WO2013125143A1

WO2013125143A1 - Method for producing photoelectric conversion device

Info

Publication number: WO2013125143A1
Application number: PCT/JP2012/082902
Authority: WO
Inventors: 幸大宮本; 智中原
Original assignee: シャープ株式会社
Priority date: 2012-02-23
Filing date: 2012-12-19
Publication date: 2013-08-29

Abstract

A method for producing a photoelectric conversion device, in which a photoelectric conversion layer (3) and/or a back-side electrode layer (4) is present in a region in which a periphery-insulated region (10) is to be formed when a periphery insulation step is carried out.

Description

Method for manufacturing photoelectric conversion device

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

Various types of solar cells that directly convert solar energy into electrical energy have been put into practical use. In particular, thin-film solar cells are being developed because they can be manufactured at low cost because of their low temperature process and easy area enlargement.

For example, Patent Document 1 (Japanese Patent Laid-Open No. 2011-181826) discloses a method for manufacturing a thin film solar cell including the following steps (i) to (iv).

(I) First, a transparent electrode layer is formed on a transparent insulating substrate, and a part of the transparent electrode layer is removed by laser light irradiation to form a first separation groove.

(Ii) Next, a photoelectric conversion layer is formed on the transparent electrode layer, a part of the photoelectric conversion layer is removed by laser light irradiation, and a second separation groove is formed.

(Iii) Next, a back electrode layer is formed on the photoelectric conversion layer, and a part of each of the photoelectric conversion layer and the back electrode layer is removed by laser light irradiation to form a scribe line.

(Iv) Thereafter, the transparent electrode layer, the photoelectric conversion layer, and the back electrode layer around the entire periphery of the transparent insulating substrate are removed by laser light irradiation to form a peripheral insulating region.

Patent Document 2 (Japanese Patent Laid-Open No. 2006-245507) discloses a method for manufacturing a thin film solar cell including the following steps (I) to (IV).

(I) First, a transparent conductive film is formed on an insulating translucent substrate, and a part of the transparent conductive film is removed by laser light irradiation to form a first separation groove.

(II) Next, a photoelectric conversion layer is formed on the transparent conductive film, a part of the transparent conductive film is removed by laser light irradiation, and a second separation groove is formed.

(III) Next, a back electrode is formed on the photoelectric conversion layer, and a part of each of the photoelectric conversion layer and the back electrode is removed by laser light irradiation to form a scribe line.

(IV) Next, a part of the transparent conductive film is removed by irradiating a laser beam in a direction orthogonal to the scribe line from the insulating translucent substrate side to form a cross scribe line.

JP 2011-181826 A JP 2006-245507 A

In the method for manufacturing a thin-film solar cell described in Patent Document 1, the step of forming the peripheral insulating region includes an electric shock accident due to leakage from a frame body such as an aluminum frame attached to the peripheral insulating region or an end of the transparent insulating substrate. It is essential to prevent.

Moreover, when the residue of the transparent conductive film, the photoelectric conversion layer, or the back electrode remains in a part of the peripheral insulating region, the appearance viewed from the insulating translucent substrate side may be impaired.

However, in the method for manufacturing a thin-film solar cell described in Patent Document 1, an insulation failure or an appearance failure may occur in the vicinity of the scribe line in the peripheral insulating region.

Further, in the method of manufacturing the thin-film solar cell described in Patent Document 2, even when the peripheral insulating region is formed, in the same manner as described above, the insulation defect or the appearance defect is poor in the vicinity of the scribe line and the cross scribe line in the peripheral insulating region. May occur.

In view of the above circumstances, an object of the present invention is to provide a method for manufacturing a photoelectric conversion device capable of suppressing the occurrence of insulation failure or appearance failure in the vicinity of a scribe line in a peripheral insulating region.

The present invention relates to a transparent insulating substrate in which a transparent electrode layer, a photoelectric conversion layer, and a back electrode layer are laminated in this order, a transparent electrode layer, a photoelectric conversion layer, and a back electrode layer on the entire periphery of the transparent insulating substrate. A peripheral insulating step of forming a peripheral insulating region by removing the laser beam by irradiation with a laser beam, and when performing the peripheral insulating step, at least one of a photoelectric conversion layer and a back electrode layer exists in the region forming the peripheral insulating region It is the manufacturing method of the photoelectric conversion apparatus which is doing.

Here, in the method for manufacturing a photoelectric conversion device of the present invention, the method further includes a scribe line forming step of forming a scribe line by linearly removing the photoelectric conversion layer and the back electrode layer, and in the scribe line forming step, a peripheral insulating step In the region where the peripheral insulating region is formed, it is preferable to leave at least one of the photoelectric conversion layer and the back electrode layer.

In the method for manufacturing a photoelectric conversion device of the present invention, the scribe line forming step includes a step of removing the photoelectric conversion layer and the back electrode layer by laser light irradiation to form a scribe line, and a peripheral insulating step in the peripheral insulating step. It is preferable that the region for forming the region includes a step of stopping the irradiation of the laser light.

In the method for manufacturing a photoelectric conversion device of the present invention, the scribe line forming step includes a step of covering a region where the peripheral insulating region is formed in the peripheral insulating step with a mask, and a photoelectric conversion layer and a back electrode layer by laser light irradiation. And a step of forming a scribe line.

In the method for manufacturing a photoelectric conversion device of the present invention, it is preferable to perform a scribe line forming step before the peripheral insulating step.

The method for producing a photoelectric conversion device of the present invention includes a step of laminating a photoelectric conversion layer on a transparent electrode layer laminated on a transparent insulating substrate, a step of laminating a back electrode layer on the photoelectric conversion layer, A part of each of the conversion layer and the back electrode layer is removed by laser light irradiation to form a scribe line, and the transparent electrode layer, the photoelectric conversion layer, and the back electrode layer on the entire periphery of the transparent insulating substrate are laser-treated. Forming a peripheral insulating region by removing the light by irradiating while moving the light. In the step of forming the peripheral insulating region, the moving speed of the laser beam may be reduced in the region where the scribe line is formed. preferable.

In the method of manufacturing a photoelectric conversion device of the present invention, it is preferable that the moving speed of the laser beam is temporarily made zero in the scribe line forming region in the step of forming the peripheral insulating region.

The method for producing a photoelectric conversion device of the present invention further includes a step of forming a cross scribe line that intersects the scribe line by removing a part of each of the photoelectric conversion layer and the back electrode layer by laser light irradiation, In the step of forming the peripheral insulating region, it is preferable to reduce the moving speed of the laser light in the formation region of the intersecting scribe line.

In the method of manufacturing a photoelectric conversion device of the present invention, it is preferable that the moving speed of the laser light is temporarily made zero in the formation region of the cross scribe line in the step of forming the peripheral insulating region.

According to the present invention, it is possible to provide a method for manufacturing a photoelectric conversion device that can suppress the occurrence of insulation failure or appearance failure in the vicinity of the scribe line in the peripheral insulating region.

FIG. 6 is a schematic cross-sectional view illustrating an example of a part of the manufacturing process of the method for manufacturing the photoelectric conversion device according to

Embodiments

1 and 3. FIG. 6 is a schematic cross-sectional view illustrating an example of a part of the manufacturing process of the method for manufacturing the photoelectric conversion device according to

Embodiments

1 and 3. FIG. 3 is a schematic plan view illustrating an example of a part of the manufacturing process of the photoelectric conversion device manufacturing method according to the first embodiment. FIG. 6 is a schematic cross-sectional view illustrating an example of a part of the manufacturing process of the method for manufacturing the photoelectric conversion device according to

Embodiments

1 and 3. 6 is a schematic plan view illustrating an example of a part of the manufacturing process of the manufacturing method of the photoelectric conversion device according to

Embodiments

1 and 3. FIG. It is the typical top view which looked at the transparent insulation board | substrate before formation of the peripheral insulation area | region in the manufacturing process of the manufacturing method of the conventional thin film solar cell from the upper direction. FIG. 6 is a schematic plan view illustrating another example of a part of the manufacturing process of the photoelectric conversion device manufacturing method according to the first embodiment. FIG. 10 is a schematic plan view illustrating an example of a part of the manufacturing process of the photoelectric conversion device manufacturing method according to the second embodiment. FIG. 12 is a schematic plan view illustrating another example of a part of the manufacturing process of the method for manufacturing the photoelectric conversion device according to the second embodiment. FIG. 12 is a schematic plan view illustrating still another example of part of the manufacturing process of the method for manufacturing the photoelectric conversion device according to the second embodiment. FIG. 10 is a schematic enlarged plan view illustrating an example of a part of the manufacturing process of the method for manufacturing the photoelectric conversion device according to the third embodiment. FIG. 10 is a schematic plan view illustrating an example of a part of the manufacturing process of the photoelectric conversion device manufacturing method according to the fourth embodiment. FIG. 10 is a schematic plan view illustrating an example of a part of the manufacturing process of the photoelectric conversion device manufacturing method according to the fourth embodiment. FIG. 10 is a schematic enlarged plan view illustrating an example of a part of the manufacturing process of the photoelectric conversion device manufacturing method according to the fourth embodiment.

Hereinafter, embodiments of the present invention will be described. In the drawings of the present invention, the same reference numerals represent the same or corresponding parts.

<Embodiment 1>
First, as shown in the schematic sectional view of FIG. 1, the transparent electrode layer 2 is laminated on the transparent insulating substrate 1. Here, as the transparent insulating substrate 1, a glass substrate etc. can be used, for example. Further, as the transparent electrode layer 2, for example, a layer made of SnO ₂ (tin oxide), ITO (Indium Tin Oxide) or ZnO (zinc oxide) can be used. The formation method of the transparent electrode layer 2 is not specifically limited, For example, conventionally well-known thermal CVD method, sputtering method, a vapor deposition method, or an ion plating method etc. can be used.

Next, as shown in the schematic cross-sectional view of FIG. 2, by irradiating the laser beam from the transparent insulating substrate 1 side and / or the transparent electrode layer 2 side by moving the laser beam linearly, A part of the corresponding transparent electrode layer 2 is removed in a stripe shape to form a first separation groove 5 for separating the transparent electrode layer 2.

As a laser beam used for forming the first separation groove 5, a fundamental wave (wavelength: 1064 nm) of YAG (Yttrium Aluminum Garnet) laser beam or a fundamental wave (wavelength: 1064 nm) of YVO ₄ (Yttrium Orthovanadate) laser beam is used. It is preferable to use it.

Next, as shown in the schematic cross-sectional view of FIG. 3, the surface of the transparent insulating substrate 1 is subjected to ultrasonic cleaning using pure water, for example, and then the transparent electrode layer 2 separated by the first separation groove 5. The photoelectric conversion layer 3 is laminated so as to cover.

As the photoelectric conversion layer 3, a semiconductor photoelectric conversion layer can be used. For example, a top cell (first photoelectric layer) in which a p layer, an i layer, and an n layer made of an amorphous silicon thin film are stacked in this order from the transparent insulating substrate 1 side. Conversion layer) and a bottom cell (second photoelectric conversion layer) in which a p layer, an i layer, and an n layer made of a microcrystalline silicon thin film are stacked in this order can be stacked on the top cell by, for example, a plasma CVD method. .

The photoelectric conversion layer 3 includes, for example, a top cell (first photoelectric conversion layer) in which a p layer, an i layer, and an n layer made of an amorphous silicon thin film are stacked in this order from the transparent insulating substrate 1 side, and a top cell. In addition, a middle cell (second photoelectric conversion layer) in which a p layer, an i layer and an n layer made of an amorphous silicon thin film are laminated in this order, and a p layer, an i layer and an n layer made of a microcrystalline silicon thin film are formed on the middle cell. The bottom cell (third photoelectric conversion layer) stacked in order may be stacked by, for example, a plasma CVD method. Note that the number of photoelectric conversion layers can be increased.

The photoelectric conversion layers from the first photoelectric conversion layer to the third photoelectric conversion layer may all be made of the same type of silicon-based semiconductor, or may be made of different types of silicon-based semiconductor.

When each photoelectric conversion layer from the first photoelectric conversion layer to the third photoelectric conversion layer includes a p-type semiconductor layer, an i-type semiconductor layer, and an n-type semiconductor layer, respectively, the p-type semiconductor layer and the i-type semiconductor Each semiconductor layer of the layer and the n-type semiconductor layer may be made of a silicon-based semiconductor, for example.

Each semiconductor layer included in the photoelectric conversion layer 3 may be made of the same kind of silicon-based semiconductor, or may be made of different types of silicon-based semiconductor. For example, the p-type semiconductor layer and the i-type semiconductor layer may be formed of amorphous silicon, and the n-type semiconductor layer may be formed of microcrystalline silicon. Further, for example, the p-type semiconductor layer and the n-type semiconductor layer may be formed of silicon carbide or silicon germanium, and the i-type semiconductor layer may be formed of silicon.

Further, each of the p-type, i-type and n-type semiconductor layers may have a single-layer structure or a multi-layer structure. In the case of a multi-layer structure, each semiconductor layer may be composed of different types of silicon-based semiconductors.

The concept of an amorphous silicon thin film includes a thin film made of a hydrogenated amorphous silicon-based semiconductor (a-Si: H) in which dangling bonds of silicon are terminated with hydrogen. The concept of a microcrystalline silicon thin film includes a thin film made of a hydrogenated microcrystalline silicon-based semiconductor (μc-Si: H) in which dangling bonds of silicon are terminated with hydrogen. The thickness of the photoelectric conversion layer 3 is not particularly limited, and can be, for example, 200 nm or more and 5 μm or less. The formation method of the photoelectric conversion layer 3 is not limited to the plasma CVD method.

Next, as shown in the schematic cross-sectional view of FIG. 4, the laser light is linearly moved in the extending direction of the first separation groove 5 and irradiated from the transparent insulating substrate 1 side and / or the photoelectric conversion layer 3 side. By doing so, a part of the photoelectric conversion layer 3 is removed in a stripe shape, and a second separation groove 6 for separating the photoelectric conversion layer 3 is formed.

As the laser beam used for forming the second separation groove 6, it is preferable to use the second harmonic (wavelength: 532 nm) of the YAG laser beam or the second harmonic (wavelength: 532 nm) of the YVO ₄ laser beam. Since the second harmonic of the YAG laser light and the second harmonic of the YVO ₄ laser light tend to pass through the transparent insulating substrate 1 and the transparent electrode layer 2 and be absorbed by the photoelectric conversion layer 3, respectively, the photoelectric conversion layer 3 The photoelectric conversion layer 3 tends to be selectively evaporated by heating.

Next, as shown in the schematic cross-sectional view of FIG. 5, the back electrode layer 4 is laminated so as to cover the photoelectric conversion layer 3. Thereby, as shown in FIG. 5, the second separation groove 6 is filled with the back electrode layer 4.

As the back electrode layer 4, for example, a laminate of a metal thin film made of silver or aluminum and a transparent conductive film such as ZnO can be used. Here, the thickness of the metal thin film can be, for example, 100 nm or more and 1 μm or less, and the thickness of the transparent conductive film can be, for example, 20 nm or more and 200 nm or less. When a transparent conductive film is installed between the back electrode layer 4 made of a single layer or multiple layers of metal thin film and the photoelectric conversion layer 3, metal atoms are transferred from the back electrode layer 4 made of metal thin film to the photoelectric conversion layer 3. It is preferable in that it can be prevented from diffusing and the reflectance of sunlight by the back electrode layer 4 tends to be improved. Needless to say, as the back electrode layer 4, only a single metal thin film layer or a plurality of metal thin film layers may be used. The method for forming the back electrode layer 4 is not particularly limited, and for example, a sputtering method or the like can be used.

Next, as shown in the schematic cross-sectional view of FIG. 6, laser light is directed in the extending direction of the first separation groove 5 and the second separation groove 6 from the transparent insulating substrate 1 side and / or the back electrode layer 4 side. A scribe line 7 is formed by removing a part of the photoelectric conversion layer 3 and the back electrode layer 4 in a stripe shape by moving in a straight line and irradiating the photoelectric conversion layer 3 and the back electrode layer 4. A line forming process is performed.

As the laser light used for forming the scribe line 7, it is preferable to use the second harmonic (wavelength: 532 nm) of the YAG laser light or the second harmonic (wavelength: 532 nm) of the YVO ₄ laser light. Since the second harmonic of the YAG laser light and the second harmonic of the YVO ₄ laser light tend to pass through the transparent insulating substrate 1 and the transparent electrode layer 2 and be absorbed by the photoelectric conversion layer 3, respectively, the photoelectric conversion layer 3 Is selectively heated, and the photoelectric conversion layer 3 and the back electrode layer 4 tend to be selectively evaporated.

Here, in the first embodiment, for example, as shown in the schematic plan view of FIG. 7, the region 9 where the peripheral insulating region is formed in the peripheral insulating step for forming the peripheral insulating region described later is irradiated with laser light. To stop. Thereby, in the scribe line forming step, the scribe line 7 is formed so that at least one of the photoelectric conversion layer 3 and the back electrode layer 4 is left in the region 9 where the peripheral insulating region is formed in the peripheral insulating step. The In FIG. 7, not all scribe lines 7 are shown for convenience of explanation.

Next, as shown in the schematic cross-sectional view of FIG. 8, the transparent electrode layer 2, the photoelectric conversion layer 3, and the back electrode layer 4 on the entire periphery of the transparent insulating substrate 1 are removed by laser light irradiation to thereby perform peripheral insulation. A peripheral insulating process for forming the region 10 is performed. Accordingly, as shown in the schematic plan view of FIG. 9, the peripheral insulating region in which the surface of the transparent insulating substrate 1 is exposed so as to surround the string 12 in which the adjacent power generation cells 11 are sequentially connected in series. 10 is formed, and the photoelectric conversion device of Embodiment 1 can be manufactured. When performing the peripheral insulating step, at least one of the photoelectric conversion layer 3 and the back electrode layer 4 exists in the region where the peripheral insulating region 10 is formed.

As the laser light used for forming the peripheral insulating region 10, it is preferable to use the fundamental wave of YAG laser light (wavelength: 1064 nm) or the fundamental wave of YVO ₄ laser light (wavelength: 1064 nm). Further, since the peripheral insulating region 10 is generally formed wide, the irradiation width of the laser light (the length in the direction orthogonal to the moving direction of the laser light) is preferably 150 μm or more, and preferably 400 μm or more. Is more preferable. Further, when the peripheral insulating region 10 is formed, the laser beam can be irradiated from the transparent insulating substrate 1 side and / or the back electrode layer 4 side.

In order to improve the state of the peripheral insulating region 10 after irradiation with laser light, the intensity distribution of the laser light is preferably a rectangular distribution in each of the moving direction and the width direction of the laser light. In this case, for example, an optical system using a galvano scan or an optical system using a square fiber can be used without any particular limitation.

In addition, on the surface of the back electrode layer 4 at both ends in the direction orthogonal to the longitudinal direction of the power generation cell 11, current extraction electrodes extending in the longitudinal direction of the power generation cell 11 are formed via a metal paste such as silver paste. You can also

Further, a transparent adhesive made of, for example, an EVA sheet or the like is placed on the surface of the back electrode layer 4 after the current extraction electrode is formed, and the transparent adhesive is, for example, PET (polyester) / Al (aluminum) / PET. After installing the backside sealing material composed of the three-layer laminated film, etc., these are thermocompression bonded, the terminal box is bonded to the backside sealing material, the inside of the terminal box is filled with silicone, and a frame body such as an aluminum frame is formed. It can also be attached.

As described above, in the method for manufacturing the photoelectric conversion device according to the first embodiment, in the scribe line forming step, the irradiation of the laser beam is stopped in the region 9 where the peripheral insulating region 10 is formed in the peripheral insulating step. The scribe line 7 is formed so that at least one of the photoelectric conversion layer 3 and the back electrode layer 4 remains.

As a result of intensive studies by the present inventors, in the conventional method for manufacturing a thin film solar cell described in Patent Document 1, peripheral insulation is achieved by removing the transparent electrode layer, the photoelectric conversion layer, and the back electrode layer by laser light irradiation. When forming the region, for example, as shown in the schematic plan view of FIG. 10, a residue 111 of the transparent electrode layer remains in the vicinity of the scribe line 107 of the peripheral insulating region 110, and this residue 111 is converted into the peripheral insulating region. This is because it has been determined that this is the cause of an insulation failure or an appearance failure in the vicinity of 110 scribe line 107.

That is, in the conventional method for manufacturing a thin-film solar cell described in Patent Document 1, in the scribe line 107 in the region where the peripheral insulating region 110 is formed, only the transparent electrode layer remains on the surface of the transparent insulating substrate. Therefore, the energy of the laser beam irradiated when forming the peripheral insulating region 110 is not sufficiently absorbed by the transparent electrode layer, and the residue 111 of the transparent electrode layer may remain.

Therefore, for example, as shown in FIG. 7, in the scribe line forming step, in the region 9 where the peripheral insulating region 10 is formed in the peripheral insulating step, the irradiation of the laser beam is stopped, so that the region before the peripheral insulating region 10 is formed. Not only the transparent electrode layer 2 but also at least one of the photoelectric conversion layer 3 and the back electrode layer 4 can be left on the entire circumference of the transparent insulating substrate 1.

Thereby, the energy of the laser beam irradiated at the time of forming the peripheral insulating region 10 is sufficiently absorbed not only in the transparent electrode layer 2 but also in at least one of the photoelectric conversion layer 3 and the back electrode layer 4 to be converted into thermal energy. Therefore, generation | occurrence | production of the residue of the transparent electrode layer 2 can be suppressed, and generation | occurrence | production of the insulation defect or appearance defect in the vicinity of the scribe line 7 of the peripheral insulating region 10 can be suppressed.

In the above description, in the scribe line forming step, the case where the irradiation of the laser beam is stopped in the region 9 where the peripheral insulating region 10 is formed in the peripheral insulating step has been described. However, the present invention is not limited to this method. .

For example, as shown in the schematic plan view of FIG. 11, in the scribe line forming process, the region 9 where the peripheral insulating area 10 is formed in the peripheral insulating process is covered with a mask 13 such as a metal plate. Irradiation can remove the photoelectric conversion layer 3 and the back electrode layer 4 to form the scribe line 7. Also in this case, not only the transparent electrode layer 2 but also at least one of the photoelectric conversion layer 3 and the back electrode layer 4 can be left on the entire periphery of the transparent insulating substrate 1 before the formation of the peripheral insulating region 10, Since generation | occurrence | production of the residue of the transparent electrode layer 2 can be suppressed, generation | occurrence | production of the insulation defect or the appearance defect in the vicinity of the scribe line 7 of the peripheral insulating region 10 can be suppressed.

Further, in this case, when the scribe line 7 is formed, it is not necessary to finely adjust the irradiation position for stopping the irradiation of the laser beam, so that the insulation failure or appearance in the vicinity of the scribe line 7 in the peripheral insulating region 10 is eliminated. The reproducibility of suppressing the occurrence of defects can be improved.

In addition, the adjustment method of the irradiation position of the laser beam at the time of formation of the scribe line 7 is not specifically limited, For example, the method of adjusting by alignment of the transparent insulating substrate 1 on the stage of a laser scribing apparatus, the transparent insulating substrate 1 Use a method of detecting the end in advance and adjusting the distance from the end of the transparent insulating substrate 1 or adjusting using an alignment mark formed when the first separation groove 5 is formed. Can do.

In the above, the first separation groove 5 and the second separation groove 6 may be formed in the region 9 where the peripheral insulating region 10 is formed in the peripheral insulating step.

<Embodiment 2>
In the method of manufacturing the photoelectric conversion device according to the second embodiment, a cross scribe line that intersects the scribe line 7 is formed, and at the time of forming the cross scribe line, the region 9 in which the peripheral insulating region 10 is formed in the peripheral insulating step. Is characterized in that at least one of the photoelectric conversion layer 3 and the back electrode layer 4 is left in the region 9 without forming a cross scribe line.

That is, the same process as in the first embodiment is performed until the process of forming the scribe line 7 is performed.

Next, as shown in the schematic plan view of FIG. 12, a step of forming the intersecting scribe line 8 by forming the intersecting scribe line 8 intersecting with the scribe line 7 is performed. Here, in the step of forming the intersecting scribe lines 8, the irradiation of the laser beam is stopped in the region 9 where the peripheral insulating region 10 is formed in the peripheral insulating step. Thereby, not only the transparent electrode layer 2 but also at least one of the photoelectric conversion layer 3 and the back electrode layer 4 remains in the region 9 where the peripheral insulating region 10 is formed in the peripheral insulating step. In the step of forming the intersecting scribe lines 8, the laser light can be irradiated from the transparent insulating substrate 1 side and / or the back electrode layer 4 side.

As a result of intensive studies by the present inventors, in the conventional method for manufacturing a thin film solar cell described in Patent Document 2, peripheral insulation is achieved by removing the transparent electrode layer, the photoelectric conversion layer, and the back electrode layer by laser light irradiation. When forming the region, the transparent electrode layer residue remains not only in the vicinity of the scribe line but also in the vicinity of the cross scribe line, and this residue is in the vicinity of the scribe line and the cross scribe line in the peripheral insulating region. This is because it has been found that this is the cause of an insulation failure or an appearance failure.

That is, in the conventional method for manufacturing a thin-film solar cell described in Patent Document 2, only the transparent electrode layer remains on the surface of the transparent insulating substrate in the scribe line and the cross scribe line in the region where the peripheral insulating region is formed. In this state, the energy of the laser beam irradiated when forming the peripheral insulating region is not sufficiently absorbed by the transparent electrode layer, and a residue of the transparent electrode layer may remain.

Therefore, for example, as shown in FIG. 12, in each of the step of forming the scribe line 7 and the step of forming the intersecting scribe line 8, the region where the peripheral insulating region 10 is formed in the step of forming the peripheral insulating region 10. 9, by stopping the laser light irradiation, not only the transparent electrode layer 2 but also at least one of the photoelectric conversion layer 3 and the back electrode layer 4 can be left in the region 9.

Thereby, in the manufacturing method of the photoelectric conversion device according to the second embodiment, the laser beam irradiated at the time of forming the peripheral insulating region 10 in both the step of forming the scribe line 7 and the step of forming the intersecting scribe line 8. Can be absorbed not only in the transparent electrode layer 2 but also in at least one of the photoelectric conversion layer 3 and the back electrode layer 4 to be converted into thermal energy, thereby suppressing the generation of residues in the transparent electrode layer 2 In addition, it is possible to suppress the occurrence of poor insulation or poor appearance in the vicinity of the scribe line 7 and the cross scribe line 8 in the peripheral insulating region 10.

In the present specification, the angle formed between the scribe line 7 and the intersecting scribe line 8 can be set to 90 ° ± 10 °, for example.

In the step of forming the intersecting scribe line 8, only the photoelectric conversion layer 3 and the back electrode layer 4 may be removed by laser light irradiation, and the transparent electrode layer 2, the photoelectric conversion layer 3, and the back electrode layer 4 may be removed. All may be removed by laser light irradiation. When forming the second scribe line 8 by removing all of the transparent electrode layer 2, the photoelectric conversion layer 3, and the back electrode layer 4 by laser light irradiation in the step of forming the intersecting scribe line 8, It is not necessary to form the intersecting scribe lines 8 by the above method.

The method of adjusting the type of laser light and the irradiation position of the laser light at the time of forming the second scribe line 8 is not particularly limited, and for example, the same type of laser light and laser light as at the time of forming the scribe line 7 are used. An irradiation position adjustment method or the like can be used.

Further, in the above description, in the region 9 where the peripheral insulating region 10 is formed in the peripheral insulating step, the case where the laser beam irradiation is stopped and the cross scribe line 8 is formed has been described. The forming method is not limited to this method.

For example, as shown in the schematic plan view of FIG. 13, in the step of forming the intersecting scribe lines 8, the region 9 in which the peripheral insulating region 10 is formed in the peripheral insulating step is covered with a mask 13 such as a metal plate. The cross scribe line 8 can also be formed by irradiating laser light. Also in this case, not only the transparent electrode layer 2 but also at least one of the photoelectric conversion layer 3 and the back electrode layer 4 can be left on the entire periphery of the transparent insulating substrate 1 before the formation of the peripheral insulating region 10, Since generation | occurrence | production of the residue of the transparent electrode layer 2 can be suppressed, generation | occurrence | production of the insulation defect or appearance defect in the vicinity of the cross scribe line 8 of the peripheral insulating region 10 can be suppressed.

Further, in this case, when the cross scribe line 8 is formed, it is not necessary to finely adjust the stop position of the laser beam irradiation. Therefore, the insulation defect or the appearance defect in the vicinity of the cross scribe line 8 in the peripheral insulating region 10 is eliminated. The reproducibility of occurrence suppression can be improved.

For example, as shown in the schematic plan view of FIG. 14, the region 9 in which the peripheral insulating region 10 is formed in the peripheral insulating step is covered in advance with a mask 13 such as a metal plate, and laser light is irradiated in this state. By doing so, the scribe line 7 and the intersecting scribe line 8 can also be formed. Also in this case, not only the transparent electrode layer 2 but also at least one of the photoelectric conversion layer 3 and the back electrode layer 4 can be left in the region 9 where the peripheral insulating region 10 is formed in the peripheral insulating step. Generation | occurrence | production of the residue of the layer 2 can be suppressed and generation | occurrence | production of the insulation defect or the appearance defect in the vicinity of the scribe line 7 and the cross scribe line 8 of the peripheral insulating region 10 can be suppressed.

Further, in this case, when the scribe line 7 and the intersecting scribe line 8 are formed, it is not necessary to finely adjust the laser beam irradiation stop position. The reproducibility of the suppression of the occurrence of insulation failure or appearance failure in the vicinity of the scribe line 8 can be further enhanced.

Since the explanation other than the above in the second embodiment is the same as that in the first embodiment, the explanation thereof is omitted here.

<Embodiment 3>
First, as shown in FIG. 1, a transparent electrode layer 2 is laminated on a transparent insulating substrate 1. Here, as the transparent insulating substrate 1, a glass substrate etc. can be used, for example. Further, as the transparent electrode layer 2, for example, a layer made of SnO ₂ (tin oxide), ITO (Indium Tin Oxide) or ZnO (zinc oxide) can be used. The formation method of the transparent electrode layer 2 is not specifically limited, For example, conventionally well-known thermal CVD method, sputtering method, a vapor deposition method, or an ion plating method etc. can be used.

Next, as shown in FIG. 2, the transparent electrode layer corresponding to the irradiated portion of the laser beam is irradiated by moving the laser beam linearly from the transparent insulating substrate 1 side and / or the transparent electrode layer 2 side. A part of 2 is removed in a stripe shape to form a first separation groove 5 for separating the transparent electrode layer 2.

As a laser beam used for forming the first separation groove 5, a fundamental wave (wavelength: 1064 nm) of YAG (Yttrium Aluminum Garnet) laser beam or a fundamental wave (wavelength: 1064 nm) of YVO ₄ (Yttrium Orthovanadate) laser beam is used. It is preferable to use it. Since the fundamental wave of YAG laser light and the fundamental wave of YVO ₄ laser light tend to pass through the transparent insulating substrate 1 and be absorbed by the transparent electrode layer 2, the transparent electrode layer 2 is selectively heated to evaporate. It tends to be able to be made.

Next, as shown in FIG. 3, the surface of the transparent insulating substrate 1 is subjected to ultrasonic cleaning using pure water, for example, and then photoelectrically covered so as to cover the transparent electrode layer 2 separated by the first separation groove 5. The conversion layer 3 is laminated.

When each photoelectric conversion layer from the first photoelectric conversion layer to the third photoelectric conversion layer includes a p-type semiconductor layer, an i-type semiconductor layer, and an n-type semiconductor layer, respectively, the p-type semiconductor layer and the i-type semiconductor Each semiconductor layer of the layer and the n-type semiconductor layer may be made of, for example, a silicon-based semiconductor.

Next, as shown in FIG. 4, the laser light is linearly moved in the extending direction of the first separation groove 5 and irradiated from the transparent insulating substrate 1 side and / or the photoelectric conversion layer 3 side. A part of the conversion layer 3 is removed in a stripe shape to form a second separation groove 6 that separates the photoelectric conversion layer 3.

Next, as shown in FIG. 5, the back electrode layer 4 is laminated so as to cover the photoelectric conversion layer 3. Thereby, as shown in FIG. 5, the second separation groove 6 is filled with the back electrode layer 4.

Next, as shown in FIG. 6, the laser beam is linearly moved in the extending direction of the first separation groove 5 and the second separation groove 6 from the transparent insulating substrate 1 side and / or the back electrode layer 4 side. By irradiating, a part of the photoelectric conversion layer 3 and the back electrode layer 4 is removed in a stripe shape, and a scribe line 7 for separating the photoelectric conversion layer 3 and the back electrode layer 4 is formed.

Next, as shown in FIG. 8, the transparent electrode layer 2, the photoelectric conversion layer 3, and the back electrode layer 4 on the entire periphery of the transparent insulating substrate 1 are removed by irradiation while moving the laser beam. As a result, as shown in FIG. 9, the peripheral insulating region 10 is formed so that the surface of the transparent insulating substrate 1 is exposed so as to surround the string 12 in which the adjacent power generation cells 11 are sequentially connected in series. The photoelectric conversion device of Embodiment 3 can be manufactured.

As the laser light used for forming the peripheral insulating region 10, it is preferable to use the fundamental wave of YAG laser light (wavelength: 1064 nm) or the fundamental wave of YVO ₄ laser light (wavelength: 1064 nm). Since the fundamental wave of the YAG laser beam and the fundamental wave of the YVO ₄ laser beam tend to pass through the transparent insulating substrate 1 and be absorbed by the transparent electrode layer 2, the transparent electrode layer 2 is selectively heated to be transparent. The electrode layer 2, the photoelectric conversion layer 3, and the back electrode layer 4 tend to evaporate and be removed. Further, since the peripheral insulating region 10 is generally formed wide, the irradiation width of the laser light (the length in the direction orthogonal to the moving direction of the laser light) is preferably 150 μm or more, and preferably 400 μm or more. Is more preferable. Further, when the peripheral insulating region 10 is formed, the laser beam can be irradiated from the transparent insulating substrate 1 side and / or the back electrode layer 4 side.

In the method of manufacturing the photoelectric conversion device according to the third embodiment, for example, as shown in the schematic enlarged plan view of FIG. 15, the scribe line 7 is formed in the formation region of the scribe line 7 when the peripheral insulating region 10 is formed. The transparent electrode layer 2 and the photoelectric conversion are performed by irradiating the laser beam by reducing the moving speed of the laser beam (that is, by narrowing the interval of the laser beam irradiation region 14) as compared with the region that is not formed. The peripheral insulating region 10 is formed by evaporating the layer 3 and the back electrode layer 4.

That is, in the conventional method for manufacturing a thin-film solar cell described in Patent Document 1, in the scribe line 107 in the region where the peripheral insulating region 110 is formed, only the transparent electrode layer remains on the surface of the transparent insulating substrate. Therefore, the energy of the laser beam irradiated when forming the peripheral insulating region 110 is not sufficiently absorbed by the transparent electrode layer, and the residue 111 of the transparent electrode layer remains.

Therefore, for example, as shown in FIG. 15, when forming the peripheral insulating region 10, the moving speed of the laser beam is reduced in the region where the scribe line 7 is formed compared to the region where the scribe line 7 is not formed. , The amount of energy applied to the formation region of the scribe line 7 is increased, and the removal capability by laser light irradiation is locally improved. Thereby, since it can suppress that the transparent electrode layer 2 remains as a residue in the formation area of the scribe line 7, generation | occurrence | production of the insulation defect or appearance defect in the vicinity of the scribe line 7 of the peripheral insulating area 10 can be suppressed. .

Further, the moving speed of the laser light in the region where the scribe line 7 is not formed when the peripheral insulating region 10 is formed is preferably 10 mm / second or more and 400 mm / second or less, and 50 mm / second or more and 150 mm / second or less. It is more preferable that it is 80 mm / second or more and 110 mm / second or less. When the moving speed of the laser light in the region where the scribe line 7 is not formed when the peripheral insulating region 10 is formed is 10 mm / second or more and 400 mm / second or less, more preferably 50 mm / second or more and 150 mm / second or less. In particular, in the case of 80 mm / second or more and 110 mm / second or less, the transparent electrode layer 2, the photoelectric conversion layer 3, and the back electrode layer 4 can be removed more efficiently and more reliably. Tends to be formed more efficiently.

Further, the moving speed of the laser light in the region where the scribe line 7 is formed when the peripheral insulating region 10 is formed is lower than the moving speed of the laser light in the region where the scribe line 7 is not formed and is 5 mm / second or more. It is preferably 200 mm / second or less, more preferably 10 mm / second or more and 100 mm / second or less, and further preferably 50 mm / second or more and 90 mm / second or less. When the peripheral insulating region 10 is formed, the moving speed of the laser light in the region where the scribe line 7 is formed is lower than the moving speed of the laser light in the region where the scribe line 7 is not formed, and is 5 mm / second or more and 200 mm / second. Or less, more preferably 10 mm / second or more and 100 mm / second or less, and particularly 50 mm / second or more and 90 mm / second or less, the transparent electrode layer 2 of the scribe line 7 is more efficiently and more reliable. Therefore, the peripheral insulating region 10 tends to be formed more efficiently.

Further, when the peripheral insulating region 10 is formed, it is preferable that the moving speed of the laser light is temporarily made zero in the region where the scribe line 7 is formed. In this case, the transparent electrode layer 2 tends to be removed more reliably.

In addition, the adjustment method of the irradiation position of the laser beam at the time of formation of the peripheral insulating region 10 is not specifically limited, For example, the method of adjusting by the alignment of the transparent insulating substrate 1 on the stage of a laser scribing apparatus, the transparent insulating substrate 1 A method of detecting the end portion of the transparent insulating substrate 1 in advance and adjusting it at a predetermined distance from the end portion of the transparent insulating substrate 1 or a method of adjusting using an alignment mark formed at the time of forming the first separation groove 5 is used. be able to.

<Embodiment 4>
In the method of manufacturing the photoelectric conversion device according to the fourth embodiment, a cross scribe line intersecting the scribe line 7 is formed, and not only the formation region of the scribe line 7 but also the formation of the cross scribe line is formed when the peripheral insulating region 10 is formed. Even in the region, the moving speed of the laser beam is reduced.

That is, in the method of manufacturing the photoelectric conversion device of the fourth embodiment, the same processes as those of the third embodiment are performed until the scribe line 7 is formed.

Next, as shown in the schematic plan view of FIG. 16, an intersecting scribe line 8 that intersects the scribe line 7 is formed. Here, when the intersecting scribe line 8 is formed, the laser beam can be irradiated from the transparent insulating substrate 1 side and / or the back electrode layer 4 side.

Next, as shown in the schematic plan view of FIG. 17, by irradiating the transparent electrode layer 2, the photoelectric conversion layer 3, and the back electrode layer 4 on the entire circumference of the transparent insulating substrate 1 while moving the laser beam. Remove and remove. As a result, the peripheral insulating region 10 where the surface of the transparent insulating substrate 1 is exposed is formed so as to surround the periphery of the string 12 in which the adjacent power generation cells 11 are sequentially connected in series. A conversion device can be made.

In the method for manufacturing the photoelectric conversion device of the fourth embodiment, for example, as shown in FIG. 15, when the peripheral insulating region 10 is formed, the region where the scribe line 7 is formed is compared with the region where the scribe line 7 is not formed. Then, the transparent electrode layer 2, the photoelectric conversion layer 3, and the back electrode layer are irradiated by irradiating the laser beam by reducing the moving speed of the laser beam (that is, by narrowing the interval between the laser beam irradiation regions 14). 4 is evaporated to form the peripheral insulating region 10.

Furthermore, in the method for manufacturing the photoelectric conversion device according to the fourth embodiment, as shown in the schematic plan view of FIG. 18, when forming the peripheral insulating region 10, Compared with the region where 8 is not formed, the moving speed of the laser beam is reduced (that is, the interval between the laser beam irradiation regions 14 is narrowed) and the transparent electrode layer 2 is irradiated with the laser beam. Then, the photoelectric conversion layer 3 and the back electrode layer 4 are evaporated to form the peripheral insulating region 10.

That is, in the conventional method for manufacturing a thin-film solar cell described in Patent Document 2, only the transparent electrode layer remains on the surface of the transparent insulating substrate in the scribe line and the cross scribe line in the region where the peripheral insulating region is formed. Thus, the energy of the laser beam irradiated when forming the peripheral insulating region is not sufficiently absorbed by the transparent electrode layer, and the residue of the transparent electrode layer remains.

Therefore, for example, as shown in FIGS. 15 and 18, when the peripheral insulating region 10 is formed, the region where the scribe line 7 and the cross scribe line 8 are formed is compared with the region where the scribe line 7 and the cross scribe line 8 are not formed. Then, by irradiating the laser beam while reducing the moving speed of the laser beam, the amount of energy applied to the formation region of the scribe line 7 and the intersecting scribe line 8 is increased, and the removal capability by the laser beam irradiation is locally improved. . Thereby, since it can suppress that the transparent electrode layer 2 remains as a residue in the formation area of the scribe line 7 and the cross scribe line 8, in the vicinity of each of the scribe line 7 and the cross scribe line 8 in the peripheral insulating region 10. Occurrence of insulation failure or appearance failure can be suppressed.

Further, at the time of forming the intersecting scribe line 8, only the photoelectric conversion layer 3 and the back electrode layer 4 may be removed by laser light irradiation, and all of the transparent electrode layer 2, the photoelectric conversion layer 3, and the back electrode layer 4 are removed. May be removed by laser light irradiation. Only when the photoelectric conversion layer 3 and the back electrode layer 4 are removed by laser light irradiation to form the cross scribe line 8, the laser beam is formed in the formation region of the cross scribe line 8 when forming the peripheral insulating region 10. It is only necessary to irradiate the laser beam at a lower moving speed.

Further, the method of adjusting the type of laser light and the irradiation position of the laser light when forming the intersecting scribe line 8 is not particularly limited, and for example, the same type of laser light and the irradiation position of the laser light as when forming the scribe line 7 are used. Can be used.

Further, the moving speed of the laser light in the formation area of the cross scribe line 8 when forming the peripheral insulating region 10 is lower than the moving speed of the laser light in the area where the scribe line 7 and the cross scribe line 8 are not formed. In addition, it is preferably 5 mm / second or more and 200 mm / second or less, more preferably 10 mm / second or more and 100 mm / second or less, and further preferably 50 mm / second or more and 90 mm / second or less. When the peripheral insulating region 10 is formed, the moving speed of the laser light in the region where the cross scribe line 8 is formed is lower than the moving speed of the laser light in the region where the scribe line 7 and the cross scribe line 8 are not formed, and 5 mm. Transparent electrode layer 2 of the crossed scribe line 8 when it is 10 mm / second or more and 200 mm / second or less, more preferably 10 mm / second or more and 100 mm / second or less, particularly 50 mm / second or more and 90 mm / second or less. Therefore, the peripheral insulating region 10 tends to be formed more efficiently.

Further, when the peripheral insulating region 10 is formed, it is preferable that the moving speed of the laser light is temporarily reduced to zero in the region where the cross scribe line 8 is formed. In this case, the transparent electrode layer 2 tends to be removed more reliably.

Since the description other than the above in the fourth embodiment is the same as that in the third embodiment, the description thereof is omitted here.

As described above, the embodiments of the present invention have been described, but it is also planned from the beginning to appropriately combine the configurations of the above-described embodiments.

The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

The present invention can be used for a method for manufacturing a photoelectric conversion device, and can be particularly preferably used for a method for manufacturing a thin film solar cell.

1 transparent insulation substrate, 2 transparent electrode layer, 3 photoelectric conversion layer, 4 back electrode layer, 5 first separation groove, 6 second separation groove, 7 scribe line, 8 cross scribe line, 9 area, 10 peripheral insulation area , 11 power generation cell, 12 string, 13 mask, 14 laser light irradiation area, 107 scribe line, 110 peripheral insulating area, 111 residue.

Claims

On the entire circumference of the transparent insulating substrate (1) with respect to the transparent insulating substrate (1) in which the transparent electrode layer (2), the photoelectric conversion layer (3), and the back electrode layer (4) are laminated in this order. A peripheral insulating step of forming the peripheral insulating region (10) by removing the transparent electrode layer (2), the photoelectric conversion layer (3) and the back electrode layer (4) by irradiation with laser light,
When performing the peripheral insulating step, in the region of forming the peripheral insulating region (10), at least one of the photoelectric conversion layer (3) and the back electrode layer (4) is present. Production method.
A scribe line forming step of forming the scribe line (7) by linearly removing the photoelectric conversion layer (3) and the back electrode layer (4);
In the scribe line forming step, at least one of the photoelectric conversion layer (3) and the back electrode layer (4) is left in a region where the peripheral insulating region (10) is formed in the peripheral insulating step. The manufacturing method of the photoelectric conversion apparatus of description.
The scribe line forming step includes a step of forming the scribe line (7) by removing the photoelectric conversion layer (3) and the back electrode layer (4) by laser light irradiation, and the peripheral insulating step. The method for manufacturing a photoelectric conversion device according to claim 2, further comprising a step of stopping irradiation of the laser light in a region where the insulating region (10) is formed.
The scribe line forming step includes a step of covering a region where the peripheral insulating region (10) is formed in the peripheral insulating step with a mask (13), and the photoelectric conversion layer (3) and the back electrode by laser light irradiation. The method for manufacturing a photoelectric conversion device according to claim 2, comprising a step of removing the layer (4) to form a scribe line (7).
The method for manufacturing a photoelectric conversion device according to any one of claims 2 to 4, wherein the scribe line forming step is performed before the peripheral insulating step.
Laminating the photoelectric conversion layer (3) on the transparent electrode layer (2) laminated on the transparent insulating substrate (1);
Laminating a back electrode layer (4) on the photoelectric conversion layer (3);
Removing a part of each of the photoelectric conversion layer (3) and the back electrode layer (4) by laser light irradiation to form a scribe line (7);
The transparent electrode layer (2), the photoelectric conversion layer (3) and the back electrode layer (4) on the entire circumference of the transparent insulating substrate (1) are removed by irradiating while moving the laser beam. Forming a peripheral insulating region (10),
In the step of forming the peripheral insulating region (10), a method for manufacturing a photoelectric conversion device, wherein a moving speed of laser light is reduced in a region where the scribe line (7) is formed.
The method for manufacturing a photoelectric conversion device according to claim 6, wherein in the step of forming the peripheral insulating region (10), the moving speed of the laser beam is temporarily made zero in the formation region of the scribe line (7).
A step of forming a crossed scribe line (8) intersecting the scribe line (7) by removing a part of each of the photoelectric conversion layer (3) and the back electrode layer (4) by laser light irradiation. Including
The method for manufacturing a photoelectric conversion device according to claim 6 or 7, wherein, in the step of forming the peripheral insulating region (10), the moving speed of the laser beam is reduced in a region where the intersecting scribe line (8) is formed.
The method for manufacturing a photoelectric conversion device according to claim 8, wherein in the step of forming the peripheral insulating region (10), the moving speed of the laser beam is temporarily made zero in the formation region of the intersecting scribe line (8).