CN114038932A - Single crystalline silicon solar cell with back containing silicon oxide-titanium nitride double-layer contact structure and preparation method thereof - Google Patents
Single crystalline silicon solar cell with back containing silicon oxide-titanium nitride double-layer contact structure and preparation method thereof Download PDFInfo
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- HEHINIICWNIGNO-UHFFFAOYSA-N oxosilicon;titanium Chemical compound [Ti].[Si]=O HEHINIICWNIGNO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000002161 passivation Methods 0.000 claims abstract description 83
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 59
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 41
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 38
- 239000010408 film Substances 0.000 claims description 122
- 239000000758 substrate Substances 0.000 claims description 104
- 239000007789 gas Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052709 silver Inorganic materials 0.000 claims description 21
- 239000004332 silver Substances 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010409 thin film Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims 1
- 238000005215 recombination Methods 0.000 abstract description 14
- 230000006798 recombination Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 28
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000003321 amplification Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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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
- H01L31/04—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
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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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0312—Inorganic materials including, apart from doping materials or other impurities, only AIVBIV compounds, e.g. SiC
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
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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
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Abstract
The invention provides a monocrystalline silicon solar cell with a back containing a silicon oxide-titanium nitride double-layer contact structure and a preparation method thereofxThe back passivation structure is a laminated passivation dielectric layer, and the laminated passivation dielectric layer is sequentially ultrathin SiO from inside to outsidexFilm and TiNyThe film, the back passivation structure outside is Al back electrode; the passivation contact layer of the back passivation contact monocrystalline silicon solar cell is positioned on the back of the cell and comprises ultrathin loose SiOxLayer and TiNyA film. SiO in the passivation structurexPrepared by nitric acid oxidation, the passivationTiN in structureyThe film is prepared by direct current magnetron sputtering; according to the invention, the passivation contact structure is introduced into the back surface of the cell, so that good full-area passivation of the back surface can be realized, the back surface recombination is reduced, the open-circuit voltage of the solar cell is improved, and the purpose of improving the photoelectric conversion efficiency is achieved.
Description
Technical Field
The invention relates to research and application of an advanced photovoltaic material in a novel photovoltaic device, in particular to a novel photovoltaic device with SiOx/TiNyPhotovoltaic device with heterojunction structure and preparation method thereof, 0<x<2，y<The method is applied to the technical fields of preparation technology of high-efficiency crystalline silicon solar cells, carrier transmission performance and crystalline silicon passivation contact composite material science.
Background
Since the first valuable crystalline silicon-based solar cell was manufactured by Bell laboratories in 1954, more and more researchers have tried to improve the power conversion efficiency of different types of solar cells, PCE, power conversion efficiency. Researches find that the third-generation solar cell has the potential of breaking through the Shockley-Queisser limit. At present, an asymmetric photovoltaic device with a contact heterojunction structure passivated at two ends is a mainstream direction of current research and manufacturing as an advanced process. Wherein, the ITO/a-SiO is formed by indium tin oxide film/indium-containing amorphous silicon oxide/n-type siliconxA novel semiconductor quasi-insulator semiconductor (SQIS) asymmetric heterojunction solar cell composed of an (In)/n-Si multi-junction material has attracted great interest due to the simple manufacturing process and low cost.
However, in the current experiment, the open circuit voltage of the novel SQIS device is difficult to exceed 0.6V. Calculating formula (pFF) according to the pseudofill factor, and assuming that the ideality factor is unchanged, the low V of the SQIS deviceocIs the primary factor that limits PCE. The 2 most important factors analyzed to affect the open circuit voltage of the device are the built-in potential and the passivated contacts. The built-in potential is due to the work function difference originating from the material, such as ITO/n-Si, whose intrinsic properties determine the open circuit voltage. Passivation properties can affect the recombination probability of minority carriers, for example, in AL-BSF, since metal can cause a high density of electronic states at the silicon bandgap, direct contact between metal and silicon can result at the metal-silicon interfaceRecombination losses of photo-generated electrons and holes result in recombination losses of the high efficiency crystalline silicon (c-Si) solar cell of more than 50%. Although annealing slows down Shockley-Read-hall (srh) recombination and reduces contact resistance. However, heavy doping induces photoelectric energy loss, especially auger recombination, band gap narrowing, and free carrier absorption, which limit device performance.
Therefore, the open circuit voltage of the device needs to be improved from this aspect, and the built-in potential needs to be improved to solve the problem of passivation contact. Therefore, the need to find a back passivation contact material with low work function, good passivation contact effect, simple process and low preparation cost for the sqs device is a key for improving the open-circuit voltage, and becomes a technical problem to be solved urgently.
Disclosure of Invention
The invention provides a monocrystalline silicon solar cell with a back containing a silicon oxide-titanium nitride double-layer contact structure and a preparation method thereof based on the existing SQIS device structure, a laminated passivation dielectric layer of a back passivation structure, and the laminated passivation dielectric layer is made of ultrathin SiOxFilm and TiNyFilm structure, the back of the single crystal silicon solar cell is covered with SiO in sequencexFilm and TiNyA film. According to the invention, the surface recombination rate of the back of the solar cell can be reduced through the back passivation contact structure, the minority carrier lifetime of the crystalline silicon cell is prolonged, the open-circuit voltage of the solar cell is increased, and the purpose of improving the photoelectric conversion efficiency is further achieved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a single crystal silicon solar cell with a back containing a silicon oxide-titanium nitride double-layer contact structure comprises an n-type Si substrate; the front surface of the n-type Si substrate is sequentially provided with ultrathin a-SiOx(In) layer, ITO film, front silver electrode, front aluminum electrode, wherein 0<x<2; a back passivation structure is arranged on the back of the n-type Si substrate, the back passivation structure is a laminated passivation dielectric layer, and the laminated passivation dielectric layer is sequentially ultrathin SiO from inside to outsidexFilm and TiNyFilm of y wherein<TiN of the back passivation structureyThe outside of the film is AlA back electrode.
Preferably, the ultra-thin a-SiOx(In) layer, ultrathin SiOxFilm and TiNyThe film is a uniform and compact film material.
Preferably, the back side passivation structure belongs to a back side surface passivation structure.
Preferably, the monocrystalline silicon solar cell with the back containing the silicon oxide-titanium nitride double-layer contact structure has ITO/a-SiOx(In)/n-Si/SiOx/TiNyAnd (5) structure. With SiOx/TiNyA structural heterojunction.
Preferably, ultra-thin a-SiOx(In) layer or ultrathin SiOxThe thickness of the film is not more than 2.0 nm.
Preferably, the ITO film has a thickness of 80nm, and TiNyThe thickness of the film is not less than 300nm, the thickness of the front silver electrode or the front aluminum electrode is not more than 500nm, and the thickness of the Al back electrode is not more than 500 nm.
The invention relates to a preparation method of a monocrystalline silicon solar cell with a back containing a silicon oxide-titanium nitride double-layer contact structure, which comprises the following steps:
step 1: cleaning a silicon wafer substrate by using an RCA (Rolling circle amplification) process, and drying by using nitrogen to obtain a pretreated n-type Si substrate;
step 2: placing the n-type Si substrate in HF solution at 120 deg.C and mass concentration of 68% or more, and generating ultrathin SiO with thickness of 1.2-1.5nm on both side surfaces of the n-type Si substrate after at least 10 minxA film;
and step 3: taking out and combining ultrathin SiOxRemoving SiO on one surface of an n-type Si substrate by using HF solution with mass percentage concentration not less than 5%xA thin film formed by removing SiO from the front surface of the n-type Si substratexFilm, ultra-thin SiO remaining on the backside of n-type Si substratexA film;
and 4, step 4: will remove SiOxPlacing the n-type Si substrate of the film on a sample holder in a radio frequency magnetron sputtering vacuum chamber, exposing the front surface of the n-type Si substrate in the radio frequency magnetron sputtering vacuum chamber, and maintaining the background vacuum degree of the vacuum chamber at not higher than 3 × 10-4Pa；
And 5: introducing Ar gas into a radio frequency magnetron sputtering vacuum chamber, keeping the gas flow of the Ar gas at 40sccm, adjusting the pressure to the working pressure of not higher than 0.5Pa after glow starting, preparing an ITO film with the thickness of 80nm at room temperature, and forming ultrathin a-SiO with the thickness of not more than 2.0nm between the ITO film and the front surface of an n-type Si substrate in the process of preparing the ITO filmxAn (In) layer as an intermediate connection layer for forming ITO/a-SiOx(In)/n-Si/SiOxThe composite structure device of (1);
step 6: mixing ITO/a-SiOx(In)/n-Si/SiOxThe composite structure device is placed on a sample rack in a direct current magnetron sputtering vacuum chamber, and the back of the n-type Si substrate is combined with the ultrathin SiOxExposing the film in a DC magnetron sputtering vacuum chamber to maintain the background vacuum degree at not higher than 3 × 10-4Pa；
And 7: introducing N into a direct current magnetron sputtering vacuum chamber2Qi, maintaining N2The gas flow of the gas is 40sccm, the pressure is adjusted to the working pressure not higher than 0.5Pa after the glow is started, and the pressure is adjusted to the ultra-thin SiO at room temperaturexPreparing TiN with thickness not less than 300nm on filmyA film;
and 8: using a mask to evaporate and prepare patterned front silver electrodes with the thickness not more than 500nm and front aluminum electrodes with the thickness not more than 500nm on the surface of the ITO film as grid line electrodes, wherein the front aluminum electrodes are fixedly connected with the ITO film through the front silver electrodes to form a front composite electrode structure;
and step 9: on TiNyAnd evaporating the surface of the film to prepare an Al back electrode with the thickness not higher than 500nm, thereby obtaining the monocrystalline silicon solar cell device with the back containing the silicon oxide-titanium nitride double-layer contact structure.
Preferably, the n-type Si substrate is an n-type monocrystalline silicon wafer.
The invention relates to a preparation method of a monocrystalline silicon solar cell with a back containing a silicon oxide-titanium nitride double-layer contact structure, which comprises the following steps:
the method comprises the following steps: cleaning a silicon wafer substrate by using an RCA (Rolling circle amplification) process, and drying by using nitrogen to obtain a pretreated n-type Si substrate;
step two: placing the n-type Si substrate in HF solution at 120 deg.C and mass concentration of 68% or more, and generating ultrathin SiO with thickness of 1.2-1.5nm on both side surfaces of the n-type Si substrate after at least 10 minxA film;
step three: bonding two surfaces with ultrathin SiOxPlacing the n-type Si substrate of the film on a sample holder in a DC magnetron sputtering vacuum chamber, and bonding the back surface of the n-type Si substrate with one side surface of the n-type Si substrate as the back surfacexExposing the film in a DC magnetron sputtering vacuum chamber to maintain the background vacuum degree at not higher than 3 × 10-4Pa；
Step IV: introducing N into a direct current magnetron sputtering vacuum chamber2Qi, maintaining N2The gas flow of the gas is not less than 40sccm, the pressure is adjusted to the working pressure not higher than 0.5Pa after the glow is started, and the ultrathin SiO on the back surface of the n-type Si substrate is arranged at room temperaturexPreparing TiN with thickness not less than 300nm on filmyA film;
step five: taking out the combined TiNyRemoving SiO on the front surface of an n-type Si substrate by using HF solution with the mass percentage concentration of not less than 5%xA thin film formed by removing SiO from the front surface of the n-type Si substratexThe rear part is exposed;
step (c): removing SiO from the front surfacexThe n-type Si substrate device is placed on a sample frame in a radio frequency magnetron sputtering vacuum chamber, so that the front surface of the n-type Si substrate is exposed in the radio frequency magnetron sputtering vacuum chamber, and the background vacuum degree of the vacuum chamber is kept to be not higher than 3 multiplied by 10-4Pa；
Step (c): introducing Ar gas into a radio frequency magnetron sputtering vacuum chamber, keeping the gas flow of the Ar gas at 40sccm, adjusting the pressure to the working pressure of not higher than 0.5Pa after glow starting, preparing an ITO film with the thickness of 80nm at room temperature, and forming ultrathin a-SiO with the thickness of not more than 2.0nm between the ITO film and the front surface of an n-type Si substrate in the process of preparing the ITO filmxAn (In) layer as an intermediate connection layer for forming ITO/a-SiOx(In)/n-Si/SiOx/TiNyThe composite structure device of (1);
step (v): using a mask to evaporate and prepare patterned front silver electrodes with the thickness not more than 500nm and front aluminum electrodes with the thickness not more than 500nm on the surface of the ITO film as grid line electrodes, wherein the front aluminum electrodes are fixedly connected with the ITO film through the front silver electrodes to form a front composite electrode structure;
step ninthly: on TiNyAnd evaporating the surface of the film to prepare an Al back electrode with the thickness not higher than 500nm, thereby obtaining the monocrystalline silicon solar cell device with the back containing the silicon oxide-titanium nitride double-layer contact structure.
Preferably, the n-type Si substrate is an n-type monocrystalline silicon wafer.
Compared with the prior art, the technical scheme of the invention has the following obvious prominent substantive characteristics and obvious advantages:
1. according to the invention, the surface recombination rate of the back of the solar cell can be reduced through the back passivation contact structure, the minority carrier lifetime of the crystalline silicon cell is prolonged, and the purpose of improving the photoelectric conversion efficiency is further achieved;
2. the back passivation contact material with low work function, good passivation contact effect, simple process and low preparation cost is developed, the passivation contact connection of the device function layer is realized, the built-in potential is improved, the SQIS device can improve the open-circuit voltage, the conversion efficiency and the current density are improved, and the performance of the monocrystalline silicon solar cell is improved.
Drawings
Fig. 1 is a schematic structural view of a single crystalline silicon solar cell according to a preferred embodiment of the present invention.
FIG. 2 is a diagram of the measured minority carrier lifetime after the first step of the present invention.
FIG. 3 is a view showing TiN obtained by performing step 3 on the other surface after step 3 in the second embodiment of the present inventiony/a-SiOx/n-Si/a-SiOx/TiNyStructure, and minority carrier lifetime measured by WT-2000.
Fig. 4 is an energy band diagram of a photovoltaic device with the structure of fig. 1 obtained through AFORS-HET software simulation according to an embodiment of the present invention.
Fig. 5 is a comparison graph of J-V curves and conversion efficiencies obtained by simulating the presence or absence of a stacked passivation dielectric layer in a photovoltaic device with the structure of fig. 1 through AFORS-HET software according to an embodiment of the present invention.
Fig. 6 is a graph showing EQE curves and integrated current density contrasts of the photovoltaic device with the structure of fig. 1 without the stacked passivation dielectric layer simulated by AFORS-HET software according to an embodiment of the present invention.
Detailed Description
As shown in fig. 1, taking an n-type single crystalline silicon solar cell as an example, the invention is implemented by combining the following modes:
example one
In the present embodiment, referring to fig. 1, a single crystalline silicon solar cell having a silicon oxide-titanium nitride double layer contact structure on the back side includes an n-type Si substrate 5; the front surface of the n-type Si substrate 5 is provided with ultrathin a-SiO sequentially and outwardsxAn (In) layer 4, an ITO film 3, a front silver electrode 2 and a front aluminum electrode 1, wherein 0<x<2; a back passivation structure is arranged on the back of the n-type Si substrate 5, the back passivation structure is a laminated passivation dielectric layer, and the laminated passivation dielectric layer is sequentially ultrathin SiO from inside to outsidex Film 6 and TiNy Film 7 of y<TiN of the back passivation structureyAn Al back electrode 8 is arranged outside the film 7.
In this embodiment, referring to fig. 1, a method for manufacturing a single crystal silicon solar cell with a back side containing a silicon oxide-titanium nitride double-layer contact structure includes the following steps:
the method comprises the following steps: cleaning a monocrystalline silicon wafer substrate by using an RCA process, and drying by blowing nitrogen to obtain a pretreated n-type Si substrate 5;
step two: placing the n-type Si substrate 5 in HF solution at 120 deg.C and 68% by mass concentration, and after 10 minutes, forming ultrathin SiO with thickness of 1.2-1.5nm on both side surfaces of the n-type Si substrate 5xA film 6;
step three: bonding two surfaces with ultrathin SiOxAn n-type Si substrate 5 of the thin film 6 is placed on a sample holder in a DC magnetron sputtering vacuum chamber, one surface of the n-type Si substrate 5 is used as a back surface, and the back surface of the n-type Si substrate 5 is bonded with ultrathin SiOxThe film 6 is exposed in a DC magnetron sputtering vacuum chamber, and the background vacuum degree is kept at 3 x 10-4Pa；
Step IV: introducing N into a direct current magnetron sputtering vacuum chamber2Qi, maintaining N2The gas flow rate of the gas was 40sccm, the pressure was adjusted to 0.5Pa after the glow was started, and the ultra-thin SiO film was formed on the back surface of the n-type Si substrate 5 at room temperaturexPreparing TiN with the thickness of 300nm on the film 6yA film 7;
step five: taking out the combined TiNyAn n-type silicon wafer substrate 5 of the thin film 7, and removing SiO on the front surface of the n-type Si substrate 5 by using HF solution with the mass percentage concentration of 5%xA thin film formed by removing SiO from the front surface of the n-type Si substrate 5xThe rear part is exposed;
step (c): removing SiO from the front surfacexThe n-type Si substrate 5 device is placed on a sample frame in a radio frequency magnetron sputtering vacuum chamber, the front surface of the n-type Si substrate 5 is exposed in the radio frequency magnetron sputtering vacuum chamber, and the background vacuum degree of the vacuum chamber is kept at 3 multiplied by 10-4Pa；
Step (c): introducing Ar gas into a radio frequency magnetron sputtering vacuum chamber, keeping the gas flow of the Ar gas at 40sccm, adjusting the pressure to 0.5Pa after glow starting, preparing an ITO film 3 with the thickness of 80nm at room temperature, and forming ultrathin a-SiO with the thickness of 2.0nm between the ITO film 3 and the front surface of an n-type Si substrate 5 in the process of preparing the ITO film 3x(In) layer 4 as an intermediate connection layer for forming ITO/a-SiOx(In)/n-Si/SiOx/TiNyThe composite structure device of (1);
step (v): using a mask to evaporate and prepare a patterned front silver electrode 2 with the thickness of 500nm and a patterned front aluminum electrode 1 with the thickness of 500nm on the surface of the ITO film 3 to serve as a grid line electrode, wherein the front aluminum electrode 1 is fixedly connected with the ITO film 3 through the front silver electrode 2 to form a front composite electrode structure;
step ninthly: on TiNyAnd evaporating the surface of the film 7 to prepare an Al back electrode 8 with the thickness of 500nm, thereby obtaining the monocrystalline silicon solar cell device with the back containing the silicon oxide-titanium nitride double-layer contact structure.
The single crystal silicon solar cell device with the back containing the silicon oxide-titanium nitride double-layer contact structure has a back passivation contact structureThe monocrystalline silicon solar cell comprises an n-type Si substrate 5, wherein a-SiO is sequentially arranged outwards on the front surface of the n-type Si substratexAn (In) layer 4, an ITO film 3, a front silver electrode 2 and a front aluminum electrode 1, wherein a back passivation structure is arranged on the back of the Si substrate, the back passivation structure is a laminated passivation dielectric layer, and the laminated passivation dielectric layer is sequentially ultrathin SiO from inside to outsidexFilm 6 and TiNyAnd (7) a film. The SiOxFilm and TiNyThe film is a uniform and compact film material. The back passivation structure belongs to a back surface passivation structure. And an Al back electrode 8 is arranged outside the back passivation structure.
Fig. 4 is an energy band diagram of the single crystal silicon solar cell device with the structure of the embodiment obtained by simulation of AFORS-HET software in the embodiment. Due to the work function difference between n-Si and ITO, a p-type inversion layer with an upward energy band bend appears on the n-Si surface, thereby generating a p-n-like junction. Under the illumination, an n-Si matrix generates electron-hole pairs, under the action of an internal electric field, photo-generated holes are collected by ITO through a tunneling-like compound mechanism, and photo-generated electrons are collected by TiN after passing through ultrathin silicon oxideyAnd (6) collecting. Meanwhile, since n-Si and SiOx/TiNyThe work function difference at the interface between them, a schottky barrier and a large valence band offset, Δ Ev ═ 2.28Ev, are formed at the interface, which effectively blocks the transport of holes and reduces the recombination of electrons. Therefore, the laminated passivation dielectric layer can play the roles of interface passivation, electron transmission and hole blocking.
Fig. 5 is a comparison graph of J-V curves and conversion efficiencies obtained by simulating the presence or absence of a stacked passivation dielectric layer in the single crystal silicon solar cell device with the structure of the present embodiment through AFORS-HET software in the present embodiment, and it can be seen from fig. 5 that after the stacked passivation layer is added to the squis device, the open-circuit voltage is increased from original 578.6mV to 744.1mV, and the photoelectric conversion efficiency is relatively increased by 30.65%. Fig. 6 is a comparison graph of the EQE curve and the integrated current density of the single crystal silicon solar cell device with the structure of the present embodiment, which is simulated by AFORS-HET software according to the present embodiment, and it can be seen from fig. 6 that the external quantum efficiency is obviously increased in the near infrared part after the stacked passivation dielectric layer is added. While according to the integral current formula JseQ ^ F (λ) EQE (λ) d λ, the increase in long-band external quantum efficiency resulting in an integrated current from 32.39mA/cm2Increased to 35.24mA/cm2For the most important reason. The back passivation contact structure reduces the surface recombination rate of the back of the solar cell, prolongs the minority carrier lifetime of the crystalline silicon cell, and further achieves the purpose of improving the photoelectric conversion efficiency.
Example two
In the present embodiment, referring to fig. 1, a single crystalline silicon solar cell having a silicon oxide-titanium nitride double layer contact structure on the back side includes an n-type Si substrate 5; the front surface of the n-type Si substrate 5 is provided with ultrathin a-SiO sequentially and outwardsxAn (In) layer 4, an ITO film 3, a front silver electrode 2 and a front aluminum electrode 1, wherein 0<x<2; a back passivation structure is arranged on the back of the n-type Si substrate 5, the back passivation structure is a laminated passivation dielectric layer, and the laminated passivation dielectric layer is sequentially ultrathin SiO from inside to outsidexFilm 6 and TiNyFilm 7 of y<TiN of the back passivation structureyAn Al back electrode 8 is arranged outside the film 7.
In this embodiment, referring to fig. 1, a method for manufacturing a single crystal silicon solar cell with a back side containing a silicon oxide-titanium nitride double-layer contact structure includes the following steps:
step 1: cleaning a monocrystalline silicon wafer substrate by using an RCA process, and drying by blowing nitrogen to obtain a pretreated n-type Si substrate 5;
step 2: placing the n-type Si substrate 5 in HF solution with the concentration of 68% by mass at 120 ℃, and generating ultrathin SiO with the thickness of 1.2-1.5nm on the two side surfaces of the n-type Si substrate 5 after 10 minutesxA film 6;
and step 3: taking out and combining ultrathin SiOxAn n-type silicon wafer substrate 5 of the thin film 6, and removing SiO on one surface of the n-type Si substrate 5 by using HF solution with the mass percentage concentration of 5%xA thin film formed by removing SiO from the front surface of the n-type Si substrate 5xFilm, ultra-thin SiO remaining on the backside of the n-type Si substrate 5xA film 6;
and 4, step 4: will remove SiOxThe thin film n-type Si substrate 5 is placed on a sample holder in a radio frequency magnetron sputtering vacuum chamberThe front surface of the n-type Si substrate 5 is exposed in a radio frequency magnetron sputtering vacuum chamber, and the background vacuum degree of the vacuum chamber is kept at 3 x 10-4Pa；
And 5: introducing Ar gas into a radio frequency magnetron sputtering vacuum chamber, keeping the gas flow of the Ar gas at 40sccm, adjusting the pressure to 0.5Pa after glow starting, preparing an ITO film 3 with the thickness of 80nm at room temperature, and forming ultrathin a-SiO with the thickness of 2.0nm between the ITO film 3 and the front surface of an n-type Si substrate 5 in the process of preparing the ITO film 3x(In) layer 4 as an intermediate connection layer for forming ITO/a-SiOx(In)/n-Si/SiOxThe composite structure device of (1);
step 6: mixing ITO/a-SiOx(In)/n-Si/SiOxThe device with the composite structure is placed on a sample rack in a direct current magnetron sputtering vacuum chamber, and the back of the n-type Si substrate 5 is combined with the ultrathin SiOxThe film 6 is exposed in a DC magnetron sputtering vacuum chamber, and the background vacuum degree is kept at 3 x 10-4Pa；
And 7: introducing N into a direct current magnetron sputtering vacuum chamber2Qi, maintaining N2The gas flow of the gas is 40sccm, the pressure is adjusted to 0.5Pa after the glow is started, and the pressure is kept at the ultra-thin SiO film at room temperaturexPreparing TiN with the thickness of 300nm on the film 6yA film 7;
and 8: using a mask to evaporate and prepare a patterned front silver electrode 2 with the thickness of 500nm and a patterned front aluminum electrode 1 with the thickness of 500nm on the surface of the ITO film 3 to serve as a grid line electrode, wherein the front aluminum electrode 1 is fixedly connected with the ITO film 3 through the front silver electrode 2 to form a front composite electrode structure;
and step 9: on TiNyAnd evaporating the surface of the film 7 to prepare an Al back electrode 8 with the thickness of 500nm, thereby obtaining the monocrystalline silicon solar cell device with the back containing the silicon oxide-titanium nitride double-layer contact structure.
The single crystal silicon solar cell device with the double-layer contact structure of silicon oxide-titanium nitride in the back part of the embodiment has a single crystal silicon solar cell with a back passivation contact structure, and comprises an n-type Si substrate 5, wherein a-SiO is sequentially arranged outwards on the front surface of the n-type Si substrate 5x(In) layer 4, ITO film 3, front silver electrode2. A front aluminum electrode 1, a back passivation structure arranged on the back of the Si substrate, a laminated passivation dielectric layer as the back passivation structure, and ultrathin SiO layers as the laminated passivation dielectric layer from inside to outsidexFilm 6 and TiNyAnd (7) a film. The SiOxFilm and TiNyThe film is a uniform and compact film material. The back passivation structure belongs to a back surface passivation structure. And an Al back electrode 8 is arranged outside the back passivation structure. Fig. 2 is a minority carrier lifetime graph measured after step 1 in this embodiment. FIG. 3 shows the TiN obtained by performing step 3 on the other surface after step 3 in the second embodimenty/a-SiOx/n-Si/a-SiOx/TiNyStructure, and minority carrier lifetime measured by WT-2000. The carrier lifetime of crystalline silicon is characterized by its effective lifetime τeffInfluence of (2) factor in the in vivo recombination lifetime τbulkAnd surface recombination velocity SeffAnd is usually at 1/τeff＝1/τbulk+2Seffthe/W approximation is described, where W is the crystalline silicon thickness. Based on the above relationship and the experimental data of fig. 2 and 3, it can be calculated that the surface recombination rate is reduced to about 1/10 after the n-type Si substrate is added with the stacked passivation dielectric layer. The back passivation contact structure reduces the surface recombination rate of the back of the solar cell, prolongs the minority carrier lifetime of the crystalline silicon cell, increases the open-circuit voltage of the solar cell, and further achieves the purpose of improving the photoelectric conversion efficiency.
In summary, the single crystal silicon solar cell with the silicon oxide-titanium nitride double-layer contact structure on the back of the above embodiment takes the n-type Si substrate 5 as the base, and the front of the n-type Si substrate is sequentially provided with the ultrathin a-SiO layer outwardsx(In) layer 4, ITO film 3, front silver electrode 2, front aluminum electrode 1, 0<x<2, a back passivation structure is arranged on the back of the n-type Si substrate, the back passivation structure is a laminated passivation dielectric layer, and the laminated passivation dielectric layer is sequentially ultrathin SiO from inside to outsidexFilm 6 and TiNyFilm 7, y<1, an Al back electrode 8 is arranged outside the back passivation structure; the passivation contact layer of the back passivation contact monocrystalline silicon solar cell is positioned on the back of the cell and comprises ultrathin SiOxLayer and TiNyA film. The passivation junctionSiO in the structurexPreparation by nitric acid oxidation of SiOxThe thickness of the film is 1-1.5nm, and TiN in the passivation structureyThe film is prepared by a direct current magnetron sputtering technology, and TiNyThe thickness of the film is not higher than 300 nm; according to the embodiment of the invention, the passivation contact structure is introduced into the back surface of the cell, so that good full-area passivation of the back surface can be realized, the back surface recombination is reduced, the open-circuit voltage of the solar cell is improved, and the purpose of improving the photoelectric conversion efficiency is achieved.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, so long as the invention is consistent with the purpose of the present invention, and the invention shall fall within the protection scope of the present invention without departing from the invention.
Claims (10)
1. A single crystal silicon solar cell with a back containing a silicon oxide-titanium nitride double-layer contact structure is characterized in that: comprises an n-type Si substrate (5); the front surface of the n-type Si substrate (5) is sequentially provided with ultrathin a-SiOxAn (In) layer (4), an ITO film (3), a front silver electrode (2) and a front aluminum electrode (1), wherein 0<x<2; a back passivation structure is arranged on the back of the n-type Si substrate (5), the back passivation structure is a laminated passivation dielectric layer, and the laminated passivation dielectric layer is sequentially ultrathin SiO from inside to outsidexFilm (6) and TiNyA film (7) wherein y<TiN of the back passivation structureyAn Al back electrode (8) is arranged outside the film (7).
2. The single crystal silicon solar cell with the back side containing a silicon oxide-titanium nitride double layer contact structure as claimed in claim 1, wherein: the ultra-thin a-SiOx(In) layer (4), ultra-thin SiOxFilm (6) and TiNyThe film (7) is a uniform and dense film material.
3. The single crystal silicon solar cell with the back side containing a silicon oxide-titanium nitride double layer contact structure as claimed in claim 1, wherein: the back passivation structure belongs to a back surface passivation structure.
4. The single crystal silicon solar cell with the back side containing a silicon oxide-titanium nitride double layer contact structure as claimed in claim 1, wherein: with ITO/a-SiOx(In)/n-Si/SiOx/TiNyAnd (5) structure.
5. The single crystal silicon solar cell with the back side containing a silicon oxide-titanium nitride double layer contact structure as claimed in claim 1, wherein: ultra-thin a-SiOx(In) layer (4) or ultra-thin SiOxThe thickness of the film (6) is not more than 2.0 nm.
6. The single crystal silicon solar cell with the back side containing a silicon oxide-titanium nitride double layer contact structure as claimed in claim 1, wherein: ITO film (3) thickness 80nm, TiNyThe thickness of the film (7) is not less than 300nm, the thickness of the front silver electrode (2) or the front aluminum electrode (1) is not more than 500nm, and the thickness of the Al back electrode (8) is not more than 500 nm.
7. A method for preparing a monocrystalline silicon solar cell with a silicon oxide-titanium nitride double-layer contact structure on the back side as claimed in any one of claims 1 to 6, characterized in that the method comprises the following steps:
step 1: cleaning a silicon wafer substrate by using an RCA (radio corporation of America) process, and drying the silicon wafer substrate by using nitrogen to obtain a pretreated n-type Si substrate (5);
step 2: placing the n-type Si substrate (5) in HF solution with the temperature of 120 ℃ and the mass percent concentration of not less than 68%, and generating ultrathin SiO with the thickness of 1.2-1.5nm on the two side surfaces of the n-type Si substrate (5) after at least 10 minutesxA film (6);
and step 3: taking out and combining ultrathin SiOxAn n-type silicon wafer substrate (5) of the film (6) is prepared by removing SiO on one surface of the n-type Si substrate (5) by using HF solution with mass percentage concentration not less than 5%xA thin film formed by removing SiO from the front surface of the n-type Si substrate (5)xThin film, retained n-typeUltra-thin SiO on the back of a Si substrate (5)xA film (6);
and 4, step 4: will remove SiOxPlacing the n-type Si substrate (5) of the film on a sample holder in a radio frequency magnetron sputtering vacuum chamber, exposing the front surface of the n-type Si substrate (5) in the radio frequency magnetron sputtering vacuum chamber, and maintaining the background vacuum degree of the vacuum chamber at not more than 3 x 10-4Pa；
And 5: introducing Ar gas into a radio frequency magnetron sputtering vacuum chamber, keeping the gas flow of the Ar gas at 40sccm, adjusting the pressure to the working pressure of not higher than 0.5Pa after glow starting, preparing an ITO film (3) with the thickness of about 80nm at room temperature, and forming ultrathin a-SiO with the thickness of not more than 2.0nm between the ITO film (3) and the front surface of an n-type Si substrate (5) in the process of preparing the ITO film (3)xAn (In) layer (4) as an intermediate connection layer for forming ITO/a-SiOx(In)/n-Si/SiOxThe composite structure device of (1);
step 6: mixing ITO/a-SiOx(In)/n-Si/SiOxThe composite structure device is placed on a sample rack in a direct current magnetron sputtering vacuum chamber, and the back of the n-type Si substrate (5) is combined with the ultrathin SiOxThe film (6) is exposed in a DC magnetron sputtering vacuum chamber, and the background vacuum degree is kept not higher than 3 x 10-4Pa；
And 7: introducing N into a direct current magnetron sputtering vacuum chamber2Qi, maintaining N2The gas flow of the gas is 40sccm, the pressure is adjusted to the working pressure not higher than 0.5Pa after the glow is started, and the pressure is adjusted to the ultra-thin SiO at room temperaturexPreparing TiN with the thickness of not less than 300nm on the film (6)yA film (7);
and 8: using a mask to evaporate and prepare a patterned front silver electrode (2) with the thickness not more than 500nm and a patterned front aluminum electrode (1) with the thickness not more than 500nm on the surface of the ITO film (3) as grid line electrodes, wherein the front aluminum electrode (1) is fixedly connected with the ITO film (3) through the front silver electrode (2) to form a front composite electrode structure;
and step 9: on TiNyAnd (3) evaporating the surface of the film (7) to prepare an Al back electrode (8) with the thickness not higher than 500nm, thereby obtaining the monocrystalline silicon solar cell device with the back containing the silicon oxide-titanium nitride double-layer contact structure.
8. The method for preparing the monocrystalline silicon solar cell with the back containing the silicon oxide-titanium nitride double-layer contact structure according to claim 7, wherein the method comprises the following steps: the n-type Si substrate (5) is an n-type monocrystalline silicon wafer.
9. A method for preparing a monocrystalline silicon solar cell with a silicon oxide-titanium nitride double-layer contact structure on the back side as claimed in any one of claims 1 to 6, characterized in that the method comprises the following steps:
the method comprises the following steps: cleaning a silicon wafer substrate by using an RCA (radio corporation of America) process, and drying the silicon wafer substrate by using nitrogen to obtain a pretreated n-type Si substrate (5);
step two: placing the n-type Si substrate (5) in HF solution with the temperature of 120 ℃ and the mass percent concentration of not less than 68%, and generating ultrathin SiO with the thickness of 1.2-1.5nm on the two side surfaces of the n-type Si substrate (5) after at least 10 minutesxA film (6);
step three: bonding two surfaces with ultrathin SiOxAn n-type Si substrate (5) of the thin film (6) is placed on a sample holder in a DC magnetron sputtering vacuum chamber, one side surface of the n-type Si substrate (5) is used as a back surface, and the back surface of the n-type Si substrate (5) is bonded with ultrathin SiOxThe film (6) is exposed in a DC magnetron sputtering vacuum chamber, and the background vacuum degree is kept not higher than 3 x 10-4Pa；
Step IV: introducing N into a direct current magnetron sputtering vacuum chamber2Qi, maintaining N2The gas flow of the gas is 40sccm, the pressure is adjusted to the working pressure not higher than 0.5Pa after the glow is started, and the ultrathin SiO on the back surface of the n-type Si substrate (5) is arranged at room temperaturexPreparing TiN with the thickness of not less than 300nm on the film (6)yA film (7);
step five: taking out the combined TiNyAn n-type silicon wafer substrate (5) of the thin film (7) is prepared by removing SiO on the front side of the n-type Si substrate (5) by using HF solution with the mass percent concentration of not less than 5%xA thin film formed by removing SiO from the front surface of the n-type Si substrate (5)xThe rear part is exposed;
step (c): removing SiO from the front surfacexPutting the n-type Si substrate (5) device into radio frequency magnetron sputtering vacuumExposing the front surface of the n-type Si substrate (5) on a sample holder in the chamber in a radio frequency magnetron sputtering vacuum chamber, and maintaining the background vacuum degree of the vacuum chamber at not higher than 3 x 10-4Pa；
Step (c): introducing Ar gas into a radio frequency magnetron sputtering vacuum chamber, keeping the gas flow of the Ar gas at 40sccm, adjusting the pressure to the working pressure of not higher than 0.5Pa after glow starting, preparing an ITO film (3) with the thickness of 80nm at room temperature, and forming ultrathin a-SiO with the thickness of not more than 2.0nm between the ITO film (3) and the front surface of an n-type Si substrate (5) in the process of preparing the ITO film (3)xAn (In) layer (4) as an intermediate connection layer for forming ITO/a-SiOx(In)/n-Si/SiOx/TiNyThe composite structure device of (1);
step (v): using a mask to evaporate and prepare a patterned front silver electrode (2) with the thickness not more than 500nm and a patterned front aluminum electrode (1) with the thickness not more than 500nm on the surface of the ITO film (3) as grid line electrodes, wherein the front aluminum electrode (1) is fixedly connected with the ITO film (3) through the front silver electrode (2) to form a front composite electrode structure;
step ninthly: on TiNyAnd (3) evaporating the surface of the film (7) to prepare an Al back electrode (8) with the thickness not higher than 500nm, thereby obtaining the monocrystalline silicon solar cell device with the back containing the silicon oxide-titanium nitride double-layer contact structure.
10. The method for preparing a single crystalline silicon solar cell having a silicon oxide-titanium nitride double layer contact structure on the back according to claim 9, wherein: the n-type Si substrate (5) is an n-type monocrystalline silicon wafer.
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