WO2011136162A1 - 光電変換装置 - Google Patents

光電変換装置 Download PDF

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Publication number
WO2011136162A1
WO2011136162A1 PCT/JP2011/060035 JP2011060035W WO2011136162A1 WO 2011136162 A1 WO2011136162 A1 WO 2011136162A1 JP 2011060035 W JP2011060035 W JP 2011060035W WO 2011136162 A1 WO2011136162 A1 WO 2011136162A1
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layer
intermediate layer
type
refractive index
type layer
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French (fr)
Japanese (ja)
Inventor
山岡　義和
茂郎 矢田
亜津美 梅田
大二 兼松
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/17—Photovoltaic cells having only PIN junction potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/17—Photovoltaic cells having only PIN junction potential barriers
    • H10F10/172—Photovoltaic cells having only PIN junction potential barriers comprising multiple PIN junctions, e.g. tandem cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/10—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material
    • H10F71/103—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material including only Group IV materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • H10F71/1224—The active layers comprising only Group IV materials comprising microcrystalline silicon
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/40—Optical elements or arrangements
    • H10F77/42—Optical elements or arrangements directly associated or integrated with photovoltaic cells, e.g. light-reflecting means or light-concentrating means
    • H10F77/48—Back surface reflectors [BSR]
    • 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
    • Y02E10/52—PV systems with concentrators
    • 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
    • Y02E10/545—Microcrystalline silicon PV cells
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a photoelectric conversion device, and particularly to a photoelectric conversion device including an intermediate layer.
  • Solar cells using polycrystalline, microcrystalline, or amorphous silicon are known.
  • a photoelectric conversion device having a structure in which thin films of microcrystalline silicon or amorphous silicon are stacked is attracting attention from the viewpoint of resource consumption, cost reduction, and efficiency.
  • a photoelectric conversion device is formed by sequentially laminating a first electrode layer, one or more semiconductor thin film photoelectric conversion units, and a second electrode layer on a substrate having an insulating surface.
  • Each photoelectric conversion unit is configured by stacking a p-type layer, an i-type layer, and an n-type layer from the light incident side.
  • As a method for improving the conversion efficiency of the photoelectric conversion device it is known to stack two or more photoelectric conversion units in the light incident direction.
  • a first photoelectric conversion unit including a photoelectric conversion layer having a wide band gap is disposed on the light incident side of the photoelectric conversion device, and then a second photoelectric conversion layer including a photoelectric conversion layer having a narrower band gap than the first photoelectric conversion unit is disposed.
  • a photoelectric conversion unit is arranged. Thereby, photoelectric conversion can be performed over a wide wavelength range of incident light, and the conversion efficiency of the entire apparatus can be improved.
  • the amorphous silicon photoelectric conversion unit (a-Si unit) 14 is used as the top cell, and the microcrystalline photoelectric conversion unit ( ⁇ c-Si unit).
  • a-Si unit amorphous silicon photoelectric conversion unit 14
  • ⁇ c-Si unit microcrystalline photoelectric conversion unit
  • the intermediate layer 20 is provided between the a-Si unit 14 and the ⁇ c-Si unit 16 .
  • zinc oxide (ZnO) or silicon oxide (SiOx) is used for the intermediate layer 20.
  • the intermediate layer 20 may also be made of a silicon oxide material, a silicon carbide material, a silicon nitride material, a carbon material such as diamond-like carbon, or the like.
  • the intermediate layer 20 has a refractive index of light lower than that of the a-Si unit 14, and reflection of light to the a-Si unit 14 occurs between the a-Si unit 14 on the light incident side and the intermediate layer 20. ing.
  • the a-Si unit 14 when light is reflected from the intermediate layer 20 to the a-Si unit 14 on the light incident side, the a-Si unit 14, the transparent electrode layer 12, the substrate 10, air, and the refractive index are small, so the a-Si unit 14. The light reflected to the side escapes from the substrate 10, causing a problem that the light cannot be used sufficiently.
  • One aspect of the present invention is a photoelectric conversion device in which a p-type layer, an i-type layer, and an n-type layer are stacked, and is disposed between the p-type layer and the i-type layer.
  • the light utilization rate in the photoelectric conversion device can be increased, and the photoelectric conversion efficiency can be improved.
  • FIG. 1 is a cross-sectional view illustrating a structure of a photoelectric conversion device 200 according to the first embodiment.
  • the photoelectric conversion device 200 in the present embodiment has an amorphous silicon photoelectric conversion unit (a-Si unit) having a wide band gap as a transparent conductive layer 32 and a top cell from the light incident side with the transparent insulating substrate 30 as the light incident side.
  • 202 has a structure in which a microcrystalline silicon photoelectric conversion unit ( ⁇ c-Si unit) 204 having a narrower band gap than the a-Si unit 202 and a back electrode layer 34 are stacked as a bottom cell.
  • ⁇ c-Si unit microcrystalline silicon photoelectric conversion unit
  • a material having transparency in at least a visible light wavelength region such as a glass substrate or a plastic substrate, can be applied.
  • a transparent conductive layer 32 is formed on the transparent insulating substrate 30.
  • the transparent conductive layer 32 is doped with tin oxide (SnO 2 ), zinc oxide (ZnO), indium tin oxide (ITO), etc. with tin (Sn), antimony (Sb), fluorine (F), aluminum (Al), etc. It is preferable to use at least one or a combination of a plurality of transparent conductive oxides (TCO).
  • zinc oxide (ZnO) is preferable because it has high translucency, low resistivity, and excellent plasma resistance.
  • the transparent conductive layer 32 can be formed by, for example, a sputtering method or a CVD method.
  • the film thickness of the transparent conductive layer 32 is preferably in the range of 0.5 ⁇ m to 5 ⁇ m. Moreover, it is preferable to provide unevenness having a light confinement effect on the surface of the transparent conductive layer 32.
  • An a-Si unit 202 is formed on the transparent conductive layer 32 by sequentially stacking a silicon-based thin film of a p-type layer 36, an i-type layer 38, and an n-type layer 40.
  • the a-Si unit 202 includes silicon-containing gas such as silane (SiH 4 ), disilane (Si 2 H 6 ), dichlorosilane (SiH 2 Cl 2 ), carbon hydrogen gas such as methane (CH 4 ), diborane (B 2 H 6 )
  • Plasma is formed from a mixed gas obtained by selecting a gas from a p-type dopant containing gas such as phosphine (PH 3 ), a n-type dopant containing gas such as phosphine (PH 3 ), and a diluting gas such as hydrogen (H 2 ). It can be formed by a plasma CVD method. Specific film formation conditions are shown in Table 1.
  • an RF plasma CVD method of 13.56 MHz is preferably applied.
  • the RF plasma CVD method can be a parallel plate type.
  • the p-type layer 36, the i-type layer 38, and the n-type layer 40 are formed in separate film formation chambers.
  • the film formation chamber can be evacuated by a vacuum pump, and has an electrode for RF plasma CVD.
  • a transfer device for the transparent insulating substrate 30, a power source and matching device for the RF plasma CVD method, a pipe for supplying gas, and the like are attached.
  • the p-type layer 36 is formed on the transparent conductive layer 32.
  • the p-type layer 36 is a p-type amorphous silicon layer (p-type a-Si: H) or p-type amorphous silicon carbide layer (p-type a-SiC) having a thickness of 10 nm to 100 nm doped with a p-type dopant (boron or the like). : H) is preferred.
  • the film quality of the p-type layer 36 can be changed by adjusting the mixing ratio of silicon-containing gas, hydrocarbon gas, p-type dopant-containing gas and dilution gas, pressure, and high-frequency power for plasma generation.
  • the i-type layer 38 is an undoped amorphous layer formed on the p-type layer 36 and having a thickness of 50 nm to 500 nm.
  • the film quality of the i-type layer 38 can be changed by adjusting the mixing ratio of the silicon-containing gas and the dilution gas, the pressure, and the high frequency power for plasma generation.
  • the i-type layer 38 becomes a power generation layer of the a-Si unit 202.
  • the n-type layer 40 is an n-type amorphous silicon layer (n-type a-Si: H) having a thickness of 10 nm or more and 100 nm or less doped with an n-type dopant (such as phosphorus) formed on the i-type layer 38 or an n-type fine layer.
  • n-type dopant such as phosphorus
  • a crystalline silicon layer (n-type ⁇ c-Si: H) is used.
  • the film quality of the n-type layer 40 can be changed by adjusting the mixing ratio of the silicon-containing gas, the hydrocarbon gas, the n-type dopant-containing gas and the dilution gas, the pressure, and the high frequency power for plasma generation.
  • the ⁇ c-Si unit 204 includes a silicon-containing gas such as silane (SiH 4 ), disilane (Si 2 H 6 ), dichlorosilane (SiH 2 Cl 2 ), a carbon hydrogen gas such as methane (CH 4 ), diborane (B 2 H 6 ) Select a gas from a p-type dopant containing gas such as phosphine (PH 3 ), a n-type dopant containing gas such as phosphine (PH 3 ), a carbon oxide gas such as carbon dioxide (CO 2 ) and a diluent gas such as hydrogen (H 2 ). It can be formed by a plasma CVD method in which a mixed gas mixture is turned into plasma to form a film. Specific film forming conditions are shown
  • the plasma CVD method it is preferable to apply, for example, the 13.56 MHz RF plasma CVD method, as with the a-Si unit 202.
  • the p-type layer 42, the i-type layer 46, and the n-type layer 50 are formed in separate film formation chambers.
  • the first intermediate layer 44 and the second intermediate layer 48 may be formed using any one of the deposition chambers of the p-type layer 36, the n-type layer 40, the p-type layer 42, and the n-type layer 50. .
  • the p-type layer 42 is formed on the n-type layer 40 of the a-Si unit 202.
  • the p-type layer 42 is preferably a microcrystalline silicon layer, an amorphous silicon layer, or a combination thereof.
  • the film quality of the p-type layer 42 can be changed by adjusting the mixing ratio of silicon-containing gas, hydrocarbon gas, p-type dopant-containing gas and dilution gas, pressure, and high-frequency power for plasma generation.
  • the first intermediate layer 44 is formed on the p-type layer 40.
  • the first intermediate layer 44 plays a role of confining light in the i-type layer 46 that is the power generation layer of the ⁇ c-Si unit 204 together with the second intermediate layer 48 described later.
  • the first intermediate layer 44 is preferably a layer containing silicon oxide doped with a p-type dopant (such as boron).
  • the first intermediate layer 44 is preferably formed by a plasma CVD method using a mixed gas obtained by mixing a silicon-containing gas, a p-type dopant-containing gas, and a diluent gas with a carbon oxide gas such as carbon dioxide (CO 2 ). It is.
  • the film quality of the first intermediate layer 44 can be changed by adjusting the additive gas species, the gas mixture ratio, the pressure, and the high frequency power for plasma generation.
  • the i-type layer 46 is formed on the first intermediate layer 44.
  • the i-type layer 46 is an undoped microcrystalline silicon film having a thickness of 0.5 ⁇ m to 5 ⁇ m.
  • the i-type layer 46 is a layer that becomes a power generation layer of the ⁇ c-Si unit 204.
  • the i-type layer 46 preferably has a laminated structure in which a buffer layer is first formed and a main power generation layer is formed on the buffer layer.
  • the buffer layer is formed under a film formation condition that provides a higher crystallization rate than that of the main power generation layer.
  • the buffer layer is formed under a film forming condition in which the crystallization rate is higher than that of the main power generation layer.
  • the film quality of the i-type layer 46 can be changed by adjusting the mixing ratio of the silicon-containing gas and the dilution gas, the pressure, and the high frequency power for plasma generation.
  • the second intermediate layer 48 is formed on the i-type layer 46.
  • the second intermediate layer 48 is preferably a layer containing silicon oxide doped with an n-type dopant (such as phosphorus).
  • the second intermediate layer 48 is preferably formed by a plasma CVD method using a mixed gas obtained by mixing a silicon-containing gas, an n-type dopant-containing gas, and a diluent gas with a carbon oxide gas such as carbon dioxide (CO 2 ). It is.
  • the film quality of the second intermediate layer 48 can be changed by adjusting the additive gas species, the gas mixing ratio, the pressure, and the high frequency power for plasma generation.
  • the n-type layer 50 is formed on the second intermediate layer 48.
  • the n-type layer 50 is an n-type microcrystalline silicon layer (n-type ⁇ c-Si: H) doped with an n-type dopant (such as phosphorus) and having a thickness of 5 nm to 50 nm.
  • the film quality of the n-type layer 50 can be changed by adjusting the mixing ratio of silicon-containing gas, hydrocarbon gas, n-type dopant-containing gas and dilution gas, pressure, and high-frequency power for plasma generation.
  • the ⁇ c-Si unit 204 is not limited to this, and an i-type microcrystalline silicon layer (i-type ⁇ c-Si: H) is used for the i-type layer 46 serving as a power generation layer. What is necessary is just to provide the 1st intermediate
  • the first intermediate layer 44 and the second intermediate layer 48 will be described in detail later.
  • a back electrode layer 34 is formed on the ⁇ c-Si unit 204.
  • the back electrode layer 34 preferably has a laminated structure of a reflective metal and a transparent conductive oxide (TCO).
  • TCO transparent conductive oxide
  • tin oxide (SnO 2 ), zinc oxide (ZnO), indium tin oxide (ITO), or the like, or those doped with impurities is used.
  • zinc oxide (ZnO) doped with aluminum (Al) as an impurity may be used.
  • metals, such as silver (Ag) and aluminum (Al) are used.
  • the transparent conductive oxide (TCO) and the reflective metal can be formed by, for example, a sputtering method or a CVD method. It is preferable that at least one of the transparent conductive oxide (TCO) and the reflective metal is provided with unevenness for enhancing the light confinement effect.
  • the back electrode layer 34 may be covered with a protective film (not shown).
  • the protective film may be a resin material such as EVA or polyimide, and may be bonded so as to cover the back electrode layer 34 with a filler that is a similar resin material. This can prevent moisture from entering the power generation layer of the photoelectric conversion device 200.
  • the transparent conductive layer 32, the a-Si unit 202, the ⁇ c-Si unit 204, and the back electrode layer 34 are separated, so that a plurality of You may make it the structure which connected the cell in series.
  • FIG. 2 shows the refractive index of each layer of the photoelectric conversion device 200 in this embodiment.
  • the refractive index n 1 of the first intermediate layer 44 is made smaller than the refractive index n p of the adjacent p-type layer 42.
  • the difference in refractive index between the first intermediate layer 44 and the i-type layer 46 is the difference in refractive index between the first intermediate layer 44 and the p-type layer 42 (n p ⁇ n 1 ).
  • the refractive index n 2 of the second intermediate layer 48 is smaller than the refractive index n n of the n-type layer 50 adjacent to each other.
  • the difference in refractive index between the second intermediate layer 48 and the i-type layer 46 (n i ⁇ n 2 ) is the difference in refractive index between the second intermediate layer 48 and the n-type layer 50 (n n ⁇ n 2 ). To be bigger than.
  • the first intermediate layer 44 and the second intermediate layer 48 can provide a light confinement effect on the i-type layer 46 of the ⁇ c-Si unit 204 serving as a bottom cell.
  • a part of the light is transmitted through the interface between the i-type layer 46 and the second intermediate layer 48, but the light passes through the n-type layer 50 and n It reaches the mold layer 50 and the back electrode layer 34, is reflected by the refractive index difference between the n-type layer 50 and the back electrode layer 34, passes through the n-type layer 50 and the second intermediate layer 48, and returns to the i-type layer 46. Returned.
  • the light reflected by the back electrode layer 34 is also confined in the i-type layer 46 by the first intermediate layer 44 and the second intermediate layer 48.
  • the first intermediate layer 44 and the second intermediate layer 44 are preferably 3.6 or less.
  • the refractive indexes n 1 and n 2 of the first intermediate layer 44 and the second intermediate layer 48 should be as low as possible so as not to deteriorate the film characteristics of the first intermediate layer 44 and the second intermediate layer 48. A value of about 2.1 is preferable.
  • the refractive index n 1 of the first intermediate layer 44 is preferably larger than the refractive index n 2 of the second intermediate layer 48. Since the refractive index n n of the refractive index n p and n-type layer 50 of p-type layer 42 is approximately the same size, the p-type layer 42 at the interface between the first intermediate layer 44, the n-type layer 50 The light introduction rate into the i-type layer 46 can be increased more than the interface with the second intermediate layer 48.
  • the film thickness d 1 of the first intermediate layer 44 is preferably set to be equal to or less than the film thickness d 2 of the second intermediate layer 48.
  • the reflectance at the interface between the first intermediate layer 44 and the i-type layer 46 is slightly lower than the reflectance at the interface between the i-type layer 46 and the second intermediate layer 48, but the light from the transparent insulating substrate 30 is reduced.
  • Light absorption in the first intermediate layer 44 on the incident side is suppressed, the amount of light reaching the i-type layer 46 can be increased, and the power generation efficiency of the entire photoelectric conversion device 200 can be increased.
  • the light absorption amount in the second intermediate layer 48 is larger than the light absorption amount in the first intermediate layer 44, but the light reflected from the back electrode layer 34 and incident on the second intermediate layer 48 is transparent.
  • Light confinement to the i-type layer 46 is smaller than the light incident on the first intermediate layer 44 from the insulating substrate 30 side and increases the reflectance at the interface between the i-type layer 46 and the second intermediate layer 48. The effect is enhanced, and the power generation efficiency of the entire photoelectric conversion device 200 can be increased.
  • the film thicknesses d 1 and d 2 of the first intermediate layer 44 and the second intermediate layer 48 are preferably 30 nm or more and 100 nm or less.
  • the film thickness d 2 of the second intermediate layer 48 is 50nm or more there is a thickness d 1 or more first intermediate layer 44 A range of 100 nm or less is preferable.
  • the refractive indexes n 1 and n 2 of the first intermediate layer 44 and the second intermediate layer 48 carbon dioxide with respect to a mixed gas of silicon-containing gas, dopant-containing gas, and dilution gas at the time of film formation (The mixing ratio of the carbon oxide gas such as CO 2 ) may be adjusted. That is, in order to further lower the refractive indexes n 1 and n 2 , the mixing ratio of oxygen-containing gas such as carbon dioxide (CO 2 ) may be increased.
  • the first intermediate layer 44 and the second intermediate layer 48 can also be adjusted by adjusting the film forming conditions such as the pressure during the film formation of the first intermediate layer 44 and the second intermediate layer 48 by the plasma CVD method and the high frequency power for plasma generation.
  • the refractive indexes n 1 and n 2 of can be changed.
  • the refractive index of each layer can be known by performing component analysis by energy dispersive X-ray analysis (EDX) on the cross section of the photoelectric conversion device 200.
  • EDX energy dispersive X-ray analysis
  • the configuration of the photoelectric conversion device 200 according to the present embodiment is as long as layers having a higher oxygen content of oxygen (O) than the i-type layer 46 are provided on both sides of the i-type layer 46 of the ⁇ c-Si unit 204. It can be determined that it has.
  • the refractive index relationship between the first intermediate layer 44 and the second intermediate layer 48 and the p-type layer 42 and the n-type layer 50 can be similarly determined.
  • the relationship between the refractive indexes of the layers can be similarly determined in other embodiments and modifications described later.
  • the first intermediate layer 44 and the second intermediate layer 48 include layers containing silicon oxide doped with impurities.
  • the present invention is not limited to this.
  • the first intermediate layer 44 and the second intermediate layer 48 may be a transparent conductive oxide (TCO) such as zinc oxide (ZnO).
  • TCO transparent conductive oxide
  • ZnO zinc oxide
  • Mg magnesium
  • the transparent conductive oxide (TCO) can be formed by, for example, a sputtering method or a CVD method.
  • a third intermediate layer 52 may be further provided as shown in the photoelectric conversion device 206 in FIG.
  • the third intermediate layer 52 is formed between the i-type layer 38 and the n-type layer 40 of the a-Si unit 202. Similar to the second intermediate layer 48, the third intermediate layer 52 is preferably a layer containing silicon oxide doped with an n-type dopant (phosphorus).
  • the third intermediate layer 52 is preferably formed by a plasma CVD method using a mixed gas obtained by mixing a silicon-containing gas, an n-type dopant-containing gas, and a diluent gas with a carbon oxide gas such as carbon dioxide (CO 2 ). It is.
  • the film quality of the third intermediate layer 52 can be changed by adjusting the additive gas species, the gas mixture ratio, the pressure, and the plasma generating high frequency power.
  • the refractive index n 3 of the third intermediate layer 52 is preferably smaller than the refractive index n ai of the i-type layer 38 and the refractive index n an of the n-type layer 40.
  • the mixing ratio of carbon oxide gas such as carbon dioxide (CO 2 ) to the mixed gas of silicon-containing gas, dopant-containing gas, and dilution gas during film formation can be adjusted.
  • the third intermediate layer 52 By further providing the third intermediate layer 52 in this way, the light that reaches the interface between the i-type layer 38 of the a-Si unit 202 and the third intermediate layer 52 is reflected by the difference in refractive index between the i-type layer 38 and the i-type layer. Returned to layer 38. As a result, the utilization factor of light in the i-type layer 38 can be increased, and advantages such as reduction in the thickness of the i-type layer 38 corresponding to the power generation layer of the a-Si unit 202 can be obtained.
  • the first intermediate layer 44 may not be provided, and the third intermediate layer 52 may be provided instead.
  • the i-type layer 46 of the ⁇ c-Si unit 204 has a light confinement effect between the third intermediate layer 52 and the second intermediate layer 48.
  • the confined light is absorbed by the n-type layer 40 and the p-type layer 42, it is preferable to provide the first intermediate layer 44.
  • a third intermediate layer 54 may be further provided as shown in the photoelectric conversion device 208 in FIG.
  • the third intermediate layer 54 is formed between the n-type layer 40 of the a-Si unit 202 and the p-type layer 42 of the ⁇ c-Si unit 204.
  • the third intermediate layer 54 is preferably a layer containing silicon oxide doped with a p-type dopant (such as boron) or an n-type dopant (such as phosphorus), like the first intermediate layer 44 or the second intermediate layer 48. It is.
  • the third intermediate layer 54 is preferably formed by a plasma CVD method using a mixed gas obtained by mixing a silicon-containing gas, a dopant-containing gas, and a diluent gas with a carbon oxide gas such as carbon dioxide (CO 2 ).
  • the film quality of the third intermediate layer 54 can be changed by adjusting the additive gas species, the gas mixture ratio, the pressure, and the plasma generating high frequency power.
  • Refractive index n 4 of the third intermediate layer 54 it is preferable to be smaller than the refractive index n p of the refractive index n an, and p-type layer 42 of n-type layer 40.
  • the mixing ratio of carbon oxide gas such as carbon dioxide (CO 2 ) to the mixed gas of silicon-containing gas, dopant-containing gas, and dilution gas at the time of film formation can be adjusted.
  • the light reaching the interface between the n-type layer 40 of the a-Si unit 202 and the p-type layer 42 of the ⁇ c-Si unit 204 is caused by the difference in refractive index between the two. Reflected and returned to the i-type layer 38 through the n-type layer 40.
  • the utilization factor of light in the i-type layer 38 can be increased, and advantages such as reduction in the thickness of the i-type layer 38 corresponding to the power generation layer of the a-Si unit 202 can be obtained.
  • the i-type layer 46 of the ⁇ c-Si unit 204 has a light confinement effect between the third intermediate layer 54 and the second intermediate layer 48.
  • the trapped light is absorbed by the p-type layer 42, it is preferable to provide the first intermediate layer 44.
  • FIG. 5 is a cross-sectional view illustrating the structure of the photoelectric conversion device 300 according to the second embodiment.
  • the photoelectric conversion device 300 according to the present embodiment instead of providing the first intermediate layer 44 and the second intermediate layer 48 in the ⁇ c-Si unit 204 like the photoelectric conversion device 200 according to the first embodiment,
  • the unit 202 is provided with a first intermediate layer 56 and a second intermediate layer 58.
  • the method for forming each layer is the same as that in the first embodiment, and thus the description thereof is omitted.
  • FIG. 6 shows the refractive index of each layer of the photoelectric conversion device 300 in this embodiment.
  • the refractive index n 2 of the refractive index n 1 and a second intermediate layer 58 of the first intermediate layer 56, the refractive index of the i-type layer 38 of a-Si unit 202 as a target of optical confinement n make it smaller than ai .
  • the refractive index n 1 of the first intermediate layer 56 is made smaller than the refractive index n ap of the adjacent p-type layer 36.
  • the difference in refractive index (n ai ⁇ n 1 ) between the first intermediate layer 56 and the i-type layer 38 is the difference in refractive index between the first intermediate layer 56 and the p-type layer 36 (n ap ⁇ n 1 ).
  • the refractive index n 2 of the second intermediate layer 58 is made smaller than the refractive index n an of the adjacent n-type layer 40.
  • the difference in refractive index between the second intermediate layer 58 and the i-type layer 38 (n ai ⁇ n 2 ) is the difference in refractive index between the second intermediate layer 58 and the n-type layer 40 (n an ⁇ n 2 ). To be bigger than.
  • the light use efficiency in the i-type layer 38 of the a-Si unit 202 serving as the top cell can be increased.
  • the refractive indexes n 1 and n 2 of 58 are preferably 3.6 or less. Further, the refractive indexes n 1 and n 2 of the first intermediate layer 56 and the second intermediate layer 58 are preferably as low as possible, for example, about 2.1.
  • the refractive index n 1 of the first intermediate layer 56 is preferably larger than the refractive index n 2 of the second intermediate layer 58. Since the refractive index n an, the refractive index n ap and n-type layer 40 of p-type layer 36 is approximately the same size, the p-type layer 36 at the interface between the first intermediate layer 56, the n-type layer 40 The light introduction rate into the i-type layer 38 can be increased from the interface with the second intermediate layer 58.
  • the film thickness d 1 of the first intermediate layer 56 is preferably set to be equal to or less than the film thickness d 2 of the second intermediate layer 58.
  • the reflectance at the interface between the first intermediate layer 56 and the i-type layer 38 is somewhat lower than the reflectance at the interface between the i-type layer 38 and the second intermediate layer 58, but the light from the transparent insulating substrate 30
  • Light absorption in the first intermediate layer 56 on the incident side is suppressed, the amount of light reaching the i-type layer 38 can be increased, and the power generation efficiency of the entire photoelectric conversion device 300 can be increased.
  • the amount of light absorbed by the second intermediate layer 58 is greater than the amount of light absorbed by the first intermediate layer 56, but the light reflected from the back electrode layer 34 and the like and incident on the second intermediate layer 58 is Light that is smaller than the light incident on the first intermediate layer 56 from the transparent insulating substrate 30 side and increases the reflectance at the interface between the i-type layer 38 and the second intermediate layer 58, thereby allowing the light to enter the i-type layer 38.
  • the confinement effect is enhanced, and the power generation efficiency of the entire photoelectric conversion device 300 can be increased.
  • the film thicknesses d 1 and d 2 of the first intermediate layer 56 and the second intermediate layer 58 are preferably 30 nm or more and 100 nm or less.
  • the film thickness d 1 of the first intermediate layer 56 is in the range of 30 nm or more and 50 nm or less
  • the film thickness d 2 of the second intermediate layer 58 is greater than or equal to the film thickness d 1 of the first intermediate layer 56 and is 50 nm or more.
  • a range of 100 nm or less is preferable.
  • ⁇ Modification 3> You may combine the structure of the photoelectric conversion apparatus 200 in 1st Embodiment, and the photoelectric conversion apparatus 300 in 2nd Embodiment. That is, as shown in FIG. 7, the first intermediate layer 56 and the second intermediate layer 58 are provided in the a-Si unit 202, and the first intermediate layer 44 and the second intermediate layer 48 are provided in the ⁇ c-Si unit 204, respectively.
  • the photoelectric conversion device 302 may be used.
  • the refractive index of each intermediate layer is not changed in the film thickness direction.
  • the refractive index of the intermediate layer is changed in the film thickness direction.
  • FIG. 8 is a cross-sectional view showing the structure of the photoelectric conversion device 400 according to the third embodiment.
  • the photoelectric conversion device 400 according to the present embodiment includes a first intermediate layer 60 and a ⁇ c-Si unit 204 instead of the first intermediate layer 44 and the second intermediate layer 48 in the photoelectric conversion device 200 according to the first embodiment.
  • a second intermediate layer 62 is provided.
  • the first intermediate layer 60 and the second intermediate layer 62 are formed such that their refractive indexes n 1 and n 2 change along the film thickness direction.
  • the first intermediate layer 60 is formed so that the refractive index n 1 gradually increases from the i-type layer 46 side to the p-type layer 42 side.
  • n 1 becomes smaller than the refractive index difference (n i ⁇ n 1 ) at the interface between the i-type layer 46 and the first intermediate layer 60, and the light transmittance can be improved.
  • the light once incident on the i-type layer 46 is reflected at some place such as between the n-type layer 50 and the back electrode layer 34 and reaches the interface between the i-type layer 46 and the first intermediate layer 60.
  • the reflectance to the i-type layer 46 can be increased by the refractive index difference (n i ⁇ n 1 ) at the interface between the i-type layer 46 and the first intermediate layer 60.
  • the refractive index n 1 of the first intermediate layer 60 is preferably set to be substantially equal to the refractive index n p of the p-type layer 42 at the interface with the p-type layer 42. Specifically, since the refractive index n p of the p-type layer 42 is about 3.6, the refractive index n 1 of the first intermediate layer 60 is about 3.6 at the interface with the p-type layer 42. It is preferable to do.
  • the refractive index n 1 of the first intermediate layer 60 is preferably as small as possible so that the film quality does not deteriorate at the interface with the i-type layer 46. Specifically, the refractive index n 1 of the first intermediate layer 60 is preferably about 2.1 at the interface with the i-type layer 46.
  • the second intermediate layer 62 is formed so that the refractive index n 2 gradually increases from the i-type layer 46 side toward the n-type layer 50 side.
  • the gradient in the refractive index n 2 in this way, the light reflected by the back electrode layer 34 and the like and incident from the n-type layer 50 side is formed between the n-type layer 50 and the second intermediate layer 62.
  • the refractive index difference (n n ⁇ n 2 ) at the interface becomes smaller than the refractive index difference (n i ⁇ n 2 ) at the interface between the i-type layer 46 and the second intermediate layer 62, and the light transmittance can be improved. it can.
  • the reflectance to the i-type layer 46 can be increased by -n 2 ).
  • the refractive index n 2 of the second intermediate layer 62 is preferably made substantially equal to the refractive index n n of the n-type layer 50 at the interface with the n-type layer 50. Specifically, since the refractive index n n of the n-type layer 50 is about 3.6, the refractive index n 2 of the second intermediate layer 62 at the interface with the n-type layer 50 is about 3.6. It is preferable to do.
  • the refractive index n 2 of the second intermediate layer 62 is preferably as small as possible so that the film quality does not deteriorate at the interface with the i-type layer 46. Specifically, the refractive index n 2 of the second intermediate layer 62 is preferably about 2.1 at the interface with the i-type layer 46.
  • the film thickness d 1 of the first intermediate layer 60 is preferably set to be equal to or less than the film thickness d 2 of the second intermediate layer 62.
  • the reflectance at the interface between the first intermediate layer 60 and the i-type layer 46 is slightly lower than the reflectance at the interface between the i-type layer 46 and the second intermediate layer 62, but the light from the transparent insulating substrate 30
  • Light absorption in the first intermediate layer 60 on the incident side is suppressed, the amount of light reaching the i-type layer 46 can be increased, and the power generation efficiency of the entire photoelectric conversion device 400 can be increased.
  • the light absorption amount in the second intermediate layer 62 is larger than the light absorption amount in the first intermediate layer 60, but the light reflected from the back electrode layer 34 and incident on the second intermediate layer 62 is transparent.
  • Light confinement to the i-type layer 46 is smaller than the light incident on the first intermediate layer 60 from the insulating substrate 30 side and increases the reflectance at the interface between the i-type layer 46 and the second intermediate layer 62. The effect is enhanced, and the power generation efficiency of the entire photoelectric conversion device 400 can be increased.
  • the film thicknesses d 1 and d 2 of the first intermediate layer 60 and the second intermediate layer 62 are preferably 30 nm or more and 100 nm or less.
  • the film thickness d 2 of the second intermediate layer 62 is 50nm or more there is a thickness d 1 or more first intermediate layer 60 A range of 100 nm or less is preferable.
  • the refractive indexes n 1 and n 2 of the first intermediate layer 60 and the second intermediate layer 62 are not limited to being continuously inclined in the film thickness direction, but as shown in FIG. It may be changed to.
  • the mixing ratio of the oxygen-containing gas such as carbon (CO 2). That is, in order to further reduce the refractive indexes n 1 and n 2 , the mixing ratio of oxygen-containing gas such as carbon dioxide (CO 2 ) may be adjusted to be higher.
  • the first intermediate layer 60 and the second intermediate layer 62 can also be adjusted by adjusting the film forming conditions such as the pressure at the time of forming the first intermediate layer 60 and the second intermediate layer 62 by the plasma CVD method and the high frequency power for plasma generation.
  • the refractive indexes n 1 and n 2 of can be changed.
  • first intermediate layer 60 and the second intermediate layer 62 may be provided in place of the first intermediate layer 56 and the second intermediate layer 58 of the a-Si unit 202 as in the second embodiment.
  • first intermediate layer 44 and the second intermediate layer 48 and the first intermediate layer 56 and the second intermediate layer 58 may be provided instead of the first intermediate layer 44 and the second intermediate layer 48 and the first intermediate layer 56 and the second intermediate layer 58 in the first to third modifications.
  • the first intermediate layer 60 and the second intermediate layer 62 may be provided. .
  • the first intermediate layer 60 and the second intermediate layer 62 may be a transparent conductive oxide (TCO) such as zinc oxide (ZnO).
  • TCO transparent conductive oxide
  • ZnO zinc oxide
  • Mg magnesium
  • the refractive indexes n 1 and n 2 of the first intermediate layer 60 and the second intermediate layer 62 may be inclined or stepped by adjusting the film formation conditions during film formation.
  • FIG. 11 is a schematic cross-sectional view illustrating the structure of a photoelectric conversion device 500 including the single crystal silicon layer 70.
  • the first intermediate layer 72, the intrinsic semiconductor layer 74, and the conductive semiconductor layer 76 are sequentially formed on the surface (first surface) of the single crystal silicon layer 70, and the back surface of the single crystal silicon layer 70 (second surface).
  • the second intermediate layer 78, the intrinsic semiconductor layer 80, and the conductive semiconductor layer 82 are formed on the surface).
  • the single crystal silicon layer 70 is preferably a 100 mm square and has a thickness of about 100 to 500 ⁇ m.
  • a first intermediate layer 72 is formed on the surface (first surface) of the single crystal silicon layer 70.
  • the first intermediate layer 72 can be formed in the same manner as the first intermediate layer 44 in the first embodiment.
  • an intrinsic semiconductor layer 74 film thickness: about 50 to 200 mm
  • a p-type amorphous silicon layer to which a p-type dopant is added.
  • a certain conductive semiconductor layer 76 (film thickness: about 50 to 150 mm) is formed. Note that although the intrinsic semiconductor layer 74 and the conductive semiconductor layer 76 are amorphous silicon, microcrystalline silicon may be used.
  • a second intermediate layer 78 is formed on the back surface (second surface) of the single crystal silicon layer 70.
  • the second intermediate layer 78 can be formed in the same manner as the second intermediate layer 48 in the first embodiment.
  • an intrinsic semiconductor layer 80 film thickness: about 50 to 200 mm
  • an n-type amorphous silicon layer to which an n-type dopant is added.
  • a certain conductive semiconductor layer 82 film thickness: about 100 to 500 mm is formed.
  • the intrinsic semiconductor layer 80 and the conductive semiconductor layer 82 are amorphous silicon, microcrystalline silicon may be used.
  • transparent conductive layers 84 and 86 having substantially the same area as these are formed. Further, collector electrodes 88 and 90 made of silver paste or the like are formed on the transparent conductive layers 84 and 86.
  • the transparent conductive layer 86 is also employed on the back surface (second surface) side, even if light enters the back surface side, it contributes to power generation.
  • FIG. 12 shows the refractive index of each layer of the photoelectric conversion device 500.
  • the refractive index n 2 of the refractive index n 1 and the second intermediate layer 78 of the first intermediate layer 72 is smaller than the refractive index n ci of the target optical confinement single crystal silicon layer 70 .
  • the refractive index n 1 of the first intermediate layer 72 is made smaller than the refractive index n pi of the adjacent intrinsic semiconductor layer 74 and conductive semiconductor layer 76.
  • the difference in refractive index (n ci ⁇ n 1 ) between the first intermediate layer 72 and the single crystal silicon layer 70 is the difference in refractive index between the first intermediate layer 72, the intrinsic semiconductor layer 74, and the conductive semiconductor layer 76.
  • the refractive index n 2 of the second intermediate layer 78 is set to be smaller than the refractive index n ni of the adjacent intrinsic semiconductor layer 80 and the conductive semiconductor layer 82.
  • the difference in refractive index (n ci ⁇ n 2 ) between the second intermediate layer 78 and the single crystal silicon layer 70 is the difference in refractive index between the second intermediate layer 78, the intrinsic semiconductor layer 80, and the conductive semiconductor layer 82. It should be smaller than (n ni ⁇ n 2 ).
  • the light that has entered the single crystal silicon layer 70 through the interface between the intrinsic semiconductor layer 80 and the second intermediate layer 78 is transmitted to the single crystal silicon layer 70 and the first crystal layer 70.
  • the light is reflected by the difference in refractive index between each other at the interface with the intermediate layer 72 and returned to the single crystal silicon layer 70.
  • it is reflected again by the difference in refractive index and returned to the single crystal silicon layer 70.
  • the first intermediate layer 72 and the second intermediate layer 78 provide an optical confinement effect on the single crystal silicon layer 70.
  • the refractive index n 1 of the first intermediate layer 72 is preferably larger than the refractive index n 2 of the second intermediate layer 78. Since the refractive index n pi of the intrinsic semiconductor layer 74 and the conductive semiconductor layer 76 and the refractive index n ni of the intrinsic semiconductor layer 80 and the conductive semiconductor layer 82 are approximately the same size, the intrinsic semiconductor layer 74 and the first intermediate layer At the interface with the layer 72, the light introduction rate into the single crystal silicon layer 70 can be higher than that at the interface between the intrinsic semiconductor layer 80 and the second intermediate layer 78.
  • the film thickness d 1 of the first intermediate layer 72 is preferably set to be equal to or less than the film thickness d 2 of the second intermediate layer 78.
  • the reflectance at the interface between the first intermediate layer 72 and the single crystal silicon layer 70 is slightly lower than the reflectance at the interface between the single crystal silicon layer 70 and the second intermediate layer 78, but the incidence of main light Light absorption in the first intermediate layer 72 disposed on the side is suppressed, the amount of light reaching the single crystal silicon layer 70 can be increased, and the power generation efficiency of the entire photoelectric conversion device 500 can be increased.
  • the light absorption amount in the second intermediate layer 78 is larger than the light absorption amount in the first intermediate layer 72, but the light that passes through the second intermediate layer 78 and reaches the single crystal silicon layer 70 is the first amount. It is smaller than the light that passes through the intermediate layer 72 and reaches the single crystal silicon layer 70, and by increasing the reflectance at the interface between the single crystal silicon layer 70 and the second intermediate layer 78, The light confinement effect is enhanced, and the power generation efficiency of the entire photoelectric conversion device 500 can be increased.
  • the first intermediate layer 72 is formed so that the refractive index n 1 gradually increases from the single crystal silicon layer 70 side toward the intrinsic semiconductor layer 74 side.
  • the second intermediate layer 78 is formed so that the refractive index n 2 gradually increases from the single crystal silicon layer 70 side toward the intrinsic semiconductor layer 80 side.
  • the refractive index n 1 of the first intermediate layer 72 is preferably substantially equal to the refractive index n pi of the intrinsic semiconductor layer 74 at the interface with the intrinsic semiconductor layer 74.
  • the refractive index n 2 of the second intermediate layer 78 is preferably set to be substantially equal to the refractive index n ni of the intrinsic semiconductor layer 80 at the interface with the intrinsic semiconductor layer 80.
  • the refractive index n 2 of the refractive index n 1 and the second intermediate layer 78 of the first intermediate layer 72, the film quality at the interface between the single crystal silicon layer 70 is preferable to be as small as possible so as not to decrease.
  • the single crystal silicon layer 70 By the inclined or stepped shape along at least one of the refractive index n 2 of the refractive index n 1 and the second intermediate layer 78 of the first intermediate layer 72 in the thickness direction, the single crystal silicon layer 70 The light confinement effect on the can be improved.
  • the first intermediate layer 72 and the second intermediate layer 78 by providing at least one of the first intermediate layer 72 and the second intermediate layer 78, an effect of improving the power generation efficiency of the photoelectric conversion device can be achieved. Further, even in a photoelectric conversion device in which two or more single crystal silicon layers 70 as power generation layers are stacked, a light confinement effect is obtained by providing the first intermediate layer 72 and the second intermediate layer 78 for each single crystal silicon layer 70. Can do.

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WO2013027469A1 (ja) * 2011-08-25 2013-02-28 シャープ株式会社 光電変換素子
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WO2013027468A1 (ja) * 2011-08-24 2013-02-28 シャープ株式会社 光電変換素子
JP2013045870A (ja) * 2011-08-24 2013-03-04 Sharp Corp 光電変換素子
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WO2013065538A1 (ja) * 2011-11-03 2013-05-10 三洋電機株式会社 光電変換装置

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