CN113782645B - Heterojunction battery manufacturing method, heterojunction battery and solar battery assembly - Google Patents
Heterojunction battery manufacturing method, heterojunction battery and solar battery assembly Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000000151 deposition Methods 0.000 claims abstract description 77
- 239000002131 composite material Substances 0.000 claims abstract description 49
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 82
- 230000008021 deposition Effects 0.000 claims description 59
- 239000011787 zinc oxide Substances 0.000 claims description 41
- 229910003437 indium oxide Inorganic materials 0.000 claims description 39
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000003780 insertion Methods 0.000 abstract description 6
- 230000037431 insertion Effects 0.000 abstract description 6
- 238000003466 welding Methods 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 68
- 229910052782 aluminium Inorganic materials 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- 229910052738 indium Inorganic materials 0.000 description 13
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 12
- 229910052733 gallium Inorganic materials 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Chemical group 0.000 description 9
- XUIMIQQOPSSXEZ-AKLPVKDBSA-N silicon-31 atom Chemical compound [31Si] XUIMIQQOPSSXEZ-AKLPVKDBSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-RNFDNDRNSA-N silicon-32 atom Chemical compound [32Si] XUIMIQQOPSSXEZ-RNFDNDRNSA-N 0.000 description 7
- 229910000881 Cu alloy Inorganic materials 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical group [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
-
- 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
- H01L31/02—Details
- H01L31/02002—Arrangements for conducting electric current to or from the device in operations
- H01L31/02005—Arrangements for conducting electric current to or from the device in operations for device characterised by at least one potential jump barrier or surface barrier
- H01L31/02008—Arrangements for conducting electric current to or from the device in operations for device characterised by at least one potential jump barrier or surface barrier for solar cells or solar cell modules
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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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/0547—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the reflecting type, e.g. parabolic mirrors, concentrators using total internal reflection
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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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0745—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
- H01L31/0747—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer
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- 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
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- 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
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Abstract
The invention belongs to the technical field of solar cells, and particularly relates to a manufacturing method of a heterojunction cell, the heterojunction cell and a solar cell module, wherein the manufacturing method comprises the following steps: sequentially depositing intrinsic amorphous silicon and doped amorphous silicon on the front side and the back side of a silicon wafer to form a semi-finished battery; depositing a positive conductive film on the front side of the semi-finished battery, and depositing a composite laminated back conductive film of TCO 1、Mx and TCO 2 on the back side of the semi-finished battery; and manufacturing metal electrodes on the positive conductive film and the composite laminated back conductive film respectively. An ultrathin metal layer is introduced into the composite laminated back conductive film, so that the conductive performance of the back film is greatly improved, meanwhile, the internal reflection of long-wavelength transmitted light is improved due to the plasma enhancement effect, and the absorption probability of the long-wavelength transmitted light in a silicon wafer is increased, so that more photocurrent is generated; in addition, the electric conductivity of the back film can be greatly improved due to the insertion of the ultrathin metal layer, and the back pattern can only remain the welding main grid, so that the consumption of back silver paste is greatly reduced, and the production cost is reduced.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a manufacturing method of a heterojunction cell, the heterojunction cell and a solar cell module.
Background
Currently, a heterojunction battery generally adopts a fully transparent conductive thin film (TCO) Indium Tin Oxide (ITO) as a back conductive channel, and the main preparation method is a magnetron sputtering method, wherein intrinsic amorphous silicon and doped amorphous silicon are sequentially deposited on the front side and the back side of a silicon wafer, then an ITO layer is deposited on the front side and the back side of a semi-finished product battery under a low temperature condition, finally silver paste is printed to construct a front electrode and a back electrode, and ohmic contact is realized by sintering at a temperature environment lower than 250 ℃.
However, the ITO thin film deposited at low temperature has poor conductivity, resulting in low photoelectric conversion efficiency of the finally fabricated heterojunction cell; in addition, silver paste adopted in the printing process is expensive, so that the production cost is greatly increased.
Disclosure of Invention
The invention provides a manufacturing method of a heterojunction battery, and aims to solve the technical problems that a conductive film of the heterojunction battery manufactured by the existing manufacturing method is poor in conductivity and high in production cost.
The invention is realized in such a way, and provides a manufacturing method of a heterojunction battery, which comprises the following steps:
sequentially depositing intrinsic amorphous silicon and doped amorphous silicon on the front side and the back side of a silicon wafer to form a semi-finished battery;
Depositing a positive conductive film on the front side of the semi-finished battery, and depositing a composite laminated back conductive film of TCO 1、Mx and TCO 2 on the back side of the semi-finished battery;
Manufacturing metal electrodes on the positive conductive film and the composite laminated back conductive film respectively;
Wherein, TCO 1 and TCO 2 are aluminum doped zinc oxide, tin doped indium oxide, indium doped zinc oxide, gallium doped zinc oxide, indium doped gallium zinc oxide, tungsten doped indium oxide, molybdenum doped indium oxide or zirconium doped indium oxide, M x is silver, aluminum, copper or silver copper alloy.
Further, the step of depositing the composite laminated back conductive film of TCO 1、Mx and TCO 2 on the opposite side of the semi-finished battery specifically includes the following steps:
And after the TCO 1 target, the M x target and the TCO 2 target are sequentially installed in the chained magnetron sputtering cavity, controlling the semi-finished battery to pass through the chained magnetron sputtering cavity so as to deposit a composite laminated back conductive film of the TCO 1、Mx and the TCO 2 on the back surface of the semi-finished battery.
Further, during the deposition of the composite laminated back conductive film of TCO 1、Mx and TCO 2, the vertical distance of the TCO 1 target, the M x target, and the TCO 2 target, respectively, from the surface of the half-finished cell is in the range of 4 to 12cm and the deposition gas pressure is in the range of 0.4 to 3 Pa.
Further, after the TCO 1 target, the M x target, and the TCO 2 target are sequentially installed in the chained magnetron sputtering chamber, the semi-finished battery is controlled to pass through the chained magnetron sputtering chamber, so as to deposit a composite laminated back conductive film of TCO 1、Mx and TCO 2 on the back surface of the semi-finished battery, which specifically includes the following steps:
Installing a TCO 1 target in the first deposition chamber, and introducing high-purity argon doped with hydrogen as sputtering gas;
Installing an M x target in the second deposition chamber, and introducing high-purity argon as sputtering gas;
installing a TCO 2 target in the third deposition chamber, and introducing high-purity argon doped with hydrogen or oxygen as sputtering gas;
Controlling the semi-finished battery to sequentially pass through the first deposition chamber, the second deposition chamber and the third deposition chamber, controlling the temperature of the semi-finished battery to be lower than 200 ℃ when passing through the first deposition chamber, controlling the temperature of the semi-finished battery to be in the range of 40-200 ℃ when passing through the second deposition chamber, and controlling the temperature of the semi-finished battery to be lower than 200 ℃ when passing through the third deposition chamber, so as to deposit the composite laminated back conductive film of TCO 1、Mx and TCO 2 on the back surface of the semi-finished battery.
Still further, in the first deposition chamber, the sputter power of the TCO 1 target is controlled to be in the range of 0.4 to 2W/cm 2, in the second deposition chamber, the M x deposition rate is controlled to be in the range of 1 to 10nm/min, and in the third deposition chamber, the sputter power of the TCO 2 target is controlled to be in the range of 1.5 to 8W/cm 2.
Still further, the thickness of TCO 1 to 30nm, the thickness of M x 5 to 20nm, and the thickness of TCO 2 30 to 90 nm.
Still further, the TCO 1 has a carrier concentration less than or equal to 1E20/cm 3,TCO2 and a resistivity less than 5E-4ohm cm.
Further, the mass fraction of the Al 2O3 of the aluminum-doped zinc oxide is in the range of 0.5% to 4%;
The mass fraction of the SnO 2 of the tin-doped indium oxide is in the range of 1-12%;
The mass fraction of In 2O3 of the indium-doped zinc oxide is In the range of 2-8%;
The mass fraction of Ga 2O3 of the gallium-doped zinc oxide is in the range of 1.2 to 6 percent;
The mass fraction of In 2O3 of the indium-gallium-doped zinc oxide is In the range of 0.8-6%, and the mass fraction of Ga 2O3 is In the range of 0.4-5%;
the mass fraction of WO 3 of the tungsten-doped indium oxide is in the range of 0.5% to 3%;
The mass fraction of MoO 3 of the molybdenum-doped indium oxide is in the range of 0.8% to 4%;
The mass fraction of the zirconium-doped indium oxide ZrO 2 is in the range of 0.4% to 2.2%.
The invention also provides a heterojunction battery, which is prepared by the manufacturing method of the heterojunction battery, and comprises the following steps:
a silicon wafer;
intrinsic amorphous silicon and doped amorphous silicon respectively arranged on the front side and the back side of the silicon wafer;
a front conductive film disposed on the front surface doped amorphous silicon, and a composite laminated back conductive film of TCO 1、Mx and TCO 2 disposed on the back surface doped amorphous silicon;
metal electrodes respectively provided on the positive conductive film and the composite laminated back conductive film;
Wherein, TCO 1 and TCO 2 are aluminum doped zinc oxide, tin doped indium oxide, indium doped zinc oxide, gallium doped zinc oxide, indium doped gallium zinc oxide, tungsten doped indium oxide, molybdenum doped indium oxide or zirconium doped indium oxide, M x is silver, aluminum, copper or silver copper alloy.
The invention also provides a solar cell module comprising the heterojunction cell.
The method has the advantages that firstly, intrinsic amorphous silicon and doped amorphous silicon are sequentially deposited on the front side and the back side of a silicon wafer to form a semi-finished battery, then a positive conducting film is deposited on the front side of the semi-finished battery, a composite laminated back conducting film of TCO 1、Mx and TCO 2 is deposited on the back side of the semi-finished battery, and finally metal electrodes are manufactured on the positive conducting film and the composite laminated back conducting film respectively; wherein, TCO 1 and TCO 2 are aluminum doped zinc oxide, tin doped indium oxide, indium doped zinc oxide, gallium doped zinc oxide, indium doped gallium zinc oxide, tungsten doped indium oxide, molybdenum doped indium oxide or zirconium doped indium oxide, M x is silver, aluminum, copper or silver copper alloy. An ultrathin metal layer is introduced into the composite laminated back conductive film, so that the conductive performance of the back film is greatly improved, meanwhile, the internal reflection of long-wavelength transmitted light is improved due to the plasma enhancement effect, and the absorption probability of the long-wavelength transmitted light in a silicon wafer is increased, so that more photocurrent is generated; in addition, the electric conductivity of the back film can be greatly improved due to the insertion of the ultrathin metal layer, so that the back pattern only remains the welding main grid, and a thin grid line is not needed, thereby greatly reducing the consumption of back silver paste and reducing the production cost.
Drawings
Fig. 1 is a flow chart of a method for manufacturing a heterojunction battery according to an embodiment of the present invention;
fig. 2 is a further flow chart of a method for fabricating a heterojunction battery according to an embodiment of the present invention;
fig. 3 is a schematic diagram of a heterojunction cell provided by an embodiment of the present invention;
Fig. 4 is an enlarged view of a portion a of fig. 3.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a manufacturing method of a heterojunction battery, which comprises the steps of sequentially depositing intrinsic amorphous silicon and doped amorphous silicon on the front side and the back side of a silicon wafer 10 to form a semi-finished battery, depositing a positive conducting film 41 on the front side of the semi-finished battery, depositing a composite laminated back conducting film 42 of TCO 1、Mx and TCO 2 on the back side of the semi-finished battery, and finally manufacturing metal electrodes on the positive conducting film 41 and the composite laminated back conducting film 42 respectively; wherein, TCO 1 and TCO 2 are aluminum doped zinc oxide, tin doped indium oxide, indium doped zinc oxide, gallium doped zinc oxide, indium doped gallium zinc oxide, tungsten doped indium oxide, molybdenum doped indium oxide or zirconium doped indium oxide, M x is silver, aluminum, copper or silver copper alloy. The ultra-thin metal layer is introduced into the composite laminated back conductive film 42, so that the conductive performance of the back film is greatly improved, and meanwhile, the internal reflection of long-wavelength transmitted light is improved due to the plasma enhancement effect, so that the absorption probability of the long-wavelength transmitted light in the silicon wafer 10 is increased, and more photocurrent is generated; in addition, the electric conductivity of the back film can be greatly improved due to the insertion of the ultrathin metal layer, so that the back pattern only remains the welding main grid, and a thin grid line is not needed, thereby greatly reducing the consumption of back silver paste and reducing the production cost.
Example 1
Referring to fig. 1, a method for fabricating a heterojunction battery is provided in the first embodiment, which includes the following steps:
S10, sequentially depositing intrinsic amorphous silicon and doped amorphous silicon on the front side and the back side of a silicon wafer to form a semi-finished battery;
s20, depositing a positive conductive film on the front surface of the semi-finished battery, and depositing a composite laminated back conductive film of TCO 1、Mx and TCO 2 on the back surface of the semi-finished battery;
S30, manufacturing metal electrodes on the positive conductive film and the composite laminated back conductive film respectively;
Wherein, TCO 1 and TCO 2 are aluminum doped zinc oxide, tin doped indium oxide, indium doped zinc oxide, gallium doped zinc oxide, indium doped gallium zinc oxide, tungsten doped indium oxide, molybdenum doped indium oxide or zirconium doped indium oxide, M x is silver, aluminum, copper or silver copper alloy.
In this embodiment, first, a first intrinsic amorphous silicon 21 and a first doped amorphous silicon 31 are sequentially deposited on the front surface of the silicon wafer 10, and then a second intrinsic amorphous silicon 22 and a second doped amorphous silicon 32 are sequentially deposited on the back surface of the silicon wafer 10, so as to form a semi-finished battery. A positive conductive film 41 is deposited on the front side of the semi-finished cell where the first doped amorphous silicon 31 is formed, and a composite laminated back conductive film 42 of TCO 1、Mx and TCO 2 is deposited on the back side of the semi-finished cell where the second doped amorphous silicon 32 is formed. Finally, the first metal electrode 51 is manufactured on the positive conductive film 41 by means of printing paste, the second metal electrode 52 is manufactured on the composite laminated back conductive film 42 of the TCO 1、Mx and the TCO 2 by means of printing paste, and good ohmic contact is achieved by sintering in a low-temperature environment, so that the heterojunction battery is manufactured.
Because the heterojunction cell has no higher optical performance requirement on the back conductive film than the front conductive film, the ultra-thin metal layer is introduced into the composite laminated back conductive film 42, so that the conductive performance of the back film is greatly improved, and meanwhile, the internal reflection of long-wavelength transmitted light is improved due to the plasma enhancement effect, so that the absorption probability of the long-wavelength transmitted light in the silicon wafer 10 is increased, and more photocurrent is generated; in addition, the electric conductivity of the back film can be greatly improved due to the insertion of the ultrathin metal layer, so that the back pattern only remains the welding main grid, and a thin grid line is not needed, thereby greatly reducing the consumption of back silver paste and reducing the production cost.
For the first doped amorphous silicon 31 and the second doped amorphous silicon 32, when the first doped amorphous silicon 31 is n-type doped amorphous silicon, the second doped amorphous silicon 32 is p-type doped amorphous silicon; when the first doped amorphous silicon 31 is p-type doped amorphous silicon, the second doped amorphous silicon 32 is n-type doped amorphous silicon.
It should be noted that, when the silicon wafer 10 is obtained, the silicon wafer 10 needs to be cleaned and textured on its surface, and the textured surface is etched on its surface by etching.
Referring to fig. 2, further, the step of depositing the composite laminated back conductive film of TCO 1、Mx and TCO 2 on the opposite side of the semi-finished battery specifically includes the following steps:
S22, after a TCO 1 target, an M x target and a TCO 2 target are sequentially installed in a chained magnetron sputtering cavity, controlling the semi-finished battery to pass through the chained magnetron sputtering cavity so as to deposit a composite laminated back conductive film of TCO 1、Mx and TCO 2 on the back surface of the semi-finished battery.
In this embodiment, the chained magnetron sputtering chamber is provided with a plurality of deposition chambers, the TCO 1 target, the M x target and the TCO 2 target are sequentially installed in each deposition chamber, then the semi-finished battery is controlled to sequentially pass through each deposition chamber in the chained magnetron sputtering chamber, and in the passing process, the sputtering power of the TCO 1 target, the M x target and the TCO 2 target is adjusted to deposit the composite laminated back conductive film 42 of the TCO 1、Mx and the TCO 2 on the opposite surface of the semi-finished battery.
Wherein during deposition of the composite laminated back conductive film 42 of TCO 1、Mx and TCO 2, the vertical distance of the TCO 1 target, the M x target, and the TCO 2 target, respectively, from the surface of the semi-finished battery is in the range of 4 to 12cm, such as 4cm, 6cm, 8cm, 10cm, 12cm, and the deposition gas pressure is in the range of 0.4 to 3Pa, such as 1.2Pa, 2Pa, 2.8Pa.
Specifically, after the TCO 1 target, the M x target, and the TCO 2 target are sequentially installed in the chained magnetron sputtering chamber, the semi-finished battery is controlled to pass through the chained magnetron sputtering chamber, so as to deposit a composite laminated back conductive film of the TCO 1、Mx and the TCO 2 on the back surface of the semi-finished battery, which specifically includes the following steps:
Installing a TCO 1 target in the first deposition chamber, and introducing high-purity argon doped with hydrogen as sputtering gas;
Installing an M x target in the second deposition chamber, and introducing high-purity argon as sputtering gas;
installing a TCO 2 target in the third deposition chamber, and introducing high-purity argon doped with hydrogen or oxygen as sputtering gas;
Controlling the semi-finished battery to sequentially pass through the first deposition chamber, the second deposition chamber and the third deposition chamber, controlling the temperature of the semi-finished battery to be lower than 200 ℃ when passing through the first deposition chamber, controlling the temperature of the semi-finished battery to be in the range of 40-200 ℃ when passing through the second deposition chamber, and controlling the temperature of the semi-finished battery to be lower than 200 ℃ when passing through the third deposition chamber, so as to deposit the composite laminated back conductive film of TCO 1、Mx and TCO 2 on the back surface of the semi-finished battery.
In this embodiment, the chained magnetron sputtering chamber is provided with at least three deposition chambers. Firstly, a TCO 1 target material is installed in a first deposition chamber, high-purity argon doped with hydrogen is introduced as sputtering gas, and the volume fraction of the hydrogen is not more than 10%; installing an M x target in the second deposition chamber, and introducing high-purity argon as sputtering gas; and then installing a TCO 2 target in the third deposition chamber, and introducing high-purity argon doped with hydrogen or oxygen as sputtering gas, wherein the volume fraction of the hydrogen is not more than 6% if the high-purity argon is doped with hydrogen, and the volume fraction of the oxygen is not more than 2% if the high-purity argon is doped with oxygen. After the target is mounted, the semi-finished battery is placed on the carrier plate, the semi-finished battery is controlled to sequentially pass through the first deposition chamber, the second deposition chamber and the third deposition chamber, the temperature of the semi-finished battery is controlled to be lower than 200 ℃ when the semi-finished battery passes through the first deposition chamber, the temperature of the semi-finished battery is controlled to be in the range of 40-200 ℃ when the semi-finished battery passes through the second deposition chamber, the semi-finished battery is not heated when the semi-finished battery passes through the third deposition chamber, and the temperature of the semi-finished battery is controlled to be lower than 200 ℃ so as to deposit the composite laminated back conductive film 42 of the TCO 1、Mx and the TCO 2 on the back surface of the semi-finished battery. Wherein, when the semi-finished battery is controlled to pass through the deposition chamber in turn, the required sputtering power is matched timely according to the thickness of the lamination, so as to smoothly realize the preparation of the composite lamination back conductive film 42.
Wherein in the first deposition chamber the sputter power of the TCO 1 target is controlled in the range of 0.4 to 2W/cm 2, e.g. 0.6W/cm 2、1W/cm2、1.4W/cm2、1.8W/cm2, in the second deposition chamber the M x deposition rate is controlled in the range of 1 to 10nm/min, e.g. 2nm/min, 4nm/min, 6nm/min, 8nm/min, 10nm/min, and in the third deposition chamber the sputter power of the TCO 2 target is controlled in the range of 1.5 to 8W/cm 2, e.g. 1.5W/cm 2、3W/cm2、4.5W/cm2、6W/cm2、7.5W/cm2.
Wherein the thickness of the TCO 1 is in the range of 5 to 30nm, such as 8nm, 16nm, 24nm, the thickness of M x is in the range of 5 to 20nm, such as 5nm, 10nm, 15nm, the thickness of the TCO 2 is in the range of 30 to 90nm, such as 40nm, 50nm, 60nm, 70nm, 80nm.
Wherein the carrier concentration of TCO 1 is less than or equal to 1E20/cm 3,TCO2 and the resistivity is less than 5E-4ohm cm.
Wherein, for TCO 1 and TCO 2, the mass fraction of Al 2O3 of the aluminum doped zinc oxide is in the range of 0.5% to 4%; the mass fraction of the SnO 2 of the tin-doped indium oxide is in the range of 1-12%; the mass fraction of In 2O3 of the indium-doped zinc oxide is In the range of 2-8%; the mass fraction of Ga 2O3 of the gallium-doped zinc oxide is in the range of 1.2 to 6 percent; the mass fraction of In 2O3 of the indium-gallium-doped zinc oxide is In the range of 0.8-6%, and the mass fraction of Ga 2O3 is In the range of 0.4-5%; the mass fraction of WO 3 of the tungsten-doped indium oxide is in the range of 0.5% to 3%; the mass fraction of MoO 3 of the molybdenum-doped indium oxide is in the range of 0.8% to 4%; the mass fraction of the zirconium-doped indium oxide ZrO 2 is in the range of 0.4% to 2.2%.
Through multiple tests, the TCO 1 is tin-doped indium oxide, the M x is silver, the TCO 2 is indium-doped zinc oxide, the thickness of the tin-doped indium oxide is 15nm, the thickness of the silver is 10nm, the thickness of the indium-doped zinc oxide is 50nm, an excellent effect can be achieved, and the sheet resistance of the laminated structure can be lower than 5ohm/sq.
Of course, other embodiments may be used to advantage, such as the following: ①TCO1 Is doped with indium tin oxide, M x is aluminum, TCO 2 is doped with indium zinc oxide; ②TCO1 Is doped with indium tin oxide, M x is copper, TCO 2 is doped with indium zinc oxide; ③TCO1 Is doped with tin indium oxide, M x is copper, TCO 2 is doped with aluminum zinc oxide; ④TCO1 For aluminum doped zinc oxide, M x is copper and TCO 2 is indium doped zinc oxide.
Example two
Referring to fig. 3, a second embodiment provides a heterojunction battery prepared by the method for manufacturing a heterojunction battery according to the first embodiment, the heterojunction battery comprising:
A silicon wafer 10;
intrinsic amorphous silicon and doped amorphous silicon respectively arranged on the front side and the back side of the silicon wafer 10;
a front conductive film 41 provided on the front surface doped amorphous silicon, and a composite laminated back conductive film 42 of TCO 1、Mx and TCO 2 provided on the back surface doped amorphous silicon;
Metal electrodes provided on the positive conductive film 41 and the composite laminated back conductive film 42, respectively;
wherein, TCO 1 and TCO 2 are aluminum doped zinc oxide, tin doped indium oxide, indium doped zinc oxide, gallium doped zinc oxide, indium doped gallium zinc oxide, tungsten doped indium oxide, molybdenum doped indium oxide or zirconium doped indium oxide, and Mx is silver, aluminum, copper or silver copper alloy.
In this embodiment, the front surface of the silicon wafer 10 is provided with a first intrinsic amorphous silicon 21 and a first doped amorphous silicon 31, the back surface is provided with a second intrinsic amorphous silicon 22 and a second doped amorphous silicon 32, the first doped amorphous silicon 31 is provided with a positive conductive film 41, the second doped amorphous silicon 32 is provided with a composite laminated back conductive film 42 of a TCO 1、Mx and a TCO 2, the positive conductive film 41 is provided with a first metal electrode 51, and the composite laminated back conductive film 42 of a TCO 1、Mx and a TCO 2 is provided with a second metal electrode 52. Because the heterojunction cell has no higher optical performance requirement on the back conductive film than the front conductive film, the ultra-thin metal layer is introduced into the composite laminated back conductive film 42, so that the conductive performance of the back film is greatly improved, and meanwhile, the internal reflection of long-wavelength transmitted light is improved due to the plasma enhancement effect, so that the absorption probability of the long-wavelength transmitted light in the silicon wafer 10 is increased, and more photocurrent is generated; in addition, the electric conductivity of the back film can be greatly improved due to the insertion of the ultrathin metal layer, so that the back pattern only remains the welding main grid, and a thin grid line is not needed, thereby greatly reducing the consumption of back silver paste and reducing the production cost.
Referring to fig. 4, on the composite laminated back conductive film 42, three layers, TCO 1、Mx and TCO 2, respectively, are provided from top to bottom.
Example III
The third embodiment provides a solar cell module including the heterojunction cell described in the second embodiment. Because the heterojunction cell has no higher optical performance requirement on the back conductive film than the front conductive film, the ultra-thin metal layer is introduced into the composite laminated back conductive film 42, so that the conductive performance of the back film is greatly improved, and meanwhile, the internal reflection of long-wavelength transmitted light is improved due to the plasma enhancement effect, so that the absorption probability of the long-wavelength transmitted light in the silicon wafer 10 is increased, and more photocurrent is generated; in addition, the electric conductivity of the back film can be greatly improved due to the insertion of the ultrathin metal layer, so that the back pattern only remains the welding main grid, and a thin grid line is not needed, thereby greatly reducing the consumption of back silver paste and reducing the production cost.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. The manufacturing method of the heterojunction battery is characterized by comprising the following steps of:
sequentially depositing intrinsic amorphous silicon and doped amorphous silicon on the front side and the back side of a silicon wafer to form a semi-finished battery;
Depositing a positive conductive film on the front side of the semi-finished battery, and depositing a composite laminated back conductive film of TCO 1、Mx and TCO 2 on the back side of the semi-finished battery;
Manufacturing metal electrodes on the positive conductive film and the composite laminated back conductive film respectively;
The TCO 1 is tin-doped indium oxide, the M x is silver, the TCO 2 is indium-doped zinc oxide, the thickness of the tin-doped indium oxide is 15nm, the thickness of the silver is 10nm, and the thickness of the indium-doped zinc oxide is 50nm, so that the sheet resistance of the composite laminated back conductive film is lower than 5ohm/sq.
2. The method of fabricating a heterojunction cell as claimed in claim 1, wherein said step of depositing a composite laminated back conductive film of TCO 1、Mx and TCO 2 on the opposite side of said semi-finished cell comprises the steps of:
And after the TCO 1 target, the M x target and the TCO 2 target are sequentially installed in the chained magnetron sputtering cavity, controlling the semi-finished battery to pass through the chained magnetron sputtering cavity so as to deposit a composite laminated back conductive film of the TCO 1、Mx and the TCO 2 on the back surface of the semi-finished battery.
3. The method of claim 2, wherein during the deposition of the composite laminated back conductive film of TCO 1、Mx and TCO 2, the vertical distance of the TCO 1 target, the M x target, and the TCO 2 target, respectively, from the surface of the half-finished cell is in the range of 4 to 12cm and the deposition gas pressure is in the range of 0.4 to 3 Pa.
4. The method for manufacturing a heterojunction cell as claimed in claim 2, wherein after the TCO 1 target, the M x target and the TCO 2 target are sequentially installed in the chained magnetron sputtering chamber, the step of controlling the semi-finished cell to pass through the chained magnetron sputtering chamber so as to deposit a composite laminated back conductive film of TCO 1、Mx and TCO 2 on the opposite surface of the semi-finished cell comprises the following steps:
Installing a TCO 1 target in the first deposition chamber, and introducing high-purity argon doped with hydrogen as sputtering gas;
Installing an M x target in the second deposition chamber, and introducing high-purity argon as sputtering gas;
installing a TCO 2 target in the third deposition chamber, and introducing high-purity argon doped with hydrogen or oxygen as sputtering gas;
Controlling the semi-finished battery to sequentially pass through the first deposition chamber, the second deposition chamber and the third deposition chamber, controlling the temperature of the semi-finished battery to be lower than 200 ℃ when passing through the first deposition chamber, controlling the temperature of the semi-finished battery to be in the range of 40-200 ℃ when passing through the second deposition chamber, and controlling the temperature of the semi-finished battery to be lower than 200 ℃ when passing through the third deposition chamber, so as to deposit the composite laminated back conductive film of TCO 1、Mx and TCO 2 on the back surface of the semi-finished battery.
5. The method of claim 4, wherein the sputter power of the TCO 1 target is controlled to be in the range of 0.4 to 2W/cm 2 in the first deposition chamber, the M x deposition rate is controlled to be in the range of 1 to 10nm/min in the second deposition chamber, and the sputter power of the TCO 2 target is controlled to be in the range of 1.5 to 8W/cm 2 in the third deposition chamber.
6. The method of claim 1, wherein the carrier concentration of the TCO 1 is less than or equal to 1E20/cm 3,TCO2 and the resistivity is less than 5E-4ohm cm.
7. The method of manufacturing a heterojunction cell as claimed in claim 1, wherein,
The mass fraction of the SnO 2 of the tin-doped indium oxide is in the range of 1-12%;
The mass fraction of In 2O3 of the indium-doped zinc oxide is In the range of 2% to 8%.
8. A heterojunction cell prepared by the method of manufacturing a heterojunction cell as claimed in any one of claims 1 to 7, comprising:
a silicon wafer;
intrinsic amorphous silicon and doped amorphous silicon respectively arranged on the front side and the back side of the silicon wafer;
a front conductive film disposed on the front surface doped amorphous silicon, and a composite laminated back conductive film of TCO 1、Mx and TCO 2 disposed on the back surface doped amorphous silicon;
metal electrodes respectively provided on the positive conductive film and the composite laminated back conductive film;
The TCO 1 is tin-doped indium oxide, the M x is silver, the TCO 2 is indium-doped zinc oxide, the thickness of the tin-doped indium oxide is 15nm, the thickness of the silver is 10nm, and the thickness of the indium-doped zinc oxide is 50nm, so that the sheet resistance of the composite laminated back conductive film is lower than 5ohm/sq.
9. A solar cell module comprising the heterojunction cell of claim 8.
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