JP2014045155A - Method of manufacturing photoelectric conversion device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectric conversion device having high photoelectric conversion efficiency.SOLUTION: A method of manufacturing a photoelectric conversion device 11 comprises the steps of: forming, on an electrode layer 2, a film M which contains a group I-B element and a group III-B element and contains a larger amount of sulfur element at a surface part opposite to the electrode layer 2 than at a center part in the thickness direction; and heating the film M in a first atmosphere containing a selenium element and a sulfur element to make it into a group I-III-VI compound semiconductor layer 3 containing a selenium element and a sulfur element as group VI-B elements.

Description

The present invention relates to a method for manufacturing a photoelectric conversion device using a semiconductor layer containing an I-III-VI group compound.

As a photoelectric conversion device used for photovoltaic power generation or the like, a semiconductor layer containing an I-III-VI group compound such as CuInSe ₂ (CIS) or Cu (In, Ga) Se ₂ (CIGS) is used as a light absorption layer. There is one in which a buffer layer such as a II-VI group compound is formed on this light absorption layer.

Such photoelectric conversion devices are required to improve photoelectric conversion efficiency. For example, in Patent Document 1, a surface layer made of Cu (In, Ga) (Se, S) ₂ (CIGSS) and having a thickness of about 150 nm is provided on the surface of the light absorption layer, and the concentration of sulfur element in the surface layer is determined. It has been proposed to improve the photoelectric conversion efficiency by improving the interfacial bonding between the light absorption layer and the buffer layer by using a concentration gradient that decreases from the surface on the buffer layer side toward the inside of the light absorption layer.

  In Patent Document 1, in order to introduce sulfur element into the surface of the light absorption layer, after forming the CIGS layer, the CIGS layer is heated in an atmosphere containing the sulfur element, whereby the selenium element on the surface of the CIGS layer is formed. Is used.

JP-A-10-135498

  However, in the method as described above, when the CIGS layer is heated in an atmosphere containing sulfur element, the selenium element escapes from the CIGS layer, and group VI defects are likely to occur. Therefore, it is difficult to further increase the photoelectric conversion efficiency.

  The present invention has been made in view of the above problems, and an object thereof is to provide a photoelectric conversion device having high photoelectric conversion efficiency.

A manufacturing method of a photoelectric conversion device according to an embodiment of the present invention includes a group I-B element and a group III-B element on an electrode layer, and is opposite to the electrode layer with respect to a central portion in the thickness direction. A step of producing a film containing a large amount of sulfur element on the surface of the film, and heating the film in a first atmosphere containing selenium element and sulfur element to obtain I-III containing selenium element and sulfur element as a VI-B group element And -VI group compound semiconductor layer.

A method for manufacturing a photoelectric conversion device according to another embodiment of the present invention includes an IB group element, a III-B group element, and a selenium element on the electrode layer, and the electrode layer is more than the central portion in the thickness direction. Forming a film containing a large amount of sulfur element on the surface portion opposite to the surface, and heating the film in a first atmosphere containing selenium element and sulfur element to convert selenium element and sulfur element as VI-B group elements And a step of forming an I-III-VI group compound semiconductor layer.

Any of the above embodiments of the present invention can provide a photoelectric conversion device with high photoelectric conversion efficiency.

It is a perspective view which shows an example 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.

  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 9 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 includes a lower electrode layer 2, an I-III-VI group compound semiconductor layer 3 (hereinafter,
I-III-VI group compound semiconductor layer is also referred to as first semiconductor layer), second semiconductor layer 4,
An upper electrode layer 5 and a collecting electrode 7 are mainly provided. 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 I-III-VI group compound semiconductor layer 3 (first semiconductor layer 3) as a light absorption layer is provided on the main surface (also referred to as one main surface) on the + Z side of the lower electrode layer 2. This is a semiconductor layer having one 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 containing an I-III-VI group compound. The I-III-VI group compound is a group IB element (also referred to as group 11 element), a group III-B element (also referred to as group 13 element), and a group VI-B element (also referred to as group 16 element). It is a compound containing. The first semiconductor layer 3 contains a sulfur element (S) and a selenium element (Se) as VI-B group elements. As such an I-III-VI group compound, for example, Cu (In, Ga) (Se, S) ₂ (also referred to as diselenium / sulfur copper indium / gallium, CIGSS), CuIn (Se, S) ₂ (Also referred to as diselene / copper indium sulfide or CISS), CuGa (Se, S) ₂ (also referred to as diselen / sulfur copper gallium or CGSS), or the like.

In addition, the 1st semiconductor layer 3 does not need to contain a sulfur element and a selenium element in the front part of the thickness direction. For example, in a portion of the first semiconductor layer 3 on the lower electrode layer 2 side, Cu (In, Ga) Se ₂ (also called copper indium selenide / gallium, CIGS), CuInSe ₂ (copper indium diselenide, In some cases, it is also referred to as CIS), CuGaSe ₂ (also referred to as copper gallium selenide, also referred to as CGS), or the like.

  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 provided on the second semiconductor layer 4, and is an electrode that extracts 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) First Example of Manufacturing Method of Photoelectric Conversion Device>
3 to 9 are cross-sectional views each schematically showing a state during the manufacture of the photoelectric conversion device 11. Each of the cross-sectional views shown in FIGS. 3 to 9 shows a state in the middle of manufacturing a portion corresponding to the cross-section shown in FIG.

  First, as shown in FIG. 3, a 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, for example, by laser scribing, in which groove processing is performed by irradiating the formation target position while scanning with laser light from a YAG laser or the like. FIG. 4 is a diagram illustrating a state after the first groove portion P1 is formed.

After forming the first groove portion P1, the surface portion on the opposite side of the lower electrode layer 2 from the central portion in the thickness direction is included on the lower electrode layer 2 and includes an IB group element and an III-B group element. (Hereinafter, the surface portion of the coating M opposite to the lower electrode layer 2 is also simply referred to as the surface portion of the coating M). Note that the central portion of the film M may not contain sulfur element. Then, the coating M is heated in a first atmosphere containing a selenium element and a sulfur element, whereby an I-III-VI group compound semiconductor layer containing a selenium element and a sulfur element as a VI-B group element (first semiconductor layer). 3).

  Thus, by forming a film M containing more sulfur element in the surface portion than in the central part in the thickness direction and heating this film M in the first atmosphere, a desired concentration distribution of sulfur element (the central part in the thickness direction) It is possible to produce the first semiconductor layer 3 having a larger amount of sulfur element in the surface portion in a good state with few defects. As a result, the photoelectric conversion efficiency is improved. In other words, by heating the film M containing sulfur element in an atmosphere containing both sulfur element and selenium element, diffusion of sulfur element in the film M is suppressed and the concentration distribution of sulfur element is maintained to some extent. In addition, the defects in the first semiconductor layer 3 can be satisfactorily filled with both the sulfur element and the selenium element in the atmosphere.

Each of the IB group element, the III-B group element, and the sulfur element may be present in the film M in a compound state, an alloy state, or a single state.

The concentration of sulfur element in the film M, when divided into three equal parts the film M in the thickness direction, the ratio of moles of Group III-B element in the surface portion (M _III) the number of moles of elemental sulfur relative to (M _S) ( The average value of M _S / M _III ) is 0.01 to 5, and the average value of M _S / M _III in the central portion is 0 to 0.9 times the average value of M _S / M _III in the surface portion. That's fine. Thereby, the 1st semiconductor layer 3 with a high sulfur element density | concentration of a surface part can be produced favorably.

The coating M is produced by using a raw material containing any one or more of group I-B elements, group III-B elements and sulfur elements, and combining them so as to obtain a desired composition ratio. Can do. Specifically, the coating M can be formed by applying a raw material solution containing the above raw materials, or by sputtering, vapor deposition, or the like. The coating M may be a laminate composed of a plurality of layers.

From the viewpoint that the film M can be easily produced with a desired composition, the film M may be produced using a raw material solution. In the raw material solution, a group I-B element, a group III-B element and a sulfur element are dissolved in a solvent. From the viewpoint of increasing the crystallinity by increasing the reactivity, a raw material solution containing an organic complex in which an organic sulfur compound is coordinated to at least one of the IB group element and the III-B group element may be used. With such an organic complex, the metal element and the sulfur element are brought close to each other, so that the reactivity is increased.

In addition, an organic sulfur compound is an organic compound containing a sulfur element, and is an organic compound having a covalent bond between a carbon element and a sulfur element. As the organic sulfur compound, for example, thiol, sulfide, disulfide and the like can be used. Specific examples of organic complexes in which organic sulfur compounds are coordinated include organic complexes in which organic sulfur compounds are coordinated to group IB elements such as copper elements and silver elements, and group III-B elements such as indium elements and gallium elements An organic complex in which an organic sulfur compound is coordinated to the organic sulfur compound, or an organic sulfur compound is coordinated to both an IB group element and an III-B group element.
A single source organic complex having a group I-B element, a group III-B element, and a sulfur element in one molecule (see U.S. Pat. No. 7,341,919) can be used.

For example, when the film M is produced by applying a raw material solution, the following may be performed. First, raw materials such as the above-described organic complex are dissolved in an organic solvent such as pyridine and aniline to prepare a raw material solution. Then, this raw material solution is deposited in the form of a film on the lower electrode layer 2 by, for example, a spin coater, screen printing, dipping, spraying, a die coater or the like, and the solvent is removed by drying. By repeating this process using a raw material solution having a different composition to form a laminated film, it contains a group IB element and a group III-B element, and is more opposite to the lower electrode layer 2 than the central part in the thickness direction. The coating M containing a large amount of sulfur element on the side surface portion can be produced. FIG. 5 is a diagram illustrating a state after the film M is formed.

  In addition, before heating the film M produced using the organic complex in a first atmosphere (an atmosphere containing selenium element and sulfur element) described later, the organic components contained in the film M are changed to selenium element and sulfur element. You may heat-decompose the organic component in the film | membrane M by heating at 50-350 degreeC in the atmosphere which does not contain, for example. Thereby, it can reduce that an organic component remains in the 1st semiconductor layer 3, and can improve the photoelectric conversion efficiency of the 1st semiconductor layer 3 more.

Further, a part of the film M may be oxidized before the film M is heated in the first atmosphere. As a method for oxidizing the film M, the film M may be heated in an atmosphere containing an oxidizing gas such as water vapor or oxygen in an inert gas such as nitrogen or argon, for example, at a partial pressure ratio of about 50 to 300 ppmv. As a result, a part of the metal element of the film M exists as a relatively stable oxide, and in the subsequent heating step in the first atmosphere, the reactivity of the liquefaction rate and the crystallization rate of other metal elements. In contrast, the metal elements present as oxides exhibit different reactivities. As a result, the reaction proceeds while the microcrystals of the I-III-VI group compound are generated and the surrounding material is still surrounded by the liquefied raw material, so that the first semiconductor layer 3 having high density and high crystallinity is obtained. There is a tendency to become easily.

And the produced membrane | film | coat M is heated at 450-600 degreeC in the 1st atmosphere containing a selenium element and a sulfur element. As a result, sulfidation and selenization of the coating M proceeds, and the I-III-VI group compound is mainly contained, and more sulfur element is contained in the surface portion opposite to the lower electrode layer 2 than the central portion in the thickness direction. The first semiconductor layer 3 can be manufactured.

The first atmosphere contains a selenium element as, for example, selenium vapor or hydrogen selenide, and contains a sulfur element as, for example, sulfur vapor or hydrogen sulfide. An inert gas such as nitrogen or argon, or a reducing gas such as hydrogen may be mixed in the first atmosphere. Further, the ratio M _S / M _Se of the mole number M _S of the sulfur element to the mole number M _Se of the selenium element in the first atmosphere may be, for example, about 1 or more and 5 or less. FIG. 6 is a diagram 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. 7 is a view showing 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 by, for example, mechanical scribing using a scribe needle. FIG. 8 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 heating. FIG. 9 is a view showing 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 a mechanical scribing process 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) Second Example of Manufacturing Method of Photoelectric Conversion Device>
In the first example of the method for manufacturing a photoelectric conversion device, a selenium element may be further added to the coating M. That is, the coating M includes a group I-B element, a group III-B group element, and a selenium element, and includes a larger amount of sulfur element in the surface portion on the side opposite to the lower electrode layer 2 than the central portion in the thickness direction. Also good. By further adding selenium element to the film M, not only the selenium element in the atmosphere but also the selenium element in the film M can be used as a selenium source in the heating step of the film M in the first atmosphere. And the selenization reaction can be carried out better.

From the viewpoint of increasing the reactivity and increasing the crystallinity, the coating M is formed of an organic complex in which an organic sulfur compound is coordinated to at least one of the group IB element and the group III-B element, and the group IB. You may produce using the raw material solution containing the organic complex which the organic selenium compound coordinated to at least 1 sort (s) of an element and a III-B group element. With such an organic complex, the metal element and the sulfur element, and the metal element and the selenium element are brought close to each other, so that the reactivity is increased.

  The organic selenium compound is an organic compound containing a selenium element, and is an organic compound having a covalent bond between a carbon element and a selenium element. As the organic selenium compound, for example, selenol, selenide, diselenide and the like can be used. Specific examples of the organic complex in which an organic selenium compound is coordinated include an organic complex in which an organic selenium compound is coordinated with an IB group element such as copper element or silver element, and an organic complex in which an organic selenium compound is coordinated with an indium element An organic complex in which an organic selenium compound is coordinated to a gallium element, or an organic selenium compound is coordinated to both a group IB element and a group III-B element, and a group IB element and III in one molecule A single-source organic complex having a group B element and a selenium element (see US Pat. No. 7,341,919) or the like can be used.

  Moreover, before heating the film M produced using the organic complex in the first atmosphere (an atmosphere containing selenium element and sulfur element), the organic component contained in the film M does not contain selenium element and sulfur element. For example, the organic component in the film M may be thermally decomposed by heating at 50 to 350 ° C. in an atmosphere. Thereby, it can reduce that an organic component remains in the 1st semiconductor layer 3, and can improve the photoelectric conversion efficiency of the 1st semiconductor layer 3 more.

  Similarly to the first example, the film M may be oxidized before the film M is heated in the first atmosphere. As a result, the first semiconductor layer 3 having a high density and high crystallinity tends to be easily obtained.

  In the second example, the photoelectric conversion device 11 can be manufactured in the same manner as in the first example except that the selenium element is added to the coating M as described above.

  The present invention is not limited to the above-described embodiment, and various changes and improvements can be made without departing from the scope of the present invention. For example, in the above-described embodiment, the coating M containing sulfur element at least on the surface portion is produced using a raw material containing sulfur element. After forming a layer containing a metal element, this film is formed in an atmosphere containing sulfur element. The film M containing sulfur element at least on the surface portion may be formed by heating at

1: Substrate 2: Lower electrode layer 3: First semiconductor layer 4: Second semiconductor layer 5: Upper electrode layer 6: Connection conductor 7: Current collecting electrode 10: Photoelectric conversion cell 11: Photoelectric conversion device M: Film

Claims (8)

On the electrode layer, a step of producing a film containing a group I-B element and a group III-B element and containing a large amount of sulfur element on the surface portion opposite to the electrode layer from the central portion in the thickness direction;
A step of heating the film in a first atmosphere containing selenium element and sulfur element to form an I-III-VI group compound semiconductor layer containing selenium element and sulfur element as a VI-B group element. Manufacturing method. The manufacturing of the photoelectric conversion device according to claim 1, wherein the film is prepared using a raw material solution containing an organic complex in which an organic sulfur compound is coordinated to at least one of a group I-B element and a group III-B element. Method.   The method for manufacturing a photoelectric conversion device according to claim 2, wherein an organic component contained in the coating is removed by thermal decomposition before the coating is heated in the first atmosphere.   The method for manufacturing a photoelectric conversion device according to claim 1, wherein the film is oxidized before the film is heated in the first atmosphere. On the electrode layer, a film containing a group I-B element, a group III-B element, and a selenium element and containing a larger amount of sulfur element in the surface portion opposite to the electrode layer than the central portion in the thickness direction is prepared. Process,
A step of heating the film in a first atmosphere containing selenium element and sulfur element to form an I-III-VI group compound semiconductor layer containing selenium element and sulfur element as a VI-B group element. Manufacturing method. An organic complex in which an organic sulfur compound is coordinated to at least one of the IB group element and the III-B group element, and an organic selenium compound as at least one of the IB group element and the III-B element. The manufacturing method of the photoelectric conversion apparatus of Claim 5 produced using the raw material solution containing the organic complex which coordinated.   The method for manufacturing a photoelectric conversion device according to claim 6, wherein an organic component contained in the coating is removed by thermal decomposition before the coating is heated in the first atmosphere.   The method for manufacturing a photoelectric conversion device according to claim 5, wherein the film is oxidized before the film is heated in the first atmosphere.

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