JPH11195795A - Integrated silicon-based thin-film photoelectric converter and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an integrated silicon-based thin-film photoelectric converter which has a superior photoelectric conversion characteristic and can generate high output under high voltage. SOLUTION: In an integrated silicon-based thin-film photoelectric converter, a back electrode layer 102, at least one crystalline silicon-based photoelectric conversion unit layer 105, a transparent conductive cap layer 111, and a transparent electrode layer 108 which are successively formed on an insulating substrate 101, are divided into a plurality of parts so that each part forms a photoelectric conversion cell, by forming a plurality of substantially linear parallel separating grooves 104 and 109 through the layers 108, 111, 105, and 102. The cells are connected in series with the grooves 104 and 109 through a plurality of parallel grooves 107 for connection.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a thin-film photoelectric conversion device, and more particularly to integration of a photoelectric conversion cell including at least one crystalline silicon-based photoelectric conversion unit layer and improvement of characteristics of the integrated silicon-based thin-film photoelectric conversion device. It is about.

[0002]

2. Description of the Related Art In recent years, photoelectric conversion devices using thin films containing crystalline silicon such as polycrystalline silicon and microcrystalline silicon have been vigorously developed. These developments are attempts to achieve both low cost and high performance of the photoelectric conversion device by forming a high-quality crystalline silicon thin film on an inexpensive substrate by a low-temperature process.
Application to useful photoelectric conversion devices such as optical sensors as well as solar cells is expected.

[0003] When a large-area photoelectric conversion device capable of producing high output at a high voltage is produced, a plurality of solar cells formed on a plurality of large substrates are connected in series in an amorphous silicon-based photoelectric conversion device. In order to improve the yield, it is common to divide a solar cell formed on one large substrate into a plurality of cells and connect the cells in series to perform integration. is there. In particular, in a pin-type amorphous silicon-based photoelectric conversion device including a p-layer, an i-layer, and an n-layer sequentially stacked from the substrate side so that light is incident from the glass substrate side, the resistance of the transparent electrode on the glass substrate is reduced. In order to reduce the loss due to the above, it is common to process the transparent electrode into a rectangular shape with a predetermined width using a laser beam, and directly connect each cell in the direction orthogonal to the longitudinal direction of the rectangular shape for integration. It is.

[0004]

In Japanese Patent Publication No. 5-3752, there is proposed a method of integrating a plurality of cells by using a method of processing by irradiating a laser beam from the transparent substrate side. However, this relates to a solar cell including a pin-type amorphous photoelectric conversion unit layer, and there is no mention of the following problem in the case of including a crystalline silicon-based photoelectric conversion unit layer, particularly, a nip-type photoelectric conversion unit layer. Not. That is, there is a problem in that the conductivity type layer included in the photoelectric conversion unit layer is instantaneously oxidized when it comes into contact with oxygen, and its electrical characteristics deteriorate. In particular, the p-type layer is more significantly degraded by oxidation than the n-type layer.

In order to avoid the deterioration of the conductivity type layer due to such oxidation, a manufacturing apparatus capable of performing a film forming process and a cell integration process consistently in a vacuum by connecting a laser processing device to a film forming device. It is possible to think. However, such manufacturing equipment is complicated, difficult and expensive to design, and therefore is not practical as a practical manufacturing equipment. That is, the laser processing apparatus is separate from the film forming apparatus, and the cell integration process is generally performed in the atmosphere.

Therefore, when the connection groove penetrating the photoelectric conversion unit layer is formed by laser processing in order to electrically connect the front electrode and the back electrode in the cell integration step, the surface of the outermost conductive type layer is exposed to the atmosphere. It is exposed and oxidized, whereby the performance of the photoelectric conversion device is reduced.
In particular, in the case of a nip type photoelectric conversion device, the p-layer is exposed to the atmosphere, and the performance of the integrated photoelectric conversion device is significantly reduced. Obtaining the device is very difficult.

In an integrated photoelectric conversion device,
The back electrode separation groove separating the back electrode layer on the insulating substrate is filled with a semiconductor layer deposited on the back electrode layer, and makes unnecessary contact parallel to the substrate via the semiconductor layer. The conductor formed in the connection groove for connecting a plurality of cells in series is in contact with the side surfaces of all the n-type, i-type, and p-type semiconductor layers included in the photoelectric conversion unit. However, the thickness of the photoelectric conversion unit in the thin-film photoelectric conversion device is extremely small, and the amorphous silicon-based photoelectric conversion unit has a high resistance of the amorphous silicon layer itself. As a result, the current hardly flows, and the current almost completely flows in the thickness direction of the photoelectric conversion unit. Therefore, the unnecessary contact as described above does not adversely affect the performance of the photoelectric conversion unit.

However, in the conventional crystalline silicon-based photoelectric conversion unit, since crystal grains grow randomly in various directions, uniform and good conductivity is required in all directions in the crystalline semiconductor layer. Therefore, the leakage of the current through the unnecessary contact portion as described above cannot be neglected, and there is a problem that the performance of the photoelectric conversion unit is deteriorated due to the leakage.

[0009] Due to the above-mentioned problems, conventionally, crystalline silicon-based photoelectric conversion cells, especially nip-type crystalline silicon-based photoelectric conversion cells, are not integrated on a single substrate, but are combed on separate substrates. It is possible to automate the manufacturing process of a large-area photoelectric conversion device that is connected in series by soldering lead wires to a plurality of photoelectric conversion units formed with the mold electrodes and that can generate high output at high voltage. It was inconvenient.

In view of the above-mentioned problems in the prior art, an object of the present invention is to use only a low-temperature process in which an inexpensive substrate can be used and to eliminate crystal grain boundaries and intragranular defects in a crystalline silicon-based thin film photoelectric conversion layer. It is an object of the present invention to provide a large-area integrated silicon-based thin-film photoelectric conversion device capable of producing a high voltage and a large output with excellent photoelectric conversion efficiency while reducing the photoelectric conversion efficiency.

[0011]

According to the present invention, there is provided an integrated silicon thin film photoelectric conversion device comprising: a back electrode layer sequentially laminated on an insulating substrate; at least one crystalline silicon photoelectric conversion unit layer; and a transparent conductive cap. The layers, and the transparent electrode layer are separated by a plurality of substantially linear and parallel separation grooves so as to form a plurality of photoelectric conversion cells, and the plurality of cells are separated by a plurality of parallel grooves. It is characterized in that they are electrically connected to each other in series via connection grooves.

Further, in the method for manufacturing an integrated silicon thin film photoelectric conversion device according to the present invention, after the transparent conductive cap layer is formed, the inter-cell connection groove is formed by a laser scribe method or a mechanical scribe method in the air. It is characterized by being formed penetrating the transparent conductive cap layer and the photoelectric conversion unit layer.

That is, as a result of repeated studies to solve the above-mentioned problems in the prior art, the present inventors have found that all of the semiconductor layers included in the photoelectric conversion unit are plasma C
By forming at low temperature by the VD method, the density of silicon crystals having a small grain size, which causes crystal nuclei of the crystalline silicon-based photoelectric conversion layer, is appropriately suppressed. In this way, a high-quality photoelectric conversion layer having a small number of grain boundaries and intragranular defects and having a strong crystal orientation along the thickness direction can be obtained. They have found that it is possible to prevent performance degradation due to integration.

[0014] The present inventors have also proposed that a transparent conductive cap layer having an appropriate thickness is formed thereon in vacuum following the formation of the photoelectric conversion unit layer in vacuum, and thereafter the atmosphere is formed. A conductive type layer included in the photoelectric conversion unit layer when forming a connection groove necessary for integration in the cap layer and the photoelectric conversion unit layer by a laser scribe method or a mechanical scribe method. It has been found that it is possible to manufacture an integrated silicon-based thin film photoelectric conversion device having excellent performance by preventing deterioration due to oxidation.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a schematic sectional partial view showing a manufacturing process of an integrated silicon-based thin film photoelectric conversion device as an example of an embodiment of the present invention. In addition,
In the drawings of the present application, dimensional relationships such as length and thickness do not reflect actual dimensional relationships for clarification and simplification of the drawings.

As shown in FIG. 1A, in the present invention, as the substrate 101, a metal such as stainless steel whose surface is insulated, an organic film having a low coefficient of expansion such as polyimide, or a material having a low melting point is used. Inexpensive glass or the like can be used. Back electrode layer 102 disposed on substrate 101
A conductive layer including at least one of the following thin films (A) and (B) may be formed by a vacuum evaporation method, a sputtering method, or the like. (A) Ti, Cr, Al, Ag, Au, Cu and P
a metal thin film made of at least one metal selected from t or an alloy thereof. (B) A transparent conductive thin film made of at least one oxide selected from ITO, SnO ₂ and ZnO.

In order to separate the back electrode layer 102 into a plurality of regions corresponding to a plurality of integrated photoelectric conversion cells, the back electrode is separated by a laser scribe method using a laser beam 103 or a mechanical scribe method. A groove 104 is formed. These back electrode separation grooves 1
Reference numeral 04 extends linearly in a direction perpendicular to the plane of FIG. As the laser beam 103, a laser beam emitted from a generally known laser such as YAG, a dye, or an excimer can be used. Further, in the mechanical scribe method, a metal film such as a diamond pen, a metal needle, etc.
A material having higher hardness and sharpness than the transparent conductive oxide film and the silicon-based thin film may be used.

In FIG. 1B, the back electrode layer 102
First, a layer of one conductivity type included in the silicon-based thin-film photoelectric conversion unit layer 105 is deposited by a plasma CVD method. This one conductivity type layer is made of, for example, n doped with 0.01% by atom or more of phosphorus which is a conductivity type determining impurity atom.
A microcrystalline silicon-based thin film or the like can be used. But,
These conditions for the first conductivity type semiconductor layer are not limited. For example, an alloy material such as microcrystalline silicon carbide or microcrystalline silicon germanium can be used instead of microcrystalline silicon. Note that the thickness of the first conductivity type semiconductor layer is set between 1 and 50 nm, more preferably within the range of 2 and 30 nm.

On the first conductivity type layer, as a photoelectric conversion layer,
A crystalline silicon-containing thin film is formed at a base temperature of 400 ° C. or less by a plasma CVD method. As the photoelectric conversion layer, a non-doped i-type polycrystalline thin film, an i-type microcrystalline thin film having a volume crystallization fraction of 80% or more, or a weak p-type or weak n-type containing a small amount of impurities, having a sufficient photoelectric conversion function. The provided crystalline silicon-based thin film can be used.
The photoelectric conversion layer is not limited thereto, and a film of an alloy material such as silicon carbide or silicon germanium may be used.

The thickness of the photoelectric conversion layer is set in the range of 0.3 to 20 μm, more preferably in the range of 0.5 to 10 μm, and is necessary and sufficient for a crystalline silicon-containing thin film photoelectric conversion layer. Is the thickness. Since the photoelectric conversion layer is formed at a low temperature of 400 ° C. or less, it contains many hydrogen atoms that terminate or inactivate defects in crystal grain boundaries or grains,
Its hydrogen content is in the range of 0.5 to 30 atomic%;
More preferably, it is in the range of 1 to 20 atomic%.

Most of the crystal grains contained in the crystalline silicon-based photoelectric conversion layer grow in a columnar manner in the thickness direction from the underlayer. Many of these grains are parallel to the film plane (11
0), and the intensity ratio of the (111) diffraction peak to the (220) diffraction peak in X-ray diffraction is 1/5 or less, more preferably 1/10 or less.

On the photoelectric conversion layer, a conductive semiconductor layer of a type opposite to the one conductive layer is deposited by a plasma CVD method. As the reverse conductivity type layer, for example, a p-type microcrystalline or amorphous silicon layer doped with 0.01% by atom or more of boron, which is a conductivity type determining impurity atom, can be used. However, these conditions for the reverse conductivity type impurity layer are not limited, and the impurity atoms may be, for example, aluminum or the like, or a layer of an alloy material such as silicon carbide or silicon germanium. The thickness of the opposite conductivity type layer is 1 to 50 nm.
And more preferably within the range of 2 to 30 nm.

FIG. 1B further shows a transparent conductive cap layer 111 which is an important feature of the present invention.
Is formed so as to cover the silicon-based thin-film photoelectric conversion unit layer 105. Such a transparent conductive cap layer 11
1 includes one or more layers selected from ITO, SnO ₂ , and ZnO, and a photoelectric conversion unit layer 10 in a vacuum.
Subsequent to the formation of 5, it can be formed by sputtering or vapor deposition in vacuum. The transparent conductive cap layer 11
The thickness of 1 is preferably in the range of 10 to 60 nm.

In FIG. 1C, a connection opening groove 107 for electrically connecting left and right adjacent photoelectric conversion cells in series is formed in the silicon-based thin-film photoelectric conversion unit layer 105 and the transparent conductive cap layer 111. Formed by a laser scribe method or a mechanical scribe in the atmosphere. These connection grooves 107 also extend linearly in a direction perpendicular to the plane of FIG.

In FIG. 1D, ITO, SnO ₂ ,
And a transparent electrode layer 108 including at least one layer selected from ZnO is formed by a sputtering method or an evaporation method so as to fill the connection groove 107 and cover the transparent conductive cap layer 111.

In FIG. 1E, as in the case of the back electrode layer 102, a transparent electrode separating groove 109 is formed in the air by a laser scribe method or a mechanical scribe method corresponding to a plurality of photoelectric conversion cells. . Furthermore, in order to efficiently extract a current from the transparent electrode layer 108 having a relatively large resistance, at least one selected from Al, Ag, Au, Cu, Pt, Cr, or the like, or an alloy layer thereof, or a plurality thereof. May be formed by a sputtering method, a vapor deposition method, a screen printing method, or the like. Thus, a large-area integrated silicon-based thin film photoelectric conversion device is completed.

[0027]

EXAMPLES The present invention will be described more specifically by describing some examples of the present invention together with some comparative examples.

Comparative Example 1 An integrated silicon-based thin film photoelectric conversion device as shown in FIG. In FIG. 2A, an Ag film having a thickness of 300 nm and a ZnO film having a thickness of 100 nm were deposited as a back electrode layer 202 on a glass substrate 201 in this order by a sputtering method. Then, a plurality of back surface electrode separation grooves 204 were formed by a laser scribing method of irradiating a laser beam 203 from the free surface side of the back surface electrode layer 202.

In FIG. 2B, a phosphorus-doped n-type microcrystalline silicon layer, a non-doped polycrystalline silicon photoelectric conversion layer, and a boron-doped p-type microcrystalline silicon layer are deposited in this order by a plasma CVD method, and a nip junction is formed. Was formed.

The n-type microcrystalline silicon layer is made of RF plasma C
It was deposited by the VD method under the following conditions. That is, the flow rate of the reaction gas is 5 sccm for silane, 200 sccm for hydrogen, and 0.05 sccc for phosphine.
m, and the pressure in the reaction chamber was set to 1 Torr. The RF power density was 150 mW / cm ² , and the film formation temperature was 200 ° C. The dark conductivity of a 300 nm thick n-type microcrystalline silicon film directly deposited on a glass substrate under the same film forming conditions was 10 S / cm. Further, the polycrystalline silicon photoelectric conversion layer formed on the n-type microcrystalline silicon layer was deposited at a film formation temperature of 350 ° C. by an RF plasma CVD method. In this polycrystalline silicon photoelectric conversion layer, the hydrogen content determined by secondary ion mass spectrometry was 5 atomic%, and the intensity ratio of the (111) diffraction peak to the (220) diffraction peak in this X-ray diffraction was 1 / It was 4. Note that the thicknesses of the n-type microcrystalline silicon layer, the polycrystalline silicon photoelectric conversion layer, and the p-type microcrystalline silicon layer included in the photoelectric conversion unit layer 205 were 10 nm, 3 μm, and 5 nm, respectively.

In FIG. 2C, a plurality of connection grooves 207 were formed through the silicon-based thin film photoelectric conversion layer 205 by using a laser scribe method in the air.

In FIG. 2D, an ITO film having a thickness of 80 nm was formed as a transparent electrode layer 208 by a sputtering method.

In FIG. 2E, a plurality of transparent electrode separation grooves 209 were formed by laser scribing in the atmosphere.

When the integrated silicon-based thin film photoelectric conversion device according to Comparative Example 1 is irradiated with AM1.5 light 210 as the incident light 210 at a light intensity of 100 mW / cm ² , the output characteristics are as follows. The short circuit current density was 4.6 V, the short circuit current density was 25.9 mA / cm ² , the fill factor was 65.4%, and the conversion efficiency was 7.8%. Further, a light degradation test was performed on the photoelectric conversion device of Comparative Example 1 by irradiating AM1.5 light at 48 ° C. with a light amount of 100 mW / cm ² , and the conversion efficiency was 7.7 even after irradiation for 550 hours.
8%, and hardly any light deterioration occurred.
This means that the crystalline silicon-based photoelectric conversion unit layer is less likely to cause light degradation.

(Example 1) An integrated silicon-based thin film photoelectric conversion device corresponding to the embodiment shown in FIG. 1 was produced as Example 1 of the present invention. 1A and 1B, after the back electrode layer 102 and the back electrode separation groove 104 are formed on the glass substrate 101 under the same conditions corresponding to the case of Comparative Example 1 in FIG. An n-type microcrystalline silicon layer included in the silicon-based thin film photoelectric conversion unit layer 105,
A polycrystalline silicon photoelectric conversion layer and a p-type microcrystalline silicon layer were formed. However, in the first embodiment, after the silicon-based thin-film photoelectric conversion unit layer 105 is formed in a vacuum,
The O cap layer 111 was formed by a sputtering method. This I
The thickness of the TO cap layer 111 was about 50 nm.

In FIG. 1C, as in the case of Comparative Example 1, a plurality of connection grooves 107 were formed by laser scribing in air.

In FIG. 1D, when the thickness of the ITO film is 3
A transparent electrode layer 108 was formed in the same manner as in Comparative Example 1 except that the thickness was set to 0 nm.

In FIG. 1E, a plurality of transparent electrode separating grooves 109 were formed as in Comparative Example 1.

The incident light 110 of AM1.5 is applied to the integrated silicon thin film photoelectric conversion device according to the first embodiment.
Is irradiated at an amount of light of 100 mW / cm ² , the open-circuit voltage is 4.6 V and the short-circuit current density is 2
6.4 mA / cm ² , fill factor 74.8%, and conversion efficiency 9.1%. At 48 ° C.
In the light degradation test of Example 1 in which the light of 1.5 was irradiated at a light quantity of 100 mW / cm ² , the conversion efficiency was 9.1% even after irradiation for 550 hours, and the light was illuminated in the same manner as in Comparative Example 1. No degradation occurred.

Comparative Example 2 An integrated tandem silicon-based thin film photoelectric conversion device as shown in FIG.
Prepared as Comparative Example 2. In FIG. 4A, a back electrode layer 402 and a back electrode separation groove 404 are formed on a glass substrate 401 as in Comparative Example 1.

In FIG. 4B, as in Comparative Example 1, a thin-film polycrystalline silicon photoelectric conversion unit layer 405 including an n-type microcrystalline silicon layer, a polycrystalline silicon photoelectric conversion layer, and a p-type microcrystalline silicon layer Was formed as a rear unit layer. However, in Comparative Example 2, an amorphous silicon photoelectric conversion unit layer 406 including a nip junction was further laminated on the rear photoelectric conversion unit layer 405 as a front photoelectric conversion unit layer. The thickness of the amorphous silicon i-layer included in the front photoelectric conversion unit layer 406 was 0.4 μm.

In FIG. 4C, a plurality of connection grooves 407 penetrating the laminated amorphous photoelectric conversion unit layer 406 and crystalline photoelectric conversion unit layer 405 are formed in the atmosphere using a laser beam 403. It was formed by a laser scribe method.

4D and 4E, a transparent electrode layer 408 and a plurality of transparent electrode separating grooves 409 were formed as in Comparative Example 1.

In the comparative example 2, the integrated
Crystalline / amorphous tandem silicon thin film photoelectric conversion
The incident light 410 of AM1.5 is applied to the device at 100 mW /
cm ^TwoOutput characteristics when irradiating with
The discharge voltage is 13.4 V and the short-circuit current density is 12.5 mA /
cm^Two, Fill factor is 62.1%, and conversion efficiency is 1
0.4%. Further, at 48 ° C., AM1.5
Light of 100mW / cm ^TwoIrradiate with the amount of light of this comparison
When the light deterioration test of Example 2 was performed, after irradiation for 550 hours
The conversion efficiency dropped to 9.0%.

(Embodiment 2) An integrated tandem silicon-based thin film photoelectric conversion device as shown in FIG.
Created as Example 2. 3A and 3B, as in Comparative Example 2, a back electrode layer 302, a plurality of back electrode separation grooves 304, and a crystalline silicon thin film photoelectric conversion as a rear photoelectric conversion unit cell are formed on a glass substrate 301. A unit layer 305 and an amorphous silicon thin film photoelectric conversion unit layer 306 as a front photoelectric conversion unit layer were formed. However, in Example 2, an ITO cap layer 311 was further formed on the amorphous silicon thin film photoelectric conversion unit layer 506 as the front photoelectric conversion unit layer, as in the case of Example 1.

In FIG. 3C, the ITO cap layer 3
11, amorphous silicon thin film photoelectric conversion unit layer 306,
And a plurality of connection grooves 307 penetrating the crystalline silicon thin film photoelectric conversion unit layer 305
Formed by a laser scribe method in the atmosphere using

3D and 3E, a transparent electrode layer 308 and a plurality of transparent electrode separating grooves 309 are formed as in the case of the first embodiment. As a result, an integrated crystalline / amorphous tandem silicon thin film photoelectric conversion device was produced.

The incident light 310 of AM1.5 is applied to the photoelectric conversion device according to the second embodiment at 100 mW / cm ^2.
The output characteristics when irradiating with a light amount of 13.4 V and a short circuit current density of 12.7 mA / c
m ² , fill factor 73.6%, and conversion efficiency 12.
5%. In addition, when the light deterioration test of Example 2 was performed by irradiating AM1.5 light at 48 ° C. with a light amount of 100 mW / cm ² , the conversion efficiency was reduced to 10.7% after irradiation for 550 hours. .

[0049]

As described above, according to the present invention, it is possible to provide an integrated silicon-based thin film photoelectric conversion device having excellent photoelectric conversion characteristics and capable of producing high output at high voltage.

[Brief description of the drawings]

FIG. 1 is a schematic sectional partial view for explaining a manufacturing process of an integrated silicon-based thin film photoelectric conversion device according to an example of an embodiment of the present invention.

FIG. 2 is a schematic cross-sectional view showing a manufacturing process of an integrated silicon-based nip type thin film photoelectric conversion device according to Comparative Example 1.

FIG. 3 shows an integrated crystalline material according to a second embodiment of the present invention.
It is a typical sectional view showing a manufacturing process of an amorphous tandem type silicon system nip type thin film photoelectric conversion device.

FIG. 4 is a schematic cross-sectional view illustrating a manufacturing process of a crystalline / amorphous tandem silicon-based nip thin film photoelectric conversion device integrated in Comparative Example 2.

[Explanation of symbols]

101, 201, 301, 401: glass substrate 102, 202, 302, 402: back electrode layer 103, 203, 303, 403: laser beam 104, 204, 304, 404: back electrode separation groove 105, 205, 305, 405 : Crystalline silicon-based photoelectric conversion unit layers 306, 406: amorphous silicon-based photoelectric conversion unit layers 107, 207, 307, 407: connection grooves 108, 208, 308, 408: transparent electrode layers 109, 209, 309, 409: Transparent electrode separation groove 110, 210, 310, 410: incident light to be photoelectrically converted 111, 311: transparent conductive cap layer

Claims (8)

[Claims] 1. A method in which a back electrode layer, at least one crystalline silicon-based photoelectric conversion unit layer, a transparent conductive cap layer, and a transparent electrode layer sequentially laminated on an insulating substrate form a plurality of photoelectric conversion cells. The cells are separated by a plurality of substantially linear and parallel separation grooves, and the plurality of cells are electrically connected to each other in series through a plurality of connection grooves parallel to the separation grooves. An integrated silicon-based thin-film photoelectric conversion device characterized by the following. 2. The crystalline silicon-based photoelectric conversion unit layer includes a crystalline photoelectric conversion layer formed by a plasma CVD method at a base temperature of 400 ° C. or less, and the crystalline photoelectric conversion layer is 80% or more. Volume crystallization fraction of 0.5
Hydrogen content in the range of 30 atomic% and 0.5-20 μm.
The photoelectric conversion device according to claim 1, wherein the photoelectric conversion device has a thickness in a range of m. 3. The crystalline photoelectric conversion layer has a preferential crystal orientation plane of (110) parallel to the film plane, and the intensity ratio of the (111) diffraction peak to the (220) diffraction peak in X-ray diffraction is higher. The photoelectric conversion device according to claim 2, wherein the ratio is 1/10 or less. 4. The photoelectric conversion unit layer according to claim 2, wherein the photoelectric conversion unit layer includes an n-type layer, the photoelectric conversion layer, and a p-type layer which are sequentially stacked from a side closer to the substrate. The photoelectric conversion device as described in the above. 5. The transparent conductive cap layer has a thickness of 10 to 6;
The photoelectric conversion device according to any one of claims 1 to 4, wherein the photoelectric conversion device has a thickness in a range of 0 nm. 6. The photoelectric conversion device according to claim 1, wherein the photoelectric conversion device is a tandem type including the crystalline silicon-based photoelectric conversion unit layer and at least one amorphous silicon-based photoelectric conversion unit layer. The photoelectric conversion device according to any one of the above items. 7. The method for manufacturing a photoelectric conversion device according to claim 1, wherein the connection groove is formed by a laser scribe method in the air after the transparent conductive cap layer is formed. Forming a transparent conductive cap layer and the silicon-based photoelectric conversion unit layer through the transparent conductive cap layer. 8. The method for manufacturing a photoelectric conversion device according to claim 1, wherein the connection groove is mechanically scribed in the air after the transparent conductive cap layer is formed. A method for manufacturing an integrated silicon-based thin-film photoelectric conversion device, wherein the integrated silicon-based thin-film photoelectric conversion device is formed so as to penetrate the transparent conductive cap layer and the silicon-based photoelectric conversion unit layer by a method.