WO2024031956A1 - Tco镀膜方法、tco镀膜设备、太阳能电池及其制备方法 - Google Patents
Tco镀膜方法、tco镀膜设备、太阳能电池及其制备方法 Download PDFInfo
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- WO2024031956A1 WO2024031956A1 PCT/CN2023/077674 CN2023077674W WO2024031956A1 WO 2024031956 A1 WO2024031956 A1 WO 2024031956A1 CN 2023077674 W CN2023077674 W CN 2023077674W WO 2024031956 A1 WO2024031956 A1 WO 2024031956A1
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- Prior art keywords
- coating
- cavity
- tco
- water vapor
- partial pressure
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- 238000000576 coating method Methods 0.000 title claims abstract description 258
- 239000011248 coating agent Substances 0.000 title claims abstract description 202
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 115
- 238000004140 cleaning Methods 0.000 claims abstract description 82
- 238000000992 sputter etching Methods 0.000 claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 238000012544 monitoring process Methods 0.000 claims abstract description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 77
- 238000001020 plasma etching Methods 0.000 claims description 38
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 31
- 238000012806 monitoring device Methods 0.000 claims description 20
- 238000002955 isolation Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 150000002366 halogen compounds Chemical class 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 230000009977 dual effect Effects 0.000 claims description 3
- 230000001939 inductive effect Effects 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 abstract description 11
- 235000012431 wafers Nutrition 0.000 description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229910003902 SiCl 4 Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910008045 Si-Si Inorganic materials 0.000 description 1
- 229910008314 Si—H2 Inorganic materials 0.000 description 1
- 229910006411 Si—Si Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/542—Controlling the film thickness or evaporation rate
- C23C14/544—Controlling the film thickness or evaporation rate using measurement in the gas phase
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67063—Apparatus for fluid treatment for etching
- H01L21/67069—Apparatus for fluid treatment for etching for drying etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67242—Apparatus for monitoring, sorting or marking
- H01L21/67253—Process monitoring, e.g. flow or thickness monitoring
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L22/00—Testing or measuring during manufacture or treatment; Reliability measurements, i.e. testing of parts without further processing to modify the parts as such; Structural arrangements therefor
- H01L22/10—Measuring as part of the manufacturing process
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L22/00—Testing or measuring during manufacture or treatment; Reliability measurements, i.e. testing of parts without further processing to modify the parts as such; Structural arrangements therefor
- H01L22/20—Sequence of activities consisting of a plurality of measurements, corrections, marking or sorting steps
-
- 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
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
-
- 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
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- 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
- H01L31/074—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 heterojunction with an element of Group IV of the Periodic Table, e.g. ITO/Si, GaAs/Si or CdTe/Si solar cells
Definitions
- the present application relates to the field of battery technology, and in particular to a TCO coating method, TCO coating equipment, solar cells and preparation methods thereof.
- HJT solar cells (referred to as heterojunction cells), HBC cells (interdigitated back contact heterojunction solar cells), or solar tandem cells are all high-efficiency solar cells.
- HJT solar cells have a low temperature coefficient and low Light-induced attenuation and high stability.
- the general preparation steps of HJT solar cells are: using n-type monocrystalline silicon wafers as substrates, first perform surface texturing and chemical cleaning to form a pyramidal concave-convex structure on the surface to improve light absorption, and then After chemical cleaning, a clean surface is formed, and then plasma chemical vapor deposition (PECVD) and other methods are used to deposit intrinsic amorphous silicon films on both surfaces of the cleaned silicon wafer, and then p-type doping is deposited on one of the surfaces.
- PECVD plasma chemical vapor deposition
- Amorphous silicon film deposit n-type doped amorphous silicon film on the other surface, and then deposit transparent conductive oxide film on both surfaces through TCO (transparent conductive oxide) coating, and then use screen printing or electroplating or inkjet printing Technology is used to produce metal electrodes, thus obtaining HJT heterojunction batteries with a symmetrical structure.
- TCO transparent conductive oxide
- the TCO film plays an important role: 1. Surface anti-reflection, forming a good anti-reflection coating layer (AR-coating) on the silicon surface to reduce the loss of light reflection on the surface of the battery; 2. Carrier collection and transmission function, forming good contact with the amorphous silicon film, effectively collecting photogenerated carriers separated into the amorphous silicon film and transmitting them to the metal electrode; 3. Surface protection function, completely covering the amorphous silicon The film blocks the influence of the external environment on the amorphous silicon passivation film. Similarly, some HBC cells or solar tandem cells also contain TCO films and play an important role.
- AR-coating anti-reflection coating layer
- the present application provides a TCO coating method, TCO coating equipment, heterojunction battery and preparation method thereof.
- TCO coating method including the following steps:
- the water vapor partial pressure in the TCO coating process step is greater than 5.0 ⁇ e -3 Pa
- stop coating or continue to complete the TCO coating process and then perform ion etching cleaning on the carrier plate so that the The water vapor partial pressure is not greater than 5.0 ⁇ e -3 Pa.
- the ion etching cleaning time is 5 minutes to 15 minutes.
- the pressure of the ion etching cleaning ranges from 0.3 Pa to 1.3 Pa.
- the ion source used in the ion etching cleaning is selected from at least one of halogen, halogen compound gas, nitrogen and inert gas.
- the ion source used in the ion etching cleaning includes at least one of halogen and halogen compound gas, and at least one of nitrogen and inert gas.
- the transparent conductive material used in the TCO coating process is selected from at least one member selected from the group consisting of transparent conductive metals, transparent conductive compounds, and transparent conductive polymers.
- the article to be plated includes a single crystal silicon wafer and an amorphous silicon film loaded on the surface of the single crystal silicon wafer.
- the amorphous silicon film includes an intrinsic amorphous silicon film and a p-type doped amorphous silicon film stacked in sequence.
- the amorphous silicon film includes sequentially stacked intrinsic amorphous silicon films and n-type Doped amorphous silicon film.
- TCO coating equipment including:
- Carrier plate used to load parts to be plated
- a first cache cavity, a first coating cavity and a second cache cavity are arranged in sequence.
- the first coating cavity is provided with a TCO coating source for TCO coating the parts to be plated on the carrier board. deal with;
- a water vapor partial pressure monitoring device for monitoring the water vapor partial pressure in the first coating chamber in the TCO coating process
- At least one plasma etching cleaning device the plasma etching cleaning device is provided in at least one of the first cache cavity and the second cache cavity, and is used when the water vapor partial pressure
- the carrier plate is cleaned by ion etching so that the partial pressure of water vapor in the first coating chamber is not greater than 5.0e -3 Pa.
- the TCO coating equipment further includes a second coating cavity and an isolation cavity, and the second coating cavity is located between the first coating cavity and the second cache cavity. , the isolation cavity is located between the first coating cavity and the second coating cavity;
- the TCO coating source is provided in the upper part of one of the first coating chamber and the second coating chamber, and the TCO coating source is provided in the lower part of the other cavity to respectively coat the two parts of the parts to be plated.
- the surface is treated with TCO coating;
- the plasma etching cleaning device is provided in at least one of the first cache cavity, the isolation cavity and the second cache cavity, and is used to monitor when the water vapor partial pressure monitoring device monitors When the partial pressure of water vapor is greater than 5.0 ⁇ e -3 Pa, perform ion etching cleaning on the carrier plate so that the partial pressure of water vapor in the first coating chamber and the second coating chamber is not greater than 5.0e - 3Pa .
- the other plasma etching cleaning device is located at the lower part of any one of the first cache cavity, the isolation cavity and the second cache cavity. , for all The upper and lower surfaces of the carrier plate are cleaned by ion etching.
- the TCO coating equipment further includes a feed cavity and a discharge cavity; the feed cavity is provided upstream of the first buffer cavity for feeding materials, and the discharge cavity A material cavity is provided downstream of the second buffer cavity for discharging materials.
- the plasma etching cleaning device is selected from one of an electron cyclotron reactor, an inductive coupler, a capacitive coupler, a dual plasma source reactor, and a magnetically enhanced reactive ion etching reactor. Or multiple combination devices.
- the water vapor partial pressure monitoring device is selected from one or a combination of a residual gas analyzer and a spectrum analyzer.
- Another aspect of the present application provides a method for preparing a solar cell, including the following steps:
- the monocrystalline silicon wafer is subjected to surface texturing and chemical cleaning to obtain a textured monocrystalline silicon wafer;
- the step of forming a transparent conductive film is performed using the TCO coating method as described above or using the TCO coating equipment as described above.
- the step of forming an amorphous silicon film includes the following steps:
- intrinsic amorphous silicon films are formed on the upper and lower surfaces of the textured single crystal silicon wafer respectively, and then P-type doped amorphous silicon films and N-type doped amorphous silicon films are formed on the upper and lower surfaces respectively.
- the step of preparing the electrode includes the following steps:
- Silver paste is screen-printed on the surface of the transparent conductive film, and then sintered at 170°C to 200°C.
- a solar cell is provided, which is produced using the solar cell preparation method as described above.
- Figure 1 is a schematic structural diagram of a TCO coating equipment according to an embodiment
- Figure 2 is a schematic structural diagram of a heterojunction battery according to an embodiment
- Figure 3 is a comparison chart of the efficiency distribution of heterojunction cells in Experiment 4 and Experiment 5.
- 1TCO coating equipment 10 carrier board; 11 first cache cavity; 111 first cache sub-cavity; 12 first coating cavity; 13 second cache cavity; 131 second cache sub-cavity; 14 water vapor partial pressure monitoring Device; 15 plasma etching cleaning device; 16 second coating chamber; 17 isolation chamber; 18 feeding chamber; 19 discharging chamber; 20 TCO coating source; 100 heterojunction cell; 110 crystalline silicon wafer; 120 intrinsic amorphous silicon film; 130P type doped amorphous silicon film; 140N type doped amorphous silicon film; 150 transparent conductive film; 160 metal electrode.
- first and second are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the number or order of indicated technical features. Therefore, features defined as “first” and “second” may explicitly or implicitly include at least one of these features.
- “plurality” means at least two, such as two, three, etc., unless otherwise expressly and specifically limited.
- the carrier plate Even if strict water control is carried out before coating, during continuous coating, the carrier plate will The accumulated water vapor will still be transferred to the coated silicon wafer or the coating chamber, and the remaining water will be dissociated into oxygen ions (O 0 , O -1 , O -2 ) and hydroxyl ions (OH - ), OH - ions It will replace the weak bonds on the surface of the amorphous film (Si-Si, Si-H, Si-H2, Si-H3), etc., change the chemical bond state of the interface, and affect the effective work function matching of the amorphous silicon/TCO interface. Increase the amorphous silicon/TCO interface contact resistance.
- One embodiment of the present application provides a TCO coating method, including the following step S10.
- the water vapor partial pressure in the TCO coating treatment step is monitored
- the water vapor partial pressure in the TCO coating treatment step is greater than 5.0 ⁇ e -3 Pa
- stop coating or continue to complete the TCO coating process and then perform ion etching cleaning on the substrate so that the water vapor partial pressure is not greater than 5.0 ⁇ e - 3 Pa.
- the parts to be plated are loaded on the carrier plate, and TCO coating processing is performed; in the TCO coating processing step, the water vapor partial pressure in the TCO coating processing step is monitored.
- the monitored water vapor partial pressure in the TCO coating processing step is When the water vapor partial pressure is greater than 5.0 ⁇ e -3 Pa, stop coating and perform ion etching cleaning on the carrier board, or continue to complete the TCO coating process and perform ion etching cleaning on the carrier board after TCO coating processing to etch away
- the residue on the carrier plate and its adsorbed moisture make the water vapor partial pressure no more than 5.0 ⁇ e - 3 Pa.
- the partial pressure of water vapor during the coating process is controlled within a specific range, and the source of water vapor fluctuations is cut off from the source. , can reduce the residual amount of water vapor on TCO coated parts, so that when TCO coating is continuously performed, the parts to be plated are always in a good and stable water vapor environment.
- the obtained TCO coated parts have excellent performance and high production stability.
- the water vapor partial pressure is in a state of dynamic change.
- the entire coating process step The water vapor partial pressure is monitored from the beginning to the end, and a series of water vapor partial pressure values are monitored, and the values also change dynamically.
- the value is greater than 5.0 ⁇
- the process conditions of ion etching cleaning are controlled to control the water vapor partial pressure to be 1.0 ⁇ e -3 Pa to 5.0 ⁇ e -3 Pa.
- the process conditions of ion etching cleaning are controlled to control the water vapor partial pressure to be lower than 2.0 ⁇ e -3 Pa.
- the process conditions of the above-mentioned ion etching cleaning include the time and/or pressure of the ion etching cleaning.
- the partial pressure of water vapor is controlled to be 1.0 ⁇ e -3 Pa to 2.0 ⁇ e -3 Pa.
- Water vapor partial pressure refers to the pressure occupied by water vapor in the air. It can be tested by membrane permeability method, temperature fixed point method and chemical methods, including but not limited to: residual gas analysis (RGA), optical spectrum analysis (OE), etc.
- RAA residual gas analysis
- OE optical spectrum analysis
- the transparent conductive material used in the above-mentioned TCO coating treatment is selected from at least one member selected from the group consisting of transparent conductive metals, transparent conductive compounds, and transparent conductive polymers.
- transparent conductive materials including but not limited to the following:
- Transparent conductive materials include transparent conductive metals, transparent conductive compounds, and transparent conductive polymers, such as indium oxide-based tin doping, tungsten doping, titanium doping, molybdenum doping, gallium doping, hydrogen doping, and zinc oxide-based aluminum Doping, gallium doping, boron doping, non-limiting examples include: gold, silver, copper, platinum, In 2 O 3 , SnO 2 , ZnO, TiN, In 2 O 3 :Sn(ITO), SnO 2 : One or a combination of In(IZO), ZnO:Al(AZO), ZnO:Ga(GZO).
- the object to be plated includes a single crystal silicon wafer and an amorphous silicon film loaded on the surface of the single crystal silicon wafer.
- the amorphous silicon film includes an intrinsic amorphous silicon film and an n-type doped amorphous silicon film that are stacked in sequence.
- the amorphous silicon film includes an intrinsic amorphous silicon film and a p-type doped amorphous silicon film that are stacked in sequence.
- the article to be plated includes a single crystal silicon wafer and a first amorphous silicon film and a second amorphous silicon film respectively loaded on two surfaces of the single crystal silicon wafer.
- the first amorphous silicon film includes in sequence
- the intrinsic amorphous silicon film and the n-type doped amorphous silicon film are stacked.
- the second amorphous silicon film includes the intrinsic amorphous silicon film and the p-type doped amorphous silicon film.
- the TCO membrane obtained at this time Can be used to prepare heterojunction solar cells, such as HJT solar cells.
- the single crystal silicon wafer is n-type single crystal silicon or p-type single crystal silicon.
- the single crystal silicon wafer is n-type single crystal silicon.
- the pressure of ion etching cleaning ranges from 0.3 Pa to 1.3 Pa.
- the ion etching cleaning time is 5 to 60 minutes.
- the water vapor partial pressure during the coating process can be no more than 5.0e -3 Pa.
- the ion source used for ion etching cleaning is selected from at least one of halogen, halogen compound gas, nitrogen and inert gas.
- the ion source used for ion etching cleaning includes at least one of halogen and halogen compound gas, and at least one of nitrogen and inert gas.
- Halogen compound gases include but are not limited to: hydrides of halogens and alkanes with 1 to 5 carbon atoms substituted by halogens.
- the ion source used for ion etching cleaning is selected from one or more gas combinations among Cl 2 , HI, HCl, HBr, CH 4 , SiCl 4 , CCl 4 , Ar, He, and N 2 become
- the ion source used for ion etching cleaning includes at least one of Cl 2 , HI, HCl, HBr, CH 4 , SiCl 4 , CCl 4 , and at least one of Ar, He, and N 2 kind.
- the above-mentioned coating treatment can adopt coating methods and technologies commonly used in the field, including but not limited to: magnetron sputtering coating technology, thermal evaporation coating technology, plasma reactive deposition technology, and opposed target sputtering coating technology. , filter cathode vacuum arc coating technology, ion plating technology, atomic layer deposition coating technology.
- the coating pressure of the above-mentioned TCO coating treatment is 0.2 Pa to 1.2 Pa
- the coating temperature is not higher than 250°C
- the oxygen/argon volume ratio is (0 to 5):100.
- TCO coating If it is necessary to perform TCO coating on both sides of the parts to be plated, do it one after another.
- the required thickness of the TCO film can be completed at one time, or the coating can be repeated multiple times to reach the required thickness.
- TCO coating equipment 1 including:
- the carrier plate 10 (not shown in Figure 1) is used to load the parts to be plated.
- the first cache cavity 11, the first coating cavity 12 and the second cache cavity 13 are arranged in sequence.
- the first coating cavity 12 is provided with a TCO coating source 20 for performing coating on the parts to be plated on the carrier board 10. TCO coating treatment.
- the water vapor partial pressure monitoring device 14 (not shown in Figure 1) is used to monitor the water vapor partial pressure in the first coating chamber 12 during the TCO coating process.
- At least one plasma etching cleaning device 15 is provided in at least one of the first cache cavity 11 and the second cache cavity 12 for monitoring when the water vapor partial pressure monitoring device 14 When the partial pressure of water vapor is greater than 5.0 ⁇ e -3 Pa, it is fed back to the plasma etching and cleaning device 15 to perform ion etching and cleaning on the carrier plate 10 so that the partial pressure of water vapor in the first coating chamber 12 is not greater than 5.0 e -3 Pa.
- the first cache cavity 11 , the first coating cavity 12 and the second cache cavity 13 are connected with each other.
- the carrier plate 10 loads the parts to be plated through the first cache cavity 11 and then enters the first coating cavity.
- the body 12 is subjected to TCO coating processing.
- the coating processing is stopped or the coating processing is continued, and the carrier board enters the third Perform plasma etching and cleaning in the second cache cavity, or re-enter the first cache cavity 11, and then perform plasma etching and cleaning to remove the remaining film material on the carrier plate and its adsorbed moisture, and cut it off from the source.
- the fluctuation source of water vapor makes the partial pressure of water vapor in the first coating chamber 12 not greater than 5.0e -3 Pa.
- the water vapor partial pressure monitoring device 14 (not shown in FIG. 1 ) is provided in the first coating chamber 12 .
- the above-mentioned TCO coating equipment 1 also includes a second coating cavity 16 and an isolation cavity 17.
- the second coating cavity 16 is located between the first coating cavity 12 and the second cache cavity 13, isolating
- the cavity 17 is provided between the first coating cavity 12 and the second coating cavity 16 .
- a TCO coating source is provided at the upper part of one of the first coating chamber 12 and the second coating chamber 16 20.
- a TCO coating source 20 is provided at the lower part of another cavity to perform TCO coating treatment on the two surfaces of the parts to be plated respectively.
- a TCO coating source 20 is provided in the upper part of the first coating chamber 12 to perform TCO coating treatment on the upper surface of the parts to be plated; a TCO coating source 20 is provided in the lower part of the second coating chamber 16 , to perform TCO coating treatment on the lower surface of the parts to be plated.
- water vapor partial pressure monitoring devices 14 which are respectively used to monitor the water vapor partial pressure in the first coating chamber 12 and the second coating chamber 16 during the TCO coating process.
- one of the two water vapor partial pressure monitoring devices 14 is located in the first coating chamber 12 and the other is located in the second coating chamber 16 .
- the plasma etching cleaning device 15 is disposed in at least one of the first cache chamber 11 , the isolation chamber 17 and the second cache chamber 13 for monitoring the water vapor partial pressure.
- the carrier plate is cleaned by ion etching so that the partial pressure of water vapor in the first coating chamber and the second coating chamber is not greater than 5.0e -3 Pa.
- first coating chamber 12 and the second coating chamber 16 are both provided, as long as the water vapor partial pressure in one of the coating chambers is greater than 5.0E -3 Pa, the carrier plate 10 will be ion etched and cleaned. .
- there are two plasma etching cleaning devices 15 one of which is located in any one of the first cache cavity 11 , the isolation cavity 17 and the second cache cavity 13 In the upper part of the body, another plasma etching cleaning device 15 is located in the lower part of any one of the first cache cavity 11, the isolation cavity 17 and the second cache cavity 13 to perform cleaning on the upper and lower surfaces of the carrier board. Ion etching cleaning.
- the two plasma etching cleaning devices 15 can be located in any one of the first cache cavity 11, the isolation cavity 17 and the second cache cavity 13 at the same time, and are respectively located at the upper and lower parts of the cavity.
- the two plasma etching cleaning devices 15 may also be respectively provided in any two cavities of the first cache cavity 11 , the isolation cavity 17 and the second cache cavity 13 .
- two plasma etching cleaning devices 15 are located in the first cache cavity 11 at the same time, and are respectively located at the upper and lower parts of the first cache cavity 11 .
- the first cache cavity 11 has a plurality of adjacent and connected first cache sub-cavities 111, Please continue to refer to FIG. 1 .
- the first cache cavity 11 has two adjacent and connected first cache sub-cavities 111 .
- two plasma etching cleaning devices 15 can be located in one of the first cache sub-cavities 111 at the same time, and respectively located at the upper and lower parts thereof; in other embodiments, one plasma etching cleaning device 15 can be located in one of the first cache sub-cavities 111 simultaneously.
- the cleaning device 15 is located at the upper part of one of the first cache sub-cavities 111
- the other plasma etching cleaning device 15 is located at the lower part of the other first cache sub-cavity 111 .
- two plasma etching cleaning devices 15 may be located in the second cache cavity 13 at the same time, and respectively located at the upper and lower parts of the second cache cavity 13 .
- the second cache cavity 13 may also have a plurality of adjacent and connected second cache sub-cavities 131 . Please continue to refer to FIG. 1 .
- the second cache cavity 13 has two adjacent and connected second cache sub-cavities 131 .
- two plasma etching cleaning devices 15 can be located in one of the second cache sub-cavities 131 at the same time, and are respectively located at the upper and lower parts of the second cache sub-cavity 131; in other embodiments , one plasma etching cleaning device 15 is located at the upper part of one of the second cache sub-cavities 131 , and the other plasma etching cleaning device 15 is located at the lower part of the other second cache sub-cavity 131 .
- the above-mentioned TCO coating equipment 1 also includes a feed cavity 18 and a discharge cavity 19; the feed cavity is provided upstream of the first buffer cavity 11 for feeding materials, and the discharge cavity 19 is provided downstream of the second buffer cavity 13 for discharging materials.
- upstream and downstream are relative positions based on the feeding direction of the parts to be plated in the TCO coating device.
- the end close to the feed is upstream, and the end close to the discharge is downstream.
- the end close to the inlet of the parts to be plated is the upstream
- the end close to the outlet is the downstream.
- the parts to be plated and the carrier plate 10 enter from the feed chamber 17, and after the TCO coating is completed, they are discharged from the discharge chamber 19.
- the plasma etching cleaning device 15 is selected from an electron cyclotron reactor
- the water vapor partial pressure monitoring device is a combination device selected from one or more of an inductive coupler, a capacitive coupler, a dual plasma source reactor and a magnetically enhanced reactive ion etching reactor.
- the water vapor partial pressure monitoring device is selected from a residual gas analyzer and a spectrum analyzer.
- the above-mentioned silicon wafer coating equipment 1 also includes a vacuum device, a heating device, a transmission device, a cold trap device, etc.
- the vacuum device is used to form the vacuum conditions in the coating chamber 111 during the coating process, and the transmission
- the device and the cold trap device are respectively used to heat and cool the coating chamber during the coating process, that is, to control the temperature in the coating chamber 111 during the coating process;
- the transmission device is used to control the carrier plate in each chamber of the coating equipment 1 during continuous production. of movement.
- One embodiment of the present application provides a method for preparing a solar cell, which is characterized by including the following steps S20-30.
- Step S20 Subject the single crystal silicon wafer to surface texturing and chemical cleaning to obtain a texturized single crystal silicon wafer.
- Monocrystalline silicon wafers can be n-type monocrystalline silicon wafers or p-type monocrystalline silicon wafers.
- Step S30 Form an amorphous silicon film on the surface of the textured single crystal silicon wafer, then form a transparent conductive film, and finally prepare electrodes to obtain a solar cell.
- the step of forming the transparent conductive film is carried out by using the TCO coating method as mentioned above or using the TCO coating equipment as mentioned above.
- the above-mentioned TCO coating method and TCO coating equipment can cut off the fluctuation source of water vapor from the source, so that when continuous TCO coating is used to prepare solar cells, the parts to be plated are always in a good and stable water vapor environment, which can improve amorphous silicon/TCO Contact properties and photoelectric properties of TCO films, and improve production stability.
- the above-mentioned steps of forming an amorphous silicon film include the following steps:
- intrinsic amorphous silicon films are formed on the upper and lower surfaces of the textured n-type single crystal silicon wafer, and then P-type doped amorphous silicon films and N-type doped amorphous silicon films are formed on the upper and lower surfaces respectively. Further, transparent conductive films are formed on the upper and lower surfaces respectively, and finally electrodes are prepared.
- the solar cell prepared at this time is a HJT heterojunction cell.
- Figure 2 is a schematic structural diagram of an HJT heterojunction cell 100 provided in one embodiment.
- the specific preparation process is as follows: putting the textured and cleaned n-type crystalline silicon wafer 110 into a device for depositing amorphous silicon films, and depositing intrinsic amorphous silicon films 120 on the upper and lower surfaces of the silicon wafer respectively.
- the thickness of the amorphous silicon film can be 4nm ⁇ 9nm, and then the P-type doped amorphous silicon film 130 and the N-type doped amorphous silicon film 140 are deposited on the upper surface and the lower surface respectively.
- the thickness of the doped amorphous silicon film is 5nm ⁇ 20 nm, and then the transparent conductive film 150 is deposited on the upper surface and the lower surface respectively, with a thickness between 50 nm and 90 nm, and the metal electrode 160 is formed on the transparent conductive film 150 on the upper and lower surfaces respectively.
- the above steps of preparing the electrode include the following steps:
- Silver paste is screen-printed on the surface of the transparent conductive film, and then sintered at 170°C to 200°C to form the metal electrode 160 .
- step S30 sequentially form an intrinsic amorphous silicon passivation layer, an N-type amorphous silicon layer and an anti-reflection layer on the front side of the textured single crystal silicon wafer, and sequentially form an intrinsic amorphous silicon passivation layer on the back side.
- One embodiment of the present application provides a solar cell, which is produced by the above-mentioned solar cell preparation method.
- the contact performance between the amorphous silicon film and the TCO film is good, and the solar cell efficiency is high.
- n-type crystalline silicon wafer placed into a TCO coating chamber where amorphous silicon films are deposited, and deposit intrinsic amorphous silicon films on the upper and lower surfaces of the silicon wafer.
- the thickness of the silicon film can be 9nm, and then deposit P-type doped amorphous silicon film 130 and N-type doped amorphous silicon on the upper surface and lower surface respectively.
- the thickness of the doped amorphous silicon film is 20nm, and a pre-coated silicon wafer is obtained.
- the coating target used is deposited on the upper and lower surfaces to obtain a transparent conductive film with a thickness of 50nm, and the TCO film is obtained. pieces.
- the process control parameters of each coating are consistent, specifically: the TCO film deposited on the front uses 973 target material, the sputtering power density is 4kW/m, Ar/ O2 is 2%, the coating pressure is 0.35Pa, and the coating temperature is 180°C;
- the TCO film was deposited using 9010 target material, with a sputtering power density of 5kW/m, Ar/O 2 of 3.5%, coating pressure of 0.45Pa, and coating temperature of 180°C.
- front deposition and back deposition are carried out in two independent coating chambers.
- Both coating chambers are equipped with water vapor monitoring devices to monitor the partial pressure of water vapor in the coating chamber.
- the TCO film-coated silicon wafers are Unload, recirculate the carrier board into the coating operation in (2) above, and record the maximum value of the water vapor partial pressure in the coating chamber after different number of cycles (RUN) (the one with the higher water vapor partial pressure in the two coating chambers value) and the thickness of the film layer deposited on the carrier.
- RUN number of cycles
- Voc open circuit voltage (mV)
- Isc short circuit current (A)
- FF fill factor
- EFF conversion efficiency (%)
- the thickness of the residual film on the carrier disk is 60 ⁇ m
- the TCO coating is completed, remove the carrier disk and send it into the cache cavity.
- the upper and lower parts of the cache cavity are equipped with plasma etching cleaning devices respectively.
- the upper and lower surfaces of the disk are cleaned by plasma etching.
- the etching gases are SiCl 4 and Ar, the etching gas pressure is 0.5 Pa, the etching power density is 1w/cm 2 , the cleaning time is 5 minutes, and then the cleaned carrier plate is used to repeat the process.
- the partial pressure of water vapor in the coating chamber and the performance of the battery are as shown in Table 2;
- Experiment 3 Experiment 3 and Experiment 2 are basically the same. The only difference is that the cleaning time in Experiment 3 is 10 minutes.
- the water vapor partial pressure in the coating chamber and the performance of the battery are shown in Table 2.
- Cleaning the substrate through ion etching can cut off the source of water vapor fluctuations during TCO coating of heterojunction cells from the source, allowing TCO to be performed under stable and suitable water vapor conditions. Coating, the performance level of the heterojunction battery produced is stable and efficient.
- Experiment 4 is basically the same as Experiment 3. The only difference is that by adjusting the ion etching cleaning time, the partial pressure of water vapor in the coating chamber is maintained at 2E -3 Pa and below. Continuously produce 10,000 pieces (pcs) of heterojunction cells, and their conversion efficiency distribution diagram is shown in Figure 3, A.
- Experiment 5 is basically the same as Experiment 4. The only difference is that the partial pressure of water vapor in the coating chamber is maintained at 6E -3 Pa and above. Continuously produce 10,000 pieces (pcs) of heterojunction cells, and their conversion efficiency distribution diagram is shown in B in Figure 3.
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Abstract
本申请涉及一种TCO镀膜方法、TCO镀膜设备、太阳能电池及其制备方法。该TCO镀膜方法中,将待镀件装载于载板上,并进行TCO镀膜处理;在所述TCO镀膜处理步骤中,监测所述TCO镀膜处理步骤中的水汽分压;当监测到所述TCO镀膜处理步骤中的水汽分压大于5.0×e-3Pa时,停止镀膜或继续完成所述TCO镀膜处理,再对所述载板进行离子刻蚀清洗,以使所述水汽分压不大于5.0×e-3Pa。该TCO镀膜方法在连续化生产时,能从源头切断水汽波动源,生产稳定性高,进而可以提高太阳能电池的生产效率及生产稳定性。
Description
本申请要求于2022年08月09日提交中国专利局、申请号为202210950302.X、发明名称为“TCO镀膜方法、TCO镀膜设备、太阳能电池及其制备方法”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。
本申请涉及电池技术领域,特别是涉及一种TCO镀膜方法、TCO镀膜设备、太阳能电池及其制备方法。
HJT太阳能电池(简称异质结电池)、HBC电池(交叉指式背接触异质结太阳电池)、或太阳能叠层电池均是高效太阳能电池,例如HJT太阳能电池就具有较低的温度系数和低光致衰减,稳定性高,HJT太阳能电池的一般制备步骤为:以n型单晶硅片为基板,先对其进行表面制绒和化学清洗,使表面形成提高光吸收的金字塔凹凸结构,再经过化学清洗后形成清洁的表面,然后采用等离子体化学气相沉积(PECVD)等方法在清洗后的硅片的两个表面均沉积本征非晶硅薄膜,然后在其中一个表面沉积p型掺杂非晶硅膜,在另一表面沉积n型掺杂非晶硅膜,再通过TCO(透明导电氧化物)镀膜在两表面沉积透明导电氧化物膜,然后通过丝网印刷或电镀或喷墨打印技术制作金属电极,如此就得到具有对称性结构的HJT异质结电池。
其中,TCO薄膜作为承上启下的重要功能层薄膜,起到重要作用:1、表面减反射作用,在硅表面形成良好的减反射镀膜层(AR-coating)降低光在电池的表面反射损失;2、载流子收集传输作用,与非晶薄膜形成良好的接触有效收集被分离到非晶硅薄膜的光生载流子并将其传输到金属电极上;3、表面保护作用,完全覆盖于非晶硅薄膜上阻挡外部环境对非晶硅钝化薄膜的影响。同样地,一些HBC电池或太阳能叠层电池中也含有TCO薄膜,并起到重要作用。
然而,传统的TCO镀膜技术中,在连续化生产时,会有水汽残留在非晶硅薄膜及TCO薄膜的接触界面上,导致生产出的电池的转换效率波动大、离散性
大,大规模生产时制得的电池的性能水平参差、不稳定。因此,传统技术仍有待改进。
发明内容
根据本申请的各种实施例,本申请提供一种TCO镀膜方法、TCO镀膜设备、异质结电池及其制备方法。
本申请是通过如下的技术方案实现的。
本申请的一个方面,提供了一种TCO镀膜方法,包括如下步骤:
将待镀件装载于载板上,并进行TCO镀膜处理;
在所述TCO镀膜处理步骤中,监测所述TCO镀膜处理步骤中的水汽分压;
当监测到所述TCO镀膜处理步骤中的水汽分压大于5.0×e-3Pa时,停止镀膜或继续完成所述TCO镀膜处理,再对所述载板进行离子刻蚀清洗,以使所述水汽分压不大于5.0×e-3Pa。
在其中一些实施例中,所述离子刻蚀清洗的时间为5min~15min。
在其中一些实施例中,所述离子刻蚀清洗的压力为0.3Pa~1.3Pa。
在其中一些实施例中,所述离子刻蚀清洗采用的离子源选自卤素、卤素化合物气体、氮气和惰性气体中的至少一种。
在其中一些实施例中,所述离子刻蚀清洗采用的离子源包括卤素及卤素化合物气体中的至少一种,及氮气和惰性气体中的至少一种。
在其中一些实施例中,所述TCO镀膜处理采用的透明导电材料选自透明导电金属、透明导电化合化物和透明导电高分子中的至少一种。
在其中一些实施例中,所述待镀件包括单晶硅片及负载于所述单晶硅片表面的非晶硅膜。
在其中一些实施例中,所述非晶硅膜包括依次层叠的本征非晶硅膜和p型掺杂非晶硅膜。
在其中一些实施例中,所述非晶硅膜包括依次层叠的本征非晶硅膜和n型
掺杂非晶硅膜。
本申请的另一方面,提供一种TCO镀膜设备,包括:
载板,用于装载待镀件;
依次设置的第一缓存腔体、第一镀膜腔体和第二缓存腔体,所述第一镀膜腔体中设有TCO镀膜源,用于对所述载板上的待镀件进行TCO镀膜处理;
水汽分压监测装置,用于监测所述TCO镀膜处理中所述第一镀膜腔体中的水汽分压;及
至少一个等离子体刻蚀清洗装置,所述等离子体刻蚀清洗装置设于所述第一缓存腔体及所述第二缓存腔体中的至少一个腔体中,用于当所述水汽分压监测装置监测到的水汽分压大于5.0×e-3Pa时,对所述载板进行离子刻蚀清洗,以使所述第一镀膜腔体内的水汽分压不大于5.0e-3Pa。
在其中一些实施例中,所述TCO镀膜设备还包括第二镀膜腔体和隔离腔体,所述第二镀膜腔体设于所述第一镀膜腔体和所述第二缓存腔体之间,所述隔离腔体设于所述第一镀膜腔体和第二镀膜腔体之间;
所述第一镀膜腔体和第二镀膜腔体中的一个腔体的上部设有所述TCO镀膜源,另一个腔体的下部设有TCO镀膜源,以分别对所述待镀件的两表面进行TCO镀膜处理;
所述水汽分压监测装置有两个,分别用于监测所述TCO镀膜处理中所述第一镀膜腔体和所述第二镀膜腔体中的水汽分压;
所述等离子体刻蚀清洗装置设于所述第一缓存腔体、所述隔离腔体及所述第二缓存腔体中的至少一个腔体中,用于当所述水汽分压监测装置监测到的水汽分压大于5.0×e-3Pa时,对所述载板进行离子刻蚀清洗,以使所述第一镀膜腔和所述第二镀膜腔内的水汽分压不大于5.0e-3Pa。
在其中一些实施例中,所述等离子体刻蚀清洗装置有两个,其中一个所述等离子体刻蚀清洗装置位于所述第一缓存腔体、所述隔离腔体及所述第二缓存腔体的任意一个腔体中的上部,另一个所述等离子体刻蚀清洗装置位于所述第一缓存腔体、所述隔离腔体及所述第二缓存腔体的任意一个腔体中的下部,以对所
述载板的上下表面进行离子刻蚀清洗。
在其中一些实施例中,所述TCO镀膜设备还包括进料腔体和出料腔体;所述进料腔体设于所述第一缓存腔体的上游以用于进料,所述出料腔体设于所述第二缓存腔体的下游以用于出料。
在其中一些实施例中,所述等离子体刻蚀清洗装置选自电子回旋加速反应器、电感耦合器、电容耦合器、双等离子体源反应器和磁增强反应离子刻蚀反应器中的一种或者多种的组合装置。
在其中一些实施例中,所述水汽分压监测装置选自残留气体分析仪和光谱分析仪的一种或者两种的组合装置。
本申请的又一方面,提供一种太阳能电池的制备方法,包括如下步骤:
将单晶硅片进行表面制绒及化学清洗处理,得到制绒后的单晶硅片;
在所述制绒后的单晶硅片的表面形成非晶硅膜,然后形成透明导电膜,最后制备电极,得到太阳能电池;
所述形成透明导电膜的步骤采用如上所述的TCO镀膜方法进行或采用如上所述的TCO镀膜设备进行。
在其中一些实施例中,所述形成非晶硅膜的步骤包括如下步骤:
先在所述制绒后的单晶硅片的上下表面分别形成本征非晶硅膜,然后在上下表面分别形成P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜。
在其中一些实施例中,所述制备电极的步骤包括如下步骤:
在所述透明导电膜的表面进行银浆丝网印刷,然后于170℃~200℃下烧结处理。
本申请的又一方面,提供一种太阳能电池,采用如上所述的太阳能电池的制备方法制得。
本发明的一个或多个实施例的细节在下面的附图和描述中提出。本发明的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。
为了更好地描述和说明本申请的实施例和/或示例,可以参考一幅或多幅附图。用于描述附图的附加细节或示例不应当被认为是对所公开的发明、目前描述的实施例和/或示例以及目前理解的这些发明的最佳模式中的任何一者的范围的限制。
图1为一实施方式的TCO镀膜设备的结构示意图;
图2为一实施方式的异质结电池的结构示意图;
图3为实验四和实验五的异质结电池的效率分布对比图。
附图标记说明:
1TCO镀膜设备;10载板;11第一缓存腔体;111第一缓存子腔体;12第
一镀膜腔体;13第二缓存腔体;131第二缓存子腔体;14水汽分压监测装置;15等离子体刻蚀清洗装置;16第二镀膜腔体;17隔离腔体;18进料腔体;19出料腔体;20TCO镀膜源;
100异质结电池;110晶体硅片;120本征非晶硅膜;130P型掺杂非晶硅薄
膜;140N型掺杂非晶硅膜;150透明导电膜;160金属电极。
1TCO镀膜设备;10载板;11第一缓存腔体;111第一缓存子腔体;12第
一镀膜腔体;13第二缓存腔体;131第二缓存子腔体;14水汽分压监测装置;15等离子体刻蚀清洗装置;16第二镀膜腔体;17隔离腔体;18进料腔体;19出料腔体;20TCO镀膜源;
100异质结电池;110晶体硅片;120本征非晶硅膜;130P型掺杂非晶硅薄
膜;140N型掺杂非晶硅膜;150透明导电膜;160金属电极。
为了更好地描述和说明这里公开的那些申请的实施例和/或示例,可以参考一幅或多幅附图。用于描述附图的附加细节或示例不应当被认为是对所公开的申请、目前描述的实施例和/或示例以及目前理解的那些申请的最佳模式中的任何一者的范围的限制。
为了便于理解本申请,下面将参照相关附图对本申请进行更全面的描述。附图中给出了本申请的较佳实施方式。但是,本申请可以以许多不同的形式来实现,并不限于本文所描述的实施方式。相反地,提供这些实施方式的目的是使对本申请的公开内容理解的更加透彻全面。
此外,术语“第一”、“第二”仅用于描述目的,而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量或顺序。由此,限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本申请的描述中,“多个”的含义是至少两个,例如两个,三个等,除非另有明确具体的限定。
除非另有定义,本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的,不是旨在于限制本申请。
综上背景技术所述,传统的TCO镀膜技术中,会有水汽残留在非晶硅薄膜及TCO薄膜的接触界面上,且在连续生产的情况下,镀膜设备中的水汽难以控制,频繁波动,在连续生产情况下很难控制TCO镀膜过程中的水汽残留量,而水汽的残留会严重影响非晶硅/TCO接触界面处的表面能、表面化学健成分以及TCO薄膜的微结构,导致非晶硅/TCO接触电阻过高、界面有效功函数难以控制,从而导致电池的填充因子(FF)低、电池转换效率低、波动大、离散性大等一系列问题,严重影响了HJT电池的大批量生产效率。
传统技术中尝试过很多方法进行除水方式,例如通过在TCO镀膜设备端增加冷阱(通用设备标准配置)、冷凝泵等方法,这些方法在一定程度上可以有效缓解水汽对HJT电池的大批量生产的负面影响,但在连续化生产时,总是会在一定周期内先快速增加后趋于饱和,且周期不定,难以控制,仍然影响大批量生产时的稳定性,同时增加了成本。
传统的连续化TCO镀膜方法中,总是聚焦于在TCO镀膜前后对镀膜腔体进行除杂或除水处理,而本申请技术人员在长时间的电池生产过程中发现:在硅片的连续化镀膜过程中,装载硅片的载板上的水汽才是导致连续镀膜生产时水汽难以精确控制的重要原因。本申请技术人员研究发现:装载硅片的载板上会沉积膜材,进而会吸附水汽,而载板一般是重复使用的,即使在镀膜之前进行严格控水,但连续镀膜时,载板上累积的水汽依然会转移至镀膜硅片上或镀膜腔中,且残留的水会被解离成氧离子(O0、O-1、O-2)和羟基离子(OH-),OH-离子会与非晶薄膜的表面弱健(Si-Si、Si-H、Si-H2、Si-H3)等产生置换,改变界面化学健状态,影响非晶硅/TCO界面的有效功函数匹配性,增大非晶硅/TCO界面接触电阻,同时,OH-离子会影响TCO薄膜的微结构状态,抑制TCO薄膜生产过程中的晶化率和离化率。因此,在传统的连续化生产过程中,总是会出现在一段时间内水汽快速增加的现象,进而使制得的异质结电池的转换效率波动大、离
散性大。
本申请的技术人员在上述研究发现的基础上,在经过大量创造性实验探究后,获得本申请中在连续化生产时,能降低硅片上的水汽残留量,制得的镀膜硅片性能优异,且生产稳定性高的TCO镀膜方法及TCO镀膜设备。
本申请一实施方式提供了一种TCO镀膜方法,包括如下步骤S10。
S10、将待镀件装载于载板上,并进行TCO镀膜处理。
在上述TCO镀膜处理步骤中,监测TCO镀膜处理步骤中的水汽分压;
当监测到TCO镀膜处理步骤中的水汽分压大于5.0×e-3Pa时,停止镀膜或继续完成TCO镀膜处理,再对载板进行离子刻蚀清洗,以使水汽分压不大于5.0×e-
3Pa。
上述TCO镀膜方法中,将待镀件装载于载板上,并进行TCO镀膜处理;在TCO镀膜处理步骤中,监测TCO镀膜处理步骤中的水汽分压,当监测到的TCO镀膜处理步骤中的水汽分压大于5.0×e-3Pa时,停止镀膜,对载板进行离子刻蚀清洗,或是继续完成TCO镀膜处理,对TCO镀膜处理后的载板进行离子刻蚀清洗,以刻蚀掉载板上的残留物及其吸附的水分,从而使水汽分压不大于5.0×e-
3Pa。通过监测镀膜处理时环境中的水汽分压,并通过刻蚀清洗载板上的残留物及其吸附的水分,使镀膜处理中的水汽分压控制在特定范围,从源头上切断水汽的波动来源,能降低TCO镀膜件上的水汽残留量,使连续进行TCO镀膜时,待镀件一直是处于良好且平稳的水汽环境中,制得的TCO镀膜件的性能优异,且生产稳定性高。
需要说明的是,当监测到TCO镀膜处理步骤中的水汽分压大于5.0×e-3Pa时,可以选择立即停止镀膜处理,将载板进行离子刻蚀清洗,刻蚀掉载板上的残留物及其吸附的水分,从而使水汽分压不大于5.0×e-3Pa;也可以继续完成TCO镀膜处理,将完成TCO镀膜处理后的载板进行离子刻蚀清洗,以刻蚀掉载板上的残留物及其吸附的水分,从而使水汽分压不大于5.0×e-3Pa。
可理解,在连续TCO镀膜处理步骤中,从TCO镀膜开始到TCO镀膜结束,随着TCO镀膜的进行,其水汽分压是处于动态变化的状态,整个镀膜处理步骤
在开始到结束的水汽分压一直被监控其,由此会监测到一系列的水汽分压的数值,且数值也是动态变化的,当监测到镀膜时的水汽分压中的数值的大于5.0×e-
3Pa时,可选择停止镀膜,然后就对载板进行离子刻蚀清洗,也可选择继续TCO镀膜处理,将此时正在进行TCO镀膜处理步骤完成,再对载板进行离子刻蚀清洗。
在其中一些实施例中,通过调控离子刻蚀清洗的工艺条件,以控制水汽分压为1.0×e-3Pa~5.0×e-3Pa。
在其中一些实施例中,通过调控离子刻蚀清洗的工艺条件,以控制水汽分压低于2.0×e-3Pa。
上述离子刻蚀清洗的工艺条件包括离子刻蚀清洗的时间和/或压力。
进一步地,通过调控离子刻蚀清洗的时间和/或压力,以控制水汽分压为1.0×e-3Pa~2.0×e-3Pa。
水汽分压是指空气中水汽所占的压力,可采用膜渗透法、温度固定点法以及化学方法等进行测试,具体包括但不限于:残留气体分析(RGA)、光谱分析(OE)等。
在其中一些实施例中,上述TCO镀膜处理采用的透明导电材料选自透明导电金属、透明导电化合化物和透明导电高分子中的至少一种。
此处对透明导电材料进行举例说明,包括但不限于如下:
透明导电材料包括透明导电金属、透明导电化合化物、透明导电高分子,例如氧化铟基锡掺杂、钨掺杂、钛掺杂、钼掺杂、镓掺杂、氢掺杂、氧化锌基铝掺杂、镓掺杂、硼掺杂,非限制性实例包括:金、银、铜、铂、In2O3、SnO2、ZnO、TiN、In2O3:Sn(ITO)、SnO2:In(IZO)、ZnO:Al(AZO)、ZnO:Ga(GZO)中的一种或多种的组合。
在其中一些实施例中,上述待镀件包括单晶硅片及负载于单晶硅片表面的非晶硅膜。
在其中一些实施例中,非晶硅膜包括依次层叠设置的本征非晶硅膜和n型掺杂非晶硅膜。
在另一些实施例中,非晶硅膜包括依次层叠设置的本征非晶硅膜和p型掺杂非晶硅膜。
在一具体的实例中,待镀件包括单晶硅片及分别负载在单晶硅片的两个表面的第一非晶硅膜和第二非晶硅膜,第一非晶硅膜包括依次层叠设置的本征非晶硅膜和n型掺杂非晶硅膜,第二非晶硅膜包括本征非晶硅膜和p型掺杂非晶硅膜,此时制得的TCO膜件可用于制备异质结太阳能电池,如HJT太阳能电池。
在其中一些实施例中,单晶硅片为n型单晶硅或p型单晶硅。
在一具体实例中,单晶硅片为n型单晶硅。
在其中一些实施例中,离子刻蚀清洗的压力为0.3Pa~1.3Pa。
在其中一些实施例中,离子刻蚀清洗的时间为5min~60min。
进一步地,通过控制离子刻蚀清洗的条件以清洗干净载板上负载的残留膜材,就可使镀膜处理时的水汽分压不大于5.0e-3Pa。
在其中一些实施例中,离子刻蚀清洗采用的离子源选自卤素、卤素化合物气体、氮气和惰性气体中的至少一种。
在其中一些实施例中,离子刻蚀清洗采用的离子源包括卤素及卤素化合物气体中的至少一种,及氮气和惰性气体中的至少一种。
卤素化合物气体包括但不限于:卤素的氢化物、被卤素取代的碳原子数为1~5的烷烃。
在其中一些实施例中,离子刻蚀清洗采用的离子源选自Cl2、HI、HCl、HBr、CH4、SiCl4、CCl4、Ar、He、N2中的一种或者多种气体组合而成
在其中一些实施例中,离子刻蚀清洗采用的离子源包括Cl2、HI、HCl、HBr、CH4、SiCl4、CCl4中的至少一种,及Ar、He、N2中的至少一种。
在其中一些实施例中,上述镀膜处理可以采用本领域常用的镀膜方法技术,包括但不限于:磁控溅射镀膜技术、热蒸发镀膜技术、等离子体反应沉积技术、对向靶溅射镀膜技术、过滤阴极真空电弧镀膜技术、离子镀技术、原子层沉积镀膜技术。
在其中一些实施例中,上述TCO镀膜处理的镀膜压力为0.2Pa~1.2Pa、镀膜温度不高于250℃、氧/氩体积比为(0~5):100。
若需要对待镀件的两面进行TCO镀膜,先后进行,可一次性完成TCO薄膜所需厚度,也可重复多次镀膜达到所需厚度。
请参考附图1所示,本申请一实施方式,提供一种TCO镀膜设备1,包括:
载板10(图1中未示出),用于装载待镀件。
依次设置的第一缓存腔体11、第一镀膜腔体12和第二缓存腔体13,第一镀膜腔体12中设有TCO镀膜源20,用于对载板10上的待镀件进行TCO镀膜处理。
水汽分压监测装置14(图1中未示出),用于监测TCO镀膜处理中第一镀膜腔体12中的水汽分压。
至少一个等离子体刻蚀清洗装置15,等离子体刻蚀清洗装置15设于第一缓存腔体11及第二缓存腔体12中的至少一个腔体中,用于当水汽分压监测装置14监测到的水汽分压大于5.0×e-3Pa时,反馈到等离子体刻蚀清洗装置15,对载板10进行离子刻蚀清洗,以使第一镀膜腔体12内的水汽分压不大于5.0e-3Pa。
可理解,第一缓存腔体11、第一镀膜腔体12和第二缓存腔体13相互连通,工作时,载板10装载待镀件通过第一缓存腔体11,再进入第一镀膜腔体12进行TCO镀膜处理,当水汽监控装置14监控到的第一镀膜腔体12内的水汽分压的最大值大于5.0e-3Pa时,停止镀膜处理或继续完成镀膜处理,载板进入第二缓存腔体中进行离子体刻蚀清洗,或重新进入第一缓存腔体11中,再进行离子体刻蚀清洗,以除去载板上残留的膜材及其吸附的水分,从源头上切断水汽的波动来源,使第一镀膜腔体12内的水汽分压不大于5.0e-3Pa。
具体地,水汽分压监测装置14(图1中未示出)设于第一镀膜腔体12中。
请继续参考图1,上述TCO镀膜设备1还包括第二镀膜腔体16和隔离腔体17,第二镀膜腔体16设于第一镀膜腔体12和第二缓存腔体13之间,隔离腔体17设于第一镀膜腔体12和第二镀膜腔体16之间。
第一镀膜腔体12和第二镀膜腔体16中的一个腔体的上部设有TCO镀膜源
20,另一个腔体的下部设有TCO镀膜源20,以分别对待镀件的两表面进行TCO镀膜处理。
在一具体的示例中,第一镀膜腔体12中的上部设有TCO镀膜源20,以对待镀件的上表面进行TCO镀膜处理;第二镀膜腔体16中的下部设有TCO镀膜源20,以对待镀件的下表面进行TCO镀膜处理。
进一步地,上述水汽分压监测装置14有两个,分别用于监测TCO镀膜处理中第一镀膜腔体12和第二镀膜腔体16中的水汽分压。
可理解,两个水汽分压监测装置14中的一个设于第一镀膜腔体12中,另一个第二镀膜腔体16中。
请继续参考图1,等离子体刻蚀清洗装置15设于第一缓存腔体11、隔离腔体17及第二缓存腔体13中的至少一个腔体中,用于当所述水汽分压监测装置监测到的水汽分压大于5.0×e-3Pa时,对载板进行离子刻蚀清洗,以使第一镀膜腔和第二镀膜腔内的水汽分压不大于5.0e-3Pa。
需要说明的是,当同时设有第一镀膜腔体12和第二镀膜腔体16,只要其中一个镀膜腔体内的水汽分压大于5.0E-3Pa,就对载板10进行离子刻蚀清洗。
在其中一些实施例中,等离子体刻蚀清洗装置15有两个,其中一个等离子体刻蚀清洗装置15位于第一缓存腔体11、隔离腔体17及第二缓存腔体13的任意一个腔体中的上部,另一个等离子体刻蚀清洗装置15位于第一缓存腔体11、隔离腔体17及第二缓存腔体13的任意一个腔体中的下部,以对载板的上下表面进行离子刻蚀清洗。
可理解,两个等离子体刻蚀清洗装置15可同时位于第一缓存腔体11、隔离腔体17及第二缓存腔体13的任意一个腔体中,且分别位于腔体的上部和下部,也可以两个等离子体刻蚀清洗装置15分别设于第一缓存腔体11、隔离腔体17及第二缓存腔体13的任意两个腔体中。
在其中一些实施例中,两个等离子体刻蚀清洗装置15同时位于第一缓存腔体11中,且分别位于第一缓存腔体11的上部和下部。
进一步地,第一缓存腔体11具有多个相邻设置且连通的第一缓存子腔体111,
请继续参考图1,第一缓存腔体11具有两个相邻设置且连通的第一缓存子腔体111。
在其中一些实施例中,两个等离子体刻蚀清洗装置15可同时位于其中一个第一缓存子腔体111中、并分别位于其上部和下部;在另一些实施例中,一个等离子体刻蚀清洗装置15位于其中一个第一缓存子腔体111的上部,另一个等离子体刻蚀清洗装置15位于另一个第一缓存子腔体111的下部。
同理,在其中一些实施例中,两个等离子体刻蚀清洗装置15可同时位于第二缓存腔体13中,且分别位于第二缓存腔体13的上部和下部。
进一步地,第二缓存腔体13也可具有多个相邻设置且连通的第二缓存子腔体131,请继续参考图1,第二缓存腔体13具有两个相邻设置且连通的第二缓存子腔体131。
在其中一些实施例中,两个等离子体刻蚀清洗装置15可同时位于其中一个第二缓存子腔体131中,且分别位于第二缓存子腔体131的上部和下部;在另一些实施例中,一个等离子体刻蚀清洗装置15位于其中一个第二缓存子腔体131的上部,另一个等离子体刻蚀清洗装置15位于另一个第二缓存子腔体131的下部。
在其中一些实施例中,上述TCO镀膜设备1还包括进料腔体18和出料腔体19;进料腔体设于第一缓存腔体11的上游以用于进料,出料腔体19设于第二缓存腔体13的下游以用于出料。
需要说明的是,上述“上游”、“下游”是以TCO镀膜装置中待镀件的进料方向为基准区分的相对位置,靠近进料的一端则为上游,靠近出料的一端则为下游,例如第一缓存腔体11中,靠近待镀件进入口的一端即为上游,第二缓存腔体13中,靠近出口的一端即为下游。
待镀件及载板10从进料腔体17进入,TCO镀膜完成后,从出料腔体19卸出。
可理解,上述TCO镀膜设备1中的各相邻腔体之间是联通的。
在其中一些实施例中,等离子体刻蚀清洗装置15选自电子回旋加速反应器、
电感耦合器、电容耦合器、双等离子体源反应器和磁增强反应离子刻蚀反应器中的一种或者多种的组合装置水汽分压监测装置选自残留气体分析仪和光谱分析仪的一种或者两种的组合装置具体地,上述硅片镀膜设备1还包括抽真空装置、加热装置、传输装置及冷阱装置等,抽真空装置用形成镀膜处理时镀膜腔111中的真空条件,传输装置和冷阱装置分别用于对镀膜处理时镀膜腔的加热和冷却,即控制镀膜处理时镀膜腔111中温度;传输装置用于控制载板在连续生产时在镀膜设备1中的各个腔室内的移动。
本申请的一实施方式,提供一种太阳能电池的制备方法,其特征在于,包括如下步骤S20~30。
步骤S20、将单晶硅片进行表面制绒及化学清洗处理,得到制绒后的单晶硅片。
单晶硅片经表面制绒形成提高光吸收的金字塔凹凸结构,再经过化学清洗后形成清洁的表面。单晶硅片可以是n型单晶硅片或p型单晶硅片。
步骤S30、在制绒后的单晶硅片的表面形成非晶硅膜,然后形成透明导电膜,最后制备电极,得到太阳能电池。
其中,形成透明导电膜的步骤采用如上所述的TCO镀膜方法进行或采用如上所述的TCO镀膜设备进行。
上述TCO镀膜方法及TCO镀膜设备能从源头上切断水汽的波动来源,使连续化TCO镀膜以制备太阳能电池时,待镀件一直是处于良好且平稳的水汽环境中,能改善非晶硅/TCO接触性能和TCO薄膜的光电性能,并提高生产稳定性。
在其中一些实施例中,上述形成非晶硅膜的步骤包括如下步骤:
先在制绒后的n型单晶硅片的上下表面分别形成本征非晶硅膜,然后在上下表面分别形成P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜。进一步地,再在上下表面分别形成透明导电膜,最后制备电极,此时制备得到的太阳能电池为HJT异质结电池。
请参考图2,图2为一实施方式提供的HJT异质结电池100的结构示意图,
其制备过程具体为:将制绒清洗过的n型晶体硅片110放入沉积非晶硅薄膜的设备中,分别在硅片上表面和下表面分别沉积本征非晶硅膜120,本征非晶硅膜的厚度可为4nm~9nm,然后上表面和下表面分别沉积P型掺杂非晶硅薄膜130和N型掺杂非晶硅膜140,掺杂非晶硅膜厚度为5nm~20nm,然后上表面及下表面分别沉积得到透明导电膜150,厚度在50nm~90nm之间,分别在上下表面的透明导电膜150上形成金属电极160。
在其中一些实施例中,上述制备电极的步骤包括如下步骤:
在透明导电膜的表面进行银浆丝网印刷,然后于170℃~200℃下烧结处理,形成金属电极160。
需要说明的是,上述太阳能电池的制备方法不仅限于制备HJT异质结电池,还可用于制备HBC电池(交叉指式背接触异质结(HBC)太阳电池)、或太阳能叠层电池。例如制备HBC电池时,步骤S30:在制绒后的单晶硅片的正面依次形成本征非晶硅钝化层、N型非晶硅层和减反层,在其背面依次形成本征非晶硅钝化层、间隔设置的P型非晶硅层与N型非晶硅层、再形成TCO导电膜,最后制备电极,得到HBC电池。本申请一实施方式,提供一种太阳能电池,采用如上述的太阳能电池的制备方法制得。
上述的太阳能电池的制备方法制得太阳能电池中,非晶硅膜与TCO膜的接触性能好,太阳能电池效率高。
下面将结合具体的实施例对本申请进行了说明,但本申请并不局限于下述实施例,应当理解,所附权利要求概括了本申请的范围,在本申请构思的引导下本领域的技术人员应意识到,对本申请的各实施例所进行的一定的改变,都将被本申请的权利要求书的精神和范围所覆盖。
以下为具体实施例。
实施例1
实验一:验证TCO镀膜时的水汽分压对电池性能的影响
(1)将制绒清洗过的n型晶体硅片放入沉积非晶硅薄膜的TCO镀膜腔体中,分别在硅片上表面和下表面分别沉积本征非晶硅膜,本征非晶硅膜的厚度可为
9nm,,然后上表面和下表面分别沉积P型掺杂非晶硅薄膜130和N型掺杂非晶硅,掺杂非晶硅膜厚度为20nm,得到预镀膜硅片。
(2)将预镀膜硅片装载在载板上送入TCO镀膜腔体进行TCO镀膜处理,采用的镀膜靶材在上表面及下表面分别沉积得到透明导电膜,厚度为50nm,得到镀TCO膜件。
其中,每次镀膜的工艺控制参数一致,具体为:正面沉积TCO薄膜采用973靶材,溅射功率密度4kW/m、Ar/O2为2%,镀膜气压0.35Pa,镀膜温度180℃;背面沉积TCO薄膜采用9010靶材,溅射功率密度5kW/m,Ar/O2为3.5%,镀膜气压0.45Pa,镀膜温度180℃。
其中,正面沉积和背面沉积分别在独立的两个镀膜腔体中进行,两个镀膜腔中均设置有水汽监控装置监控镀膜腔体中的水汽分压,镀膜完成后,将镀TCO膜硅片卸出,将载板重新循环进上述(2)中的镀膜操作,记录不同循环圈数(RUN)后,镀膜腔体中的水汽分压的最大值(两个镀膜腔体中水汽分高的值)、载板上沉积的膜层的厚度,具体请见表1。
(3)将上述镀TCO膜件采用银浆丝网印刷,于170℃~200℃下烧结后形成金属电极,得到HJT异质结电池,并对HJT异质结电池的性能进行测试,具体测试请参考标准GB/T6495.1-1996。
其中,Voc:开路电压(mV),Isc:短路电流(A),FF:填充因子,EFF:转换效率(%)
具体结果请见表1。
表1
由表1实验数据可知:在连续化生产中,镀膜腔内水汽分压(Pa)会经历逐渐增高的历程、电池效率随载板使用次数增加先增加后迅速减少,在约500RUN时,电池转换效率(EFF)最高、达到24.18%,然后急剧下降,1000RUN时电池转换效率下降至23.72%。
实验二:验证载板残留水汽对电池的影响
重复进行上述实验一,当载盘残留膜的厚度为60μm时,TCO镀膜完毕后取下载盘送入缓存腔体中,缓存腔体的上部及下部分别设有等离子体刻蚀清洗装置,对载盘的上下表面进行等离子体刻蚀清洗,刻蚀气体为SiCl4和Ar,刻蚀气压0.5Pa,刻蚀功率密度1w/cm2,清洗时间为5min,然后使用该清洗后的载板重复进行上述步骤(2)~(3),镀膜腔体中的水汽分压及制得的电池性能如表2所示;
实验三:实验三和实验二基本相同,不同之处仅在于,实验三中的清洗时间为10min,镀膜腔体中的水汽分压及制得的电池性能如表2所示。
表2
由表2数据可知:对载板进行等离子体刻蚀清洗5min,镀膜腔体中对应水汽残留量从1.0E-2下降到4.5E-3,电池效率恢复到24.06%,得到明显改善,达到较优水平。进一步进行10min离子刻蚀清洗时,对应水汽残留量从1.0E-2下降到1.5E-3,电池效率恢复到24.18%,得到明显改善,达到优异水平,可见连续TCO镀膜时,载板上是残留物对镀膜时的水汽分压产生重要影响,通过离子刻蚀清洗载板可以从源头切断异质结电池的TCO镀膜时的水汽波动源,使其在稳定的、适宜的水汽条件下进行TCO镀膜,制得的异质结电池的性能水平稳定、高效。
实验四:实验四与实验三基本相同,不同之处仅在于:通过调节离子刻蚀清洗的时间,使镀膜腔体中水汽分压保持在2E-3Pa及以下。连续生产10000件(pcs)异质结电池,其转换效率分布图如图3中A所示。
实验五:实验五与实验四基本相同,不同之仅在于:镀膜腔体中水汽分压保持在6E-3Pa及以上。连续生产10000件(pcs)异质结电池,其转换效率分布图如图3中B所示。
从图3中A和B的异质结电池的转换效率分布趋势可看出:采用本申请的HJT异质结电池的TCO镀膜方法进行连续化生产时,通过对水汽残留量的监控,并对水汽残留量超标的载盘进行在线等离子体刻蚀清洗,以从源头切断水汽波动来源,以解决不稳定的水汽波动对制得的HJT异质结电池的转换效率的负面影响,从而有效提高HJT异质结电池量产时产品的良率及效率、且离散率小,大批量生产时的稳定性高。
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本申请构思的前提下,还可以做出若干变形和改进,这些都属于本申请的保护范围。因此,本申请专利的保护范围应以所附权利要求为准,说明书及附图可以用于解释权利要求的内容。
Claims (19)
- 一种TCO镀膜方法,其特征在于,包括如下步骤:将待镀件装载于载板上,并进行TCO镀膜处理;在所述TCO镀膜处理步骤中,监测所述TCO镀膜处理步骤中的水汽分压;当监测到所述TCO镀膜处理步骤中的水汽分压大于5.0×e-3Pa时,停止镀膜或继续完成所述TCO镀膜处理,再对所述载板进行离子刻蚀清洗,以使所述水汽分压不大于5.0×e-3Pa。
- 如权利要求1所述的TCO镀膜方法,其特征在于,所述离子刻蚀清洗的时间为5min~15min。
- 如权利要求1~2任一项所述的TCO镀膜方法,其特征在于,所述离子刻蚀清洗的压力为0.3Pa~1.3Pa。
- 如权利要求1~3任一项所述的TCO镀膜方法,其特征在于,所述离子刻蚀清洗采用的离子源选自卤素、卤素化合物气体、氮气和惰性气体中的至少一种。
- 如权利要求1~4任一项所述的TCO镀膜方法,其特征在于,所述离子刻蚀清洗采用的离子源包括卤素及卤素化合物气体中的至少一种,及氮气和惰性气体中的至少一种。
- 如权利要求1~5任一项所述的TCO镀膜方法,其特征在于,所述TCO镀膜处理采用的透明导电材料选自透明导电金属、透明导电化合化物和透明导电高分子中的至少一种。
- 如权利要求1~6任一项所述的TCO镀膜方法,其特征在于,所述待镀件包括单晶硅片及负载于所述单晶硅片表面的非晶硅膜。
- 如权利要求7所述的TCO镀膜方法,其特征在于,所述非晶硅膜包括依次层叠的本征非晶硅膜和p型掺杂非晶硅膜。
- 如权利要求7~8任一项所述的TCO镀膜方法,其特征在于,所述非晶硅膜包括依次层叠的本征非晶硅膜和n型掺杂非晶硅膜。
- 一种TCO镀膜设备,其特征在于,包括:载板,用于装载待镀件;依次设置的第一缓存腔体、第一镀膜腔体和第二缓存腔体,所述第一镀膜腔体中设有TCO镀膜源,用于对所述载板上的待镀件进行TCO镀膜处理;水汽分压监测装置,用于监测所述TCO镀膜处理中所述第一镀膜腔体中的水汽分压;及至少一个等离子体刻蚀清洗装置,所述等离子体刻蚀清洗装置设于所述第一缓存腔体及所述第二缓存腔体中的至少一个腔体中,用于当所述水汽分压监测装置监测到的水汽分压大于5.0×e-3Pa时,对所述载板进行离子刻蚀清洗,以使所述第一镀膜腔体内的水汽分压不大于5.0e-3Pa。
- 如权利要求10所述的TCO镀膜设备,其特征在于,所述TCO镀膜设备还包括第二镀膜腔体和隔离腔体,所述第二镀膜腔体设于所述第一镀膜腔体和所述第二缓存腔体之间,所述隔离腔体设于所述第一镀膜腔体和第二镀膜腔体之间;所述第一镀膜腔体和第二镀膜腔体中的一个腔体的上部设有TCO镀膜源,另一个腔体的下部设有TCO镀膜源,以分别对所述待镀件的两表面进行TCO镀膜处理;所述水汽分压监测装置有两个,分别用于监测所述TCO镀膜处理中所述第一镀膜腔体和所述第二镀膜腔体中的水汽分压;所述等离子体刻蚀清洗装置设于所述第一缓存腔体、所述隔离腔体及所述第二缓存腔体中的至少一个腔体中,用于当所述水汽分压监测装置监测到的水汽分压大于5.0×e-3Pa时,对所述载板进行离子刻蚀清洗,以使所述第一镀膜腔和所述第二镀膜腔内的水汽分压不大于5.0e-3Pa。
- 如权利要求11所述的TCO镀膜设备,其特征在于,所述等离子体刻蚀清洗装置有两个,其中一个所述等离子体刻蚀清洗装置位于所述第一缓存腔体、所述隔离腔体及所述第二缓存腔体的任意一个腔体中的上部,另一个所述等离子体刻蚀清洗装置位于所述第一缓存腔体、所述隔离腔体及所述第二缓存腔体的任意一个腔体中的下部,以对所述载板的上下表面进行离子刻蚀清洗。
- 如权利要求10~12任一项所述的TCO镀膜设备,其特征在于,所述TCO 镀膜设备还包括进料腔体和出料腔体;所述进料腔体设于所述第一缓存腔体的上游以用于进料,所述出料腔体设于所述第二缓存腔体的下游以用于出料。
- 如权利要求10~13任一项所述的TCO镀膜设备,其特征在于,所述等离子体刻蚀清洗装置选自电子回旋加速反应器、电感耦合器、电容耦合器、双等离子体源反应器和磁增强反应离子刻蚀反应器中的一种或者多种的组合装置。
- 如权利要求10~13任一项所述的TCO镀膜设备,其特征在于,所述水汽分压监测装置选自残留气体分析仪和光谱分析仪的一种或者两种的组合装置。
- 一种太阳能电池的制备方法,其特征在于,包括如下步骤:将单晶硅片进行表面制绒及化学清洗处理,得到制绒后的单晶硅片;在所述制绒后的单晶硅片的表面形成非晶硅膜,然后形成透明导电膜,最后制备电极,得到太阳能电池;所述形成透明导电膜的步骤采用如权利要求1~9任一项所述的TCO镀膜方法进行或采用如权利要求10~15任一项所述的TCO镀膜设备进行。
- 如权利要求16所述的太阳能电池的制备方法,其特征在于,所述形成非晶硅膜的步骤包括如下步骤:先在所述制绒后的单晶硅片的上下表面分别形成本征非晶硅膜,然后在上下表面分别形成P型掺杂非晶硅薄膜和N型掺杂非晶硅薄膜。
- 如权利要求16~17任一项所述的太阳能电池的制备方法,其特征在于,所述制备电极的步骤包括如下步骤:在所述透明导电膜的表面进行银浆丝网印刷,然后于170℃~200℃下烧结处理。
- 一种太阳能电池,其特征在于,采用如权利要求16~18任一项所述的太阳能电池的制备方法制得。
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