JP2015065286A - Method of manufacturing photoelectric conversion device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a highly efficient photoelectric conversion device by an easy method using an optical complex.SOLUTION: A method of manufacturing a photoelectric conversion device 11 comprises the steps of: preparing a raw material solution obtained by dissolving in an organic solvent a single source complex which contains a group 11 element, a group 13 element, an organic sulfur compound, and an organic selenium compound in one complex molecule; applying the raw material solution onto an electrode layer 2 to form a film M; and heating the film M in a first atmosphere containing a sulfur element, thereby making the film M into a group I-III-VI compound layer 3 containing as group 16 elements a selenium element and a sulfur element.

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 a chalcopyrite structure I-III-VI group compound such as CuInSe ₂ (referred to as CIS) or Cu (In, Ga) Se ₂ (referred to as CIGS) is used. There is a light absorption layer in which a buffer layer such as a II-VI group compound is formed on the light absorption layer. The light absorption layer is produced by forming a precursor layer made of a metal using a vacuum film forming apparatus such as a sputtering method and then heating it in an atmosphere containing selenium element to form selenium.

Such a photoelectric conversion device is required to further improve the photoelectric conversion efficiency. For example, in Patent Document 1, a surface layer made of Cu (In, Ga) (Se, S) ₂ (referred to as CIGSS) having a thickness of about 150 nm is provided on the surface of a light absorption layer made of CIGS, and sulfur in the surface layer is formed. It has been proposed to provide a concentration gradient so that the element concentration decreases from the surface on the buffer layer side toward the inside of the light absorption layer. With such a configuration, the interface bonding property between the light absorption layer and the buffer layer can be improved, and the photoelectric conversion efficiency can be improved.

  In this patent document 1, in order to provide the said surface layer on the surface of a light absorption layer, after forming a CIGS layer, this CIGS layer is heated in the atmosphere containing a sulfur element, The selenium element of the surface of a CIGS layer Is used to replace sulfur with elemental sulfur.

In addition, further cost reduction is desired for the photoelectric conversion device, and a method for easily manufacturing a semiconductor layer containing an I-III-VI group compound has been studied. In Patent Document 2, it is proposed to use a complex called Single Source Precursor in which Cu and In or Ga and an organic selenium compound are present in one complex molecule. A semiconductor layer using such a complex can be prepared by dissolving a complex in a solvent to prepare a raw material solution, applying the raw material solution, and heating it. There is no need to use a film device, and a semiconductor layer made of CIS or CIGS can be easily manufactured.

  Therefore, it is considered that a highly efficient photoelectric conversion device can be manufactured by an easy method by combining Patent Document 1 and Patent Document 2.

JP-A-10-135498 US Pat. No. 6,992,202

  However, even if a CIGS layer is formed using the complex as described above and heated in an atmosphere containing a sulfur element as in Patent Document 1, a heterogeneous phase different from the chalcopyrite structure is easily formed, and photoelectric conversion is performed. It is difficult to improve efficiency.

  The present invention has been made in view of the above problems, and an object thereof is to produce a highly efficient photoelectric conversion device by an easy method using a complex.

  A method for manufacturing a photoelectric conversion device according to one embodiment of the present invention is a raw material solution in which a single source complex containing a group 11 element, a group 13 element, an organic sulfur compound, and an organic selenium compound in one complex molecule is dissolved in an organic solvent. Preparing a film by applying the raw material solution on the electrode layer, and heating the film in a first atmosphere containing sulfur element to contain selenium element and sulfur element as a group 16 element And a step of forming a group I-III-VI compound layer.

  According to the above embodiment of the present invention, a highly efficient photoelectric conversion device can be manufactured by an easy method.

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 a graph which shows an example of concentration distribution of the 16th group element of the 1st semiconductor layer. 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 layer 3 (hereinafter, the I-III-VI group compound layer is also referred to as a first semiconductor layer), a second semiconductor layer. 4, the upper electrode layer 5 and the current 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, 1 to 3 mm
Blue plate glass (soda lime glass) having a certain thickness 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 containing a chalcopyrite-based I-III-VI group compound. The I-III-VI group compounds are 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 group 16 element (also referred to as a VI-B group element). It is a compound containing. The first semiconductor layer 3 contains at least a selenium (Se) element and a sulfur (S) element as group 16 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.

The first semiconductor layer 3 has a total number of atoms (M _S + M _Se ) of the number of atoms _S of the element _S and the number of atoms of the element M _Se on the surface 3 a opposite to the lower electrode layer 2. The relative atomic ratio M _S / (M _S + M _Se ) of the S element with respect to increases as the distance from the lower electrode layer 2 increases. With such a configuration, the band gap can be increased in the surface portion 3a of the first semiconductor layer 3 that makes a pn junction with the second semiconductor layer 4, so that the pn junction is improved and the interface recombination is suppressed. And the open circuit voltage can be increased. As a result, the photoelectric conversion efficiency of the photoelectric conversion device 11 can be increased.

  The composition distribution in the thickness direction of the first semiconductor layer 3 is expressed, for example, as shown in FIG. The composition distribution in the thickness direction of the first semiconductor layer 3 can be measured by various elemental analysis methods. For example, for the S element and the Se element, elemental analysis is performed by X-ray electron spectroscopy (XPS) while the first semiconductor layer 3 is shaved in the thickness direction by sputtering or the like, or a cross section of the first semiconductor layer 3 is obtained. Can be measured by elemental analysis by energy dispersive X-ray analysis (EDS) using a transmission electron microscope (TEM).

The concentration distribution of the S element and the Se element in the first semiconductor layer 3 is such that when the first semiconductor layer 3 is equally divided into three in the thickness direction, the relative atomic number ratio M _S / (M _S + M _Se ) in the center portion. The average value of the relative atomic number ratio M _S / (M _S + M _Se ) in the surface portion on the second semiconductor layer 4 side is 0.02 to 0.8, than further average value of the relative atomic ratio _{M S / (M S + M} Se) the average value of the relative number of atomic ratio _{M S / (M S + M} Se) is in the central portion in the surface portion of the second semiconductor layer 4 side It may be larger than 0.02.

  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, 5 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 transmissive property) 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 connecting conductor 6 is shown in FIG.
As shown in FIG. 4, the current collecting electrode 7 is constituted by an extending portion in the Y-axis direction. 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>
4 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. 4 to 9 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, 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 P1, a raw material solution is applied on the lower electrode layer 2 to produce a film M. The raw material solution is obtained by dissolving a single source complex containing a group 11 element, a group 13 element, an organic sulfur compound, and an organic selenium compound in one complex molecule in an organic solvent. The single source complex contained in the raw material solution is, for example, a complex molecule represented by Structural Formula 1.

In Formula 1, ^{M 1} represents a Group 11 element, ^{M 2} represents a Group 13 element. R ¹ to R ⁴ each represent an organic group, may be a structure in which each of R ¹ to R ⁴ are different, two or more (or a whole) may be the same structure. Two or more of R ^{1 to} R ⁴ may be linked to form a saturated or unsaturated ring. Examples of R ^{1 to} R ⁴ include an alkyl group and an aryl group, and these may be substituted with an arbitrary substituent. Specific examples of R ^{1 to} R ⁴ include, for example, a methyl group, an ethyl group, a propyl group, and a phenyl group. Moreover, ^{1 to 3} of X ^{1 to} X ⁴ represent S element and the rest represents Se element. That is, R ¹ -X ¹ , R ² -X ² , R ³ -X ³ and R ⁴ -X ⁴ each represent an organic sulfur compound or an organic selenium compound. The organic sulfur compound is an organic compound containing an S element such as thiols, and is an organic compound having a covalent bond between a carbon (C) element and an S element. The organic selenium compound is an organic compound containing Se element such as selenols,
It is an organic compound having a covalent bond between C element and Se element. L ^{1 and} L ² are ligands each having an unshared electron pair and function as a Lewis base. L ^{1 to} L ² are those having higher coordinating power than the organic sulfur compounds and organic selenium compounds represented by R ^{1 to} X ^{1 to} R ^{4 to} X ⁴ , for example, V 1 having an unshared electron pair. An organic compound having a functional group including a group B element (also referred to as a group 15 element) or a functional group including a group VI-B element having an unshared electron pair is used. Further, L ^{1 to} L ² may have different structures or the same structure. Examples of L ^{1 to} L ² include P (Ph) ₃ and P (C ₄ H ₉ ) ₃ (Ph is a phenyl group). L ^{1 to} L ² may be linked to form a saturated or unsaturated ring.

  For example, the single source complex contained in the raw material solution used when producing the film M includes a first single source complex containing copper (Cu) as a group 11 element and indium (In) as a group 13 element; A mixture with a second single source complex containing Cu as the Group 11 element and gallium (Ga) as the Group 13 element may be used. In this case, the first semiconductor layer 3 to be generated becomes an I-III-VI group compound layer containing Cu, In, and Ga, and photoelectric conversion with respect to sunlight can be performed more satisfactorily.

  An example of such a first single source complex is shown in Structural Formula 2, and an example of the second single source complex is shown in Structural Formula 3.

  The organic solvent contained in the raw material solution is not particularly limited as long as it can dissolve the single source complex. For example, a polar organic solvent or the like can be used. Specific examples of the polar organic solvent include nitrogen-containing organic solvents having unshared electron pairs such as pyridine and aniline.

The film M can be produced by depositing the above raw material solution on the lower electrode layer 2 by, for example, a spin coater, screen printing, dipping, spraying, a die coater or the like, and removing the solvent by drying. You may repeat this process and may form the membrane | film | coat M thickly. FIG. 5 is a diagram illustrating a state after the film M is formed.

Next, this film M is heated in a first atmosphere containing S element, so that Se element and S element are included as group 16 elements, and relative surface ratio 3a on the side opposite to lower electrode layer 2 has a relative atomic ratio. M _S / (M _S + M _Se ) increases as the distance from the lower electrode layer 2 increases.
The -VI group compound layer (first semiconductor layer 3) can be produced satisfactorily. That is, by producing the film M using the above-mentioned single source complex, it is possible to satisfactorily incorporate the S element in the first atmosphere into the surface of the film M and perform crystallization well. As a result, it is possible to effectively suppress the occurrence of a heterogeneous phase other than the chalcopyrite structure, and to produce a good first semiconductor layer 3 having a concentration gradient of S element on the surface portion 3a. This is because when the single-source complex contains both the S element and the Se element, a mixed crystal of a metal sulfide and a metal selenide is easily formed by heating the coating M, and the first crystal is the first to the mixed crystal. It is considered that the S element in the atmosphere is likely to react well. Thus, the photoelectric conversion efficiency of the photoelectric conversion device 11 can be improved satisfactorily by using the first semiconductor layer 3 having a concentration gradient of S element at the surface portion 3a and having few different phases. In addition, the heating temperature of the film | membrane M in a 1st atmosphere can be 400-650 degreeC, for example. FIG. 6 is a diagram showing a state after the first semiconductor layer 3 is formed.

The first atmosphere contains S element in a state of sulfur vapor, hydrogen sulfide, or the like. The first atmosphere may contain an S element in a non-oxidizing gas in order to easily control the sulfurization reaction of the coating M. The non-oxidizing gas refers to an inert gas such as nitrogen or argon or a reducing gas such as hydrogen. In particular, from the viewpoint of easily decomposing and removing the organic components in the film M, the first atmosphere containing an S element in hydrogen gas may be used. The amount of the S element contained in the non-oxidizing gas is such that the number of moles of sulfur atoms is, for example, 10 ⁻⁶ times to 5 × 10 5 ⁻² times, more preferably 10 ⁻⁵ times to 5 × 10 ⁻³ times G. If it is such a range, while being able to take in S element well in the membrane | film | coat M, it can reduce effectively that the sulfurization of the membrane | film | coat M advances excessively and a heterogeneous phase arises.

  Further, when the coating M is heated in the first atmosphere, the concentration of the S element in the first atmosphere may be increased with the heating time. As a result, the organic component remaining in the film M can be decomposed and removed more satisfactorily before the sulfidation of the film M proceeds in a state where there is little S element or no S element at the start of heating. As a result, a good first semiconductor layer 3 with few impurities can be obtained.

  Moreover, before heating the film M in the first atmosphere, the organic components contained in the single source complex of the film M may be removed by thermal decomposition. By performing such steps, the first semiconductor layer 3 can be crystallized better, and the first semiconductor layer 3 with fewer defects can be manufactured. In addition, as a removal method of the organic component of the film | membrane M, the film | membrane M should just be heated at 100-350 degreeC in inert gas, for example.

  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) Method for producing single source complex>
An example of a method for producing the single source complex is shown below. First, copper (I) chloride (8 mmol, 0.
795 g) and triphenylphosphine (16 mmol, 4.197 g) in toluene 100
Into this solution, anhydrous indium chloride (8 mmol, 1.770 g) or anhydrous gallium chloride (8 mmol, 1.409 g) dissolved in 20 ml of methanol is mixed. The mixture is stirred while being heated at 50 ° C. for 2 hours.

  Further, sodium methoxide (32 mmol, 1.764 g), thiophenol (16 mmol, 1.765 g), and benzeneselenol (16 mmol, 2.533 g) are dissolved in 20 ml of methanol and heated to 60 ° C. in advance. The solution was added to the above mixture. The mixture is stirred while heating at 60 ° C. for 3 hours. Then, methanol is evaporated and removed by setting the heating temperature to 100 ° C. The remaining solution is filtered while hot to remove impurities. When the filtrate is allowed to stand at room temperature, the target product is precipitated. By filtering this, the compound for forming a semiconductor of the structural formula (2) or the structural formula (3) can be obtained.

  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 example of the manufacturing method of the photoelectric conversion device described above, the first semiconductor layer 3 is manufactured by heating the film M in the first atmosphere containing the S element, but the film M is heated in the first atmosphere. After that, the film M may be heated in an atmosphere containing Se element, or the film M may be heated in an atmosphere containing Se element before the film M is heated in the first atmosphere. Alternatively, Se element may be included in the first atmosphere.

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 (5)

Preparing a raw material solution in which a single source complex containing a group 11 element, a group 13 element, an organic sulfur compound and an organic selenium compound in one complex molecule is dissolved in an organic solvent;
Applying the raw material solution on the electrode layer to produce a film;
And heating the film in a first atmosphere containing a sulfur element to form a I-III-VI group compound layer containing a selenium element and a sulfur element as a group 16 element.   The method for manufacturing a light conversion device according to claim 1, wherein the concentration of the elemental sulfur in the first atmosphere is increased with heating time.   The method for manufacturing a photoelectric conversion device according to claim 1, wherein hydrogen is contained in the first atmosphere.   The method for manufacturing a photoelectric conversion device according to claim 1, wherein an organic component contained in the single source complex is removed by thermal decomposition before the film is heated in the first atmosphere.   The single source complex includes copper as the group 11 element and indium as the group 13 element, and copper as the group 11 element and gallium as the group 13 element. The manufacturing method of the photoelectric conversion apparatus in any one of Claims 1 thru | or 4 using a mixture with 2 single source complexes.

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