CN117253926A - Crystalline silicon heterojunction double-sided solar cell with synergistic effect of chemical passivation and field effect passivation and preparation method thereof - Google Patents
Crystalline silicon heterojunction double-sided solar cell with synergistic effect of chemical passivation and field effect passivation and preparation method thereof Download PDFInfo
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- 230000002195 synergetic effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- 239000010409 thin film Substances 0.000 claims abstract description 25
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- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- 229910052796 boron Inorganic materials 0.000 claims abstract description 23
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000005641 tunneling Effects 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 63
- 229910052710 silicon Inorganic materials 0.000 claims description 63
- 239000010703 silicon Substances 0.000 claims description 63
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- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 20
- 238000000151 deposition Methods 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 8
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000231 atomic layer deposition Methods 0.000 claims description 7
- 239000000969 carrier Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 claims description 5
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
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- 238000000576 coating method Methods 0.000 claims description 3
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- 238000005215 recombination Methods 0.000 claims description 3
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 239000003574 free electron Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- 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 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000064 phosphane Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010937 tungsten Substances 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
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- 239000010949 copper Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000003376 silicon Chemical class 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for 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
- H01L31/04—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 at least one potential-jump barrier or surface barrier
- 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 at least one potential-jump barrier or surface barrier 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 at least one potential-jump barrier or surface barrier 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 at least one potential-jump barrier or surface barrier 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 or HIT® solar cells; solar cells
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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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
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- 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 System
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- 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
- H01L31/208—Particular post-treatment of the devices, e.g. annealing, short-circuit elimination
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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
Abstract
A crystalline silicon heterojunction double-sided solar cell with synergistic effect of chemical passivation and field effect passivation and a preparation method thereof are provided, wherein the crystalline silicon heterojunction double-sided solar cell comprises an n-type monocrystalline silicon or p-type monocrystalline silicon substrate, a boron doped hydrogenated nano silicon thin film layer which is positioned on one side of the substrate and is used as an emitter layer or a window electrode layer, an aluminum oxide thin layer, a boron doped hydrogenated nano silicon thin film layer, a transparent conductive layer and a metal electrode which are sequentially arranged on the substrate from inside to outside, a phosphorus doped hydrogenated nano silicon thin film layer which is positioned on the other side of the substrate and is used as a window layer or an emitter layer, and a hydrogenated amorphous silicon oxynitride thin layer, a phosphorus doped hydrogenated nano silicon thin film layer, a transparent conductive layer and a metal electrode which are sequentially arranged on the substrate from inside to outside. According to the invention, the oxide thin layer with high fixed charge is adopted to play roles of the passivation layer and the tunneling layer, and the light absorption generated by the passivation layer is reduced while the passivation effect is enhanced by utilizing the composite passivation synergistic effect from two dimensions of field effect passivation of the tunneling oxide layer, chemical passivation of the tunneling oxide layer and chemical passivation of the nano silicon thin film layer.
Description
Technical Field
The invention relates to a technology in the field of solar photovoltaic cells, in particular to a crystalline silicon heterojunction double-sided solar cell with a synergistic effect of chemical passivation and field effect passivation and a preparation method thereof.
Background
In the existing crystalline silicon solar cell, the surface of a general substrate is subjected to compound passivation in two modes, namely chemical passivation, and surface state density is reduced through a saturated interface suspension bond, and hydrogen and oxygen atoms are usually taken as main materials; and secondly, field effect passivation is realized through fixed charges in the insulating layer or high charge concentration in the insulating layer. The amorphous silicon/crystalline silicon heterojunction solar cell comprises an intrinsic amorphous silicon film and a doped amorphous silicon film which are deposited on two sides of a substrate, and the structure integrates the advantages of the crystalline silicon cell and the thin film cell, has the advantages of simple structure, few process steps, low process temperature, good temperature characteristics and the like, and is one of hot spot directions for obtaining the high-efficiency solar cell. The amorphous silicon/crystalline silicon heterojunction solar cell in the current industry adopts an intrinsic hydrogenated amorphous silicon film as a passivation layer. Hydrogenated amorphous silicon has a low surface state density (-3 x 10) 10 cm -2 ) Resulting in very good chemical passivation but without fixed charge, without field effect passivation and with a thickness typically above 5nm, there is parasitic absorption. Therefore, in order to realize the synergistic effect of chemical passivation and field effect passivation on the crystalline silicon heterojunction double-sided solar cell, dielectric passivation films with fixed charges of different polarities need to be deposited on the front and back sides of the crystalline silicon textured surface, and the ideal passivation requirement is that the surface state density of the dielectric passivation film is low but the density of the fixed charges is high. The existing heterojunction solar cell with hydrogenated amorphous silicon oxynitride film as passivation layer adopts silicon oxynitride film on both sides of the cell, field effect passivation advantage caused by fixed charge is not considered, and the thickness of the adopted silicon oxynitride film exceeds 2nm, and the thickness is several under the condition of the thicknessThe tunneling effect of carriers is almost absent, only considering the chemical passivation properties of silicon oxynitride. In the existing floating junction back passivation crystalline silicon battery, a silicon substrate is in direct contact with a metal electrode, so that carrier recombination is easy to occur.
Disclosure of Invention
The invention provides a crystalline silicon heterojunction double-sided solar cell with a synergistic effect of chemical passivation and field effect passivation and a preparation method thereof, aiming at the defects in the prior art, the effect of a passivation layer and a tunneling layer is achieved by adopting an oxide thin layer with high fixed charge, the passivation effect is enhanced by utilizing the synergistic effect of composite passivation from two dimensions of the field effect passivation of the tunneling oxide layer, the chemical passivation of the tunneling oxide layer and the nano silicon thin film layer, the problem of low photo-generated carrier collection efficiency of the heterojunction cell is solved, the passivation effect of the cell is enhanced, and the light absorption generated by the passivation layer is reduced.
The invention is realized by the following technical scheme:
the invention relates to a crystalline silicon heterojunction double-sided solar cell with a synergistic effect of chemical passivation and field effect passivation, which comprises the following components: an n-type monocrystalline silicon or p-type monocrystalline silicon substrate, a boron doped hydrogenated nano silicon (nc-Si (p): H) film layer which is positioned at one side of the substrate and is used as an emitter layer or a window electrode layer, and aluminum oxide (AlO) which is sequentially arranged on the substrate from inside to outside x ) The thin layer, the boron doped hydrogenated nano silicon thin film layer, the transparent conductive layer, the metal electrode, the phosphorus doped hydrogenated nano silicon thin film layer which is positioned at the other side of the substrate and used as a window layer or an emitter layer, and hydrogenated amorphous silicon oxynitride (SiO) which is sequentially arranged on the substrate from inside to outside x N y H) a thin layer, a phosphorus doped hydrogenated nano silicon (nc-Si (n): H) thin film layer, a transparent conductive layer and a metal electrode.
The monocrystalline silicon substrate is specifically an n-type or p-type Cz monocrystalline silicon wafer or a casting monocrystalline silicon wafer, wherein the doping element of the n-type monocrystalline silicon is P, as or Sb, and the doping element of the p-type monocrystalline silicon is B, al or Ga.
The thickness of the alumina thin layer is 0.5-2nm, and the negative charge density is-5×10 12 cm -2 Magnitude, by regulating and controlling the electron concentration on the surface of siliconAnd the value and proportion of the hole concentration on the surface of the silicon are used for reducing the product of the hole concentration and the silicon, so that the difference of the surface concentration of free electrons and holes is pulled, the recombination of surface carriers is reduced, and the carriers pass through the alumina thin layer in a tunneling mode without being blocked.
The alumina thin layer adopts an Atomic Layer Deposition (ALD) method, and trimethyl aluminum (TMA) and water vapor (H) are alternately introduced 2 O) wherein the number of deposition cycles is 4-14, the process temperature is 100-400 ℃, and the chamber pressure is 0.1-10mbar.
The thickness of the hydrogenated amorphous silicon oxynitride thin layer is 0.5-2nm, and the positive charge density is between +8x10 10 —～+1×10 12 cm -2 In order of magnitude, there is also superior field effect passivation, with carriers tunneling through the hydrogenated amorphous silicon oxynitride thin layer without being blocked.
The hydrogenated amorphous silicon oxynitride thin layer is introduced with N by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method 2 、N 2 O and SiH 4 Gas preparation, wherein N 2 O flow range is 10-50sccm, N 2 O:SiH 4 The gas flow ratio is 5:3-10:3, the process temperature is 200-400 ℃, and the chamber pressure is 0.1-5mbar.
The thickness of the boron doped hydrogenated nano silicon film layer and the phosphorus doped hydrogenated nano silicon film layer is 3-20nm, and the boron doped hydrogenated nano silicon film layer and the phosphorus doped hydrogenated nano silicon film layer are prepared by plate type Very High Frequency (VHF) -PECVD deposition.
The transparent conductive layer has a thickness of 50-150nm and is made of Indium Tin Oxide (ITO), tungsten doped indium oxide (IWO), or SCOT conductive film (In) 2 O 3 :ZrO 2 :TiO 2 :Ga 2 O 3 =98.5:0.5:0.5:0.5) or aluminum doped zinc oxide (AZO) prepared by magnetron sputtering or ion reactive coating (RPD).
The metal electrode is a grid line electrode, which is prepared from Ag, au or Cu by screen printing, vacuum evaporation or electroplating.
The invention relates to a preparation method of the crystalline silicon heterojunction double-sided solar cell, which comprises the following steps:
in the step 1, the method comprises the following steps, adopts the resistivity of 0.5 to 3 Ω cm an n-type or p-type Cz single crystal silicon wafer or a cast Cz CCCCCCCCCCCCCCCCCCCCCCCCCCCCC removing a linear cutting damage layer on the surface of the silicon wafer by using alkali solution;
step 2, corroding the silicon wafer obtained in the step 1 by using KOH or NaOH alkali solution, and forming pyramid structures on the front surface and the rear surface of the silicon wafer to play a light trapping role;
step 3, the silicon wafer obtained in the step 2 is placed into ALD equipment, and a nano-thickness tunneling alumina layer is formed on one side of the silicon wafer boron doped hydrogenated nano-silicon thin film layer;
step 4, putting the silicon wafer obtained in the step 3 into plate-type VHF-PECVD, introducing silane and borane gas, and depositing a boron doped hydrogenated nano silicon film layer on the surface of the silicon wafer;
step 5, the silicon wafer obtained in the step 4 is put into PECVD equipment in a turnover way, and a tunneling silicon oxynitride layer with nanometer thickness is formed on one side of the silicon wafer phosphorus doped hydrogenated nanometer silicon film layer;
step 6, the silicon wafer obtained in the step 5 is placed in plate-type VHF-PECVD, silane and phosphane gas are introduced, and a phosphorus doped hydrogenated nano silicon film layer is deposited on the surface of the silicon wafer;
step 7, coating the silicon wafer obtained in the step 6 by magnetron sputtering or ion reaction, and respectively depositing transparent conductive layers on the front surface and the back surface of the silicon wafer;
and 8, respectively forming grid-line Ag, au or Cu electrodes on the front and back surfaces of the silicon wafer by using a screen printing, vacuum evaporation or electroplating method.
Technical effects
The invention uses the thin layer with fixed negative charge and fixed positive charge at the same time to make AlO with fixed negative charge x The thin layer repels electrons in the carriers and tunnels holes, siO with fixed positive charge x N y H thin layer repels the hole in the carrier and tunnels the electron, not only realize the field effect passivation by using the fixed charge of the H thin layer, but also realize the chemical passivation by using oxygen atoms and hydrogen atoms introduced during the deposition to saturate the dangling bond on the surface of the crystal silicon substrate; compared with the prior art, the invention is more beneficial to improving the heterojunction batteryOpen circuit voltage. Hole tunneling through AlO x Thin layer, electron tunneling through SiO x N y H thin layer, but not blocked by the thin layer, is beneficial to increasing the effective current of the heterojunction battery.
Drawings
FIG. 1 is a schematic view of a single crystal silicon substrate after texturing;
FIG. 2 is a schematic diagram of a structure of a tunneling oxide layer and a hydrogenated nano-silicon layer deposited on one side of a front surface field of a substrate;
FIG. 3 is a schematic diagram of a structure with a tunneling oxide layer and a hydrogenated nano-silicon layer deposited on the emitter side of the substrate;
FIG. 4 is a schematic view of a structure for depositing transparent conductive layers on both sides of a cell;
FIG. 5 illustrates a double-sided heterojunction solar cell formed by preparing metal gate line electrodes on both sides of the cell;
in the figure: the semiconductor device comprises a 1 p-type or n-type monocrystalline silicon substrate, a 2 front surface field side tunneling oxide layer, a 3 front surface field side hydrogenated nano silicon layer, a 4 emitter side tunneling oxide layer, a 5 emitter side hydrogenated nano silicon layer, a 6 transparent conductive layer and a 7 metal electrode.
Detailed Description
Example 1
As shown in fig. 5, this embodiment relates to a crystalline silicon heterojunction double-sided solar cell with synergistic effect of chemical passivation and field effect passivation, comprising: an n-type monocrystalline silicon substrate 1, a hydrogenated silicon oxynitride thin layer 2, a phosphorus doped hydrogenated nano silicon thin film layer 3, a phosphorus doped hydrogenated nano silicon thin film layer, a silicon nitride oxide thin film layer and a silicon nitride oxide thin film layer, wherein the hydrogenated silicon nitride oxide thin film layer 2, the phosphorus doped hydrogenated nano silicon thin film layer 3, the phosphorus doped nano silicon thin film layer and the silicon nitride oxide thin film layer are sequentially arranged on the front surface of the substrate from inside to outside the AZO transparent conductive layer 6 and the Ag metal electrode 7 are sequentially arranged on the aluminum oxide thin layer 4, the boron doped hydrogenated nano silicon layer 5, the AZO transparent conductive layer 6 and the Ag metal electrode 7 on the back surface of the substrate from inside to outside.
As shown in fig. 1 to 4, the preparation method of the embodiment specifically includes:
and 1, adopting a monocrystalline silicon substrate. N-type Cz silicon with the crystal orientation of (100), the resistivity of 1 Ω & cm and the thickness of 150 μm is used as a battery substrate, and KOH solution with the concentration of 10-20% is used for removing the linear cutting damaged layer at the temperature of 75-100 ℃.
Step 2, preparing pyramid suede on the surface of monocrystalline silicon: and (3) texturing the n-type crystalline silicon substrate obtained in the step (1) by adopting a KOH solution with the concentration of 1% -3% and an isopropanol solution with the concentration of 3% -10%, and then carrying out standard RCA cleaning to obtain the pretreated n-type crystalline silicon substrate 1 with pyramid textured surfaces on the front and back surfaces, as shown in figure 1.
Step 3, preparing a hydrogenated silicon oxynitride thin layer on the front surface: placing the silicon wafer obtained in the step 2 into PECVD equipment, and introducing N 2 、N 2 O and SiH 4 Gas is used for depositing SiO (silicon dioxide) on the front surface of a silicon wafer through chemical reaction x N y H layer 2; wherein N is 2 O flow range is 10-50sccm, N 2 O:SiH 4 The gas flow ratio is 5:3-10:3, the process temperature is 200-500 ℃, the chamber pressure is 0.1-5mbar, and the preferable N is 2 O flow is 20sccm, N 2 O:SiH 4 The gas flow ratio is 25:9, the process temperature is 350 ℃, the chamber pressure is 0.5mbar, and the SiO is obtained x N y H thickness is 1.0nm.
Step 4, preparing a front surface phosphorus doped hydrogenated nano silicon layer: placing the silicon wafer obtained in the step 3 into a vacuum chamber of plate type VHF-PECVD, and using H under the condition that the temperature of a silicon wafer substrate is 200 DEG C 2 、SiH 4 And pH (potential of Hydrogen) 3 As a reaction gas, a phosphorus doped hydrogenated nano silicon layer 3 is grown on the surface of the hydrogenated silicon oxynitride thin layer 2, and as a window layer, the thickness is preferably 10nm, and the obtained silicon wafer and film are shown in FIG. 2. The VHF-PECVD has a very high frequency of 20-50MHz.
Step 5, preparing a back surface aluminum oxide thin layer: turning the silicon wafer obtained in the step 4 into ALD equipment, and alternately introducing TMA and H 2 O steam is used for depositing an alumina thin layer 4, the TMA cycle time is 4-14 times, the process temperature is 100-400 ℃, and the chamber pressure is 0.1-10mbar; preferably TMA is circulated 7 times at 250deg.C under a chamber pressure of 1mbar to obtain AlO x The thickness is 1.0nm.
Step 6, preparing a back surface boron doped hydrogenated nano silicon layer: placing the silicon wafer obtained in the step 5 into another vacuum chamber of plate type VHF-PECVD, and using H under the condition of 200 DEG C 2 、SiH 4 And B 2 H 6 As a reaction gasIn the body, a boron doped hydrogenated nano silicon layer 5 is grown on the surface of the aluminum oxide thin layer 4 to serve as a back surface emitter layer, and the thickness is preferably 15nm. The VHF-PECVD has a very high frequency of 20-50MHz. After steps 5 and 6, the obtained silicon wafer and film are shown in figure 3.
Step 7, preparing a transparent conductive layer: and (3) placing the silicon wafer obtained in the step (6) into a vacuum chamber of a magnetron sputtering device, and respectively depositing a transparent conductive AZO film layer (6) on the outer sides of the front surface phosphorus doped hydrogenated nano silicon layer and the back surface boron doped hydrogenated nano silicon layer by using a magnetron sputtering method, as shown in figure 4. The thickness of the AZO film layer is preferably 80nm.
Step 8, preparing a metal gate line electrode: and (3) printing a layer of low-temperature conductive silver paste on two sides of the silicon wafer obtained in the step (7) by adopting a screen printing method, and then sintering at a low temperature of preferably 250 ℃ to form good ohmic contact so as to form front and back silver grid line electrodes (7) as shown in fig. 5.
Example 2
In this example, p-type cast monocrystalline silicon was used as a substrate, a SCOT transparent conductive layer was used instead of an AZO transparent conductive layer, and a Cu metal electrode was used instead of an Ag metal electrode, as compared with example 1.
As shown in fig. 1 to 4, the preparation method of the embodiment specifically includes:
and 1, adopting a monocrystalline silicon substrate. P-type cast monocrystalline silicon with resistivity of 0.5 omega cm and thickness of 160 mu m is used as a battery substrate, and KOH solution with concentration of 10% -20% is used for removing a linear cutting damage layer at the temperature of 80 ℃.
Step 2, preparing pyramid suede on the surface of monocrystalline silicon: and (3) texturing the p-type crystalline silicon substrate obtained in the step (1) by adopting a KOH solution with the concentration of 1% -3% and an isopropanol solution with the concentration of 3% -10%, and then carrying out standard RCA cleaning to obtain the pretreated p-type crystalline silicon substrate 1 with pyramid textured surfaces on the front and back surfaces, as shown in figure 1.
Step 3, preparing a front surface aluminum oxide thin layer: placing the silicon wafer obtained in the step 2 into ALD equipment, and alternately introducing TMA and H 2 O vapor deposition of tunneling AlO x Layer 2, where TThe MA cycle number is preferably 10 times, the process temperature is 280 ℃, and the chamber pressure is 0.8mbar, so as to obtain AlO x The thickness is 1.4nm.
Step 4, preparing a front surface boron doped hydrogenated nano silicon layer: placing the silicon wafer obtained in the step 3 into a vacuum chamber of plate type VHF-PECVD, and using H under the condition of 200 ℃ as well 2 、SiH 4 And B 2 H 6 As a reaction gas, in AlO x The surface of the layer 2 is grown with a boron doped hydrogenated nano silicon layer 3 as a window layer, and the thickness is preferably 10nm. After the steps 3 and 4, the obtained silicon wafer and film are shown in figure 2.
Step 5, preparing a hydrogenated silicon oxynitride thin layer on the back surface: placing the silicon wafer obtained in the step 4 into PECVD equipment in a turned mode, and introducing N 2 、N 2 O and SiH 4 Gas is used for depositing SiO (silicon dioxide) on the back surface of the silicon wafer through chemical reaction x N y H layer 4; wherein N is 2 The O flow is preferably 20sccm, N 2 O:SiH 4 The gas flow ratio is preferably 25:9, the process temperature is 300 ℃, the chamber pressure is 0.8mbar, and SiO is obtained x N y H thickness 1.5nm.
Step 6, preparing a back surface phosphorus doped hydrogenated nano silicon layer: placing the silicon wafer obtained in the step 5 into a vacuum chamber of plate type VHF-PECVD, and using H under the condition that the temperature of a silicon wafer substrate is 200 DEG C 2 、SiH 4 And pH (potential of Hydrogen) 3 As a reaction gas, in SiO x N y The surface of the H layer 4 is grown with a phosphorus doped hydrogenated nano silicon layer 5 as a back surface emitter layer, the thickness is preferably 15nm, and the obtained silicon chip and film are shown in figure 3. The VHF-PECVD has a very high frequency of 20-50MHz.
Step 7, preparing a transparent conductive layer: and (3) placing the silicon wafer obtained in the step (6) into a vacuum chamber of a magnetron sputtering device, and respectively depositing a transparent conductive SCOT film layer (6) on the outer sides of the front boron doped hydrogenated nano silicon layer and the back phosphorus doped hydrogenated nano silicon layer by using a magnetron sputtering method, as shown in figure 4. The thickness of the SCOT film layer is preferably 60nm.
Step 8, preparing a metal gate line electrode: and (3) respectively depositing a layer of low-temperature conductive copper paste grid line on two sides of the silicon wafer obtained in the step (7) by adopting a method of combining vacuum evaporation and a mask plate, and then sintering at a low temperature of preferably 200 ℃ to form good ohmic contact, so as to form front-side and back-side copper grid line electrodes (7) as shown in fig. 5.
The crystalline silicon heterojunction double-sided solar cell with the synergistic effect of chemical passivation and field effect passivation obtained through the steps uses a monocrystalline silicon wafer as a substrate and AlO with fixed negative charge x Thin layer and fixed positive charge SiO x N y The H thin layer is a full passivation layer, the boron doped hydrogenated nano silicon layer and the phosphorus doped hydrogenated nano silicon layer are used as contact layers with the transparent conductive layer, oxygen atoms and hydrogen atom saturated surface dangling bonds are introduced into the surface of the silicon wafer, excellent passivation performance, effective carrier transmission, parasitic light absorption reduction and good contact can be achieved at the same time, and the high-efficiency heterojunction double-sided solar cell is easy to obtain.
The foregoing embodiments may be partially modified in numerous ways by those skilled in the art without departing from the principles and spirit of the invention, the scope of which is defined in the claims and not by the foregoing embodiments, and all such implementations are within the scope of the invention.
Claims (10)
1. A crystalline silicon heterojunction double-sided solar cell with synergistic effect of chemical passivation and field effect passivation, comprising: an n-type monocrystalline silicon or p-type monocrystalline silicon substrate, a boron doped hydrogenated nano silicon (nc-Si (p): H) film layer which is positioned at one side of the substrate and is used as an emitter layer or a window electrode layer, and aluminum oxide (AlO) which is sequentially arranged on the substrate from inside to outside x ) The thin layer, the boron doped hydrogenated nano silicon thin film layer, the transparent conductive layer, the metal electrode, the phosphorus doped hydrogenated nano silicon thin film layer which is positioned at the other side of the substrate and used as a window layer or an emitter layer, and hydrogenated amorphous silicon oxynitride (SiO) which is sequentially arranged on the substrate from inside to outside x N y H) a thin layer, a phosphorus doped hydrogenated nano silicon (nc-Si (n): H) thin film layer, a transparent conductive layer and a metal electrode.
2. The crystalline silicon heterojunction double-sided solar cell with synergistic effect of chemical passivation and field effect passivation according to claim 1, wherein the monocrystalline silicon substrate is specifically an n-type or p-type Cz czochralski monocrystalline silicon wafer or a cast monocrystalline silicon wafer, wherein the doping element of n-type monocrystalline silicon is P, as or Sb, and the doping element of p-type monocrystalline silicon is B, al or Ga.
3. The crystalline silicon heterojunction double-sided solar cell with synergistic effect of chemical passivation and field effect passivation as claimed in claim 1, wherein the thickness of the alumina thin layer is 0.5-2nm, and the negative charge density is-5×10 12 cm -2 The magnitude of the magnitude is reduced by regulating the numerical value and the proportion of the electron concentration on the surface of silicon and the hole concentration on the surface of silicon, so that the surface concentration difference between free electrons and holes is pulled, the surface carrier recombination is reduced, and the carriers pass through the alumina thin layer in a tunneling mode and are not blocked.
4. The crystalline silicon heterojunction double-sided solar cell with synergistic effect of chemical passivation and field effect passivation as claimed in claim 1, wherein the thin layer of alumina is alternately introduced with Trimethylaluminum (TMA) and water vapor (H) by atomic layer deposition 2 O) wherein the number of deposition cycles is 4-14, the process temperature is 100-400 ℃, and the chamber pressure is 0.1-10mbar.
5. The crystalline silicon heterojunction double-sided solar cell with synergistic effect of chemical passivation and field effect passivation as claimed in claim 1, wherein the hydrogenated amorphous silicon oxynitride thin layer has a thickness of 0.5-2nm and a positive charge density of +8x10 10 —～+1×10 12 cm -2 In order of magnitude, carriers tunnel through the thin hydrogenated amorphous silicon oxynitride layer without being blocked.
6. The crystalline silicon heterojunction double-sided solar cell with synergistic effect of chemical passivation and field effect passivation as claimed in claim 1, wherein the hydrogenated amorphous silicon oxynitride thin layer is introduced by adopting a plasma enhanced chemical vapor deposition methodN 2 、N 2 O and SiH 4 Gas preparation, wherein N 2 O flow range is 10-50sccm, N 2 O:SiH 4 The gas flow ratio is 5:3-10:3, the process temperature is 200-400 ℃, and the chamber pressure is 0.1-5mbar.
7. The crystalline silicon heterojunction double-sided solar cell with the synergistic effect of chemical passivation and field effect passivation as claimed in claim 1, wherein the thickness of the boron doped hydrogenated nano silicon thin film layer and the thickness of the phosphorus doped hydrogenated nano silicon thin film layer are 3-20nm, and the crystalline silicon heterojunction double-sided solar cell is prepared by plate type very high frequency PECVD deposition.
8. The crystalline silicon heterojunction double-sided solar cell with synergistic effect of chemical passivation and field effect passivation as claimed In claim 1, wherein the thickness of the transparent conductive layer is 50-150nm, which is made of indium tin oxide, tungsten doped indium oxide, SCOT conductive film (In 2 O 3 :ZrO 2 :TiO 2 :Ga 2 O 3 =98.5:0.5:0.5:0.5) or aluminum-doped zinc oxide, prepared by magnetron sputtering or ion reaction plating.
9. The crystalline silicon heterojunction double-sided solar cell with the synergistic effect of chemical passivation and field effect passivation according to claim 1, wherein the metal electrode is a grid line electrode, which is prepared by adopting Ag, au or Cu and adopting a screen printing, vacuum evaporation or electroplating method.
10. The crystalline silicon heterojunction double-sided solar cell of synergistic effect of chemical passivation and field effect passivation as claimed in any one of claims 1 to 9, characterized by comprising the following steps:
in the step 1, the method comprises the following steps, adopts the resistivity of 0.5 to 3 Ω cm an n-type or p-type Cz single crystal silicon wafer or a cast Cz CCCCCCCCCCCCCCCCCCCCCCCCCCCCC removing a linear cutting damage layer on the surface of the silicon wafer by using alkali solution;
step 2, corroding the silicon wafer obtained in the step 1 by using KOH or NaOH alkali solution, and forming pyramid structures on the front surface and the rear surface of the silicon wafer to play a light trapping role;
step 3, the silicon wafer obtained in the step 2 is placed into ALD equipment, and a nano-thickness tunneling alumina layer is formed on one side of the silicon wafer boron doped hydrogenated nano-silicon thin film layer;
step 4, putting the silicon wafer obtained in the step 3 into plate-type VHF-PECVD, introducing silane and borane gas, and depositing a boron doped hydrogenated nano silicon film layer on the surface of the silicon wafer;
step 5, the silicon wafer obtained in the step 4 is put into PECVD equipment in a turnover way, and a tunneling silicon oxynitride layer with nanometer thickness is formed on one side of the silicon wafer phosphorus doped hydrogenated nanometer silicon film layer;
step 6, the silicon wafer obtained in the step 5 is placed in plate-type VHF-PECVD, silane and phosphane gas are introduced, and a phosphorus doped hydrogenated nano silicon film layer is deposited on the surface of the silicon wafer;
step 7, coating the silicon wafer obtained in the step 6 by magnetron sputtering or ion reaction, and respectively depositing transparent conductive layers on the front surface and the back surface of the silicon wafer;
and 8, respectively forming grid-line Ag, au or Cu electrodes on the front and back surfaces of the silicon wafer by using a screen printing, vacuum evaporation or electroplating method.
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