JP2015026711A - Method of manufacturing photoelectric conversion device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve photoelectric conversion efficiency of a photoelectric conversion device.SOLUTION: A method of manufacturing a photoelectric conversion device 11 includes a first step for preparing material solution in which a metal complex in which organic ligand is coordinated to metal element is mixed with organic solvent, a second step for forming a coat 3x by applying the material solution to an electrode layer 2, a third step in which the organic solvent is evaporated by radiating infrared light that can absorb the organic solvent to the coat 3x, a fourth step in which the electrode layer 2 is heated from a side opposite to the coat 3x while continuing radiation of infrared light to the coat 3x so that an organic component in the coat 3x is thermally decomposed to form a thermal decomposition coat 3a, and a fifth step in which the thermal decomposition coat 3a is heated in an atmosphere containing chalcogen element to provide a semiconductor layer 3 containing metal chalcogenide.

Description

  The present invention relates to a method for manufacturing a photoelectric conversion device using a semiconductor layer containing a metal chalcogenide.

  As a photoelectric conversion device used for solar power generation or the like, there is one in which a light absorption layer is formed of a metal chalcogenide such as CIS or CIGS. Such a photoelectric conversion device is described in Patent Document 1, for example.

  A photoelectric conversion device using such a metal chalcogenide has a configuration in which a plurality of photoelectric conversion cells are arranged side by side in a plane. Each photoelectric conversion cell has a substrate such as glass, a lower electrode such as a metal electrode, a photoelectric conversion layer including a light absorption layer and a buffer layer, and an upper electrode such as a transparent electrode and a metal electrode in this order. It is constructed by stacking. In addition, the plurality of photoelectric conversion cells are electrically connected in series by electrically connecting the upper electrode of one adjacent photoelectric conversion cell and the lower electrode of the other photoelectric conversion cell by a connecting conductor. Yes.

  Such a light absorption layer containing a metal chalcogenide is formed by forming a film containing a metal chalcogenide raw material on the lower electrode and heat-treating the film.

  As a raw material for the metal chalcogenide, a salt or complex of an element constituting the metal chalcogenide is used. For example, Patent Document 2 describes that a single source precursor in which Cu, Se, In, or Ga is present in one organic compound is used as a raw material for metal chalcogenide. Yes.

JP 2000-299486 A US Pat. No. 6,992,202

  A photoelectric conversion device including a metal chalcogenide is always required to improve photoelectric conversion efficiency. This photoelectric conversion efficiency indicates the rate at which sunlight energy is converted into electric energy in the photoelectric conversion device. For example, the value of the electric energy output from the photoelectric conversion device is the amount of sunlight incident on the photoelectric conversion device. Divided by the value of energy and derived by multiplying by 100.

  This invention is made | formed in view of the said subject, and aims at the improvement of the photoelectric conversion efficiency in a photoelectric conversion apparatus.

The method for manufacturing a photoelectric conversion device according to one embodiment of the present invention includes a first step of preparing a raw material solution in which a metal complex in which an organic ligand is coordinated to a metal element is mixed in an organic solvent, and the method described above on an electrode layer. A second step of forming a film by applying a raw material solution; a third step of evaporating the organic solvent by irradiating the film with infrared light that can be absorbed by the organic solvent; and A fourth step of thermally decomposing organic components in the film by heating the electrode layer from the side opposite to the film while continuing the irradiation with the infrared light to form a pyrolytic film; And a fifth step of forming the semiconductor layer containing the metal chalcogenide by heating the decomposition film in an atmosphere containing the chalcogen element.

  According to the embodiment of the present invention, a photoelectric conversion device with high photoelectric conversion efficiency can be provided.

It is a perspective view which shows an example of embodiment of the photoelectric conversion apparatus produced using the manufacturing method of the photoelectric conversion apparatus which concerns on one Embodiment of this invention. It is sectional drawing of the photoelectric conversion apparatus of FIG. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows typically the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows typically the mode of the heating process of the film | membrane in the middle of manufacture of a photoelectric conversion apparatus. It is a graph which shows an example of the temperature profile in the middle of manufacture of a photoelectric conversion apparatus.

  Hereinafter, a method for manufacturing a photoelectric conversion device according to an embodiment of the present invention will be described with reference to the drawings. In the drawings, parts having similar configurations and functions are denoted by the same reference numerals, and redundant description is omitted in the following description. Further, the drawings are schematically shown, and the sizes, positional relationships, and the like of various structures in the drawings are not accurately illustrated.

<(1) Configuration of photoelectric conversion device>
FIG. 1 is a perspective view showing an example of a photoelectric conversion device 11 manufactured by using a method for manufacturing a photoelectric conversion device according to an embodiment of the present invention. FIG. 2 is an XZ sectional view of the photoelectric conversion device 11 of FIG. 1 to 10 are provided with a right-handed XYZ coordinate system in which the arrangement direction of photoelectric conversion cells 10 (the horizontal direction in the drawing in FIG. 1) is the X-axis direction.

  The photoelectric conversion device 11 has a configuration in which a plurality of photoelectric conversion cells 10 are arranged in parallel on a substrate 1. In FIG. 1, only two photoelectric conversion cells 10 are shown for convenience of illustration, but an actual photoelectric conversion device 11 has a large number of photoelectric conversion cells in the X-axis direction of the drawing or further in the Y-axis direction of the drawing. The conversion cells 10 are arranged two-dimensionally (two-dimensionally).

  Each photoelectric conversion cell 10 mainly includes a lower electrode layer 2, a first semiconductor layer 3, a second semiconductor layer 4, an upper electrode layer 5, and a collecting electrode 7. In the photoelectric conversion device 11, the main surface on the side where the upper electrode layer 5 and the collecting electrode 7 are provided is a light receiving surface. In addition, the photoelectric conversion device 11 is provided with three types of groove portions such as first to third groove portions P1, P2, and P3.

  The substrate 1 supports the plurality of photoelectric conversion cells 10 and is made of, for example, a material such as glass, ceramics, resin, or metal. For example, as the substrate 1, blue plate glass (soda lime glass) having a thickness of about 1 to 3 mm may be used.

  The lower electrode layer 2 is a conductive layer provided on one main surface of the substrate 1. For example, molybdenum (Mo), aluminum (Al), titanium (Ti), tantalum (Ta), or gold (Au). Or a laminated structure of these metals. The lower electrode layer 2 has a thickness of about 0.2 to 1 μm and is formed by a known thin film forming method such as a sputtering method or a vapor deposition method.

  The first semiconductor layer 3 as the light absorption layer is provided on a main surface (also referred to as one main surface) on the + Z side of the lower electrode layer 2 and has a first conductivity type (here, p-type conductivity type). ) And has a thickness of about 1 to 3 μm. The first semiconductor layer 3 is a semiconductor layer mainly containing metal chalcogenide. Note that the phrase “mainly containing metal chalcogenide” means containing metal chalcogenide in an amount of 70 mol% or more. The metal chalcogenide is a compound of a metal element and a chalcogen element. The chalcogen element refers to sulfur (S), selenium (Se), and tellurium (Te) among group 16 elements (also referred to as group VI-B elements).

  Examples of the metal chalcogenide include a group 11 element (also referred to as a group IB element), a group 13 element (also referred to as a group III-B element) and a chalcogen element, a group I-III-VI group compound, a group 11 element, Group I-II-IV-VI group compounds which are compounds of Group 12 element (also referred to as Group II-B element), Group 14 element (also referred to as Group IV-B element) and chalcogen element, and Group 12 element and chalcogen element The II-VI group compound etc. which are these compounds may be employ | adopted.

Examples of the I-III-VI group compound include CuInSe ₂ (indium diselenide,
CIS), Cu (In, Ga) Se ₂ (also called copper indium selenide / gallium, CIGS) and the like. Examples of the I-II-IV-VI group compound include Cu ₂ ZnSnS ₄ (also referred to as CZTS), Cu ₂ ZnSn (S, Se) ₄ (also referred to as CZTSSe), and Cu ₂ ZnSnSe ₄ (also referred to as CZTSe). ). Moreover, as a II-VI group compound, CdTe etc. are mentioned, for example.

  The second semiconductor layer 4 is a semiconductor layer provided on one main surface of the first semiconductor layer 3. The second semiconductor layer 4 has a conductivity type (here, n-type conductivity type) different from that of the first semiconductor layer 3. By joining the first semiconductor layer 3 and the second semiconductor layer 4, positive and negative carriers generated by photoelectric conversion in the first semiconductor layer 3 are favorably separated. Note that semiconductors having different conductivity types are semiconductors having different conductive carriers. Further, when the conductivity type of the first semiconductor layer 3 is p-type as described above, the conductivity type of the second semiconductor layer 4 may be i-type instead of n-type. Furthermore, there may be a mode in which the conductivity type of the first semiconductor layer 3 is n-type or i-type and the conductivity type of the second semiconductor layer 4 is p-type.

The second semiconductor layer 4 includes, for example, cadmium sulfide (CdS), indium sulfide (In ₂ S ₃ ), zinc sulfide (ZnS), zinc oxide (ZnO), indium selenide (In ₂ Se ₃ ), In (OH , S), (Zn, In) (Se, OH), and (Zn, Mg) O. From the viewpoint of reducing current loss, the second semiconductor layer 4 can have a resistivity of 1 Ω · cm or more. The second semiconductor layer 4 is formed by, for example, a chemical bath deposition (CBD) method or the like.

  The second semiconductor layer 4 has a thickness in the normal direction of one main surface of the first semiconductor layer 3. This thickness is set to, for example, 10 to 200 nm.

The upper electrode layer 5 is a transparent conductive film having an n-type conductivity provided on the second semiconductor layer 4, and is an electrode for extracting charges generated in the first semiconductor layer 3. The upper electrode layer 5 is made of a material having a lower resistivity than the second semiconductor layer 4. The upper electrode layer 5 includes what is called a window layer, and when a transparent conductive film is further provided in addition to the window layer, these may be regarded as an integrated upper electrode layer 5.

The upper electrode layer 5 mainly includes a material having a wide forbidden band, transparent, and low resistance. As such a material, for example, a metal oxide semiconductor such as ZnO, In ₂ O ₃ and SnO ₂ can be adopted. These metal oxide semiconductors may contain any element of Al, B, Ga, In, F, and the like. Specific examples of the metal oxide semiconductor containing such an element include, for example, AZO (Aluminum Zinc Oxide), GZO (Gallium Zinc Oxide),
Examples include IZO (Indium Zinc Oxide), ITO (Indium Tin Oxide), and FTO (Fluorine tin Oxide).

  The upper electrode layer 5 is formed to have a thickness of 0.05 to 3.0 μm by sputtering, vapor deposition, chemical vapor deposition (CVD), or the like. Here, from the viewpoint of good charge extraction from the first semiconductor layer 3, the upper electrode layer 5 has a resistivity of less than 1 Ω · cm and a sheet resistance of 50Ω / □ or less. Can do.

  The second semiconductor layer 4 and the upper electrode layer 5 can be made of a material having a property (also referred to as light transmittance) that allows light to easily pass through the wavelength region of light absorbed by the first semiconductor layer 3. Thereby, a decrease in light absorption efficiency in the first semiconductor layer 3 caused by providing the second semiconductor layer 4 and the upper electrode layer 5 is reduced.

  In addition, from the viewpoint of improving the light transmittance, the effect of preventing loss of light reflection and the light scattering effect, and further transmitting the current generated by the photoelectric conversion, the upper electrode layer 5 can have a thickness of 0.05 to 0.5 μm. Further, from the viewpoint of reducing the light reflection loss at the interface between the upper electrode layer 5 and the second semiconductor layer 4, the absolute refractive index is substantially between the upper electrode layer 5 and the second semiconductor layer 4. It can be made the same.

  The collecting electrodes 7 are spaced apart in the Y-axis direction, and each extend in the X-axis direction. The collector electrode 7 is an electrode having conductivity, and is made of a metal such as silver (Ag), for example.

  The collecting electrode 7 plays a role of collecting charges generated in the first semiconductor layer 3 and taken out in the upper electrode layer 5. If the current collecting electrode 7 is provided, the upper electrode layer 5 can be thinned.

  The charges collected by the collector electrode 7 and the upper electrode layer 5 are transmitted to the adjacent photoelectric conversion cell 10 through the connection conductor 6 provided in the second groove portion P2. For example, the connection conductor 6 is constituted by a portion extending in the Y-axis direction of the current collecting electrode 7 as shown in FIG. Thereby, in the photoelectric conversion apparatus 11, one lower electrode layer 2 of the adjacent photoelectric conversion cell 10 and the other collector electrode 7 are electrically connected via the connection conductor 6 provided in the second groove portion P2. Connected in series. In addition, the connection conductor 6 is not limited to this, You may be comprised by the extension part of the upper electrode layer 5. FIG.

  The current collecting electrode 5 has a width of 50 to 400 μm so that good conductivity is ensured and a decrease in the light receiving area that affects the amount of light incident on the first semiconductor layer 3 is minimized. Can be.

<(2) Method for Manufacturing Photoelectric Conversion Device>
3 to 10 are cross-sectional views schematically showing a state during the manufacture of the photoelectric conversion device 11. Each of the cross-sectional views shown in FIGS. 3 to 10 shows a state in the middle of manufacturing a portion corresponding to the cross-section shown in FIG.

  First, the lower electrode layer 2 made of Mo or the like is formed on substantially the entire surface of the cleaned substrate 1 using a sputtering method or the like. Then, the first groove portion P1 is formed from the linear formation target position along the Y direction on the upper surface of the lower electrode layer 2 to the upper surface of the substrate 1 immediately below the formation position. The first groove portion P1 can be formed by, for example, a scribe process in which a groove process is performed by irradiating a formation target position while scanning a laser beam by a YAG laser or the like. FIG. 3 is a diagram illustrating a state after the first groove portion P1 is formed.

  After forming the first groove portion P1, as shown in FIG. 4, a film 3x is formed by applying a raw material solution on the lower electrode layer 2. This raw material solution is obtained by mixing a metal complex in which an organic ligand is coordinated with a metal element in an organic solvent. The metal element used for the metal complex is a metal element constituting the metal chalcogenide contained in the first semiconductor layer 3. The metal complex mixed in the raw material solution may be one type or a mixture of plural types.

  From the viewpoint of improving the chalcogenization of the metal element and increasing the crystallinity of the first semiconductor layer, an organic chalcogen compound may be used as the organic ligand used in the metal complex. An organic chalcogen compound is an organic compound containing a chalcogen element, and is an organic compound having a covalent bond between a carbon element and a chalcogen element. Examples of the organic chalcogen compound include thiol, sulfide, disulfide, selenol, selenide, diselenide, tellurol, telluride, ditelluride and the like.

When the first semiconductor layer 3 includes, for example, a group I-III-VI compound as a metal chalcogenide, the raw material solution includes a group 11 element and a group 13 element. In this case, as the metal complex, a multimetallic complex containing a plurality of types of metal elements in one complex molecule (here, a multimetallic complex containing both a group 11 element and a group 13 element) may be used, or Alternatively, a mixture of a Group 11 metal complex containing a Group 11 element and a Group 13 metal complex containing a Group 13 element may be used. As the multimetallic complex, for example, as shown in Patent Document 2, a single complex molecule includes a group 11 element and a group 13 element, and an organic ligand such as thiol or selenol is coordinated to these elements. There are one source precursors and the like. Examples of the Group 11 metal complex include a metal complex in which an organic ligand such as an organic acid, thiol, or selenol is coordinated with a Group 11 element. Examples of the group 13 metal complex include a metal complex in which an organic ligand such as an organic acid, thiol, or selenol is coordinated with a group 13 element.

  Further, when the first semiconductor layer 3 includes a group I-II-IV-VI compound as a metal chalcogenide, the raw material solution includes a group 11 element, a group 12 element, and a group 14 element. Also in this case, a multimetallic complex may be used as the metal complex, or a mixture of a plurality of metal complexes may be used.

  Further, when the first semiconductor layer 3 contains a II-VI group compound as a metal chalcogenide, the raw material solution contains a Group 12 element. In this case, a group 12 metal complex in which an organic ligand is coordinated to a group 12 element can be used as the metal complex.

  As the organic solvent used for the raw material solution, a solvent capable of dissolving or dispersing the metal complex can be used. From the viewpoint that it is possible to dissolve the metal complex well to form a good film 3x, a polar solvent such as an amine organic solvent may be used. In particular, an amine organic solvent having a phenyl group such as pyridine or aniline may be used from the viewpoint of high solubility and easy adjustment of a raw material solution having a stable concentration and good handleability.

  As a method of forming the film 3x on the lower electrode layer 2, a method of applying a raw material solution on the lower electrode layer 2 in a film shape by, for example, a spin coater, screen printing, dipping, spraying, or a die coater is used. it can.

  After forming the film 3x, a heating process of the film 3x is performed in an inert gas atmosphere such as nitrogen in order to remove organic components such as an organic solvent and an organic ligand contained in the film 3x. In this heating step, first, a step of evaporating the organic solvent is performed by irradiating the film 3x with infrared light that can be absorbed by the organic solvent in the raw material solution. Specifically, as shown in FIG. 11, the substrate 1 on which the film 3x is formed is disposed between the heating device L1 and the heating device L2, and the upper surface of the film 3x (the surface opposite to the lower electrode layer 2). ) Is irradiated with infrared light from the heating device L1 to heat the coating 3x. The infrared light used here is light having a wavelength of 0.7 to 1000 μm, and has light having a wavelength that can be absorbed by the organic solvent in the raw material solution. An example of the temperature profile of the atmosphere of the heating process at this time is shown in FIG. In FIG. 12, the horizontal axis indicates the heating time of the heating process of the film 3x, and the vertical axis indicates the temperature of the atmosphere of the heating process. When the heating time in FIG. 12 is 0 to 300 seconds, infrared rays are irradiated from the heating device L1 to heat the film 3x, and the organic solvent in the film 3x is evaporated. From the viewpoint of effectively reducing the stress generated near the interface between the film 3x and the lower electrode layer 2 by selectively heating the film 3x, the infrared light irradiated from the heating device L1 is 4 to 1000 μm. You may use the far-infrared light of the wavelength.

  Thereafter, while continuing to irradiate the coating 3x with infrared light from the heating device L1, further heating the lower electrode layer 2 from the side opposite to the coating 3x using the heating device L2, thereby further increasing the temperature of the atmosphere. Raise the temperature. Thereby, the organic component in the film 3x can be thermally decomposed, and the film 3x can be converted into a thermally decomposed film 3a (see FIG. 5). In the heating time of 300 to 340 seconds in FIG. 12, the heat treatment is performed on the film 3x from both the heating devices L1 and L2, and the organic components in the film 3x are thermally decomposed. Here, as the heating device L2, for example, an infrared lamp having a wavelength of 0.7 to 1000 μm and capable of emitting light having a wavelength that can be absorbed by the lower electrode layer 2 can be used. When this infrared lamp is used, the substrate 1 is an infrared lamp applied to the lower electrode layer 2 by using a substrate (for example, glass) that can transmit light having a wavelength that can be absorbed by the lower electrode layer 2. Irradiation becomes possible.

  As described above, by heating the coating 3x with the heating device L1 and then removing the organic components in the coating 3x by heating with the heating devices L1 and L2, cracks and the like are generated in the coating 3x. Can be effectively reduced, and the film 3x can be made into a favorable pyrolytic film 3a. As a result, this pyrolytic film 3a can be chalcogenized satisfactorily, and the first semiconductor layer 3 having high photoelectric conversion efficiency can be obtained.

  The heating device L2 is not limited to an infrared lamp as described above. For example, the heating device L2 may be a heat source such as a hot plate, and the lower electrode layer 2 may be heated via the substrate 1 by bringing the heating device L2 into contact with the substrate 1. In this case, the substrate 1 does not have to transmit infrared light, and the selection range of the material of the substrate 1 is expanded. In addition, when the lower electrode layer 2 is directly heated using the infrared lamp as described above as the heating device L1, warpage or the like hardly occurs when the coating 3x is heated, and the generation of cracks in the coating 3x can be further reduced. .

  The pyrolysis film 3a thus formed may be a single layer, but in order to increase the thickness of the first semiconductor layer 3, the above steps are repeated to form a plurality of layers (FIG. 6). Then, a laminate of three layers) may be used. That is, a film is further formed using the raw material solution on the pyrolysis film 3a in the same manner as the method for producing the pyrolysis film 3a, and this is formed using the heating devices L1 and L2 in FIG. The thermal decomposition film 3b may be formed by performing a heat treatment with the temperature profile. Further, after the formation of the thermal decomposition film 3b, the thermal decomposition film 3c may be similarly formed on the thermal decomposition film 3b.

After forming the pyrolysis films 3a to 3c, the pyrolysis films 3a to 3c are heated in an atmosphere containing a chalcogen element to form the first semiconductor layer 3 containing a metal chalcogenide. That is, when the metal element in the pyrolysis coatings 3a to 3c and the chalcogen element in the atmosphere or the chalcogen element is contained in the pyrolysis coatings 3a to 3c, the metal element and atmosphere in the pyrolysis coatings 3a to 3c. The metal chalcogenide is generated by reaction with the chalcogen element in the inside and in the pyrolytic coatings 3a to 3c. The atmosphere containing the chalcogen element may be a gas atmosphere such as sulfur vapor, selenium vapor, tellurium vapor, hydrogen sulfide, hydrogen selenide or hydrogen telluride, or a chalcogen element as described above in a non-oxidizing gas. Or a mixed gas atmosphere containing a hydride of a chalcogen element. Examples of the non-oxidizing gas include an inert gas such as nitrogen and a reducing gas such as hydrogen. Moreover, the heating temperature of the pyrolytic films 3a to 3c is, for example, 400 to 600 ° C., and the heating time is, for example, 0.5 to 5 hours. FIG. 7 is a view showing a state after the first semiconductor layer 3 is formed.

  After the formation of the first semiconductor layer 3, the second semiconductor layer 4 and the upper electrode layer 5 are sequentially formed on the first semiconductor layer 3.

  The second semiconductor layer 4 can be formed by a solution growth method (also referred to as a CBD method). For example, cadmium acetate and thiourea are dissolved in ammonia water, and the substrate 1 that has been formed up to the formation of the first semiconductor layer 3 is immersed in the second semiconductor layer 3 so as to contain the second CdS on the first semiconductor layer 3. The semiconductor layer 4 can be formed.

  The upper electrode layer 5 is a transparent conductive film containing, for example, indium oxide (ITO) containing Sn as a main component, and can be formed by a sputtering method, a vapor deposition method, a CVD method, or the like. FIG. 8 is a diagram illustrating a state after the second semiconductor layer 4 and the upper electrode layer 5 are formed.

  After the upper electrode layer 5 is formed, the second groove portion P2 is formed from the linear formation target position along the Y direction on the upper surface of the upper electrode layer 5 to the upper surface of the lower electrode layer 2 immediately below it. The second groove portion P2 can be formed, for example, by performing scribing using a scribe needle having a scribe width of about 40 to 50 μm continuously several times while shifting the pitch. Alternatively, the second groove portion P2 may be formed by scribing after the tip shape of the scribe needle is expanded to an extent close to the width of the second groove portion P2. Alternatively, the second groove part P2 may be formed by fixing two or more than two scribe needles in contact with each other or in proximity to each other and performing scribing once to several times. FIG. 9 is a diagram illustrating a state after the second groove portion P2 is formed. The second groove portion P2 is formed at a position slightly deviated in the X direction (+ X direction in the drawing) from the first groove portion P1.

  After forming the second groove P2, the current collecting electrode 7 and the connection conductor 6 are formed. For the collector electrode 7 and the connection conductor 6, for example, a conductive paste (also referred to as a conductive paste) in which a metal powder such as Ag is dispersed in a resin binder or the like is printed so as to draw a desired pattern. It can be formed by drying and solidifying. The solidified state is the solidified state after melting when the binder used in the conductive paste is a thermoplastic resin, and after curing when the binder is a curable resin such as a thermosetting resin or a photocurable resin. Including both states. FIG. 10 is a diagram illustrating a state after the current collecting electrode 7 and the connection conductor 6 are formed.

  After forming the current collection electrode 7 and the connection conductor 6, the 3rd groove part P3 is formed from the linear formation object position of the upper surface of the upper electrode layer 5 to the upper surface of the lower electrode layer 2 just under it. The width | variety of the 3rd groove part P3 can be about 40-1000 micrometers, for example. Moreover, the 3rd groove part P3 can be formed by mechanical scribing similarly to the 2nd groove part P2. In this way, the photoelectric conversion device 11 shown in FIGS. 1 and 2 is manufactured by forming the third groove portion P3.

<(3) Other Examples of Manufacturing Method of Photoelectric Conversion Device>
The present invention is not limited to the above-described embodiment, and various modifications and improvements can be made without departing from the scope of the present invention.

  For example, in the above-described method for manufacturing a photoelectric conversion device, when the coating 3x is subjected to the heat treatment with the temperature profile of FIG. 12 using the heating devices L1 and L2 of FIG. 11, water (steam), oxygen, etc. An oxidizing gas may be further included. Such an oxidizing gas can be contained in an inert gas such as nitrogen or argon in a partial pressure ratio of 50 to 1000 ppmv, for example. In this way, the organic component is thermally decomposed and removed in an atmosphere containing an oxidizing gas, so that the metal element is oxidized to some extent. As a result, it is possible to increase the strength of the pyrolysis film 3a due to the generation of the metal oxide, to further reduce the occurrence of cracks, peeling from the lower electrode layer 2, and the like, and to obtain a better pyrolysis film 3a. . In particular, excessive oxidation can be suppressed and water can be used as the oxidizing gas from the viewpoint of excellent handleability.

1: Substrate 2: Lower electrode layer 3: First semiconductor layer 3a: First pyrolysis film 3b: Second pyrolysis film 4: Second semiconductor layer 5: Upper electrode layer 6: Connection conductor 7: Collection Electrode 10: Photoelectric conversion cell 11: Photoelectric conversion device L1, L2: Heating device

Claims (6)

A first step of preparing a raw material solution in which a metal complex in which an organic ligand is coordinated to a metal element is mixed in an organic solvent;
A second step of forming a film by applying the raw material solution on the electrode layer;
A third step of evaporating the organic solvent by irradiating the film with infrared light that can be absorbed by the organic solvent;
A fourth step of thermally decomposing organic components in the film by heating the electrode layer from the side opposite to the film while continuing to irradiate the film with the infrared light; ,
And a fifth step of forming the semiconductor layer containing metal chalcogenide by heating the pyrolysis film in an atmosphere containing a chalcogen element.   The method for manufacturing a photoelectric conversion device according to claim 1, wherein an organic chalcogen compound is used as the organic ligand.   The method for producing a photoelectric conversion device according to claim 1, wherein a polymetallic complex containing both a group 11 element and a group 13 element is used as the metal complex.   The method for producing a photoelectric conversion device according to claim 1, wherein a group 11 metal complex containing a group 11 element and a group 13 metal complex containing a group 13 element are used as the metal complex.   The method for manufacturing a photoelectric conversion device according to claim 1, further comprising an oxidizing gas in the atmosphere in the fourth step.   The method for manufacturing a photoelectric conversion device according to claim 5, wherein the oxidizing gas is water.

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