystal semiconductor layer 5 is not limited to the amorphous silicon semiconductor layer described above. If the i-type semiconductor layer is amorphous, at least one of the p-type semiconductor layer and the n-type semiconductor layer has microcrystals. Or a hydrogenated amorphous silicon alloy layer. For example, it is more preferable that the p-type semiconductor layer on the light incident side is a hydrogenated amorphous silicon carbide layer because it has high translucency and low light loss.

  The non-single-crystal semiconductor layer 5 may be formed by a catalytic CVD method or the like. In addition, when the plasma CVD method and the catalytic CVD method are combined, photodegradation can be suppressed and reliability is improved. Since the first conductive type amorphous silicon semiconductor layer, the intrinsic type amorphous silicon semiconductor layer, and the second conductive type amorphous silicon semiconductor layer can be continuously deposited under the respective film forming conditions by the CVD method, the cost is low. It can be formed in time and is suitable.

For example, a p-type a-Si: H layer (“a-Si” means amorphous silicon and “: H” means hydrogen dope) which is a first conductivity type amorphous silicon semiconductor layer is a raw material. SiH ₄ gas, H ₂ gas, and B ₂ H ₆ gas (diluted to 500 ppm with H ₂ gas) are used as gases, and the flow rates of these gases are optimized respectively. The thickness of the p-type a-Si: H layer is preferably 50 to 200 mm, more preferably 80 to 120 mm. When the thickness is less than 50 mm, an internal electric field cannot be formed in the semiconductor layer 5, and when the thickness is more than 200 mm, the light amount loss in the p-type a-Si: H layer increases. Further, the first conductive type amorphous silicon semiconductor layer, p-type band gap than the a-Si is larger p-type _{a-Si x C y (x} + y = 1), p -type _{a-Si x N y (x} + y = 1), p-type _{a-Si x C y N z} (x + y + z = 1) or either p-type smaller than optical absorption coefficient in a-Si p-type [mu] c-Si (microcrystalline Si in), p-type nc- Any of Si (nanocrystal Si) may be used.

The i-type a-Si: H layer, which is an intrinsic type amorphous silicon semiconductor layer, is formed by using SiH ₄ gas and H ₂ gas as source gases and optimizing the flow rates of these gases. The thickness of the i-type a-Si: H layer is preferably 500 to 5000 mm, more preferably 1000 to 2500 mm (0.15 μm to 0.25 μm). When the thickness is less than 500 mm, sufficient photocurrent cannot be obtained, and when the thickness is more than 5000 mm, light cannot be transmitted to the dye-sensitized photoelectric conversion body.

The n-type a-Si: H layer that is the second conductive type amorphous silicon semiconductor layer uses SiH ₄ gas, H ₂ gas, and PH ₃ gas (those diluted to 1000 ppm with H ₂ gas) as source gases, The flow rates of these gases are optimized and formed. The thickness of the n-type a-Si: H layer is preferably 50 to 200 mm, more preferably 80 to 120 mm. If it is thinner than 50 mm, an internal electric field cannot be formed in the semiconductor layer 23, and if it is thicker than 200 mm, the light quantity loss in the n-type a-Si: H layer increases. As the second conductivity type amorphous silicon semiconductor layer, a band gap than the n-type a-Si is larger n-type _{a-Si x C y (x} + y = 1), n -type _{a-Si x N y (x} + y = 1), any of the n-type _{a-Si x C y n z} (x + y + z = 1), or n-type than light absorption coefficient is small a-Si n-type [mu] c-Si, may be either n-type nc-Si .

  The temperature during the formation of the first conductive type amorphous silicon semiconductor layer, the intrinsic type amorphous silicon semiconductor layer, and the second conductive type amorphous silicon semiconductor layer is preferably 150 ° C. to 300 ° C. in any case, More preferably, the temperature is 180 ° C to 240 ° C. Even if the temperature is lower or higher than the range of 150 ° C. to 300 ° C., it is difficult to obtain an optical semiconductor having good characteristics.

<Intermediate layer>
The intermediate layer 6a is a layer (catalyst layer) for facilitating transfer of charges between the semiconductor layer 5 and the electrolyte layer 7a. On the other hand, the intermediate layer 6b is a layer for facilitating transfer of charges between the electrolyte layer 7a and the second light-transmissive conductive layer 3b. The intermediate layers 6a and 6b are made of platinum, palladium, rhodium, carbon, and the like. For example, the intermediate layers 6a and 6b are made of Pt, Pt, by a vacuum evaporation method, a sputtering method, a thermal decomposition method that thermally decomposes the applied complex, a spin coating method, an electrodeposition method, Intermediate layers 6a and 6b made of a platinum group element such as Pd are formed.

  Further, depending on the spin coating method, intermediate layers 6a and 6b made of polyethylene dioxythiophene (PEDOT) (which may be doped with polystyrene sulfonate, toluene sulfonate, or the like) can be formed.

  Depending on the electrodeposition method, intermediate layers 6a and 6b made of an organic semiconductor material such as polyvinyl carbazole or carbon can be formed.

  The intermediate layer 6a may be a laminate of a plurality of layers. Further, in order to reduce light loss (reflection, etc.) due to a difference in refractive index between the semiconductor layer 5 and the electrolyte layer 7a, a transparent dielectric layer and an intermediate layer may be sequentially laminated on the intermediate layer 6a. The transparent dielectric layer is preferably titanium oxide, zinc oxide, tin oxide, or a metal oxide obtained by adding impurities to these. The refractive index of the transparent dielectric layer is preferably between the refractive index of the semiconductor layer 5 and the electrolyte layer 7a. Furthermore, the intermediate layer 6a is preferably laminated on the transparent dielectric layer. In this case, there is an effect of facilitating transfer of charges between the transparent dielectric layer and the electrolyte layer 7a.

<Electrolyte layer>
The electrolyte layer 7a is preferably a hole transporter such as a p-type semiconductor, a liquid electrolyte, a solid electrolyte, an electrolytic salt, or a gel electrolyte. Other examples of the material for the electrolyte layer 7a include a transparent conductive oxide, an organic hole transport agent, and an ultrathin metal layer.

  The permeable electrolyte layer 7a functions to fill the pores of the porous semiconductor layer 4a on which the dye is adsorbed, and the liquid electrolyte layer 7a exhibits the best carrier movement, but liquid leakage, etc. In this respect, gel electrolytes and solid electrolytes are preferable.

The transparent conductive oxide is preferably a compound semiconductor containing monovalent copper, GaP, NiO, CoO, FeO, Bi ₂ O ₃ , MoO ₂ , Cr ₂ O _3, etc. A semiconductor is good. Suitable compound semiconductors include CuI, CuInSe ₂ , Cu ₂ O, CuSCN, CuS, CuInS ₂ , and CuAlSe ₂ , and among these, CuI and CuSCN are preferred, and CuI is most preferred because it is easy to manufacture.

  As the liquid electrolyte, a quaternary ammonium salt, a Li salt, or the like is used. The composition of the liquid electrolyte is, for example, an organic solvent such as ethylene carbonate, propylene carbonate, dimethyl sulfoxide, acetonitrile, ionic liquid, γ-butyrolactone or methoxypropionitrile, and iodine such as tetrapropylammonium iodide or lithium iodide. A compound prepared by mixing a compound, iodine or the like can be used.

  The gel electrolyte is roughly classified into a chemical gel and a physical gel. A chemical gel is a gel formed by a chemical bond by a cross-linking reaction or the like, and a physical gel is gelled near room temperature by a physical interaction. As a material for the gel electrolyte, a host polymer such as polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polyvinyl alcohol, polyacrylic acid, or polyacrylamide is mixed into acetonitrile, ethylene carbonate, propylene carbonate or a mixture thereof for polymerization. A gel electrolyte is preferred.

  When a gel electrolyte or a solid electrolyte is used as the electrolyte layer 7a, a low-viscosity precursor is contained in the porous semiconductor layer 4a, and is two-dimensional or three-dimensional by means of heating, ultraviolet irradiation, electron beam irradiation, or the like. It can be gelled or solidified by causing a crosslinking reaction.

  Examples of the solid electrolyte having ion conductivity include solid electrolytes having a polymer chain such as polyethylene oxide, polyethylene oxide, or polyethylene, and a salt such as sulfonimidazolium salt, tetracyanoquinodimethane salt, and dicyanoquinodiimine salt. preferable.

  Examples of the molten salt of iodide used in the above liquid electrolyte and gel electrolyte include imidazolium salt, quaternary ammonium salt, isoxazolidinium salt, isothiazolidinium salt, pyrazolidium salt, pyrrolidinium salt, pyridinium salt, etc. The iodide can be used. Further, as a molten salt of iodide, 1,1-dimethylimidazolium iodide, 1, methyl-3-ethylimidazolium iodide, 1-methyl-3-pentylimidazolium iodide, 1-methyl-3- Isopentylimidazolium iodide, 1-methyl-3-hexylimidazolium iodide, 1-methyl-3-ethylimidazolium iodide, 1,2-dimethyl-3-propylimidazole iodide, 1-ethyl-3- Examples thereof include isopropyl imidazolium iodide and pyrrolidinium iodide.

  Examples of the organic hole transporting agent include triphenyldiamine (TPD1, TPD2, TPD3), thiophene derivatives and polymers thereof, polyacene such as pentacene, rubrene, phthalocyanine derivatives, metal phthalocyanine, OMeTAD (2, 2 ′, 7, 7 '-Tetrakis (N, N di-P-methoxyphenylamines) 9,9'-pyrobifluorene) and the like.

<Porous semiconductor layer>
As the porous semiconductor layer 4a adsorbing the dye, an electron transporter (n-type metal oxide semiconductor) layer such as a porous titanium oxide layer is particularly good, and the porous layer is formed on the second light-transmitting conductive layer 3b. The semiconductor layer 4a is formed.

  The porous semiconductor layer 4a is preferably made of an n-type metal oxide semiconductor, and more preferably a large number of granular or linear bodies (needle bodies, tube bodies, columnar bodies, etc.) are gathered. It is good that In the porous semiconductor layer 4a, the bonding area with the second light-transmissive conductive layer 3b is improved, and the surface area for supporting the dye is increased, so that the conversion efficiency can be increased. In addition, the surface of the porous semiconductor layer 4a has a concavo-convex shape, which brings about a light confinement effect and can further increase the conversion efficiency.

As the material and composition of the metal oxide semiconductor, titanium oxide (TiO ₂ ) is optimal, and in addition, titanium (Ti), zinc (Zn), tin (Sn), niobium (Nb), indium (In) , Yttrium (Y), lanthanum (La), zirconium (Zr), tantalum (Ta), hafnium (Hf), strontium (Sr), barium (Ba), calcium (Ca), vanadium (V), etc. A metal oxide semiconductor composed of at least one of them is preferable. In addition, the metal oxide semiconductor contains one or more of non-metallic elements such as nitrogen (N), carbon (C), fluorine (F), sulfur (S), chlorine (Cl), and phosphorus (P). May be.

  All of these metal oxide semiconductors are of the n-type whose electron energy band gap is in the range of 2 eV to 5 eV, which is larger than the energy of visible light, and whose conduction band is lower than the conduction band of the dye at the electron energy level. .

  The porosity of the porous semiconductor layer 4a is preferably 20% to 80%, and more preferably 40% to 60%. By making the porosity of this degree of porosity, the surface area of the porous semiconductor layer 4a can be increased to 1000 times or more of the case where there are no holes, and light absorption, power generation and electron conduction can be performed efficiently. it can.

  The shape of the porous semiconductor layer 4a is preferably a shape having a large surface area and a small electric resistance, and is preferably composed of fine particles or fine linear bodies. The average particle diameter or average line diameter is preferably 5 nm to 500 nm, and more preferably 10 nm to 200 nm. If the thickness is less than 5 nm, the material cannot be miniaturized. If the thickness exceeds 500 nm, the junction area with the substrate 8 is reduced and the photocurrent is significantly reduced.

  The thickness of the porous semiconductor layer 4a is preferably 0.1 μm to 50 μm, more preferably 1 μm to 20 μm. If the thickness is less than 0.1 μm, the photoelectric conversion action is extremely small and is not suitable for practical use. If the thickness exceeds 50 μm, it is difficult for light to pass through the porous semiconductor layer 4a and light enters the porous semiconductor layer 4a. It becomes difficult.

When the porous semiconductor layer 4a is made of titanium oxide, it is manufactured as follows. First, acetylacetone is added to TiO ₂ anatase powder, and then kneaded with deionized water to prepare a titanium oxide paste stabilized with a surfactant. Next, the prepared paste is applied onto the second light-transmitting conductive layer 3b by a doctor blade method at a constant rate, and is 300 to 600 ° C., preferably 400 to 500 ° C. in the atmosphere. The porous semiconductor layer 4a is formed by treating for min-60 min, preferably 20 min-40 min. This method is simple and effective when it can be formed in advance on the second light-transmitting conductive layer 3b having heat resistance as shown in FIG.

  The porous semiconductor layer 4b can also be formed by the same material and the same formation method as the porous semiconductor layer 4a.

<Dye>
The dye has a characteristic that the photocurrent efficiency (IPCE) with respect to incident light, so-called sensitivity, extends to the longer wavelength side than the absorption limit wavelength of the non-single-crystal semiconductor layer 5 and the electrolyte layer 7a. Any pigment is effective. The intrinsic limiting amorphous silicon semiconductor layer or iodine-based electrolyte has an absorption limit wavelength of about 700 nm, and any dye that exhibits IPCE above about 700 nm may be used.

  Therefore, a dye having a sensitivity as long as possible, a dye having a peak sensitivity longer than the peak sensitivity of the non-single-crystal semiconductor layer 5, and a peak longer than the peak sensitivity of the intrinsic amorphous silicon semiconductor layer. A dye having sensitivity, a dye having a peak sensitivity at a wavelength longer than about 700 nm of the absorption limit wavelength of the intrinsic type amorphous silicon semiconductor layer, and the like are preferable.

  As such a dye, a bis-type squarylium cyanine dye is preferable because the peak wavelength of IPCE is close to 800 nm. Azurenium salt compounds, squalinic acid derivatives, triallylpyrazoline, hydrazone derivatives, biphenyldiamine derivatives, tri-p-tolylamine (TPTA), trisazo pigments, τ-type non-metals with high sensitivity (IPCE) at wavelengths of 700 nm or more Phthalocyanine, titanyl phthalocyanine, squarylium cyanine, black dye (product name “Black dye” manufactured by Solaronics), coumarin, β-diketonate, Re complex, Os complex, Ni complex, Pd complex, Pt complex, phthalocyanine derivative, porphyrin derivative And other pigments are effective.

  Examples of the method for adsorbing the dye on the porous semiconductor layer 4b include a method of immersing the second light-transmissive conductive layer 3b on which the porous semiconductor layer 4b is formed in a solution in which the dye is dissolved. At this time, the temperature of the solution and the atmosphere is not particularly limited, and for example, room temperature is good under atmospheric pressure, and the immersion time can be appropriately adjusted depending on the dye, the type of solvent, the concentration of the solution, and the like.

  Examples of the solvent used for dissolving the dye include a mixture of one or more alcohols such as ethanol, ketones such as acetone, ethers such as diethyl ether, nitrogen compounds such as acetonitrile, and the like.

Further, the dye concentration in the solution is preferably about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol / l (l (liter); 1l = 1000 cm ³ ).

Other materials of the dye may be metal complex dyes, organic dyes, organic pigments, inorganic dyes, inorganic pigments, inorganic semiconductors, and the like. In addition, the shape of one dye is at least one of ultra-thin films of nanometer order in which the molecule and thickness affect the band gap, fine particles, ultra-fine particles in the nanometer order in which the particle diameter affects the band gap, and quantum dots It may consist of In particular, in the case of semiconductor ultrafine particles, the band gap is no longer a value specific to the material, and it depends on the size. Even with a material having a very small band gap (1 eV or less), the band gap can be increased by nano-sizing. As a result, the absorption wavelength of the dye can be selected, and the spectral sensitivity of the stacked photoelectric conversion element can be easily controlled. Examples of the semiconductor ultrafine particles include CdS, CdSe, PbS, PbSe, CdTe, Bi ₂ S ₃ , InP, Si, Ge, CIGS (Cu (In, Ga) Se ₂ ), CIS (CuInS ₂ ), FeS ₂ , Ag _2. S, Sb ₂ S ₃ , ZnS, Fe ₂ O _{3 and the} like.

<Second translucent conductive layer>
The second light transmissive conductive layer 3b is a light transmissive conductive layer having high corrosion resistance. Tin-doped indium oxide layer (ITO layer), impurity-doped indium oxide layer (In ₂ O ₃ layer), antimony-doped tin oxide (SnO ₂ : Sb (ATO)) formed by low-temperature growth sputtering method or low-temperature spray pyrolysis method Layer). Alternatively, a fluorine-doped tin oxide layer (SnO ₂ : F layer) formed by a thermal CVD method or a spray deposition method may be used. Further, an impurity-doped zinc oxide layer (ZnO layer) formed by a solution growth method may be used. Further, a metal layer such as nickel (Ni), titanium (Ti), platinum (Pt) having high corrosion resistance may be used. Moreover, what laminated | stacked these layers may be used. Furthermore, even a metal layer such as silver (Ag), aluminum (Al), and stainless steel (SUS) having low corrosion resistance may be formed by laminating layers of the above materials having high corrosion resistance.

  The second translucent conductive layer 3b can be patterned as shown in FIG. 1 by a laser ablation method, a sand blast method, or an etching method.

<Board>
In the configuration of FIG. 1, the first and second photoelectric conversion elements 1a and 2b can be connected in series by the first and second light-transmitting conductive layers 3a and 3b. An insulating substrate such as an inorganic substrate, a glass substrate, or a plastic substrate on which the second light-transmitting conductive layers 3a and 3b are formed is preferable. The material of the insulating substrate is a resin such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), polyimide, polycarbonate, inorganic materials such as blue plate glass, soda glass, borosilicate glass, ceramics, or conductive resin, organic-inorganic hybrid. Good materials.

  The thickness of the substrate 8 is preferably 0.01 mm to 5 mm, more preferably 0.02 mm to 3 mm. If it is less than 0.01 mm, the mechanical strength tends to be insufficient, and if it exceeds 5 mm, the weight tends to increase.

<Insulating sealing member>
The insulating sealing member 9 is preferably made of an inorganic material or a plastic material that does not leak electrolyte solution from the electrolyte layers 7a and 7b and can electrically insulate the first light-transmitting conductive layers 3a and 3b. As the inorganic material, glass frit, low-temperature cured glass, and solder are preferable. Plastic materials include thermoplastic resins (manufactured by DuPont, trade names: “Hi-Milan”, “Binell”, etc.), thermosetting resins (epoxy resins, acrylic resins, silicone resins, polyisobutylene resins, urethane resins, etc.), optical A curable resin (epoxy resin, acrylic resin, silicone resin, polyisobutylene resin, urethane resin, or the like) is preferable.

  Examples of the photoelectric conversion device of the present invention will be described below. A photoelectric conversion device having the configuration of FIG. 1 was produced as follows.

<Formation process of porous semiconductor layer 4b>
As the translucent substrate 2, a first translucent conductive layer 3a composed of a SnO ₂ : F layer (F-doped SnO ₂ layer (FTO layer)) having a sheet resistance of 10Ω / □ (square) is formed by laser ablation. A prepared glass substrate was prepared.

Next, a semiconductor layer 4b made of porous titanium oxide was formed on the first translucent conductive layer 3a. The porous semiconductor layer 4b was formed as follows. First, acetylacetone was added to anatase powder of titanium oxide (TiO ₂ ) and then kneaded with deionized water to prepare a titanium oxide paste stabilized with a surfactant. The produced paste was pattern-printed on the first light-transmitting conductive layer 3a made of the FTO layer by a printing method, and baked at 450 ° C. for 20 minutes in the air to form a porous semiconductor layer 4b.

<Formation Step of Non-Single Crystal Semiconductor Layer 5>
Next, using a plasma CVD apparatus, a mask is placed on the first light-transmitting conductive layer 3a, and p-type a-Si as the first conductive type amorphous silicon semiconductor layer is formed as the non-single-crystal semiconductor layer 5. : H layer (H-doped amorphous silicon (a-Si) layer), i-type a-Si as intrinsic type amorphous silicon semiconductor layer: n-type a as second conductivity type amorphous silicon semiconductor layer -Si: H layers were successively formed in a vacuum.

The p-type a-Si: H layer uses SiH ₄ gas, H ₂ gas, and B ₂ H ₆ gas (diluted to 500 ppm with H ₂ gas) as source gases, and the flow rates of these gases are 3 sccm and 10 sccm, respectively. The thickness was 2 sccm and the thickness was 90 mm (9 nm).

The i-type a-Si: H layer was formed using SiH ₄ gas and H ₂ gas as source gases, the flow rates of these gases being 30 sccm and 80 sccm, respectively, and the thickness being 2000 mm (200 nm).

The n-type a-Si: H layer uses SiH ₄ gas, H ₂ gas, and PH ₃ gas (diluted to 1000 ppm with H ₂ gas) as source gases, and the flow rates of these gases are 3 sccm, 30 sccm, and 6 sccm, respectively. And a thickness of 100 mm (10 nm).

  The temperature of the glass substrate during the formation of the p-type a-Si: H layer, i-type a-Si: H layer, and n-type a-Si: H layer was 220 ° C. in all cases.

  The p-type a-Si: H layer may be a p-type a-SiC layer that is a wide band gap material. In that case, light absorption can be reduced, spectral sensitivity in the vicinity of 400 nm can be improved, and conversion efficiency can be improved.

  Here, when the porous semiconductor layer 4b can be formed by low-temperature baking at 200 ° C. or lower, the porous semiconductor layer 4b may be formed after the non-single-crystal semiconductor layer 5 is formed first.

<Formation process of intermediate layer 6a>
Next, a Pt layer as the intermediate layer 6a was formed on the non-single-crystal semiconductor layer 5 with a thickness of 5 nm by a sputtering method.

<Formation process of porous semiconductor layer 4a>
As the substrate 8, a glass substrate was prepared in which a second light-transmitting conductive layer 3 b composed of a SnO ₂ : F layer (F-doped SnO ₂ layer (FTO layer)) having a sheet resistance of 10Ω / □ (square) was patterned. .

A porous semiconductor layer 4a made of titanium oxide was formed on the second translucent conductive layer 3b. The porous semiconductor layer 4a was formed as follows. First, acetylacetone was added to TiO ₂ anatase powder, and then kneaded with deionized water to prepare a titanium oxide paste stabilized with a surfactant. The produced paste was pattern-printed on the second light-transmitting conductive layer 3b by a printing method and baked at 450 ° C. for 20 minutes in the air to form a porous semiconductor layer 4a.

<Process for forming intermediate layer 6b>
Next, a Pt layer as the intermediate layer 6b was formed on the second light-transmitting conductive layer 3b with a thickness of 5 nm by a sputtering method.

<The manufacturing process of the 1st photoelectric conversion element 1a and the 2nd photoelectric conversion element 1b>
About the translucent board | substrate 2 and the board | substrate 8 which formed each layer by said each process, the insulating sealing member 9 which consists of a thermoplastic resin (the Du Pont company make, brand name: "High Milan") is used, and the 1st and 1st The two photoelectric conversion elements 1a and 1b were electrically separated, and the outer peripheral portions of the translucent substrate 2 and the substrate 8 were bonded and sealed.

  Next, a red dye (Ru complex) (manufactured by Solaronics, product name “Red Die”) is dissolved in the second photoelectric conversion element 1b from the through holes of the light-transmitting substrate 2 and the substrate 8 (not shown). The ethanol solution was injected and circulated, and the dye was supported on the surface of the porous semiconductor layer 4b.

  Also, the first photoelectric conversion element 1a has a black dye dye having sensitivity at a longer wavelength than the absorption of the i-type a-Si: H layer of the non-single-crystal semiconductor layer 5 and the electrolyte layer 7a from the through hole. An ethanol solution in which (Ru complex) (manufactured by Solaronics, product name “Black Die”) was dissolved was injected and circulated, and the dye was supported on the surface of the porous semiconductor layer 4a.

Next, as an electrolyte layer 7b suitable for the red dye of the second photoelectric conversion element 1b from the through hole of the substrate 8 (not shown), imidazolyl or the like is added to iodine (I ₂ ), lithium iodide (LiI), and acetonitrile solution. A mixture of these additives was injected.

In the first photoelectric conversion element 1a, an electrolyte layer 7a suitable for a black dye is obtained by mixing iodine (I ₂ ), lithium iodide (LiI), and an acetonitrile solution with an additive such as imidazolium. Injected.

  Next, the through holes of the translucent substrate 2 and the substrate 8 were sealed with a photocurable epoxy resin.

As a result of examining the solar cell operating characteristics by irradiating AM1.5, 100 mW / cm ² pseudo-sunlight to the W-type photoelectric conversion device of the example manufactured as described above, the short-circuit current density was 11 mA / cm ^2. Obtained. Note that the short-circuit current density is calculated using the area of a single photoelectric conversion element constituting the photoelectric conversion device.

(Comparative example)
A conventional photoelectric conversion device having the configuration shown in FIG. 2 was produced as follows.

<Step of forming titanium oxide layer 46>
As the transparent glass substrate 42, a glass substrate on which a light-transmitting conductive layer 43 composed of a SnO ₂ : F layer (F-doped SnO ₂ layer (FTO layer)) having a sheet resistance of 10Ω / □ (square) was prepared. A porous titanium oxide layer 46 was formed on one main surface as follows. First, acetylacetone was added to anatase powder of titanium oxide (TiO ₂ ) and then kneaded with deionized water to prepare a titanium oxide paste stabilized with a surfactant. The produced paste was pattern-printed on the first light-transmitting conductive layer 43 by a printing method and baked at 450 ° C. for 20 minutes in the air to form a porous titanium oxide layer 46.

<Formation process of platinum layer 44>
Next, the platinum layer 44 was formed on the translucent conductive layer 43 with a thickness of 5 nm by a sputtering method.

  Furthermore, another transparent glass substrate 42 having the titanium oxide layer 46 and the platinum layer 44 was prepared.

<The manufacturing process of the 1st and 2nd photoelectric conversion elements 41a and 41b>
With respect to the two transparent glass substrates 42 produced by the above steps, the first and second photoelectric substrates are formed using the insulating sealing member 47 made of a thermoplastic resin (manufactured by DuPont, trade name: “High Milan”). The conversion elements 41a and 41b were electrically separated, and the outer peripheral portions of the two transparent glass substrates 42 were bonded and sealed.

  Next, with respect to each of the first and second photoelectric conversion elements 41a and 41b, a red dye (Ru complex) (product name “Red Dye”, manufactured by Solaronics Co., Ltd.) is inserted from a through-hole of the transparent glass substrate 42 (not shown). The dissolved ethanol solution was injected and circulated, and the dye was adsorbed and supported on the surface of the titanium oxide layer 46.

Next, a mixture of iodine (I ₂ ), lithium iodide (LiI), and an acetonitrile solution mixed with an additive such as imidazolyl was injected as an electrolyte layer 45 suitable for the red dye dye from the through hole.

  Next, the through hole was sealed with a photocurable epoxy resin (not shown).

The W-type photoelectric conversion device of the comparative example thus manufactured was irradiated with AM1.5 and 100 mW / cm ² pseudo-sunlight and the solar cell operating characteristics were examined. As a result, the short-circuit current density was 6 mA / cm ^2. Obtained. Note that the short-circuit current density is calculated using the area of a single photoelectric conversion element constituting the photoelectric conversion device.

It is sectional drawing which shows an example of embodiment about the photoelectric conversion apparatus of this invention. It is sectional drawing which shows an example of the conventional photoelectric conversion apparatus.

Explanation of symbols

1a: 1st photoelectric conversion element 1b: 2nd photoelectric conversion element 2: Translucent substrate 3a: 1st translucent conductive layer 3b: 2nd translucent conductive layer 4a, 4b: Porous semiconductor Layer 5: Non-single-crystal semiconductor layers 6a and 6b: Intermediate layers 7a and 7b: Electrolyte layer 8: Substrate 9: Insulating sealing member

Claims (7)

  A light-transmitting substrate having a light-transmitting conductive layer formed on one main surface, and a conductive layer formed on one main surface of the light-transmitting substrate and disposed opposite to the one main surface of the light-transmitting substrate Are disposed adjacent to each other in the lateral direction between the transparent substrate and the transparent substrate, and are connected in series by the transparent conductive layer and the conductive layer, and the current directions are opposite to each other. The first and second photoelectric conversion elements have photoelectric converters having different unit area output currents, and have a low unit area output current. A photoelectric conversion device, wherein a light receiving area of the photoelectric conversion element having a converter is larger than a light receiving area of the photoelectric conversion element having a photoelectric converter having a high unit area output current.   The photoelectric conversion device according to claim 1, wherein three or more of the first and second photoelectric conversion elements are alternately arranged.   Said 1st and 2nd photoelectric conversion element has a translucent thin film type photoelectric conversion body which has a non-single-crystal semiconductor layer in the direction which has a photoelectric conversion body with low unit area output current, and unit area 3. The photoelectric conversion device according to claim 1, wherein the photoelectric conversion device having a higher output current has a dye-sensitized photoelectric conversion device.   The photoelectric conversion element having a photoelectric conversion body with a low unit area output current is a stacked photoelectric film in which a translucent thin film photoelectric conversion body including a non-single-crystal semiconductor layer and a dye-sensitized photoelectric conversion body are stacked. The photoelectric conversion device according to claim 3, wherein the photoelectric conversion device is a conversion element.   5. The photoelectric conversion device according to claim 4, wherein in the stacked photoelectric conversion element, the dye-sensitized photoelectric conversion body has a spectral sensitivity to the transmitted light of the thin film photoelectric conversion body.   The photoelectric according to claim 3, wherein the dye-sensitized photoelectric conversion body in the photoelectric conversion element having a photoelectric conversion body having a high unit area output current is disposed on the translucent substrate side. Conversion device.   The photoelectric conversion device according to claim 1, wherein the first and second photoelectric conversion elements have the same output current.

Images