JP5997021B2 - Photoelectric conversion device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a photoelectric conversion device and a manufacturing method thereof.

  There is a photoelectric conversion device including a light absorption layer made of a compound semiconductor or the like. In this photoelectric conversion device, for example, a plurality of photoelectric conversion cells are arranged side by side in a plane. In each photoelectric conversion cell, on a substrate such as glass, a lower electrode mainly composed of a metal electrode, a photoelectric conversion layer composed of a semiconductor layer mainly including a light absorption layer and a buffer layer, and mainly a transparent electrode and a metal An upper electrode made of an electrode or the like is laminated in this order. In addition, the plurality of photoelectric conversion cells are electrically connected in series by electrically connecting the upper electrode of one adjacent photoelectric conversion cell and the lower electrode of the other photoelectric conversion cell by a connecting conductor. Yes. Thereby, a practical voltage can be acquired.

  Such a photoelectric conversion device is manufactured as follows. First, a plurality of lower electrodes separated into strips by the first groove are formed on the substrate. Next, the 2nd groove part which divides | segments the photoelectric converting layer formed on it along a 1st groove part is formed. Next, an upper electrode is formed on the photoelectric conversion layer, and a connection conductor is formed in the second groove portion by a portion where the upper electrode extends. Further, a photoelectric conversion layer and an upper electrode, which are sequentially stacked on the plurality of lower electrodes, are formed with a third groove that divides the second electrode along the second groove. Thereby, the photoelectric conversion apparatus which can isolate | separate one photoelectric conversion cell and the other photoelectric conversion cell which adjoin by the 3rd groove part is manufactured (for example, refer patent document 1).

Japanese Patent Laid-Open No. 10-200142

  In the above-described method, a groove is formed to provide a gap in a part of the lower electrode by a laser scribing method or the like. In this case, the groove is easily formed in a tapered shape toward the substrate. In some cases, the adhesion between the light-absorbing layer and the light-absorbing layer deteriorates, and the reliability of photoelectric conversion efficiency decreases.

A photoelectric conversion device according to an aspect of the present invention includes a lower electrode formed by forming a first lower electrode and a second lower electrode on a substrate with a space therebetween, and the first lower electrode and the substrate from above the first lower electrode. A photoelectric conversion device having a photoelectric conversion layer formed on the second lower electrode and a transparent electrode formed on the photoelectric conversion layer , when viewed in a cross section across the interval and perpendicular to the upper surface of the substrate In addition, each end of the first lower electrode and the second lower electrode in the interval is curved such that one end is concave and the other end is convex.

Further, a method for manufacturing a photoelectric conversion device according to one embodiment of the present invention includes a lower electrode formation step in which columnar crystal grains are arranged in a thickness direction by epitaxially growing a lower electrode on a substrate using a sputtering method. Removing a part of the lower electrode by spraying a pressurized liquid to form a gap, and forming a photoelectric conversion layer on the lower electrode and the substrate arranged with the gap A photoelectric conversion layer forming step and a transparent electrode forming step of forming a transparent electrode on the photoelectric conversion layer, wherein the lower electrode forming step is parallel to the upper surface of the substrate. in the first direction, such is the lower electrode while changing the incident angle of the sputtered particles with respect to the substrate from an acute angle to an obtuse angle in the step of epitaxially growing

  According to the photoelectric conversion device and the manufacturing method thereof according to one aspect of the present invention, one end of each end of the first lower electrode and the second lower electrode in the interval between the first lower electrode and the second lower electrode is Due to the convex shape and the other end being curved in a concave shape, the adhesion between the lower electrode and the light absorption layer at the end of the first lower electrode and the second lower electrode can be improved by the anchor effect.

  Moreover, even if a crack occurs in the light absorption layer, it is possible to reduce the propagation of the crack between the first lower electrode side and the second lower electrode side.

It is a top view which shows typically the structure of the photoelectric conversion apparatus which concerns on one Embodiment. It is a figure which shows the XZ cross section in the position shown with the dashed-dotted line II-II in FIG. It is a flowchart which shows the manufacturing flow of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus, (b) is an enlarged view in P1 vicinity. (A) is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus, (b) is an enlarged view in P1 vicinity. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows the outline of a blasting apparatus typically. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows the XZ cross section in the position shown with the dashed-dotted line XI-XI in FIG. It is a figure which shows typically the state in the middle of manufacture of the photoelectric conversion apparatus of a reference example. It is a figure which shows typically the state in the middle of manufacture of the photoelectric conversion apparatus of a reference example. (A) is a photograph substitute figure in a convex edge part, (b) is a photograph substitute figure in a concave edge part.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In the drawings, parts having the same configuration and function 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, 2, and 4 to 13 are provided with a right-handed XYZ coordinate system in which the arrangement direction of photoelectric conversion cells 10 (the right direction in the drawing in FIG. 1) is the + X direction.

<Schematic configuration of photoelectric conversion device>
As shown in FIG. 1 and FIG. 2, a photoelectric conversion device 100 according to an embodiment includes a substrate 1 and a plurality of photoelectric conversion cells 10 arranged in a plane on the substrate 1. Adjacent photoelectric conversion cells 10 are separated by a groove P3. In FIG. 1 and FIG. 2, only a part of the two photoelectric conversion cells 10 is shown for convenience of illustration.

In the photoelectric conversion apparatus 100, a predetermined number of photoelectric conversion cells 10 can be arranged in a plane in the left-right direction of the drawing. Here, the predetermined number may be eight, for example. For example, electrodes for outputting voltage and current generated by power generation may be arranged at both ends in the ± X direction of the photoelectric conversion device 100. In the photoelectric conversion device 100, for example, a large number of photoelectric conversion cells 10 may be arranged in a matrix.

  In the photoelectric conversion apparatus 100, if a large number of photoelectric conversion cells 10 are arranged on a plane with high density, conversion efficiency is improved. The conversion efficiency indicates a rate at which sunlight energy is converted into electric energy in the photoelectric conversion device 100. For example, the conversion efficiency can be derived by dividing the value of the electric energy output from the photoelectric conversion device 100 by the value of the energy of sunlight incident on the photoelectric conversion device 100 and multiplying by 100.

  By the way, the some photoelectric conversion cell 10 contains the 1st photoelectric conversion cell 10a and the 2nd photoelectric conversion cell 10b which were distribute | arranged in order in + X direction as a 1st direction. Here, the connection part 5 that electrically connects the first photoelectric conversion cell 10a and the second photoelectric conversion cell 10b in series is a second groove part (hereinafter referred to as a groove part) as a gap part located in the first photoelectric conversion cell 10a. P2). A third groove (hereinafter referred to as a groove P3) is disposed on the lower electrode 2 to which the connecting part 5 is connected.

<Basic configuration of photoelectric conversion cell>
Each photoelectric conversion cell 10 includes a stacked portion 34 in which the lower electrode 2, the photoelectric conversion layer 3, and the light receiving surface side electrode portion 4 are sequentially stacked on the substrate 1. Each photoelectric conversion cell 10 is provided with a first groove (hereinafter referred to as a groove P1) and a groove P2. And in each photoelectric conversion cell 10, the main surface by which the light-receiving surface side electrode part 4 is arrange | positioned becomes a light-receiving surface.

  The substrate 1 supports a plurality of photoelectric conversion cells 10. As main materials included in the substrate 1, for example, glass, ceramics, resin, metal, and the like can be employed. In the present embodiment, the substrate 1 is soda lime glass. Moreover, the thickness of the board | substrate 1 should just be about 1 mm or more and 3 mm or less, for example. Furthermore, for example, the shape of the substrate 1 may be a flat plate shape.

  The lower electrode 2 is a conductive layer disposed on one main surface (also referred to as an upper surface) of the + Z side of the substrate 1. As main materials contained in the lower electrode 2, for example, various metals having conductivity such as Mo, Al, Ti, Ta, and Au can be adopted. Moreover, the thickness of the lower electrode 2 should just be about 0.2 micrometer or more and 1 micrometer or less, for example. The lower electrode 2 can be formed by, for example, a sputtering method.

  The photoelectric conversion layer 3 is disposed on the lower electrode 2. The photoelectric conversion layer 3 includes a first semiconductor layer 31 and a second semiconductor layer 32. The first semiconductor layer 31 and the second semiconductor layer 32 are stacked on the lower electrode 2 in this order.

The first semiconductor layer 31 is disposed on one main surface (also referred to as an upper surface) of the + Z side of the lower electrode 2. The first semiconductor layer 31 mainly includes a semiconductor having the first conductivity type, and absorbs light to generate a charge. Here, as the semiconductor having the first conductivity type, for example, a I-III-VI group compound semiconductor which is a chalcopyrite compound semiconductor can be applied. The first conductivity type may be a p-type conductivity, for example.

The I-III-VI group compound semiconductor is a semiconductor mainly containing an I-III-VI group compound. Note that the semiconductor mainly containing the I-III-VI group compound means that the semiconductor contains 70 mol% or more of the I-III-VI group compound. Also in the following description, “mainly included” means “70 mol% or more included”. I-III-VI group compounds mainly consist of group IB elements (also referred to as group 11 elements), group III-B elements (also referred to as group 13 elements), and group VI-B elements (also referred to as group 16 elements). It is a compound contained in.

Examples of the I-III-VI group compound include Cu (In, Ga) Se ₂ (also referred to as CIGS), Cu (In, Ga) (Se, S) ₂ (also referred to as CIGSS), and CuInSe ₂ (also referred to as CIS). Say) can be employed. Cu (In, Ga) Se ₂ is a compound mainly containing Cu, In, Ga, and Se. Cu (In, Ga) (Se, S) ₂ is a compound mainly containing Cu, In, Ga, Se, and S. Here, the first semiconductor layer 31 mainly contains CIGS.

In addition, if the 1st semiconductor layer 31 mainly contains the I-III-VI group compound semiconductor, even if the thickness of the 1st semiconductor layer 31 is 10 micrometers or less, the photoelectric conversion efficiency by the 1st semiconductor layer 31 Can be enhanced. For this reason, the thickness of the 1st semiconductor layer 31 should just be about 1 micrometer or more and about 3 micrometers or less, for example.

  The first semiconductor layer 31 can be formed by a vacuum process such as a sputtering method or an evaporation method. The first semiconductor layer 31 can also be formed by a process called a coating method or a printing method. In the application method or the printing method, for example, a solution containing a metal element mainly contained in the first semiconductor layer 31 is applied on the lower electrode 2, and then drying and heat treatment are performed.

  The second semiconductor layer 32 is disposed on one main surface (also referred to as an upper surface) of the first semiconductor layer 31 on the + Z side, and has a second conductivity type different from the first conductivity type of the first semiconductor layer 31. It mainly contains semiconductors. Here, semiconductors having different conductivity types are semiconductors having different conductive carriers. The second conductivity type may be an n-type conductivity type, for example. Note that the conductivity type of the first semiconductor layer 31 may be n-type, and the conductivity type of the second semiconductor layer 32 may be p-type. Here, a heterojunction region is formed between the first semiconductor layer 31 and the second semiconductor layer 32. Therefore, in the photoelectric conversion cell 10, photoelectric conversion can occur in the first semiconductor layer 31 and the second semiconductor layer 32 that form the heterojunction region.

The second semiconductor layer 32 mainly includes a compound semiconductor. Examples of the compound semiconductor included in the second semiconductor layer 32 include CdS, In ₂ S ₃ , ZnS, ZnO, In ₂ Se ₃ , In (OH, S), (Zn, In) (Se, OH), and ( Zn, Mg) O or the like may be employed. If the second semiconductor layer 32 has a resistivity of 1 Ω · cm or more, the generation of leakage current can be reduced. The second semiconductor layer 32 can be formed by, for example, a chemical bath deposition (CBD) method or the like.

  Further, the thickness of the second semiconductor layer 32 may be about 10 nm or more and about 200 nm or less, for example. If the thickness of the second semiconductor layer 32 is not less than 100 nm and not more than 200 nm, the second electrode is formed when the transparent electrode 41 of the light-receiving surface side electrode portion 4 is formed on the second semiconductor layer 32 by sputtering or the like. Damage is unlikely to occur in the semiconductor layer 32.

  The light receiving surface side electrode portion 4 is disposed on one main surface (also referred to as an upper surface) of the + Z side of the photoelectric conversion layer 3. The light receiving surface side electrode portion 4 includes a transparent electrode 41 and a plurality of upper electrodes 42. The transparent electrode 41 and the upper electrode 42 are stacked on the photoelectric conversion layer 3 in this order.

  The transparent electrode 41 is disposed on one main surface (also referred to as an upper surface) of the + Z side of the photoelectric conversion layer 3. The transparent electrode 41 is, for example, a transparent conductive layer having an n-type conductivity type. The transparent electrode 41 is an electrode that extracts charges generated in the photoelectric conversion layer 3. The transparent electrode 41 only needs to mainly contain a material having a lower resistivity than the second semiconductor layer 32. The transparent electrode 41 may include what is called a window layer, and may include a window layer and a transparent conductive layer.

The transparent electrode 41 mainly includes a material having a wide forbidden band, transparent, and low resistance. As such a material, for example, ZnO, a compound of ZnO, a metal oxide semiconductor such as ITO containing Sn and SnO ₂ can be adopted. The ZnO compound only needs to contain any one element of Al, B, Ga, In, and F.

  The transparent electrode 41 can be formed by sputtering, vapor deposition, chemical vapor deposition (CVD), or the like. The thickness of the transparent electrode 41 may be, for example, about 0.08 μm or more and about 2.0 μm or less. Here, if the transparent electrode 41 has a resistivity of less than 1 Ω · cm and a sheet resistance of 50 Ω / □ or less, charges can be satisfactorily extracted from the photoelectric conversion layer 3 through the transparent electrode 41. .

  Here, if the second semiconductor layer 32 and the transparent electrode 41 have a property (also referred to as light transmissive property) that allows light to easily pass through the wavelength band of light that can be absorbed by the first semiconductor layer 31. The decrease in light absorption efficiency in the first semiconductor layer 31 can be reduced. Moreover, if the thickness of the transparent electrode 41 is 0.05 μm or more and 0.5 μm or less, the light transmittance in the transparent electrode 41 is enhanced, and the current generated by the photoelectric conversion can be transmitted well by the transparent electrode 41. . Furthermore, if the absolute refractive index of the transparent electrode 41 and the absolute refractive index of the second semiconductor layer 32 are substantially the same, the incident light generated by the reflection of light at the interface between the transparent electrode 41 and the second semiconductor layer 32 will be described. Loss can be reduced.

  The plurality of upper electrodes 42 are arranged on one main surface (also referred to as an upper surface) of the + Z side of the transparent electrode 41. The plurality of upper electrodes 42 can be formed, for example, by applying a conductive paste on the upper surface of the transparent electrode 41 and then drying and solidifying the conductive paste. The conductive paste can be produced, for example, by adding particles such as a metal filler having high light reflectivity and conductivity to a binder such as a translucent resin. In this case, the upper electrode 42 includes a large number of conductive particles, and the high conductivity of the upper electrode 42 can be ensured by the large number of particles coming into contact with each other.

  The plurality of upper electrodes 42 are separated in the + Y direction perpendicular to the + X direction as the first direction, and each upper electrode 42 extends in the + X direction. Here, the photoelectric conversion layer 3 is provided with a slit-like groove P2 as a gap. And the some upper electrode 42 is electrically connected to the lower electrode 2 of the adjacent photoelectric conversion cell 10 by the connection part 5 distribute | arranged to the groove part P2. Specifically, the plurality of first upper electrodes 42a in the first photoelectric conversion cell 10a are extended from the second photoelectric conversion cell 10b to the inside of the first photoelectric conversion cell 10a by the connection portion 5 disposed in the groove portion P2. Connected to the second lower electrode 2b. That is, between the adjacent first photoelectric conversion cell 10a and the second photoelectric conversion cell 10b, the first light receiving surface side electrode portion 4a disposed in the first photoelectric conversion cell 10a and the adjacent second photoelectric conversion cell. The second lower electrode 2b disposed in 10b is connected by the connecting portion 5.

  The plurality of upper electrodes 42 plays a role of collecting charges generated in the photoelectric conversion layer 3 and taken out by the transparent electrode 41. By providing the plurality of upper electrodes 42, conductivity in the transparent electrode 41 is supplemented. For this reason, the transparent electrode 41 can be thinned. As a result, it is possible to ensure both the charge extraction efficiency and the improvement of light transmittance in the transparent electrode 41.

  The charges collected by the transparent electrode 41 and the plurality of upper electrodes 42 are transmitted to the adjacent photoelectric conversion cell 10 through the connection portion 5. Thereby, in the photoelectric conversion apparatus 100, the adjacent photoelectric conversion cells 10 are electrically connected in series.

Further, when the width of the plurality of upper electrodes 42 is not less than 20 μm and not more than 400 μm, good conduction between the adjacent photoelectric conversion cells 10 is ensured, and the amount of light incident on the first semiconductor layer 31 is reduced. Can be reduced. Note that the interval in the + Y direction between the plurality of upper electrodes 42 arranged in one photoelectric conversion cell 10 may be about 2.5 mm, for example.

<Arrangement of groove and its role>
The groove part P1 extends along the + Y direction. The groove portion P <b> 1 is arranged from the upper surface of the lower electrode 2 to the upper surface of the substrate 1. In the photoelectric conversion device 100, the plurality of lower electrodes 2 are arranged on the substrate 1 at intervals in the + X direction as the first direction because one or more grooves P <b> 1 are arranged. FIG. 2 shows a state in which the first to third lower electrodes 2a to 2c are sequentially arranged on the substrate 1 at intervals in the + X direction as the plurality of lower electrodes 2.

  As shown in FIG. 2, in one photoelectric conversion cell 10, the lower electrode 2 includes a first region 21 located on the −X side of the trench P <b> 1 and a second region 22 located on the + X side of the trench P <b> 1. Including. In one photoelectric conversion cell 10, the groove part P <b> 1 electrically separates the first region 21 and the second region 22.

  The extending portion of the first semiconductor layer 31 disposed immediately above is embedded in the groove portion P1. For this reason, in one photoelectric conversion cell 10, the 1st field 21 and the 2nd field 22 are electrically separated by slot P1.

  Specifically, in the first photoelectric conversion cell 10a, the first stacked portion 34a is arranged from the first lower electrode 2a through the substrate 1 to the second lower electrode 2b. In the first stacked unit 34a, the first semiconductor layer 31a, the second semiconductor layer 32a, and the first light receiving surface side electrode unit 4a are sequentially stacked in the + Z direction as the second direction. Further, in the second photoelectric conversion cell 10b, the second stacked portion 34b is disposed from the second lower electrode 2b through the substrate 1 to the third lower electrode 2c. In the second stacked portion 34b, the first semiconductor layer 31b, the second semiconductor layer 32b, and the second light receiving surface side electrode portion 4b are stacked in order in the + Z direction. The width of the groove P1 may be, for example, about 50 μm or more and about 400 μm or less.

  In addition, between the first photoelectric conversion cell 10a and the second photoelectric conversion cell 10b adjacent in the ± X direction, the second region 22 of the first photoelectric conversion cell 10a and the first region 21 of the second photoelectric conversion cell 10b. Are included in the second lower electrode 2 b as one lower electrode 2. In other words, the second lower electrode 2b extends from the second photoelectric conversion cell 10b to the first photoelectric conversion cell 10a. Thereby, the 2nd field 22 of the 1st photoelectric conversion cell 10a and the 1st field 21 of the 2nd photoelectric conversion cell 10b are electrically connected.

  Hereinafter, the structure of the groove P1 (hereinafter also referred to as a gap) will be described in more detail.

  An embodiment of the photoelectric conversion device according to the present invention includes a lower electrode 2 in which a first lower electrode 2a and a second lower electrode 2b are formed on a substrate 1 at an interval, and the substrate from above the first lower electrode 2a. 1 is a photoelectric conversion device 100 having a photoelectric conversion layer 3 formed over the second lower electrode 2b and a transparent electrode 41 formed on the photoelectric conversion layer 3, the first lower portion in the interval Each end 8 of the electrode 2a and the second lower electrode 2b is curved such that one end 8a is convex and the other end 8b is concave (see FIG. 7).

  One end 8a is convex (see FIG. 16 (a)) and the other end 8b is concave (see FIG. 16 (b)), so that the lower electrode 2 with respect to a force perpendicular to the substrate 1 is curved. And the photoelectric conversion layer 3 can be improved by an anchor effect at each end 8. The adhesion to a force in a direction perpendicular to the substrate 1 can be further increased.

Here, the end portion 8a is curved in a convex shape, and the other end portion 8b is curved in a concave shape.
It is possible to reduce the propagation and connection of the crack 7 between a and the end portion 8b, the adhesion between the lower electrode 2 and the photoelectric conversion layer 3, and the lower electrode 2 and the substrate 1 The adhesion between the two can be maintained.

  For example, as shown in FIG. 14, when both the end portions 8 are concave, cracks 7 easily occur between the end portion 8 (the upper portion thereof) and the photoelectric conversion layer 3. The crack 7 propagates and the cracks 7 from both ends 8a and 8b may be connected.

  Further, for example, as shown in FIG. 15, when both end portions 8 are convex, cracks 7 easily occur between the end portion 8 (the lower portion thereof) and the substrate 1, and the lower electrode 2 and the substrate 1. The crack 7 (peeling) propagates between the two, and the cracks 7 from both ends 8a and 8b may be connected.

  On the other hand, in the embodiment of the present invention, as shown in FIG. 7, the first lower electrode 2a side and the second lower electrode 2b side have different starting points at which cracks 7 are likely to occur. It is possible to reduce the propagation and connection of cracks 7 from the end portion 8a (upper portion thereof) on the 2a side and the end portion 8b (lower portion thereof) on the second lower electrode 2b side.

  Furthermore, in the embodiment of the photoelectric conversion device of the present invention, the first lower electrode 2a and the second lower electrode 2b are arranged with columnar crystal grains, and the crystal grain boundary 6 between the crystal grains has the A part of the photoelectric conversion layer 3 is impregnated.

  Thereby, the adhesiveness between the lower electrode 2 and the photoelectric conversion layer 3 is improved, and the photoelectric conversion efficiency can be improved by increasing the substantial contact area between the lower electrode 2 and the photoelectric conversion layer 3.

  That is, in the first lower electrode 2a and the second lower electrode 2b, columnar crystal grains are continuously arranged in the thickness direction, but the crystal grain boundary 6 is curved. If a part is impregnated with the crystal grain boundary 6, the adhesion to a force in a direction perpendicular to the substrate 1 can be further increased.

  Next, the groove P2 is a slit-like gap extending along the + Y direction. The groove part P2 separates the photoelectric conversion layer 3 in the ± X directions in each photoelectric conversion cell 10.

  Specifically, for example, the groove portion P2 is spaced from the end portion of the groove portion P1 by a distance W1, and the second lower electrode 2b extends from the upper surface of the first transparent electrode 41a included in the first light receiving surface side electrode portion 4a. Arranged up to the top. Here, the interval W1 is, for example, not less than 30 μm and not more than 150 μm. Furthermore, the connection part 5 is distribute | arranged to the groove part P2. The connecting portion 5 is disposed so as to penetrate the first semiconductor layer 31a and the second semiconductor layer 32a. And the 1st light-receiving surface side electrode part 4a and the 2nd lower electrode 2b extended | stretched from the 2nd photoelectric conversion cell 10b to the inside of the 1st photoelectric conversion cell 10a are electrically connected by the connection part 5. FIG. By the way, the first light receiving surface side electrode portion 4a includes a first transparent electrode 41a disposed on the second semiconductor layer 32a and a first upper electrode 42a disposed on the first transparent electrode 41a. Yes. And the connection part 5 is electrically connected with the 1st upper electrode 42a distribute | arranged on the 1st transparent electrode 41a of the 1st light-receiving surface side electrode part 4a, for example. Note that the connecting portion 5 may be configured integrally with the first upper electrode 42a, for example. Thereby, it can be said that the connection part 5 is a part of 1st upper electrode 42a.

For example, the groove part P2 is arranged from the upper surface of the second transparent electrode 41b included in the second light receiving surface side electrode part 4b to the upper surface of the third lower electrode 2c. Here, in the groove part P2,
A connecting part 5 is arranged. The connecting portion 5 is disposed so as to penetrate the first semiconductor layer 31b and the second semiconductor layer 32b. The connecting portion 5 electrically connects the second light receiving surface side electrode portion 4b and the third lower electrode 2c extending from the + X side into the second photoelectric conversion cell 10b. Meanwhile, the second light receiving surface side electrode portion 4b includes a second transparent electrode 41b disposed on the second semiconductor layer 32b and a second upper electrode 42b disposed on the second transparent electrode 41b. It is out. And the connection part 5 is electrically connected with the 2nd upper electrode 42b distribute | arranged on the 2nd transparent electrode 41b of the 2nd light-receiving surface side electrode part 4b, for example. Note that the connecting portion 5 may be configured integrally with the second upper electrode 42b, for example. Thereby, it can be said that the connection part 5 is a part of 2nd upper electrode 42b.

  Further, the width of the groove P2 may be, for example, about 50 μm or more and about 400 μm or less.

  The groove part P3 extends in the + Y direction between two adjacent photoelectric conversion cells 10. The groove portion P3 is spaced from the end portion of the groove portion P2 by a distance W2, and is arranged from one main surface (also referred to as an upper surface) of the photoelectric conversion cell 10 to the upper surface of the lower electrode 2. That is, the groove part P3 is an area for electrically separating the photoelectric conversion layer 3 and the light receiving surface side electrode part 4 from each other between two photoelectric conversion cells 10 adjacent in the ± X direction. Here, the interval W2 is about 30 μm or more and about 150 μm or less. Specifically, the groove portion P3 electrically connects the photoelectric conversion layer 3 and the light receiving surface side electrode portion 4 between the first photoelectric conversion cell 10a and the second photoelectric conversion cell 10b adjacent in the ± X direction. Are separated. The width of the groove P3 may be, for example, about 40 μm or more and about 600 μm or less. Further, when the photoelectric conversion device 100 is modularized, for example, an insulating material such as a resin enters each groove P3.

  Further, when each photoelectric conversion cell 10 is seen through from above the light receiving surface (here, + Z side), each photoelectric conversion cell 10 is provided with a groove portion P1, a groove portion P2, and a groove portion P3 in this order in the + X direction. Yes. Each photoelectric conversion cell 10 includes a region (second region 22) that includes the groove portion P2 and is sandwiched between the groove portion P1 and the groove portion P3, a region where the groove portion P1 is disposed, and a remaining region (first region). 1 region 21). The remaining area is an area contributing to power generation (also referred to as a power generation area).

<Method for Manufacturing Photoelectric Conversion Device>
Here, an example of a manufacturing process of the photoelectric conversion device 100 having the above configuration will be described.

  FIG. 3 is a flowchart illustrating the manufacturing flow of the photoelectric conversion apparatus 100. 4 to 11 are XZ cross-sectional views schematically showing a state in the process of manufacturing the photoelectric conversion device 100. FIG. 12 is a plan view schematically showing a state during the manufacture of the photoelectric conversion device 100.

  In step Sp1 of FIG. 3, the substrate 1 (see FIG. 4) is prepared. The board | substrate 1 should just be a flat thing which has a substantially rectangular board surface which consists of soda-lime glass etc., for example.

  In step Sp2, the lower electrode 2 (see FIG. 5) is formed on substantially the entire main surface of the cleaned substrate 1 by using a sputtering method or the like. In the present embodiment, the lower electrode 2 is preferably made of molybdenum, which has a high melting point, a low reactivity with selenium, and a practical material.

In Step Sp3, a groove portion P1 (see FIG. 6) extending in the + Y direction is formed from a predetermined formation target position on the upper surface of the lower electrode 2 to the upper surface of the substrate 1 immediately below it. Groove P1
Can be formed, for example, by being ejected to a predetermined formation target position while the abrasive liquid 53 of a water jet is scanned (see FIG. 11). At this time, a plurality of lower electrodes 2 arranged in the + X direction are formed on the substrate 1. Specifically, for example, as shown in FIG. 6, first to third lower electrodes 2 a to 2 c arranged in order in the + X direction are formed. That is, Step Sp2 and Step Sp3 correspond to the lower electrode forming step.

  Hereinafter, the manufacturing method of the structure of the groove part P1 (interval) will be described in more detail.

  An embodiment of the method for manufacturing a photoelectric conversion device of the present invention includes a lower electrode forming step of arranging columnar crystal grains in a thickness direction by epitaxially growing the lower electrode 2 on the substrate 1 using a sputtering method, By removing the lower electrode 2 by ejecting a pressurized liquid, a removal step for providing a gap, and a photoelectric conversion on the lower electrode 2 and the substrate 1 arranged with the gap. It is a manufacturing method of the photoelectric conversion apparatus 100 provided with the photoelectric converting layer forming process which forms the layer 3, and the transparent electrode forming process which forms the transparent electrode 41 on the said photoelectric converting layer 3, Comprising: In the said lower electrode forming process The lower electrode is epitaxially grown while changing the incident angle of the sputtered particles with respect to the substrate 1.

  First, in the lower electrode forming step, the film is formed while changing the incident angle of the sputtered particles with respect to the substrate 1 to control the direction in which crystal grains grow epitaxially. For example, the sputtered particles are formed on the main surface of the substrate 1. The crystal grain boundary 6 of the crystal grains of the lower electrode 2 can be curved by changing the direction in which the light is incident in the order of the right oblique direction, the vertical direction, and the left oblique direction.

  Then, the crystal grains of the lower electrode 2 tend to be cleaved along the crystal grain boundary 6. If the pressurized liquid is ejected to partially remove the lower electrode 2 and provide an interval, the first electrode is obtained. The cleavage surface of the crystal grain boundary 6 at the end 8a of the lower electrode 2a and the end 8b of the second lower electrode 2b can be curved such that one end 8a is concave and the other end 8b is convex. .

  In Step Sp4, the first semiconductor layer 31 (see FIG. 7) is formed on the lower electrode 2. Here, for example, a film 310 (see FIG. 7) containing a metal element mainly contained in the first semiconductor layer 31 is formed on the lower electrode 2.

  In the present embodiment, the film 310 is formed, for example, by performing a drying process after a raw material solution containing a metal element mainly contained in the first semiconductor layer 31 is applied on the lower electrode 2. The

The raw material solution should just contain a IB group metal, a III-B group metal, a chalcogen element containing organic compound, and a Lewis basic organic solvent, for example. A solvent (hereinafter, also referred to as a mixed solvent S) containing a chalcogen element-containing organic compound and a Lewis basic organic solvent can favorably dissolve the Group IB metal and the Group III-B metal. If it is such a mixed solvent S, the raw material solution from which the total density | concentration of the IB group metal and the III-B group metal with respect to the mixed solvent S will be 6 mass% or more can be produced. Moreover, since the solubility of the said metal can be raised by using such mixed solvent S, a high concentration raw material solution can be obtained. Next, the raw material solution will be described in detail.

The chalcogen element-containing organic compound is an organic compound containing a chalcogen element. The chalcogen element refers to S, Se, or Te among VI-B group elements. When the chalcogen element is S, examples of the chalcogen element-containing organic compound include thiol, sulfide, disulfide, thiophene, sulfoxide, sulfone, thioketone, sulfonic acid, sulfonic acid ester, and sulfonic acid amide. Of the above-mentioned compounds, thiol, sulfide, disulfide and the like are likely to form a complex with a metal. Moreover, if the chalcogen element-containing organic compound has a phenyl group, the coating property can be improved. Examples of such compounds include thiophenol, diphenyl sulfide and the like and derivatives thereof.

  When the chalcogen element is Se, examples of the chalcogen element-containing organic compound include selenol, selenide, diselenide, selenoxide, and selenone. Of the above-mentioned compounds, selenol, selenide, diselenide and the like easily form a complex with a metal. Moreover, if it is phenyl selenol, phenyl selenide, diphenyl diselenide, etc. which have a phenyl group, and these derivatives, applicability | paintability can be improved.

  When the chalcogen element is Te, examples of the chalcogen element-containing organic compound include tellurol, telluride, and ditelluride.

  A Lewis basic organic solvent is an organic solvent containing a substance that can be a Lewis base. Examples of the Lewis basic organic solvent include pyridine, aniline, triphenylphosphine, and derivatives thereof. When the boiling point of the Lewis basic organic solvent is 100 ° C. or higher, the coating property can be improved.

Moreover, the IB group metal and the chalcogen element-containing organic compound are preferably chemically bonded. Furthermore, the III-B group metal and the chalcogen element-containing organic compound are preferably chemically bonded. Furthermore, the chalcogen element-containing organic compound and the Lewis basic organic solvent are preferably chemically bonded. Such chemical bonding facilitates preparation of a higher concentration raw material solution of 8% by mass or more. Examples of the chemical bond described above include a coordinate bond between elements. Such chemical bonds can be confirmed by, for example, NMR (Nuclear Magnetic Resonance) method. In this NMR method, the chemical bond between the Group IB metal and the chalcogen element-containing organic compound can be detected as a peak shift in multinuclear NMR of the chalcogen element. Moreover, the chemical bond between the III-B group metal and the chalcogen element-containing organic compound can be detected as a peak shift of multinuclear NMR of the chalcogen element. Moreover, the chemical bond between the chalcogen element-containing organic compound and the Lewis basic organic solvent can be detected as a peak shift derived from the organic solvent. The number of moles of chemical bonds between the group IB metal and the chalcogen element-containing organic compound is 0.1 times or more and 10 times or less of the number of moles of chemical bonds between the chalcogen element-containing organic compound and the Lewis basic organic solvent. Any range is acceptable.

  The mixed solvent S may be prepared by mixing a chalcogen element-containing organic compound and a Lewis basic organic solvent so as to be liquid at room temperature. Thereby, handling of the mixed solvent S becomes easy. For example, the chalcogen element-containing organic compound may be mixed in an amount of 0.1 to 10 times the Lewis basic organic solvent. Thereby, the above-mentioned chemical bond can be formed satisfactorily, and a high concentration group I-B metal and group III-B metal solution can be obtained.

The raw material solution is obtained, for example, by directly dissolving the group IB metal and the group III-B metal in the mixed solvent S. With such a method, it is possible to reduce contamination of impurities other than the component of the compound semiconductor into the first semiconductor layer 3. In addition, any of the IB group metal and the III-B group metal may be a metal salt. Here, dissolving the Group I-B metal and the Group III-B metal directly in the mixed solvent S means that the single metal ingot or the alloy ingot is directly mixed into the mixed solvent S and dissolved. Say. Thereby, the bare metal of the single metal or the alloy is not required to be dissolved in the solvent after being changed into another compound (for example, a metal salt such as chloride). Therefore, with such a method, it is possible to simplify the process and reduce the inclusion of impurities other than the elements constituting the first semiconductor layer 3 in the first semiconductor layer 3. Thereby, the purity of the first semiconductor layer 3 is increased.

  Examples of the group IB metal include Cu and Ag. The group IB metal may be one kind of element or may contain two or more kinds of elements. When two or more kinds of IB group metal elements are used, a mixture of two or more kinds of IB group metals may be dissolved in the mixed solvent S at a time. On the other hand, after IB group metal of each element is dissolved in the mixed solvent S, these may be mixed.

The group III-B metal is, for example, Ga or In. The group III-B metal may be one kind of element or may contain two or more kinds of elements. In the case where two or more Group III-B metal elements are used, a mixture of two or more Group III-B metals may be dissolved in the mixed solvent S at a time. On the other hand, after the group III-B metal of each element is dissolved in the mixed solvent S, these may be mixed.

In the film forming step, the raw material solution containing the I-III-VI group compound is formed on the substrate 1 having the first electrode layer 2 on the first to the third lower electrodes 2a to 2c and between the adjacent lower electrodes. The coating 310 is formed by applying on the corresponding groove P1. As the coating method of the raw material solution S, for example, a spin coater, screen printing, dipping, spraying or a die coater is used.

Next, a precursor is formed by heat-treating the film 310 at a temperature of 250 ° C. or higher and 350 ° C. or lower. Next, the substrate 1 on which the precursor is formed is heated to 400 ° C. or more and 600 ° C. or less in a hydrogen gas atmosphere containing hydrogen selenide (H ₂ Se) gas. Through such a heat treatment process, the first conductive type first semiconductor layer 31 is formed by grain growth of the precursor.

  In step Sp5, the second conductivity type second semiconductor layer 32 (see FIG. 8) is formed on the first semiconductor layer 31. Thereby, the photoelectric conversion layer 3 in which the first semiconductor layer 31 and the second semiconductor layer 32 are stacked is formed.

  The second semiconductor layer 32 can be formed by, for example, a chemical bath deposition (CBD) method. Specifically, for example, the first semiconductor layer 31 is immersed in a solution prepared by dissolving cadmium acetate and thiourea in aqueous ammonia, so that the second semiconductor layer 32 mainly containing CdS is formed. Can be formed.

  In this way, the photoelectric conversion layer 3 is formed by Step Sp4 and Step Sp5. That is, Step Sp4 and Step Sp5 correspond to the photoelectric conversion layer forming step. Moreover, the film formation process mentioned above and the semiconductor formation process which forms the 1st and 2nd semiconductor layer are contained in the photoelectric converting layer formation process.

  In Step Sp6, the transparent electrode 41 (see FIG. 9) is formed on the photoelectric conversion layer 3. The transparent electrode 41 can be formed by, for example, a sputtering method, a vapor deposition method, a chemical vapor deposition (CVD) method, or the like. Specifically, for example, a transparent transparent electrode 41 mainly including ZnO added with Al is formed on the second semiconductor layer 32.

  In step Sp7, a groove P2 (see FIG. 10) extending in the + Y direction is formed in a region extending from the upper surface of the transparent electrode 41 to the upper surface of the lower electrode 2. This step Sp7 corresponds to a gap forming step. The groove portion P2 is formed by partially removing the photoelectric conversion layer 3 and the transparent electrode 41 on the lower electrode 2.

  In step Sp7, the groove P2 is formed by processing. As shown in FIG. 11, the water jet device 50 includes, for example, a work table 51, an injection nozzle 52, and an abrasive solution 53.

  The work table 51 is for mounting the photoelectric conversion layer 3 and the substrate 1 to be processed, and is moved in the X and Y directions by a servo motor controlled by a sequencer or the like. The work table 51 has a thickness of 1 cm or more and 3 cm or less, and a size larger than the substrate 1 by 1 cm or more and 5 cm or less. The work table 51 is, for example, a metal plate such as stainless steel coated with a hard material such as alumina. The work table 51 is provided with a plurality of through-holes having a diameter of 1 mm or more and about 5 mm or less penetrating from the upper surface to the lower surface. And the board | substrate 1 is fixed in a predetermined position by decompressing the inside of these through-holes with a vacuum pump.

  The injection nozzle 52 includes an abrasive liquid 53 and a compressed air pipe (not shown). The injection nozzle 52 has a structure capable of discharging the abrasive liquid 53 at a predetermined pressure from the discharge port at the lower end portion.

  The formation of the groove portion P2 is performed by the following procedure, for example. First, the substrate 1 on which the lower electrode 2, the photoelectric conversion layer 3, and the transparent electrode 41 are formed is placed on the work table 51. Next, the work table 51 is moved so that the injection nozzle 52 is positioned above the portion where the groove portion P2 is formed. Next, the work table 51 is moved along a certain direction (Y direction in the present embodiment) while discharging the abrasive grains 53 from the tip of the injection nozzle 52. At this time, the abrasive fluid 53 collides with the photoelectric conversion layer 3 and the transparent electrode 41, thereby removing a part of the photoelectric conversion layer 3 and the transparent electrode 41. In this water jet treatment, the photoelectric conversion layer 3 and the transparent electrode 41 are continuously dug to partially remove the photoelectric conversion layer 3 and the transparent electrode 41 to form a gap (groove portion P2). Yes.

  The particle size of the abrasive grains of the abrasive liquid 53 used in the water jet treatment may be, for example, about 0.5 μm or more and 10 μm or less. The abrasive grains only need to be made of a material that can remove the photoelectric conversion layer 3 and the transparent electrode 41 and that the lower electrode 2 is difficult to be cut. For example, alumina, silicon carbide, calcium carbonate, glass beads, metal powder, or resin is used as the material of such abrasive grains. Moreover, if resin is used for the material of an abrasive grain, the damage to the lower electrode 2 will be reduced. Thereby, the fall of the resistance of the lower electrode 2 is reduced.

  The conditions of the water jet process are the discharge pressure and discharge amount of the abrasive liquid 53, the shape and dimensions of the discharge port of the injection nozzle 52, and the movement of the work table 51 while observing the depth and width of the groove P2 to be formed. What is necessary is just to determine optimally considering speed, the distance of the injection nozzle 52 and the board | substrate 1, etc. FIG. Further, the water jet treatment may be performed after a mask having an opening having a predetermined length and thickness on a metal plate is disposed on the transparent electrode 41. The water jet treatment may be performed after applying a photoresist or the like on the transparent electrode 41 and forming a resin mask having an opening at a position where the groove P2 is to be formed. If such a mask is used, it becomes easy to form a groove P2 having a smaller width.

  As described above, in the present embodiment, after forming the transparent electrode 41, the photoelectric conversion layer 3 and the transparent electrode 41 on the lower electrode 2 are partially removed by water jet treatment to form the groove P2. As a result, the shavings or abrasive liquid 53 of the photoelectric conversion layer 3 generated by the water jet process hardly remains between the photoelectric conversion layer 3 and the transparent electrode 41. As a result, in the present embodiment, the increase in resistance due to the residue (the shavings or the abrasive liquid 53 of the photoelectric conversion layer 3) between the photoelectric conversion layer 3 and the transparent electrode 41 is reduced, and thus the photoelectric conversion with high conversion efficiency is performed. A conversion device can be manufactured.

  Moreover, according to this embodiment, since the transparent electrode 41 is sequentially formed after the photoelectric conversion layer 3 is formed, alteration or oxidation of the photoelectric conversion layer 3 (second semiconductor layer 32) is easily reduced. Further, as described above, even when a mask is used during the water jet process, the mask can be prevented from contacting the photoelectric conversion layer 3, so that damage to the semiconductor layer (second semiconductor layer 32) that may occur when the mask is removed. It is easy to be reduced.

  Further, as in the present embodiment, when formed by a manufacturing method including the above-described film forming step and semiconductor layer forming step, the raw material solution can contain selenium of a VI-B group element in advance. Thereby, compared with the method of forming the 1st semiconductor layer 31 by sputtering method, the quantity of the hydrogen selenide gas introduce | transduced at the time of a heat processing process is reduced. As a result, it becomes difficult to supply selenium excessively, so that when the lower electrode 2 is formed of molybdenum, it is difficult to form a molybdenum selenide layer between the lower electrode 2 and the first semiconductor layer 31. Therefore, the adhesive strength between the lower electrode 2 and the first semiconductor layer 31 can be increased. Thus, even when the adhesive strength is increased, the photoelectric conversion layer 3 is easily removed from the lower electrode 2 as compared with the conventional mechanical scribing method or the like if the above-described water jet treatment is used.

  In step Sp8, the upper electrode 42 (see FIGS. 12 and 13) is formed from a predetermined formation target position on the upper surface of the transparent electrode 41 to the inside of the groove portion P2. That is, this step Sp8 corresponds to the upper electrode forming step. For example, the upper electrode 42 is applied so that the conductive paste has a predetermined pattern from a predetermined formation target position on the upper surface of the transparent electrode 41 to the inside of the groove portion P2, and the conductive paste after application is solidified by drying. Can be formed. Thus, as shown in FIG. 1, the upper electrode 42 is electrically connected to the second lower electrode 2b from the first transparent electrode 41a located on the first lower electrode 2a through the groove portion P2. The connecting portion 5 disposed in the groove portion P2 corresponds to a part of the upper electrode 42. The upper electrode 42 and the connection portion 5 can be formed by applying a conductive paste, for example, by screen printing or the like. This conductive paste is, for example, a metal or alloy filler such as gold, silver, palladium, copper, or nickel kneaded in an epoxy resin or an acrylic resin. Thus, by forming the upper electrode 42, the resistance component is reduced as compared with a mode in which the transparent electrode 41 extends to the groove portion P <b> 2 and the adjacent photoelectric conversion cells are electrically connected.

  Moreover, you may further provide the blow process which blows gas in the groove part P2 vicinity between step Sp7 and step Sp8. In step Sp7, residue such as abrasive particles scattered during shaving or blasting of the photoelectric conversion layer 3 may occur on the bottom of the groove P2 or on the transparent electrode 41 near the groove P2. In the blowing step, the residue can be removed by blowing a gas such as air or nitrogen in the vicinity of the groove P2, so that the interface between the transparent electrode 41 and the upper electrode 42 or the connecting part 5 and the lower electrode 2 is removed. The increase in the resistance component at the interface with can be reduced.

  Through the above steps Sp1 to Sp8, the plurality of lower electrodes 2, the first semiconductor layer 31, the second semiconductor layer 32, and the light receiving surface side electrode portion 4 are sequentially stacked on the substrate 1 in the + Z direction as the second direction. A stacked body 234 is formed (see FIG. 13). In addition, the light receiving surface side electrode portion 4 that is electrically connected to the lower electrode 2 through the connection portion 5 located in the groove portion P2 disposed in the second semiconductor layer 32 and the first semiconductor layer 31 is formed.

  In the next step Sp9, a groove P3 (see FIGS. 1 and 2) is formed in a region extending from the upper surface of the light receiving surface side electrode portion 4 to the upper surface of the lower electrode 2. Thereby, the photoelectric conversion apparatus 100 in which a plurality of photoelectric conversion cells 10 are arranged on the substrate 1 is obtained.

  Specifically, in Step Sp9, at least a portion of the stacked body 234 located on the + X direction side as the first direction with respect to the stacked body 234 is cut linearly along the Y direction. The linear groove portion P3 extends from the upper surface of the light receiving surface side electrode portion 4 of the multilayer body 234 to the upper surface of the lower electrode 2. Thereby, the 1st lamination part 34a and the 2nd lamination part 34b which are located in a line with the + X direction are formed. The first stacked portion 34a is disposed, for example, in a region extending over the substrate 1 from the first lower electrode 2a through at least the groove portion P2 as a gap portion between the first lower electrode 2a and the second lower electrode 2b. It ’s fine. Moreover, the 2nd laminated part 34b should just be distribute | arranged on the 2nd lower electrode 2b, for example.

1: Substrate 2: Lower electrodes 2a to 2c: First to third lower electrodes 3: Photoelectric conversion layer 4: Light receiving surface side electrode portion 4a: First light receiving surface side electrode portion 4b: Second light receiving surface side electrode portion 5 : Connection part 6: Grain boundary 7: Crack 8: End part of lower electrode 8a: End part of first lower electrode, 8b: End part of second lower electrode 10: Photoelectric conversion cell 10a, 10b: First and second photoelectrics Conversion cells 31, 31a, 31b: first semiconductor layers 32, 32a, 32b: second semiconductor layers 34: stacked portions 34a, 34b: first and second stacked portions 41: transparent electrodes 41a, 41b: first and second Transparent electrode 42: Upper electrodes 42a, 42b: First and second upper electrodes 50: Water jet device 51 Work table 52 Injection nozzle 53 Abrasive fluid 100 Photoelectric conversion device 234 Laminate 310 Film P1-P2 Groove

Claims (4)

A lower electrode formed by forming a first lower electrode and a second lower electrode on the substrate at an interval;
A photoelectric conversion layer formed over the first lower electrode, the substrate, and the second lower electrode;
A photoelectric conversion device having a transparent electrode formed on the photoelectric conversion layer,
When viewed in a cross section crossing the interval and perpendicular to the upper surface of the substrate, each end of the first lower electrode and the second lower electrode in the interval has one end recessed, and the other end Is a photoelectric conversion device curved in a convex shape. The first lower electrode and the second lower electrode are arranged in a row of columnar crystal grains,
The photoelectric conversion device according to claim 1, wherein a part of the photoelectric conversion layer is impregnated in a crystal grain boundary between the crystal grains. A lower electrode forming step in which columnar crystal grains are arranged in a row by epitaxially growing the lower electrode on the substrate using a sputtering method;
A removal step of partially removing the lower electrode by spraying pressurized liquid to provide a gap;
A photoelectric conversion layer forming step of forming a photoelectric conversion layer on the lower electrode and the substrate arranged with the gap; and
A method for producing a photoelectric conversion device, comprising a transparent electrode forming step of forming a transparent electrode on the photoelectric conversion layer,
The lower electrode forming step is a step of epitaxially growing the lower electrode while changing an incident angle of sputtered particles with respect to the substrate from an acute angle to an obtuse angle in a first direction parallel to the upper surface of the substrate ,
The said removal process is a manufacturing method of the photoelectric conversion apparatus which is a process of removing the said lower electrode layer partially along the direction which is parallel to the said upper surface, and cross | intersects the said 1st direction . In the lower electrode formation step, the lower electrode is formed of molybdenum,
The photoelectric conversion layer forming step includes a film forming step of forming a film by applying a raw material solution containing an I-III-VI group compound on the lower electrode and the interval, and heating the film to form a first film. 4. The photoelectric conversion device according to claim 3, further comprising: a semiconductor layer forming step of forming a second semiconductor layer having a second conductivity type on the first semiconductor layer after forming the first semiconductor layer having a conductivity type. Manufacturing method.