JP5232362B2 - A manufacturing method of an integrated thin film photoelectric conversion device, and an integrated thin film photoelectric conversion device obtainable by the manufacturing method. - Google Patents

Description

  The present invention relates to a manufacturing method capable of exhibiting high performance while reducing the number of necessary steps when integrating thin film photoelectric conversion devices, and to a thin film photoelectric conversion device obtainable by the manufacturing method.

  In recent years, in order to reduce the manufacturing cost of solar cells, thin film solar cells that require less raw materials have attracted attention, and their development and production have been vigorously performed. Further, in addition to the conventional amorphous thin film solar cell, a crystalline thin film solar cell has also been developed, and a laminated thin film solar cell called a hybrid solar cell in which these are laminated has been put into practical use.

  A thin-film solar cell generally includes a transparent electrode, one or more semiconductor thin-film photoelectric conversion units, and a back electrode that are sequentially stacked on a light-transmitting substrate. One photoelectric conversion unit includes an i-type layer sandwiched between a p-type layer and an n-type layer.

  The transparent electrode usually has many fine irregularities on its surface in order to scatter light incident from the translucent substrate side and effectively confine it in the photoelectric conversion unit, and its height difference is generally 0.03 μm. ~ 0.3 μm. As an index that quantitatively indicates the degree of light scattering, for example, there is a haze rate. The haze ratio is expressed by (diffuse transmittance / total light transmittance) × 100 [%] (JIS K7136). In general, the haze ratio increases as the height difference between the projections and depressions increases, or as the interval between the projections and depressions of the projections and depressions increases, and the light incident in the photoelectric conversion unit is effectively confined.

  The i-type layer is a substantially intrinsic semiconductor layer and occupies most of the thickness of the photoelectric conversion unit, and the photoelectric conversion action mainly occurs in the i-type layer. For this reason, this i-type layer is usually called an i-type photoelectric conversion layer or simply a photoelectric conversion layer. The photoelectric conversion layer is not limited to an intrinsic semiconductor layer, and may be a layer doped in a small amount of p-type or n-type within a range where loss of light absorbed by a doped impurity (dopant) does not become a problem. The photoelectric conversion layer is preferably thicker for light absorption, but if it is thicker than necessary, the cost and time for film formation increase.

  On the other hand, the p-type and n-type conductive semiconductor layers serve to generate an internal electric field in the photoelectric conversion unit, and the open-circuit voltage (Voc), which is one of the important characteristics of the thin film solar cell, depends on the magnitude of the internal electric field. ) Value is affected. However, these conductive semiconductor layers are inactive layers that do not directly contribute to photoelectric conversion, and light absorbed by impurities doped in the conductive semiconductor layer is a loss that does not contribute to power generation. Therefore, it is preferable that the p-type and n-type conductive semiconductor layers have a thickness as small as possible as long as a sufficient internal electric field can be generated. The thickness of the conductive semiconductor layer is generally about 20 nm or less.

  Here, the photoelectric conversion unit or the thin-film solar cell has an amorphous photoelectric conversion layer that occupies the main part regardless of whether the p-type and n-type conductive semiconductor layers contained therein are amorphous or crystalline. A thing with an amorphous photoelectric conversion layer or a crystalline thin film solar cell is called a crystalline photoelectric conversion unit or a crystalline thin film solar cell.

  As a method of improving the conversion efficiency of a thin film solar cell, there is a method of stacking two or more photoelectric conversion units. In this case, the front unit including the photoelectric conversion layer having a large band gap is disposed on the light incident side of the thin film solar cell, and the rear unit including the photoelectric conversion layer having the small band gap is sequentially disposed behind the front unit. Photoelectric conversion is enabled over a wide wavelength range of light, thereby improving the conversion efficiency of the entire solar cell. Among such stacked solar cells, those in which an amorphous silicon photoelectric conversion unit and a crystalline silicon photoelectric conversion unit are stacked one by one and electrically connected in series are called silicon hybrid solar cells. For example, the wavelength of light that can be photoelectrically converted by i-type amorphous silicon is up to about 800 nm on the long wavelength side, but i-type crystalline silicon photoelectrically converts light up to a wavelength of about 1150 nm longer than that. Can do.

  An amorphous silicon photoelectric conversion layer with a large light absorption coefficient can obtain a sufficient short-circuit current density (Jsc) even with a thickness of about 0.3 μm, but a crystalline silicon photoelectric conversion layer with a small light absorption coefficient is long. In order to sufficiently absorb light having a wavelength, it is preferable to have a thickness of about 1 to 3 μm. That is, the crystalline silicon photoelectric conversion layer is usually desired to have a thickness of about 3 to 10 times that of the amorphous silicon photoelectric conversion layer. Similarly, in the silicon hybrid solar cell, the thickness ratio between the two needs to be about 3 to 10 times.

By the way, since the thin film solar cell is formed on the translucent substrate with the transparent electrode, the photoelectric conversion unit, and the back electrode layer by a vapor phase growth method such as CVD or sputtering, the area of the thin film solar cell can be increased with the aim of reducing the equipment cost. It is being advanced. On the other hand, since the resistivity of the transparent electrode is about 10 ⁻² to 10 ⁻⁴ Ωcm, which is larger than that of the metal, the resistance loss at the transparent electrode increases as the area increases. Here, the resistivity is a volume resistance ratio, and is a value calculated by the product of the sheet resistance and the thickness of the transparent electrode. For this reason, integration is generally performed in which a plurality of strip-shaped unit elements are formed on a single translucent substrate by a technique such as laser scribing and connected in series. Furthermore, in order to improve reliability during integration, for example, Patent Document 1 performs laser scribing to separate the photoelectric conversion unit into strips after forming a transparent conductor layer continuously on the surface of the photoelectric conversion unit, It discloses a method of preventing performance degradation due to the formation of a natural oxide film on the surface of the photoelectric conversion unit by performing a cleaning process for removing the fusing residue.

However, in order to suppress the cost reduction due to the simplification of the manufacturing process and the decrease in the manufacturing yield due to the fluctuation of the equipment state in one process, the cleaning process for removing the fusing residue as described above is performed. It is considered desirable not to. However, as described in Patent Document 1, the occurrence of fusing residue during laser scribing is unavoidable, and in particular, a cleaning process is indispensable in the manufacturing process of a large-area integrated thin film photoelectric conversion device. For this reason, in the present invention, the occurrence of fusing residue is suppressed without performing the cleaning process after laser scribing of the photoelectric conversion unit, the contact resistance between the transparent electrode and the transparent conductor layer is reduced, and the transparent conductor layer The purpose is to increase the Jsc and the fill factor (FF) of the solar cell and improve the transparency by improving the transparency.
JP-A-9-8337

The method for manufacturing an integrated thin film photoelectric conversion device according to the present invention includes: 1) forming a plurality of transparent electrodes divided by a lower separation groove on a substrate; and 2) contacting each of the plurality of transparent electrodes to perform photoelectric conversion. Forming a unit and a transparent metal oxide layer having a resistivity greater than 0.01 Ωcm, 3) adjoining the lower separation groove, removing the photoelectric conversion unit and the transparent metal oxide layer, A connection groove is formed by laser scribing so as to be exposed, and 4) so as to be electrically connected to one of the two adjacent transparent electrodes via the connection groove without performing a cleaning process after the connection groove is formed. the contact with the transparent metal oxide layer on a transparent metal oxide layer, forming a transparent conductor layer resistivity is less than or equal to 0.01? cm, and a back electrode made of metallic layers on the transparent Akirashirube collector layer 5) With a transparent electrode and a back electrode At least the back surface electrode, the transparent conductor layer, and the transparent metal oxide layer in the vicinity of each connection groove are removed to form an upper separation groove so that a plurality of unit elements including the sandwiched region are connected in series. The electrode is divided into a plurality of regions corresponding to a plurality of unit elements.

That is, the present invention is expressed with description of FIG. 1, a light transmitting substrate 1, a transparent electrode 2, the photoelectric conversion unit 3, a transparent metal oxide layer 5c, and a transparent conductor layer 5t, back electrode comprising a 5 m, production method of an integrated thin film photoelectric conversion device in which unit elements of multiple has a series-connected structure state, and are, at least following the step in this order.
Forming a plurality of transparent electrodes 2 each divided by a lower separation groove 12 on the translucent substrate 1 ;
Forming a photoelectric conversion unit 3 in contact with each of the plurality of transparent electrodes 2 ;
Forming a transparent metal oxide layer 5c having a resistivity greater than 0.01 Ωcm on the photoelectric conversion unit 3 ;
A part of the photoelectric conversion unit 3 and the transparent metal oxide layer 5c in the vicinity of the lower separation groove 12 is removed so that a part of the transparent electrode 2 is exposed and in the lower separation groove 12 the connection groove 13 Ku is placed such that the contact, forming by laser scribing;
Without performing a cleaning treatment after forming the connection groove 13, on the transparent metal oxide layer 5c,
Transparent conductor layer 5t resistivity in contact with the transparent metal oxide layer 5c is less than 0.01? Cm, and a back electrode 5m consisting metallic layer on the transparent Akirashirube collector layer 5t,
Forming a unit element comprising a region sandwiched between the transparent electrode 2 and the back electrode 5m; and a step of electrically connecting to one of the two adjacent transparent electrodes 2 via the connection groove 13 ; to connect to each other in series, by removing a portion of the back surface electrode 5m and the transparent Akirashirube collector layer 5t and transparent metal oxide layer 5c and the photoelectric conversion unit 3 in the vicinity of each said connection groove 13, step a portion of the transparent electrode 2 is a top portion Hanaremizo 15 formed so as to expose, respectively divided into a plurality of areas corresponding to rear surface electrode 5m into a plurality of unit elements.

  The present invention is also a method for manufacturing an integrated thin film photoelectric conversion device, wherein the photoelectric conversion unit is mainly composed of silicon.

  The present invention is also a method for manufacturing an integrated thin film photoelectric conversion device, wherein the transparent metal oxide layer contains zinc oxide as a main component.

  In the present invention, the transparent metal oxide layer may be formed by a CVD method using a gas containing an organometallic vapor and not containing a group III (group 3) element, or the amount of group III (group 3) element added is 0.1. It is a manufacturing method of the integrated thin film photoelectric conversion apparatus formed by the sputtering method using the sputtering target of 2 weight% or less.

According to the present invention, the resistivity of the transparent conductor layer electrically connected to the transparent electrode is 0.01 Ωcm or less. For this reason, even if a fusing residue is present in the groove after the connection groove is formed, the contact resistance between the transparent electrode and the transparent conductor layer is kept small. Furthermore, it designed so that the resistivity of the transparent metal oxide layer which contact | connects a photoelectric conversion unit might become larger than 0.01 ohm-cm.
In summary, a sufficiently high FF was obtained without performing cleaning after forming the connection grooves.
Thereby, the washing | cleaning process after connection groove formation can be skipped. On the other hand, since the transparent metal oxide layer is larger than 0.01 Ωcm as described above, the transparency to light having a wavelength in the range from red light to the near infrared region is excellent. For this reason, it can prevent that the light which passed through the photoelectric conversion unit and reached | attained the back surface side is absorbed by a transparent metal oxide layer, and becomes loss. For this reason, Jsc and FF of the thin film photoelectric conversion device can be simultaneously increased, and high photoelectric conversion performance can be obtained.

  Hereinafter, an integrated amorphous silicon solar cell as an embodiment of the present invention will be described with reference to FIG.

  A transparent electrode 2 is formed on the translucent substrate 1.

  As the translucent substrate 1, a plate-like member or a sheet-like member made of glass, transparent resin or the like is used.

  The transparent electrode 2 is made of a metal oxide such as tin oxide or zinc oxide, and is formed using a method such as CVD, sputtering, or vapor deposition. The transparent electrode 2 has the effect of increasing the scattering of incident light by producing fine irregularities on the surface by devising the formation conditions. The height difference of the unevenness is about 0.03 to 0.3 μm, the haze ratio is about 5 to 30%, and the sheet resistance is set to about 5 to 20 Ω / □. The transparent electrode 2 is divided into a plurality of strip-shaped regions by a linear lower separation groove 12 using laser scribing.

  An amorphous silicon photoelectric conversion unit 3 is formed on the transparent electrode 2. The amorphous silicon photoelectric conversion unit 3 includes an amorphous p-type silicon carbide layer 3p, an amorphous i-type silicon photoelectric conversion layer 3i, and an n-type silicon layer 3n. The material of the amorphous i-type silicon photoelectric conversion layer 3i may contain not only silicon but also a band gap adjusting element such as carbon and germanium. The n-type silicon layer 3n may be amorphous or may contain a crystalline material, and may contain elements such as oxygen, nitrogen and carbon.

A high frequency plasma CVD method is suitable for forming the amorphous silicon photoelectric conversion unit 3. As the formation conditions, a substrate temperature of 100 to 250 ° C., a pressure of 30 to 1500 Pa, and a high frequency power density of 0.01 to 0.5 W / cm ² are preferably used. As a source gas used for forming the photoelectric conversion unit, a silicon-containing gas such as SiH ₄ or Si ₂ H ₆ or a mixture of these gases and hydrogen is used. B ₂ H ₆ or PH ₃ is preferably used as the dopant gas for forming the p-type or n-type layer in the photoelectric conversion unit. In addition, when oxygen or nitrogen is contained in the n-type layer, carbon dioxide or ammonia is preferably used in addition to the above gas.

  A transparent metal oxide layer 5c having a resistivity greater than 0.01 Ωcm is formed on the n-type silicon layer 3n. The reason why the above resistivity is desirable is not necessarily clear, but if the resistivity is greater than 0.01 Ωcm, the laser light absorption in the transparent metal oxide layer 5c is almost eliminated, and the laser light absorption in the photoelectric conversion unit is efficiently performed. Since it is performed or the transparent metal oxide layer is sublimated and prevented from re-adhering to the vicinity of the connection groove, it becomes difficult to cause a fusing residue in the connection groove or a burr to the cross section of the connection groove. It is estimated to be. Moreover, the upper limit of the resistivity of the transparent metal oxide layer 5c is about 100 Ωcm. When the transparent metal oxide layer is formed by a CVD method using an organic metal vapor-containing gas, the resistivity of the obtained film is in the above order unless a Group III (Group 3) doping gas is added. This is because the resistivity of the obtained film is in the above order when an operation for reducing oxygen vacancies in the transparent metal oxide layer is performed even when the sputtering method is used. For the transparent metal oxide layer 5c, a metal oxide having excellent transparency such as ZnO or ITO is used. In forming the transparent metal oxide layer 5c, a gas containing an organometallic vapor such as diethyl zinc and not containing a group III (group 3) element is used. A sputtering method using a sputtering target or a sputtering method using a sputtering target in which the addition amount of a group III (group 3) element such as B, Al, Ga, In, or Y is 0.2 wt% or less is preferably used. Ar is usually used as the sputtering gas. The transparent metal oxide layer 5c is preferably formed without breaking the vacuum after forming the n-type silicon layer 3n from the viewpoint of shortening tact time and preventing contamination of the surface of the n-type silicon layer 3n. The surface of the mold silicon layer 3n may be once exposed to the atmosphere.

  The amorphous silicon photoelectric conversion unit 3 and the transparent metal oxide layer 5 c are divided into a plurality of strip-shaped regions by connection grooves 13 formed adjacent to the lower separation grooves 12.

  On the transparent metal oxide layer 5c, a transparent conductor layer 5t having a resistivity of 0.01 Ωcm or less and a back electrode 5m made of a metal layer formed on the transparent conductor layer 5t are formed. When the resistivity of the transparent conductor layer 5t is in the above range, the contact between the transparent conductor layer 5t and the transparent electrode 2 can be easily made, and the FF of the integrated solar cell is improved. For the transparent conductor layer 5t, a metal oxide having excellent conductivity and transparency such as ZnO and ITO is used, and for the back electrode 5m, Ag, Al or an alloy thereof is preferably used. In forming the transparent conductor layer 5t and the back electrode 5m, methods such as sputtering and vapor deposition are preferably used.

  At least three layers (preferably the amorphous silicon photoelectric conversion unit 3 in addition to the back electrode 5m, the transparent conductor layer 5t, and the transparent metal oxide layer 5c) are formed adjacent to the connection groove 13. The electrode grooves 15 are divided into a plurality of strip-shaped regions. Thereby, two adjacent strip-shaped unit elements 10 a and 10 b are connected in series through the connection groove 13.

  Although the above description has been made for a single-layer solar cell having only an amorphous silicon photoelectric conversion unit, a single-layer solar cell having only a crystalline silicon photoelectric conversion unit may be used, or an amorphous silicon photoelectric conversion unit and a crystal It may be a hybrid stacked solar cell in which porous silicon photoelectric conversion units are stacked. Alternatively, a three-layer stacked solar cell in which a crystalline silicon photoelectric conversion unit is further stacked on an amorphous silicon photoelectric conversion unit or a crystalline silicon photoelectric conversion unit may be used. Further, as a material of the photoelectric conversion unit, copper indium gallium selenide (CIGS) other than silicon, cadmium tellurium (CdTe), or the like may be contained as a main component.

  Below, Examples 1-2 are demonstrated as an integrated amorphous silicon solar cell by this invention, comparing with Comparative Examples 1-4, referring FIG.

Example 1
1 is a cross-sectional view schematically showing an integrated amorphous silicon solar cell manufactured in Example 1. FIG.

  First, 910 mm × 455 mm × 4 mm thick white plate glass was used as the translucent substrate 1. On one main surface of the translucent substrate 1, a transparent electrode 2 having a fine uneven structure on the surface made of tin oxide was formed by a thermal CVD method. The thickness of the obtained transparent electrode 2 was 0.8 μm, the haze ratio measured with a C light source from the transparent electrode 2 side in a haze meter NDH5000W type manufactured by Nippon Denshoku was 11%, and the sheet resistance was 8Ω / □. . Next, in order to divide the transparent electrode 2 into a plurality of belt-like patterns, a YAG fundamental wave pulse laser is irradiated onto the translucent substrate 1 to form a lower separation groove 12 having a width of 50 μm and ultrasonic cleaning. And drying.

Next, in order to form the amorphous silicon photoelectric conversion unit 3, the transparent substrate 1 on which the transparent electrode 2 is formed is introduced into a high-frequency plasma CVD apparatus, and an amorphous p-type silicon carbide having a thickness of 150 mm is introduced. A (p-type a-SiC) layer 3p was formed. In the formation of the p-type a-SiC layer 3p, SiH ₄ , hydrogen, B ₂ H ₆ diluted with hydrogen, and CH ₄ were used as reaction gases, and the thickness of the p-type a-SiC layer 3p became 80 mm. While maintaining the discharge at that time, the supply of hydrogen-diluted B ₂ H ₆ and CH ₄ was stopped, and the remaining 70 mm of film was formed. Subsequently, an amorphous i-type silicon photoelectric conversion layer 3i having a thickness of 0.27 μm and an n-type microcrystalline silicon layer 3n having a thickness of 150 mm were sequentially stacked. Further, the translucent substrate 1 was transferred from the high-frequency plasma CVD apparatus to a high-frequency sputtering apparatus in a vacuum to form a transparent metal oxide layer 5c made of ZnO having a thickness of 600 mm. In forming the transparent metal oxide layer 5c, a sputtering target doped with 0.1% by weight of Al or In in ZnO was used, Ar gas was used as a sputtering gas, and the pressure was set to 0.7 to 1.5 Pa. The resistivity calculated from the sheet resistance value measured by forming the transparent metal oxide layer 5c on the glass under the same conditions with a thickness of 600 mm was 0.1 Ωcm. Further, even when a 99.99% pure ZnO target not doped with a group III (group 3) element was used, almost the same resistivity was obtained.

Thereafter, in order to divide the amorphous silicon photoelectric conversion unit 3 into a plurality of strip patterns, the substrate is taken out into the atmosphere, and the translucent substrate 1 is irradiated with a YAG second harmonic pulse laser to thereby connect the substrate 60 μm in width. A groove 13 was formed. Subsequently, a transparent conductor layer 5t made of ZnO having a thickness of 300 mm and a back electrode 5m made of Ag having a thickness of 2000 mm were formed by DC sputtering without performing a cleaning process. In the formation of the transparent conductor layer 5t, a sputtering target doped with 3.2% by weight of Al in ZnO was used, Ar gas was used as the sputtering gas, and the pressure was 0.27 Pa. The resistivity calculated from the sheet resistance value measured by forming the transparent conductor layer 5t on the glass with a thickness of 300 mm under the same conditions was 0.003 Ωcm.
Finally, in order to divide the amorphous silicon photoelectric conversion unit 3, the transparent metal oxide layer 5c, the transparent conductor layer 5t, and the back electrode 5m into a plurality of strip patterns, a YAG second harmonic pulse laser is transmitted. Irradiating the conductive substrate 1, an upper separation groove 15 having a width of 60 μm is formed, and an integrated amorphous crystal in which strip-like amorphous silicon solar cells adjacent to the left and right as shown in FIG. 1 are electrically connected in series. Quality silicon solar cells were fabricated. This integrated amorphous silicon solar cell is configured by 100 stages of amorphous silicon solar cells having a width of 8.9 mm and a length of 430 mm connected in series. A total of 10 integrated amorphous silicon solar cells were produced by the same method. The integrated amorphous silicon solar cell thus obtained was subjected to simulated sunlight having an energy density of 100 mW / cm ² in a spectrum approximated to an air mass of 1.5, under the conditions of the measurement atmosphere and the temperature of the solar cell of 25 ± 1 ° C. The current-voltage characteristics were measured. Table 1 shows the measurement results of the open circuit voltage Voc, short circuit current density Jsc, fill factor FF, and conversion efficiency Eff (average value of 10 sheets) obtained by dividing the obtained open circuit voltage by 100 and converted per stage.

Table 1 is a table showing the characteristics of the integrated amorphous silicon solar cells shown in Examples 1-2 and Comparative Examples 1-4.

(Comparative Example 1)
The comparative example 1 is different from the first example only in that the resistivity of the transparent metal oxide layer 5c is changed to 0.005 Ωcm (calculated from the sheet resistance value measured by forming 600 上 on the glass). It was. Table 1 shows the measurement results of the obtained solar cell. When Example 1 and Comparative Example 1 are compared, the average performance is significantly reduced simply by reducing the resistivity of the transparent metal oxide layer 5c. It is presumed that this is mainly due to the occurrence of burrs due to the transparent metal oxide layer 5c sublimated by absorption of laser light being reattached in the connection groove 13 when the connection groove 13 is formed.

(Comparative Example 2)
The comparative example 2 was different from the comparative example 1 only in that an ultrasonic cleaning process with water was added after the connection groove 13 was formed. Table 1 shows the measurement results of the obtained solar cell. When Example 1 and Comparative Example 2 are compared, the performance difference is not large, but it can be seen that Jsc is higher in Example 1 due to the higher transparency of the transparent metal oxide layer 5c.

(Comparative Example 3)
In Comparative Example 3, compared with Example 1, the formation of the transparent metal oxide layer 5c is omitted, and an ultrasonic cleaning step with water is added after the formation of the connection groove 13, and the resistivity 0 is set as the transparent conductor layer 5t. .1 Ωcm (calculated from a sheet resistance value measured by forming 900 mm on glass) and having a thickness of 900 mm was different. Table 1 shows the measurement results of the obtained solar cell. When Example 1 and Comparative Example 3 are compared, when the transparent electrode 2 and the transparent conductor layer 5t having a high resistivity are in direct contact and the solar cells are connected in series, the FF of the integrated solar cell is greatly increased. It turns out that it is getting worse.

(Example 2)
Example 2 was different from Example 1 only in that the resistivity of the transparent metal oxide layer 5c was changed to 3 Ωcm (calculated from the sheet resistance value measured by forming 6000 mm on glass). . Table 1 shows the measurement results of the obtained solar cell. It can be seen that the performance similar to that of the first embodiment is obtained in the second embodiment.

(Comparative Example 4)
Comparative Example 4 differs from Example 1 only in that the resistivity of the transparent conductor layer 5t was changed to 0.05 Ωcm (calculated from the sheet resistance value measured by forming 300 Å on glass). It was. Table 1 shows the measurement results of the obtained solar cell. When Example 1 and Comparative Example 4 are compared, if the transparent electrode 2 and the transparent conductor layer 5t having a high resistivity are in direct contact with each other and the solar cells are connected in series as in the result of Comparative Example 3, integration is performed. It can be seen that the FF of the produced solar cell is lowered.

  As described above, according to the present invention, it is possible to increase the Jsc and FF of the integrated thin film photoelectric conversion device and obtain high performance while omitting the cleaning step after the connection groove formation when integrating the thin film photoelectric conversion device according to the present invention. It becomes possible.

1 is a schematic cross-sectional view of an integrated amorphous silicon solar cell according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Translucent substrate 2 Transparent electrode 3 Amorphous silicon photoelectric conversion unit 3p Amorphous p-type silicon carbide layer 3i Amorphous i-type silicon photoelectric conversion layer 3n N-type silicon layer 5c Transparent metal oxide layer 5t Transparent conductor Layer 5m Back electrode 12 Lower separation groove 13 Connection groove 15 Upper separation groove

Claims (4)

And the transparent substrate, a transparent electrode, a photoelectric conversion unit, and a transparent metal oxide layer, and a transparent conductor layer, comprising a back electrode, integrated thin film photoelectric having unit elements of several are connected in series structure A method for manufacturing a conversion device , comprising at least:
Forming a plurality of transparent electrodes, each of which is divided by a lower separation groove, on a translucent substrate ;
Forming a photoelectric conversion unit in contact with each of the plurality of transparent electrodes ;
Forming a transparent metal oxide layer having a resistivity greater than 0.01 Ωcm on the photoelectric conversion unit ;
Removing a portion of the photoelectric conversion unit and the transparent metal oxide layer in the vicinity of the lower separation grooves, so that a portion of the transparent electrode is exposed, and Ku distribution such that contact with said lower isolation trench Forming the placed connection groove by laser scribing ;
A transparent conductor layer having a resistivity in contact with the transparent metal oxide layer of 0.01 Ωcm or less on the transparent metal oxide layer without performing a cleaning treatment after forming the connection groove, and the transparent conductor layer in a and transparent electrode and the rear surface electrode; a back electrode made of metallic layers of the upper, recent two steps are formed so as to electrically connected to one via the connection groove of the transparent electrode of the next the unit element consisting of a region sandwiched between to connect to each other in series, removing a portion of each said connecting said back electrode and the transparent conductive material layer and the transparent metal oxide layer in the vicinity of the groove and the photoelectric conversion unit to step a portion of the transparent electrode is an upper portion away groove formed so as to expose, respectively divided into a plurality of areas corresponding to rear surface electrodes into a plurality of unit elements;
The manufacturing method of the integrated thin film photoelectric conversion apparatus which has these in this order.   The method for manufacturing an integrated thin film photoelectric conversion device according to claim 1, wherein the photoelectric conversion unit is mainly composed of silicon.   The method of manufacturing an integrated thin film photoelectric conversion device according to claim 1, wherein the transparent metal oxide layer contains zinc oxide as a main component. The transparent metal oxide layer is formed by a CVD method using a gas containing an organometallic vapor and not containing a group III (group 3) element, or sputtering with a group III (group 3) element addition amount of 0.2 wt% or less. sputtering method using a target, Ru is formed by the manufacturing method of an integrated thin film photoelectric converter according to claim 3.