WO2005109526A1 - Convertisseur photoélectrique en pellicule mince - Google Patents

Convertisseur photoélectrique en pellicule mince Download PDF

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WO2005109526A1
WO2005109526A1 PCT/JP2005/007872 JP2005007872W WO2005109526A1 WO 2005109526 A1 WO2005109526 A1 WO 2005109526A1 JP 2005007872 W JP2005007872 W JP 2005007872W WO 2005109526 A1 WO2005109526 A1 WO 2005109526A1
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semiconductor layer
photoelectric conversion
type
layer
amorphous
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PCT/JP2005/007872
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English (en)
Japanese (ja)
Inventor
Susumu Fukuda
Tomomi Meguro
Mitsuru Ichikawa
Kenji Yamamoto
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Kaneka Corporation
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Priority to JP2006512957A priority Critical patent/JPWO2005109526A1/ja
Publication of WO2005109526A1 publication Critical patent/WO2005109526A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
    • H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
    • H01L31/105—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PIN type
    • H01L31/1055—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PIN type the devices comprising amorphous materials of Group IV of the Periodic Table
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells

Definitions

  • the present invention provides a means for improving the conversion efficiency of a thin-film photoelectric conversion device, and relates to a thin-film photoelectric conversion device including a photoelectric conversion unit formed on a transparent conductive film.
  • thin-film solar cells which are typical examples of thin-film photoelectric conversion devices
  • crystalline thin-film solar cells have been developed in addition to conventional amorphous thin-film solar cells. Batteries are also being put into practical use.
  • a thin-film solar cell generally includes a transparent conductive film, at least one semiconductor thin-film photoelectric conversion unit, and a back electrode that are sequentially laminated on an insulating substrate at least on the surface.
  • One photoelectric conversion unit includes an i-type layer sandwiched between a p-type layer and an n-type layer.
  • the thickness of the photoelectric conversion unit is occupied by the i-type layer, which is substantially an intrinsic semiconductor layer, and the photoelectric conversion action mainly occurs in the i-type layer. Therefore, it is preferable that the thickness of the i-type layer, which is a photoelectric conversion layer, be large for light absorption, but if it is made thicker than necessary, the cost and time for the deposition increase.
  • the p-type or n-type conductive layer plays a role of generating a diffusion potential in the photoelectric conversion unit, and the magnitude of the diffusion potential is one of the important characteristics of the thin-film solar cell, namely, open-circuit.
  • the value of the terminal voltage depends.
  • these conductive type layers are inactive layers that do not contribute to photoelectric conversion, and light absorbed by impurities doped into the conductive type layers does not contribute to power generation and is lost. Therefore, it is preferable that the thicknesses of the p-type and n-type conductive layers be as small as possible within a range in which a sufficient diffusion potential is generated.
  • An example of a thin-film solar cell including an amorphous photoelectric conversion unit is an amorphous thin-film silicon solar cell using amorphous silicon for an i-type photoelectric conversion layer. Further, as an example of a thin-film solar cell including a crystalline photoelectric conversion unit, a crystalline thin-film silicon solar cell using microcrystalline silicon or polycrystalline silicon for an i-type photoelectric conversion layer is given.
  • a method of improving the conversion efficiency of a thin-film solar cell there is a method of stacking two or more semiconductor thin-film photoelectric conversion units to form a tandem type.
  • a photoelectric conversion unit having a large band gap of the photoelectric conversion layer is arranged on the light incident side of the thin-film solar cell, and a photoelectric conversion unit having a small band gap of the photoelectric conversion layer is sequentially arranged behind the photoelectric conversion unit.
  • This allows photoelectric conversion over a wide wavelength range of incident light, thereby improving the conversion efficiency of the entire solar cell.
  • tandem-type thin-film solar cells those containing both an amorphous photoelectric conversion unit and a crystalline photoelectric conversion unit may be particularly called a hybrid-type thin-film solar cell.
  • an amorphous silicon photoelectric conversion unit using i-type amorphous silicon having a wide band gap for a photoelectric conversion layer and an amorphous silicon photoelectric conversion unit using a narrow band gap i-type crystalline silicon for a photoelectric conversion layer In a hybrid thin-film solar cell with stacked crystalline silicon photoelectric conversion units, 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.
  • Type crystalline silicon can photoelectrically convert longer light up to about 100 nm, so that a wider range of incident light can be effectively photoelectrically converted.
  • the above-mentioned photoelectric conversion unit is composed of, for example, indium oxide (In 2 O 3) and antimony oxide prepared by adding tin in a small amount (hereinafter referred to as a dope, and a substance added in a small amount hereinafter is referred to as a dopant).
  • ITO transparent conductive film composed of a film (hereinafter referred to as ITO).
  • ITO transparent conductive film composed of a film (hereinafter referred to as ITO).
  • tin oxide (SnO) and zinc oxide (ZnO) are particularly excellent in cost and high permeability, and
  • a plasma CVD method is used as a method of forming a photoelectric conversion unit.
  • a transparent conductive film and a photoelectric conversion unit are required. It is desirable that the contact resistance at the bonding interface be low. Therefore, by forming a crystalline semiconductor layer having high crystallinity and low resistance as the P-type semiconductor layer of the photoelectric conversion unit formed directly above the transparent conductive film, the junction interface between the transparent conductive film and the photoelectric conversion unit is formed.
  • a method is used to reduce contact resistance.
  • Patent Document 1 discloses a structure in which an amorphous silicon layer containing boron is disposed adjacently between a transparent conductive film made of zinc oxide and conductive silicon carbide.
  • the amorphous silicon layer containing boron does not contribute to photoelectric conversion, there is a problem that the amount of light incident on the i-type semiconductor layer is reduced by light absorption by the amorphous silicon layer.
  • the amorphous silicon layer has a higher resistance than the crystalline silicon layer and cannot sufficiently reduce the contact resistance at the junction interface between the transparent conductive film and the photoelectric conversion unit. .
  • Patent Document 2 discloses a first conductive semiconductor layer formed of an amorphous semiconductor layer and a crystalline semiconductor layer sequentially stacked on a transparent conductive film, an intrinsic semiconductor layer formed of a crystalline semiconductor layer, And a method for preventing damage to a transparent conductive film by first forming an amorphous semiconductor layer on a transparent conductive film as a crystalline solar cell including a second conductive semiconductor layer.
  • the amorphous semiconductor layer of the first conductive semiconductor layer is also a layer that does not contribute to photoelectric conversion due to the silicon force as in Patent Document 1, and the amount of light incident on the i-type semiconductor layer decreases. The problem has not been solved.
  • Patent Document 1 JP-A-11-340485
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2002-134769
  • the present invention solves the above-mentioned problems of the prior art and provides a method for forming a good junction interface between a transparent conductive film and a photoelectric conversion unit, thereby improving conversion efficiency. It aims to obtain a high photoelectric conversion device.
  • the photoelectric conversion device of the present invention includes at least one photoelectric conversion unit in which a p-type semiconductor layer, an i-type semiconductor layer, and an n-type semiconductor layer are sequentially stacked on a transparent conductive film positioned on the light incident side.
  • a crystalline semiconductor layer, and a second amorphous semiconductor layer are sequentially stacked.
  • the first amorphous semiconductor layer is provided with a photoelectric conversion device characterized in that the first amorphous semiconductor layer is made of an amorphous silicon carnoid. It is intended to provide a photoelectric conversion device characterized by being made of amorphous silicon carbide or amorphous silicon carbide. Further, the photoelectric conversion device is characterized in that the i-type semiconductor layer of the photoelectric conversion unit closest to the light incident side is made of amorphous silicon. In addition, the transparent conductive film provides a photoelectric conversion device made of tin oxide, and a photoelectric conversion device made of zinc oxide is also preferably used.
  • a good bonding interface can be formed between the transparent conductive film and the photoelectric conversion unit.
  • the light absorption loss by the p-type semiconductor layer is small, and the amount of incident light on the i-type semiconductor layer that contributes to photoelectric conversion increases, so that the conversion efficiency of the thin-film solar cell can be improved.
  • FIG. 1 is a schematic cross-sectional view showing a laminated structure of a conventional amorphous silicon solar cell.
  • FIG. 2 is a schematic sectional view showing a laminated structure of the amorphous silicon solar cell of the present invention.
  • FIG. 3 is a schematic sectional view showing a laminated structure of a conventional hybrid silicon solar cell.
  • FIG. 4 is a schematic sectional view showing a laminated structure of the hybrid silicon solar cell of the present invention.
  • the first amorphous semiconductor layer is formed on the side near the transparent conductive film as the ⁇ -type semiconductor layer of the photoelectric conversion unit. This prevents the transparent conductive film from being exposed to a high-density plasma atmosphere at the initial stage of the formation of the ⁇ -layer semiconductor layer, as compared with the case where the crystalline semiconductor layer is formed directly on the transparent conductive film. Therefore, in the case of using the oxide film as the transparent conductive film, the oxide film becomes a metal under a high-density plasma atmosphere containing hydrogen. The problem of reduction to tin can be prevented.
  • the first amorphous semiconductor layer is made of p-type amorphous silicon carbide, so that light absorption loss is small and the amount of light incident on the i-type semiconductor layer contributing to photoelectric conversion increases. Conversion efficiency can be improved.
  • the p-type amorphous silicon carbide can be formed by a plasma CVD method. For example, with the substrate in the deposition chamber heated, silane gas and methane gas as source gases, hydrogen gas as diluent gas, diborane gas as doping gas, etc. were introduced into the deposition chamber, and the pressure in the deposition chamber was adjusted to a predetermined pressure. Supply high frequency power to the electrodes above. As a result, the source gas is decomposed, and p-type amorphous silicon carbide is formed on the substrate.
  • the crystalline semiconductor layer laminated as a p-type semiconductor layer on the first amorphous semiconductor layer reduces the resistance of the p-type semiconductor layer to reduce the resistance at the junction between the transparent conductive film and the photoelectric conversion unit. Used to reduce contact resistance.
  • the crystalline semiconductor layer p-type crystalline silicon such as microcrystalline silicon or polycrystalline silicon is preferably used, but is not limited thereto. Note that the surface of the transparent conductive film before the deposition of the crystalline semiconductor layer is covered with the first amorphous semiconductor layer, so that a crystalline semiconductor layer with high crystallinity and low resistance is formed.
  • the transparent conductive film iridescent tin
  • the transparent conductive film is not reduced to metallic tin.
  • the first amorphous semiconductor layer covering the surface of the transparent conductive film functions as an underlayer when the crystalline semiconductor layer is laminated.
  • a crystalline semiconductor layer having high crystallinity and low resistance can be obtained.
  • the present inventor has proposed that, when oxidized zinc is used as a transparent conductive film, by forming the crystalline semiconductor layer having p-type microcrystalline silicon power, the fill factor (FF) of a thin film solar cell can be improved.
  • p-type crystalline silicon is formed by plasma CVD can do. For example, while heating the substrate in the film forming chamber, silane gas as a source gas, hydrogen gas as a diluting gas, diborane gas as a doping gas, etc.
  • the film forming chamber is introduced into the film forming chamber, and the pressure in the film forming chamber is adjusted to a predetermined pressure. Supply high frequency power to the electrodes. As a result, the source gas is decomposed, and P-type crystalline silicon is formed on the substrate. The crystallinity of the crystalline silicon is adjusted to a predetermined value by changing the flow ratio of silane gas as a source gas to hydrogen gas as a diluent gas, the magnitude of high frequency power, pressure, and the like.
  • a second amorphous semiconductor layer By stacking a second amorphous semiconductor layer on a crystalline semiconductor layer as a p-type semiconductor layer, unevenness of the film surface formed as the crystalline semiconductor layer grows, Since the grain boundaries are covered and the film surface becomes smooth, the film quality of the i-type semiconductor layer subsequently formed on the p-type semiconductor layer is improved, and the film quality distribution can be reduced.
  • the second amorphous semiconductor layer p-type amorphous silicon carbide or p-type amorphous silicon is preferably used.
  • P-type amorphous silicon carbide can be formed by a method similar to that of the first amorphous semiconductor layer.
  • p-type amorphous silicon can be formed by a method similar to that of the first amorphous semiconductor layer except that only silane gas is used as a source gas.
  • the present inventor has found that when the thickness of the first amorphous semiconductor layer is 0.3 nm or more and 2 nm or less, the effects of the above invention can be obtained. That is, if the film thickness is smaller than 0.3 nm, the first amorphous semiconductor layer cannot cover the entire surface of the transparent conductive film.
  • the portion not covered by the first amorphous semiconductor layer is reduced to metallic tin in a high-density plasma atmosphere, and the transparent conductive film is formed. The transmittance decreases.
  • the first amorphous semiconductor layer does not sufficiently function as an underlayer when the crystalline semiconductor layer is stacked, and thus the crystal is formed on the zinc oxide.
  • a crystalline semiconductor layer having high crystallinity and low resistance cannot be obtained. If the film thickness is larger than 2 nm, the light absorption loss due to the first amorphous semiconductor layer cannot be ignored, and the amount of light incident on the i-type semiconductor layer decreases, so that high V and conversion efficiency can be obtained. Can not!/,.
  • the present inventors have found that the effects of the above invention can be obtained if the thickness of the crystalline semiconductor layer is 2 nm or more and lOnm or less.
  • the film thickness is smaller than 2 nm, the p-type semiconductor Since a crystalline semiconductor layer having high crystallinity and low resistance required for the body layer cannot be obtained, there arises a problem that the contact resistance at the junction interface between the transparent conductive film and the photoelectric conversion unit does not decrease.
  • the film thickness is larger than lOnm, the light absorption loss due to the crystalline semiconductor layer cannot be ignored as in the case of the first amorphous semiconductor layer, and the amount of light incident on the i-type semiconductor layer decreases. I can't get efficiency.
  • the present inventor has found that the effect of the above invention can be obtained if the thickness of the second amorphous semiconductor layer is 0.5 nm or more and lOnm or less. That is, if the film thickness is smaller than 0.5 nm, it is not possible to cover the surface irregularities and the crystal grain boundaries formed during the growth of the crystalline semiconductor layer, so that the i-type film formed on the p-type semiconductor layer is not covered. The film quality of the semiconductor layer cannot be improved. If the film thickness is larger than lOnm, the light absorption loss due to the second amorphous semiconductor layer cannot be ignored and the amount of light incident on the i-type semiconductor layer decreases, so that high conversion efficiency cannot be obtained. ⁇
  • the p-type semiconductor layer in particular, the p-type amorphous silicon carnoid constituting the second amorphous semiconductor layer and the p-type amorphous silicon
  • amorphous silicon it is preferable to use amorphous silicon as the i-type semiconductor layer.
  • the present invention can also be applied to a tandem thin-film solar cell in which two or more photoelectric conversion units are stacked.
  • a tandem thin-film solar cell having a crystalline photoelectric conversion unit in which a high-quality i-type semiconductor layer and an n-type semiconductor layer are sequentially stacked, a wide bandgap V-type, i-type amorphous silicon is converted to an amorphous i-type.
  • i-type crystalline silicon for the semiconductor layer and narrow bandgap and using i-type crystalline silicon for the crystalline i-type semiconductor layer makes it possible to effectively photoelectrically convert a wider range of incident light. As a result, the conversion efficiency of the thin-film solar cell as a whole can be improved.
  • the transparent conductive film positioned on the light incident side may include:
  • oxidized tin or oxidized zinc can be used, but it is limited to this as long as it satisfies the characteristics required for a transparent conductive film and has low contact resistance at the junction interface with the photoelectric conversion unit. It is not done.
  • a photoelectric conversion device as shown in FIG. A glass substrate 11 having a thickness of 0.7 mm was carried into the film forming chamber, and the temperature of the substrate was adjusted to 150 ° C. Thereafter, diborane diluted to 500 Oppm with argon was introduced at 700 sccm, water was introduced at 100 sccm, and getyl dumbbell was introduced at 50 sccm. The pressure at this time was lTorr. Under these conditions, a transparent conductive film 12 consisting of an oxide zinc film was deposited to a thickness of 1500 nm. The film thickness was measured with an ellipsometer.
  • the resistivity, the haze rate, and the transmittance of the produced zinc oxide film were measured using a resistance meter, a haze meter, and a spectrophotometer, respectively.
  • the resistivity measured boss was haze in 3 X 10- 3 ⁇ 'cm C light source 19%, transmittance at a wavelength of lOOOnm was 76%.
  • a plasma CVD method is used to form a p-type amorphous silicon carbide layer 13p with a thickness of 15 nm as a p-type semiconductor layer and an i-type amorphous silicon film with a thickness of 300 nm as an i-type semiconductor layer.
  • a photoelectric conversion unit 13 including a layer 13i and an n-type microcrystalline silicon layer 13n having a thickness of 30 nm was formed as an n-type semiconductor layer. Thereafter, a 90-nm-thick zinc oxide layer 141 doped with aluminum and a 300-nm-thick silver 142 were successively formed as the back electrode layer 14 by a sputtering method.
  • the photoelectric conversion device (light receiving area lcm 2 ) obtained as described above was irradiated with AMI.5 light at a light intensity of 100 mWZcm 2 and the output characteristics were measured at 25 ° C. 0.833V, short circuit current density (Jsc) 15. Fill factor (FF) was 0.685 and conversion efficiency (Eff) was 8.90%.
  • Example 1 a photoelectric conversion device as shown in FIG. 2 was manufactured. Under the same conditions as in Comparative Example 1, a transparent conductive film 22 made of an oxidized zinc film was deposited on a glass substrate 21 having a thickness of 0.7 mm. Thereafter, the p-type semiconductor layer 23 is formed on the transparent conductive film 22 by using a plasma CVD method. A p-type amorphous silicon carbide layer 23p1 having a thickness of lnm was formed as a first amorphous semiconductor layer of p. Subsequently, a 5 nm-thick p-type microcrystalline silicon layer 23p2 was formed as a crystalline semiconductor layer of the p-type semiconductor layer 23p.
  • a 5 nm-thick p-type amorphous silicon carbide layer 23p3 was formed as a second amorphous semiconductor layer of the p-type semiconductor layer.
  • the p-type amorphous silicon carbide layer 23pl as the first amorphous semiconductor layer and the p-type amorphous silicon carbide layer 23p3 as the second amorphous semiconductor layer were the same as in Comparative Example 1. It was formed under the following conditions.
  • the p-type microcrystalline silicon layer 23p2 which is a crystalline semiconductor layer, is formed by introducing 10 sccm of diborane, 600 sccm of hydrogen, and 3 sccm of silane, which are diluted to 100 ppm with hydrogen, into a film forming chamber. , A power density of 100 mWZcm 2 , a pressure of 450 Pa, and a substrate temperature of 170 ° C.
  • a photoelectric conversion comprising an i-type amorphous silicon layer 23i having a thickness of 300 nm as an i-type semiconductor layer and an n-type microcrystalline silicon layer 23 ⁇ having a thickness of 30 nm as an n-type semiconductor layer.
  • the conversion unit 23 was formed.
  • a 90 nm-thick zinc oxide layer 241 and a 300 nm-thick silver 242 doped with aluminum were sequentially formed as a back electrode layer 24 by a Snotter method.
  • a photoelectric conversion device having a configuration similar to that of FIG. 1 was manufactured.
  • a glass substrate 11 having a thickness of 0.7 mm was carried into the film-forming chamber, and a viramid-shaped oxide tin film having a thickness of 800 nm was formed as a transparent electrode layer 12 by a thermal CVD method.
  • the film thickness was measured with an ellipsometer.
  • the sheet resistance and the haze ratio of the produced Suzuki tin film were measured using a resistance meter and a haze meter, respectively. As a result, the sheet resistance was about 9 ⁇ b.
  • the haze ratio measured with the C light source was 12%.
  • a 15 nm-thick p-type amorphous silicon carbide layer 13p, i is formed as a p-type semiconductor layer by a plasma CVD method.
  • a photoelectric conversion unit 13 including an i-type amorphous silicon layer 13i having a thickness of 300 nm as a type semiconductor layer and an n-type microcrystalline silicon layer 13 ⁇ having a thickness of 30 nm as an n-type semiconductor layer was formed.
  • a 90-nm-thick oxidized zinc layer 141 and a 300-nm-thick silver 142 doped with aluminum were sequentially formed as the back electrode layer 14 by a sputtering method.
  • the photoelectric conversion device (light receiving area lcm 2 ) obtained as described above was irradiated with AMI.5 light at a light intensity of 100 mWZcm 2 and the output characteristics were measured at 25 ° C. 852V, short circuit current density Ci sc) 15.
  • the fill factor (FF) was 0.710 and the conversion efficiency (Eff) was 9.37%.
  • Example 2 a photoelectric conversion device having a configuration similar to that of FIG. 2 was manufactured.
  • a transparent conductive film 22 made of an oxide tin film was deposited on a glass substrate 21 under the same conditions as in Comparative Example 2.
  • a p-type amorphous silicon carbide layer 23pl having a thickness of lnm is formed as a first amorphous semiconductor layer of the p-type semiconductor layer 23p by a plasma CVD method. did.
  • a p-type microcrystalline silicon layer 23p2 having a thickness of 3 nm was formed as a crystalline semiconductor layer of the p-type semiconductor layer 23p.
  • a p-type amorphous silicon carbide layer 23p3 having a thickness of 5 nm was formed as a second amorphous semiconductor layer of the p-type semiconductor layer.
  • the amorphous silicon caroid layer 23p3 was formed under the same conditions as in Example 1.
  • a 300 nm-thick i-type amorphous silicon layer 23i as an i-type semiconductor layer and a 30 nm-thick n-type microcrystalline silicon layer 23 ⁇ as an n-type semiconductor layer are formed.
  • the photoelectric conversion unit 23 was formed.
  • a 90-nm-thick zinc oxide layer 241 doped with aluminum and a 300-nm-thick silver 242 were sequentially formed as a back electrode layer 24 by a sputtering method.
  • the photoelectric conversion device (light receiving area lcm 2 ) obtained as described above was irradiated with AMI.5 light at a light intensity of 100 mWZcm 2 and the output characteristics were measured at 25 ° C. 871V, short-circuit current density (Jsc) 15.
  • the fill factor (FF) was 0.713, and the conversion efficiency (Eff) was 9.81% .
  • Comparative Example 2 and Example 2 the open-circuit voltage, short-circuit current density, curve factor, and conversion efficiency Improvements in properties were seen for all.
  • Example 2 the thickness of the p-type semiconductor layer is small, and the tin oxide film is not reduced during the formation of the crystalline semiconductor layer due to the presence of the first amorphous semiconductor layer. And the short-circuit current density improved. Also, by laminating the crystalline semiconductor layer in the p-type semiconductor layer, the contact resistance at the junction interface between the transparent conductive film and the photoelectric conversion unit was reduced, and the fill factor was improved.
  • a photoelectric conversion device in which two photoelectric conversion units were stacked as illustrated in FIG. 3 was manufactured.
  • a transparent conductive film 32 made of an oxide zinc film was deposited on a glass substrate 31 under the same conditions as in Comparative Example 1.
  • a 15 nm-thick p-type amorphous silicon carbide layer 33p as a p-type semiconductor layer and a 300 nm-thick i-type amorphous silicon A first photoelectric conversion unit 33 including a layer 33i and an n-type microcrystalline silicon layer 33 ⁇ having a thickness of 3 Onm as an n-type semiconductor layer was formed.
  • a second photoelectric conversion unit 34 comprising a ⁇ -type microcrystalline silicon layer 34 ⁇ having a thickness of 15 nm, an i-type crystalline silicon layer 34 i having a thickness of 2500 nm, and an n-type microcrystalline silicon layer 34 ⁇ having a thickness of 15 nm is formed. Formed sequentially. Thereafter, as the back electrode layer 35, an aluminum-doped zinc oxide layer 351 having a thickness of 90 ⁇ m and a thickness of 300 nm and silver 352 having a thickness of 300 nm were sequentially formed by sputtering.
  • the photoelectric conversion device (light receiving area lcm 2 ) obtained as described above was irradiated with AMI.5 light at a light intensity of 100 mWZc m 2 and the output characteristics were measured at 25 ° C. 1.336 V, short circuit current density (Jsc) 11.
  • the fill factor (FF) was 0.653 and the conversion efficiency (Eff) was 10.35%.
  • Example 3 a photoelectric conversion device in which two photoelectric conversion units were stacked as shown in FIG. 4 was manufactured. Under the same conditions as in Comparative Example 3, a transparent conductive film 42 made of a zinc oxide film was deposited on a glass substrate 41. Thereafter, a 0.5 nm-thick p-type amorphous silicon carcinoid layer 43pl is formed on the transparent conductive film 42 as a first amorphous semiconductor layer of the p-type semiconductor layer 43p by using a plasma CVD method. Was formed. Subsequently, a 4 nm-thick p-type microcrystalline silicon layer 43p2 was formed as a crystalline semiconductor layer of the p-type semiconductor layer 43p.
  • a 7-nm-thick p-type amorphous silicon carnoid layer 43p3 is formed as a second amorphous semiconductor layer of the p-type semiconductor layer 43p. Formed. Note that a p-type amorphous silicon carbide layer 43pl, which is a first amorphous semiconductor layer, a p-type microcrystalline silicon layer 43p2, which is a crystalline semiconductor layer, and a p-type amorphous semiconductor layer 43p2, which is a second amorphous semiconductor layer. The type amorphous silicon carbide layer 43p3 was formed under the same conditions as in Example 1.
  • a first i-type amorphous silicon layer 43i having a thickness of 300 nm as an i-type semiconductor layer and an n-type microcrystalline silicon layer 43 ⁇ having a thickness of 30 nm as an n-type semiconductor layer were formed.
  • the photoelectric conversion unit 43 was formed. Further, under the same conditions as in Comparative Example 3, a 15-nm thick P-type microcrystalline silicon layer 44p, a 2500 nm-thick i-type crystalline silicon layer 44i, and a 15 ⁇ m-thick ⁇ -type microcrystalline silicon layer 44 ⁇ Two photoelectric conversion units 44 were sequentially formed.
  • a 90 nm-thick oxidized zinc layer 451 doped with aluminum and a 300 nm-thick silver 452 were sequentially formed by a sputtering method.
  • the photoelectric conversion device (light receiving area lcm 2 ) obtained as described above was irradiated with AMI. 5 light at 100 mWZcm 2 and the output characteristics were measured at 25 ° C, the open circuit voltage (Voc) was measured. Is 1.364V and short circuit current density (Jsc) is 12.
  • the fill factor (FF) was 0.721 and the conversion efficiency (Eff) was 12.14%.
  • Example 4 a photoelectric conversion device having the configuration shown in FIG. Example 4 differs from Example 1 in that a 5 nm-thick p-type amorphous silicon layer 23p3 was formed as a second amorphous semiconductor layer of the p-type semiconductor layer 23p.
  • the p-type amorphous silicon layer 23p3, which is the second amorphous semiconductor layer, is formed at the time of film formation as compared with the film formation conditions of the amorphous silicon carnoid layer 23pl, which is the first amorphous semiconductor layer.
  • a film was formed under the same conditions except that methane gas was removed from the gas used.
  • the photoelectric conversion device (light receiving area lcm 2 ) obtained as described above was irradiated with AMI.5 light at a light intensity of 100 mWZcm 2 and the output characteristics were measured at 25 ° C. 0.872V, short circuit current density (Jsc) is 15.9mA / cm 2 , fill factor (FF) is 0.705, and conversion efficiency (Eff) is 9.77% .Comparison between Comparative Example 1 and Example 4. As a result, the characteristics were improved in all of the open-circuit voltage, short-circuit current density, fill factor, and conversion efficiency.

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Abstract

Est décrit un convertisseur photoélectrique de grande efficacité de conversion qui peut être obtenu par un procédé permettant d’obtenir une bonne interface de jonction entre une pellicule conductrice transparente et une unité de conversion photoélectrique. Spécifiquement, une couche de semi-conducteur de type p d’une unité de conversion photoélectrique la plus proche du côté de la lumière incidente qui est adjacente à une couche conductrice transparente a une structure dans laquelle une première couche de semi-conducteur amorphe, une couche de semi-conducteur cristallin et une deuxième couche de semi-conducteur amorphe sont séquentiellement empilées. La première couche de semi-conducteur amorphe est préférablement formée par un carbure de silicium amorphe ; la deuxième couche de semi-conducteur amorphe est préférablement formée par un carbure de silicium amorphe ou un silicium amorphe ; et la couche conductrice amorphe transparente est préférablement formée d’oxyde d’étain ou d’oxyde de zinc.
PCT/JP2005/007872 2004-05-12 2005-04-26 Convertisseur photoélectrique en pellicule mince WO2005109526A1 (fr)

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JP2008124325A (ja) * 2006-11-14 2008-05-29 Kaneka Corp 薄膜光電変換装置とその製造方法
WO2009001647A1 (fr) * 2007-06-25 2008-12-31 Sharp Kabushiki Kaisha Convertisseur photoélectrique, convertisseur photoélectrique intégré et procédé de fabrication du convertisseur photoélectrique
JP2010517271A (ja) * 2007-01-18 2010-05-20 アプライド マテリアルズ インコーポレイテッド 多接合太陽電池並びにそれを形成するための方法及び装置
JP2011029259A (ja) * 2009-07-22 2011-02-10 Kaneka Corp 薄膜光電変換装置
JP2013084721A (ja) * 2011-10-07 2013-05-09 Sharp Corp 光電変換素子および光電変換素子の製造方法

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US20090293954A1 (en) * 2008-05-30 2009-12-03 Semiconductor Energy Laboratory Co., Ltd. Photoelectric Conversion Device And Method For Manufacturing The Same
TWI413267B (zh) * 2009-01-30 2013-10-21 Ulvac Inc 光電轉換裝置之製造方法、光電轉換裝置、光電轉換裝置之製造系統、及光電轉換裝置製造系統之使用方法

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Publication number Priority date Publication date Assignee Title
JP2008124325A (ja) * 2006-11-14 2008-05-29 Kaneka Corp 薄膜光電変換装置とその製造方法
JP2010517271A (ja) * 2007-01-18 2010-05-20 アプライド マテリアルズ インコーポレイテッド 多接合太陽電池並びにそれを形成するための方法及び装置
WO2009001647A1 (fr) * 2007-06-25 2008-12-31 Sharp Kabushiki Kaisha Convertisseur photoélectrique, convertisseur photoélectrique intégré et procédé de fabrication du convertisseur photoélectrique
JP2011029259A (ja) * 2009-07-22 2011-02-10 Kaneka Corp 薄膜光電変換装置
JP2013084721A (ja) * 2011-10-07 2013-05-09 Sharp Corp 光電変換素子および光電変換素子の製造方法

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