JP2013125813A - Manufacturing method for photoelectric conversion device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the photoelectric conversion efficiency of a photoelectric conversion device.SOLUTION: A manufacturing method for a photoelectric conversion device 11 comprises: forming a plurality of lower electrode layers 2 on a substrate 1; forming a coating layer C in a part of the respective principal surfaces of the plurality of lower electrode layers 2 in a belt like shape; forming a first semiconductor layer 3 on the plurality of lower electrode layers 2 and on the substrate 1; forming a second semiconductor layer 4 on the first semiconductor layer 3; forming a groove P2 in the first semiconductor layer 3 by removing the coating layer C; forming a connection conductor 7 for electrically connecting the lower electrode layer 2 and the second semiconductor layer 4 in the groove P2; and forming a plurality of photoelectric conversion cells 10 electrically connected with each other by separating the first semiconductor layer 3 and the second semiconductor layer 4.

Description

  The present invention relates to a method for manufacturing a photoelectric conversion device in which a plurality of photoelectric conversion cells are connected.

As a photoelectric conversion device used for photovoltaic power generation or the like, there is one using a chalcopyrite-based I-III-VI group compound semiconductor such as CIGS having a high light absorption coefficient as a photoelectric conversion layer (
For example, see Patent Literature 1 and Patent Literature 2). CIGS has a high light absorption coefficient and is suitable for reducing the thickness, area, and cost of photoelectric conversion devices, and research and development of next-generation solar cells using the photoelectric conversion device is being promoted.

  Such a chalcopyrite photoelectric conversion device includes a photoelectric conversion device in which a lower electrode layer such as a metal electrode, a photoelectric conversion layer, and an upper electrode layer such as a transparent electrode and a metal electrode are stacked in this order on a substrate such as glass. It is configured by having a configuration in which a plurality of conversion cells are arranged in a plane. The plurality of photoelectric conversion cells are electrically connected in series by connecting the upper electrode layer of one adjacent photoelectric conversion cell and the other lower electrode layer with a connecting conductor.

  Some photoelectric conversion devices using other materials such as Si-based for the light absorption layer (photoelectric conversion layer) have the same configuration.

JP 2000-299486 A JP 2002-37395 A

  Such a connection conductor is produced by removing the photoelectric conversion layer formed on the lower electrode layer by a mechanical scribing method, and then providing a conductor at the removal portion. Since the loss of the current value is reduced as the electrical resistance at the connection portion between the connection conductor and the lower electrode layer is reduced, the photoelectric conversion efficiency of the photoelectric conversion device is increased.

  However, in the mechanical scribing method described above, the photoelectric conversion layer cannot be completely removed from the lower electrode layer, and the photoelectric conversion layer sometimes remains on the lower electrode layer. In such a case, the contact resistance is increased at the remaining portion, and it is difficult to increase the photoelectric conversion efficiency.

  This invention is made | formed in view of the said subject, and it aims at improving the photoelectric conversion efficiency by making the electrical connection of the connection conductor and lower electrode layer in a photoelectric conversion apparatus favorable.

A method for manufacturing a photoelectric conversion device according to an embodiment of the present invention is a method for manufacturing a photoelectric conversion device in which a plurality of photoelectric conversion cells are electrically connected to each other, and is arranged in a plane with a gap on a substrate. Forming a plurality of lower electrode layers formed, forming a coating layer in a part of a main surface of each of the plurality of lower electrode layers, forming the plurality of lower electrode layers on the plurality of lower electrode layers and the substrate Forming a first conductive type first semiconductor layer, and forming a second conductive type second semiconductor layer having a different conductivity type from the first conductive type on the first semiconductor layer. Removing the covering layer to form a groove in which the lower electrode layer is exposed in the first semiconductor layer; electrically connecting the lower electrode layer and the second semiconductor layer in the groove; Forming a connecting conductor for connecting to a plurality of parts, and a plurality of the lower parts By dividing the first semiconductor layer and the second semiconductor layer on the electrode layer, and a step of forming a plurality of said photoelectric conversion cells are electrically connected to each other.

  According to the present invention, the photoelectric conversion efficiency in the photoelectric conversion device is improved.

It is a perspective view which shows an example of embodiment of a photoelectric conversion apparatus. It is sectional drawing of the photoelectric conversion apparatus of FIG. It is sectional drawing which shows the mode in the middle of manufacture of a photoelectric conversion apparatus. It is sectional drawing which shows the mode in the middle of manufacture of a photoelectric conversion apparatus.

  Hereinafter, a method for producing a photoelectric conversion device according to an embodiment of the present invention will be described in detail with reference to the drawings.

<Configuration of photoelectric conversion device>
FIG. 1 is a perspective view illustrating an example of a photoelectric conversion device manufactured using the method for manufacturing a photoelectric conversion device according to an embodiment of the present invention, and FIG. 2 is a cross-sectional view thereof. In the photoelectric conversion device 11, a plurality of photoelectric conversion cells 10 are arranged on the substrate 1 and are electrically connected to each other. In FIG. 1, only two photoelectric conversion cells 10a and 10b are shown for convenience of illustration. However, in the actual photoelectric conversion device 11, there are many photoelectric conversion cells in the horizontal direction of the drawing or in a direction perpendicular thereto. The photoelectric conversion cells 10 may be arranged in a plane (two-dimensionally).

  1 and 2, a plurality of lower electrode layers 2 are arranged in a plane on a substrate 1. 1 and 2, the plurality of lower electrode layers 2 include lower electrode layers 2 a to 2 c that are arranged at intervals in one direction. A first semiconductor layer 3a is provided from the lower electrode layer 2a through the substrate 1 to the lower electrode layer 2b. In addition, a second semiconductor layer 4a having a conductivity type different from that of the first semiconductor layer 3a is provided on the first semiconductor layer 3a. Further, on the lower electrode layer 2b, the connection conductor 7a is provided along the surface (side surface) of the first semiconductor layer 3a or through the first semiconductor layer 3a. The connection conductor 7a electrically connects the second semiconductor layer 4a and the lower electrode layer 2b. The lower electrode layer 2a, the lower electrode layer 2b, the first semiconductor layer 3a, the second semiconductor layer 4a, and the connection conductor 7a constitute one photoelectric conversion cell 10a.

  Similarly, another photoelectric conversion cell 10b is provided adjacent to the photoelectric conversion cell 10a. That is, the first semiconductor layer 3b and the second semiconductor layer 4b are provided from the lower electrode layer 2b to the lower electrode 2c. Further, on the lower electrode 2c, a connection conductor 7b for electrically connecting the second semiconductor layer 4b and the lower electrode layer 2c is provided. The lower electrode layer 2b, the lower electrode layer 2c, the first semiconductor layer 3b, the second semiconductor layer 4b, and the connection conductor 7b constitute one photoelectric conversion cell 10b.

  The photoelectric conversion cell 10a and the photoelectric conversion cell 10b both use the lower electrode 2b. With such a configuration, the photoelectric conversion cell 10a and the photoelectric conversion cell 10b are connected in series, and the high-output photoelectric conversion device. 11

  In addition, although the photoelectric conversion apparatus 11 in this embodiment assumes what enters light from the 2nd semiconductor layer 4 side, it is not limited to this, Light enters from the board | substrate 1 side. There may be.

  The substrate 1 is for supporting the photoelectric conversion cell 10. Examples of the material used for the substrate 1 include glass, ceramics, resin, and metal. As the substrate 1, for example, blue plate glass (soda lime glass) having a thickness of about 1 to 3 mm can be used.

  The lower electrode layer 2 (lower electrode layers 2a, 2b and 2c) is a conductor such as Mo, Al, Ti or Au provided on the substrate 1. The lower electrode layer 2 is formed to a thickness of about 0.2 μm to 1 μm using a known thin film forming method such as sputtering or vapor deposition.

The first semiconductor layer 3 (first semiconductor layers 3a and 3b) is a first conductivity type semiconductor layer. The first semiconductor layer 3 has a thickness of about 1 μm to 3 μm, for example. Examples of the first semiconductor layer 3 include silicon, II-VI group compounds, I-III-VI group compounds, and I-II-IV-VI group compounds.

  The II-VI group compound is a compound semiconductor of a II-B group (also referred to as a group 12 element) and a VI-B group element (also referred to as a group 16 element). Examples of II-VI group compounds include CdTe.

The I-III-VI group compound is a compound of a group IB element (also referred to as a group 11 element), a group III-B element (also referred to as a group 13 element), and a group VI-B element. Examples of the I-III-VI group compound include CuInSe ₂ (also referred to as copper indium selenide, CIS), Cu (In, Ga) Se ₂ (also referred to as copper indium selenide / gallium, CIGS), Cu ( In, Ga) (Se, S) ₂ (also referred to as diselene / copper indium / gallium / CIGSS). Alternatively, the first semiconductor layer 3 may be composed of a multi-component compound semiconductor thin film such as copper indium selenide / gallium having a thin film of selenite / copper indium sulfide / gallium layer as a surface layer.

The I-II-IV-VI group compound is a compound of a group IB element, a group II-B element, a group IV-B element (also referred to as a group 14 element), and a group VI-B element. 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). Can be mentioned.

  The first semiconductor layer 3 can be formed by a so-called vacuum process such as a sputtering method or an evaporation method, or can be formed by a process called a coating method or a printing method. A process referred to as a coating method or a printing method is a process in which a complex solution of constituent elements of the first semiconductor layer 3 is applied onto the lower electrode layer 2 and then dried and heat-treated.

  The second semiconductor layer 4 (second semiconductor layers 4 a and 4 b) is a semiconductor layer having a second conductivity different from that of the first semiconductor layer 3. When the first semiconductor layer 3 and the second semiconductor layer 4 are electrically joined to each other, a photoelectric conversion layer from which charges can be favorably extracted is formed. For example, if the first semiconductor layer 3 is p-type, the second semiconductor layer 4 is n-type. The first semiconductor layer 3 may be n-type and the second semiconductor layer 4 may be p-type. A high-resistance buffer layer may be interposed between the first semiconductor layer 3 and the second semiconductor layer 4.

  The second semiconductor layer 4 may be formed by stacking a material different from that of the first semiconductor layer 3 on the first semiconductor layer 3, or the surface portion of the first semiconductor layer 3 may be other than the first semiconductor layer 3. It may be modified by elemental doping.

The second semiconductor layer 4 includes CdS, ZnS, ZnO, In ₂ S ₃ , In ₂ Se ₃ , In (OH, S), (Zn, In) (Se, OH), and (Zn, Mg) O. Etc. In this case, the second semiconductor layer 4 is formed with a thickness of 10 to 200 nm by, for example, a chemical bath deposition (CBD) method. In (OH, S) refers to a compound mainly containing In, OH, and S. (Zn, In) (Se, OH) refers to a compound mainly containing Zn, In, Se, and OH. (Zn, Mg) O refers to a compound mainly containing Zn, Mg and O.

  As shown in FIGS. 1 and 2, an upper electrode layer 5 may be further provided on the second semiconductor layer 4. The upper electrode layer 5 is a layer having a lower resistivity than the second semiconductor layer 4, and it is possible to take out charges generated in the first semiconductor layer 3 and the second semiconductor layer 4 satisfactorily. From the viewpoint of further increasing the photoelectric conversion efficiency, the resistivity of the upper electrode layer 5 may be less than 1 Ω · cm and the sheet resistance may be 50 Ω / □ or less.

  The upper electrode layer 5 is a 0.05 to 3 μm transparent conductive film such as ITO or ZnO. In order to improve translucency and conductivity, the upper electrode layer 5 may be composed of a semiconductor having the same conductivity type as the second semiconductor layer 4. The upper electrode layer 5 can be formed by sputtering, vapor deposition, chemical vapor deposition (CVD), or the like.

  Further, as shown in FIGS. 1 and 2, a collecting electrode 8 may be further formed on the upper electrode layer 5. The current collecting electrode 8 is for taking out charges generated in the first semiconductor layer 3 and the second semiconductor layer 4 more satisfactorily. For example, as shown in FIG. 1, the collector electrode 8 is formed in a linear shape from one end of the photoelectric conversion cell 10 to the connection conductor 7. As a result, the current generated in the first semiconductor layer 3 and the fourth semiconductor layer 4 is collected to the current collecting electrode 8 via the upper electrode layer 5, and to the adjacent photoelectric conversion cell 10 via the connection conductor 7. Good conductivity.

  The collector electrode 8 may have a width of 50 to 400 μm from the viewpoint of increasing the light transmittance to the first semiconductor layer 3 and having good conductivity. The current collecting electrode 8 may have a plurality of branched portions.

  The collector electrode 8 is formed, for example, by printing a metal paste in which a metal powder such as Ag is dispersed in a resin binder or the like in a pattern and curing it.

  1 and 2, the connection conductor 7 (connection conductors 7 a and 7 b) is a conductor provided in a groove that penetrates the first semiconductor layer 3, the second semiconductor layer 4, and the second electrode layer 5. is there. The connection conductor 7 can be made of metal, conductive paste, or the like. In FIG. 1 and FIG. 2, the collector electrode 8 is extended to form the connection conductor 7, but this is not limitative. For example, the upper electrode layer 5 may be stretched.

<Method for Manufacturing Photoelectric Conversion Device>
Next, a manufacturing process of the photoelectric conversion device 11 will be described. FIGS. 3A to 3D and FIGS. 4E to 4F are cross-sectional views illustrating a state during the manufacture of the photoelectric conversion device 11. The cross-sectional views shown in FIGS. 3 and 4 show a state in the middle of manufacturing a portion corresponding to the cross-section shown in FIG.

First, as shown in FIG. 3A, 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 P <b> 1 is formed in a part of the lower electrode layer 2. The first groove portion P1 may be formed by laser scribe processing in which groove processing is performed by irradiating a formation target position while scanning with a YAG laser or other laser light. FIG. 3A is a diagram illustrating a state after the first groove portion P1 is formed.

  After the first groove portion P1 is formed, the first groove portion P1 is located at a position where the connection conductor 7 on the lower electrode layer 2 is formed, that is, at a position slightly shifted from the first groove portion P1 on the lower electrode layer 2. A band-shaped covering portion C along the line is formed. For the covering portion C, an organic material, an inorganic material, or a mixture thereof can be used. In the step of forming the first semiconductor layer 3, the temperature is raised to a high crystallization temperature (for example, 500 to 600 ° C.), so that the covering layer C is made of a heat resistant material that can withstand such a temperature. Used. As such a heat-resistant material, for example, an organic material having a thermal decomposition temperature of 500 ° C. or higher, such as polyimide or silicone resin, can be used. Moreover, if it is an inorganic material, what cannot be sintered easily at the crystallization temperature when the 1st semiconductor layer 3 is formed may be used. Examples of such inorganic materials include alumina, silica, titania and the like.

  The covering layer C is formed by pasting the organic material or the inorganic material into a desired pattern on the lower electrode layer 2 by screen printing or the like, for example, using a binder such as acrylic resin or a solvent such as alcohol. It is formed by printing. FIG. 3B is a diagram illustrating a state after the coating layer C is formed.

  After the coating layer C is formed, the precursor layer 3PR that becomes the first semiconductor layer 3 is formed on the substrate other than the coating layer C on the lower electrode layer 2 and the substrate in the first groove P1, by sputtering or coating. It is formed by law. The precursor layer 3PR may be a layer containing a raw material of a compound constituting the first semiconductor layer 3, or a layer containing fine particles of a compound constituting the first semiconductor layer 3. For example, when the first semiconductor layer 3 is CIGS, the coating layer contains Cu element, In element, and Ga element as a simple substance or a compound. FIG. 3C is a diagram showing a state after the precursor layer 3PR is formed.

  After the precursor layer 3PR is formed, the precursor layer 3PR is heated to, for example, 500 to 600 ° C. and crystallized to become the first semiconductor layer 3. In addition, in the heating of the precursor layer 3PR, an element included in the compound constituting the first semiconductor layer 3 may be included in the atmosphere. FIG. 3D shows a state after the first semiconductor layer 3 is formed.

  After the first semiconductor layer 3 is formed, the second semiconductor layer 4 and the upper electrode layer 5 are sequentially formed on the first semiconductor layer 3 by a CBD method, a sputtering method, or the like. FIG. 4E is a diagram showing a state after the second semiconductor layer 4 and the upper electrode layer 5 are formed.

  After the second semiconductor layer 4 and the upper electrode layer 5 are formed, the coating layer C is removed by etching, peeling, laser scribe processing, mechanical scribe processing, blast processing, or the like, and the lower electrode is formed in the first semiconductor layer 3. A second groove portion P2 where the layer 2 is exposed is formed. FIG. 4F shows a state after the second groove portion P2 is formed. The mechanical scribe process refers to a process in which the coating layer C is removed from the lower electrode layer 2 by, for example, scribing using a scribe needle or drill having a scribe width of about 40 μm to 50 μm. Blasting is processing in which the coating layer C is removed from the lower electrode layer 2 by hitting water, inorganic particles, or organic particles.

  Since the coating layer C includes an organic material or a non-sintered inorganic material, the coating layer C has a low strength and can be removed very easily. When the crystallized first semiconductor layer 3 is removed by mechanical scribing as in the prior art, the first semiconductor layer 3 remains on the lower electrode layer 2 so that the connection conductor 7 and the lower electrode layer 2 Although there was a tendency that the electrical resistance in the connection portion was increased, the electrical connection between the connection conductor 7 and the lower electrode layer 2 is improved by using the manufacturing method using the coating layer C as described above. . As a result, the photoelectric conversion efficiency of the photoelectric conversion device 11 is improved.

  From the viewpoint of satisfactorily removing the coating layer C, the coating layer C includes a plurality of inorganic particles, and these inorganic particles are difficult to sinter at the crystallization temperature of the first semiconductor layer 3. There may be. In this case, the coating layer C is easily peeled off from the lower electrode layer 2.

  Further, the coating layer C may include a conductive material. In this case, even when the covering layer C remains on the lower electrode layer 2 when the covering layer C is removed, the resistance is unlikely to increase because it contains a conductive material. As such a coating layer C, for example, a layer containing metal particles such as gold, silver, platinum, palladium, copper, or a layer containing semiconductor particles such as titania can be used.

  After the second groove P2 is formed, a conductive paste in which a metal powder such as Ag is dispersed in a resin binder, for example, is printed in a pattern on the upper electrode layer 5 and in the second groove P2, and this is heated. Curing electrode 8 and connecting conductor 7 are formed by curing. FIG. 4G is a diagram showing a state after the collecting electrode 8 and the connecting conductor 7 are formed.

  Finally, the first semiconductor layer 3 to the current collecting electrode 8 are removed by mechanical scribing at a position shifted from the second groove P2, and are divided into a plurality of photoelectric conversion cells, which are shown in FIG. 1 and FIG. Thus, the photoelectric conversion device 11 is obtained.

<Modification of Method for Manufacturing Photoelectric Conversion Device>
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, when the first semiconductor layer 3 is a chalcopyrite compound such as CIGS, an alkali metal element may be included in the coating layer C. Since the chalcopyrite compound is crystallized at the time of crystallization due to the presence of the alkali metal element, the alkali metal element is provided from the coating layer C, so that the first semiconductor particularly in the vicinity of the second groove portion P2. The crystallization of the layer 3 is easily promoted. As a result, peeling of the first semiconductor layer 3 in the vicinity of the second groove portion P2 is effectively reduced.

The alkali metal element may be added to the coating layer C in the state of a compound such as an alkali metal salt such as NaClO ₄ or KClO ₄ .

  Further, when the first semiconductor layer 3 is a metal chalcogenide such as CIGS, CZTS, CdTe, or the like, a chalcogen element may be included in the coating layer C. The chalcogen element is S, Se, or Te among VI-B group elements (also referred to as group 16 elements). Thereby, the chalcogen element is provided from the coating layer C, and the crystallization of the first semiconductor layer 3 is easily promoted in the vicinity of the second groove portion P2. As a result, peeling of the first semiconductor layer 3 in the vicinity of the second groove portion P2 is effectively reduced.

  The chalcogen element may be added to the coating layer C in the state of a chalcogen element-containing organic compound such as phenyl selenol or thiophenol.

  In the above embodiment, the coating layer C is removed after the second semiconductor layer 4 and the upper electrode layer 5 are formed. However, after the coating layer C is removed first, the second semiconductor layer 4 is removed. And the upper electrode layer 5 may be formed. Alternatively, the connection conductor 7 may be formed after the covering layer C is removed, and then the second semiconductor layer 4 and the upper electrode layer 5 may be formed.

1: substrate 2, 2a, 2b: lower electrode layer 3, 3a, 3b: first semiconductor layer 4, 4a, 4b: second semiconductor layer 7, 7a, 7b: connection conductor 10, 10a, 10b: photoelectric conversion Cell 11: Photoelectric conversion device C: Coating layer

Claims (5)

A method for manufacturing a photoelectric conversion device in which a plurality of photoelectric conversion cells are electrically connected to each other,
Forming a plurality of lower electrode layers arranged in a plane with a gap on the substrate;
Forming a coating layer in a part of a main surface of each of the plurality of lower electrode layers,
Forming a first conductive type first semiconductor layer on the plurality of lower electrode layers and the substrate;
Forming a second semiconductor layer of a second conductivity type having a conductivity type different from the first conductivity type on the first semiconductor layer;
Removing the covering layer to form a groove in which the lower electrode layer is exposed in the first semiconductor layer;
Forming a connection conductor for electrically connecting the lower electrode layer and the second semiconductor layer in the groove,
Forming the plurality of photoelectric conversion cells electrically connected to each other by dividing the first semiconductor layer and the second semiconductor layer on the plurality of lower electrode layers. A method for manufacturing a photoelectric conversion device.   A material containing a plurality of inorganic particles is used as the coating layer, and the temperature of the coating layer in the step of forming the first semiconductor layer is maintained at a temperature lower than the sintering temperature of the inorganic particles. The manufacturing method of the photoelectric conversion apparatus of Claim 1.   The method for manufacturing a photoelectric conversion device according to claim 1, wherein the coating layer includes a conductive material.   4. The method for manufacturing a photoelectric conversion device according to claim 1, wherein a chalcopyrite compound is used for the first semiconductor layer, and an alkali metal element is included in the coating layer. 5. 5. The method of manufacturing a photoelectric conversion device according to claim 1, wherein a metal chalcogenide is used for the first semiconductor layer, and a chalcogen element is included in the coating layer.

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