CN114765234B - Annealing enhancement back passivation method for P-type crystalline silicon double-sided battery - Google Patents
Annealing enhancement back passivation method for P-type crystalline silicon double-sided battery Download PDFInfo
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- 238000000137 annealing Methods 0.000 title claims abstract description 156
- 238000002161 passivation Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 14
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 80
- 230000008021 deposition Effects 0.000 claims abstract description 36
- 230000002708 enhancing effect Effects 0.000 claims abstract 4
- 238000000151 deposition Methods 0.000 claims description 38
- 230000007547 defect Effects 0.000 abstract description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 46
- 229910052710 silicon Inorganic materials 0.000 description 25
- 239000010703 silicon Substances 0.000 description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 23
- 235000013842 nitrous oxide Nutrition 0.000 description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 238000009792 diffusion process Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000006798 recombination Effects 0.000 description 7
- 101100409194 Rattus norvegicus Ppargc1b gene Proteins 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000006388 chemical passivation reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000005669 field effect Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000005215 recombination Methods 0.000 description 3
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 2
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 2
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010344 co-firing Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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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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- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/308—Oxynitrides
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/42—Silicides
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
Abstract
The invention relates to the field of back passivation of P-type crystalline silicon double-sided solar cells. The annealing and enhancing back passivation method for the P-type crystalline silicon double-sided battery comprises the following steps of first SiON film deposition, first annealing, second SiON film deposition, second annealing, third SiON film deposition, third annealing, fourth SiN film deposition, third SiN film deposition and fourth annealing. According to the method, the SiON film layer is reasonably split and spliced with the annealing process, so that internal defects when the SiON film layer is too thick can be reduced.
Description
Technical Field
The invention relates to the field of back passivation of P-type crystalline silicon double-sided solar cells.
Background
The P-type crystalline silicon double-sided battery can greatly reduce the back surface electrical recombination rate by forming the passivation layer on the back surface of the solar battery, form a good internal optical back reflection mechanism, and improve the open-circuit voltage and short-circuit current of the battery, thereby improving the conversion efficiency of the battery.
The double-sided PERC battery has the advantage of double-sided power generation at lower manufacturing cost, and finally becomes a main stream product in the PERC battery.
The production steps of the perc silicon solar cell are as follows: 1. providing a p-type silicon substrate, and firstly cleaning; 2. forming an n-type diffusion layer (n-type emitter) of a reverse conductivity type on a p-type silicon substrate by using a phosphorus oxychloride (pocl 3) liquid source diffusion method; 3. etching with hydrofluoric acid after forming the diffusion layer to remove pn junction at the cross-section edge of the silicon wafer generated by diffusion; 4. depositing sinx on the front n-type diffusion layer to form a dielectric layer, and depositing alox/sinx on the back to form a passivation layer; 5. performing laser windowing on a passivation layer on the back surface of the perc silicon solar cell; 6. screen printing is carried out on the dielectric layer on the front side of the battery, front side silver paste is dried to form a front side electrode, screen printing is carried out on the passivation layer perforated on the back side of the p-type substrate, and back side silver paste is dried to form a back side electrode; 7. co-firing, the electrodes are sufficiently dry while forming good electrical contact. The core of the perc solar cell is that an alumina film is coated on the backlight surface of a silicon wafer to passivate the silicon, the surface passivation of the alumina is controlled by chemical passivation and field effect passivation, the chemical passivation effect of the alumina is hydrogen passivation, the alumina prepared under different conditions has different hydrogen contents, hydrogen can be combined with internal defects of the silicon wafer and suspension bonds at grain boundaries, and the recombination center is reduced, so that an important factor of passivation effect is realized, and the hydrogen exists in-oh groups or-chx of the film. The alumina-to-silicon interface has a high fixed negative charge density, qf of about 1012-1013cm-2, and exhibits good field effect passivation by shielding the minority carriers from the p-type silicon surface. Negative charges in the aluminum oxide film layer and minority carriers (electrons) in the p-type silicon matrix are mutually repelled, so that the combination of the negative charges and a recombination center of the silicon wafer surface is blocked, and the surface recombination rate is reduced. However, the back plating of the p-type battery is realized, the aluminum oxide adopts an atomic layer growth technology, the speed is slower, the time consumption is longer, the reaction cost is easy to increase, and the current back passivation technology has lower long-wave reflection and lower short-circuit current.
The perc solar cell has the advantages of simple process, low cost and high compatibility with the existing cell production line, is a newly developed high-efficiency solar cell, is widely focused in the industry, and is expected to become the main stream direction of the future high-efficiency solar cell. Production of conventional silicon solar cells, the pec silicon solar cell production steps are as follows: 1. providing a p-type silicon substrate, and firstly cleaning; 2. forming an n-type diffusion layer (n-type emitter) of a reverse conductivity type on a p-type silicon substrate by using a phosphorus oxychloride (pocl 3) liquid source diffusion method; 3. etching with hydrofluoric acid after forming the diffusion layer to remove pn junction at the cross-section edge of the silicon wafer generated by diffusion; 4. depositing sinx on the front n-type diffusion layer to form a dielectric layer, and depositing alox/sinx on the back to form a passivation layer; 5. performing laser windowing on a passivation layer on the back surface of the perc silicon solar cell; 6. screen printing is carried out on the dielectric layer on the front side of the battery, front side silver paste is dried to form a front side electrode, screen printing is carried out on the passivation layer perforated on the back side of the p-type substrate, and back side silver paste is dried to form a back side electrode; 7. co-firing, the electrodes are sufficiently dry while forming good electrical contact. The core of the perc solar cell is that an alumina film is coated on the backlight surface of a silicon wafer to passivate the silicon, the surface passivation of the alumina is controlled by chemical passivation and field effect passivation, the chemical passivation effect of the alumina is hydrogen passivation, the alumina prepared under different conditions has different hydrogen contents, hydrogen can be combined with internal defects of the silicon wafer and suspension bonds at grain boundaries, and the recombination center is reduced, so that an important factor of passivation effect is realized, and the hydrogen exists in-oh groups or-chx of the film. The alumina-to-silicon interface has a high fixed negative charge density, qf of about 1012-1013cm-2, and exhibits good field effect passivation by shielding the minority carriers from the p-type silicon surface. Negative charges in the aluminum oxide film layer and minority carriers (electrons) in the p-type silicon matrix are mutually repelled, so that the combination of the negative charges and a recombination center of the silicon wafer surface is blocked, and the surface recombination rate is reduced. However, the back plating of the p-type battery is realized, the aluminum oxide adopts an atomic layer growth technology, the speed is slower, the time consumption is longer, the reaction cost is easy to increase, and the current back passivation technology has lower long-wave reflection and lower short-circuit current.
Disclosure of Invention
The invention discloses an annealing enhancement back passivation method for a P-type crystalline silicon double-sided battery, and aims to improve the influence of positive charges which are unfavorable for passivation effect in the preparation of the back passivation process and further improve the passivation level of the double-sided battery back passivation process through the optimization of the preparation process.
The technical scheme adopted by the invention is as follows: the annealing and back passivation enhancement method for the P-type crystalline silicon double-sided battery is carried out according to the following steps of
Step one, first SiON film deposition and first annealing, wherein the thickness of a first SiON film formed after the first SiON film deposition is 10-12nm, and the annealing adopts vacuum annealing and NH 3 Annealing, wherein the first total annealing time is 250-400s, and the ratio of the first total annealing time to the thickness of the first SiON film layer in seconds is 30-35 in terms of nano-value;
step two, depositing a second SiON film layer and annealing the second SiON film layer, wherein the thickness of the second SiON film layer formed after the second SiON film layer is 8-10nm, and the annealing adopts vacuum annealing and NH 3 Annealing, wherein the second total annealing time is 150-300s, and the ratio of the second total annealing time to the second SiON film thickness is 30-35 in terms of nano-value;
thirdly, depositing a second SiON film layer and annealing the second SiON film layer, wherein the thickness of a third SiON film layer formed after the third SiON film layer is 3-5nm, and the annealing adopts vacuum annealing and N annealing 2 O+NH 3 Annealing, wherein the third total annealing time is 200-300s, and the ratio of the third total annealing time to the third SiON film thickness is 60-80 in terms of seconds; the total thickness of the three SiON film layers is 25-30nm;
step four, a SiN film layer deposition structure, wherein the SiN film layer adopts three layers of deposition, and gas SiH is deposited when the first SiN film layer is deposited 4 With NH 3 The ratio of SiH4 to NH3 is 1/3.5-1/4.5, the deposition time is 350-400s, the ratio of SiH4 to NH3 is 1/6.5-1/7.5, the deposition time is 250-300s, the deposition time of SiH is the third layer 4 The ratio of NH3 to the film is 1/9.5-1/10.5, the deposition time is 100-200s, and the total thickness of the three SiN film layers is 60-70nm.
Fifth, annealing is carried out for the fourth time, vacuum annealing is adopted for the SiN film layer, the annealing temperature is 440-460 ℃, and the annealing time is 100-200s.
When a SiON film layer is deposited in the first step, the pressure is 1500-2000mTorr, the power is 10000-12000W, the temperature is 450-500 ℃, the pulse switching ratio is 1:16, the volume ratio of SiH4/NH3/N2O is 1/1/2.0-2.5/1/5.0, and the time is 30-35s; no gas is introduced during vacuum annealing, the annealing temperature is 450-500 ℃, the power, the pressure and the duty ratio are all zero, the duration is 50-100s, and the NH is that 3 During annealing, NH 3 The flow is 5000-7000sccm, the pressure is 1500-2000mTorr, the temperature is 450-500 ℃, the power is 10000-12000W, the pulse switching ratio is 1:13-1:16, and the duration is 200-300s.
When SiON film is deposited in the second step, the pressure is 1500-2000mTorr, the power is 10000-12000W, the temperature is 450-500 ℃, the pulse switching ratio is 1:16, the volume ratio of SiH4/NH3/N2O is 1/1/2-2.5/1/5.0, the time is 25-30s, no gas is introduced during vacuum annealing, the annealing temperature is 450-500 ℃, the power, the pressure and the duty ratio are all zero, the duration is 50-100s, and the NH time is 50-100s 3 During annealing, the duration is 100-200s, NH 3 The flow is 5000-7000sccm, the pressure is 1500-2000mTorr, the temperature is 450-500 ℃, the power is 10000-12000W, and the pulse switching ratio is 1:13-1:16.
When a SiON film layer is deposited in the third step, the pressure is 1500-2000mTorr, the power is 10000-12000W, the temperature is 450-500 ℃, the pulse switching ratio is 1:16, the volume ratio of SiH4/NH3/N2O is 1/1/2-2.5/1/5.0, the time is 10-15s, no gas is introduced during vacuum annealing, the annealing temperature is 450-500 ℃, the power, the pressure and the duty ratio are all zero, and the duration is 50-100s; n (N) 2 The time length is 25-50s during O annealing 2 The O flow is 3500-4500sccm, the pressure is 1500-2000mTorr, the temperature is 450-500 ℃, the power is 10000-12000W, and the pulse switching ratio is 1:13-1:16; NH (NH) 3 During annealing, the duration is 100-200s, NH 3 The flow is 5000-7000sccm, the pressure is 1500-2000mTorr, the temperature is 450-500 ℃, the power is 10000-12000W, and the pulse switching ratio is 1:13-1:16.
In the fourth step, when the first SiN film layer is deposited, the pressure is 1500-2000mTorr, the temperature is 450-500 ℃, the power is 10000-12000W, and the pulse switching ratio is 1:15-1:17.5; when the second SiN film layer is deposited and the third SiN film layer is deposited, the pressure is 1500-2000mTorr, the temperature is 450-500 ℃, the power is 10000-12000W, and the pulse switching ratio is 1:15-1:17.5.
the beneficial effects of the invention are as follows: because of the characteristics of the SiON layer, the back film suitable for preparing the double-sided battery needs to adopt a formula structure with high silicon-nitrogen ratio and high laughing gas flow, however, under the formula structure, the thickness of the SiON film exceeds a certain critical value of 10-15nm, and the passivation level is greatly reduced. According to the invention, by adopting a PECVD mode and adopting step deposition and step annealing, and reasonably controlling the time proportion relation between step deposition and step annealing, the SiON film thickness window can be widened, and the passivation level of the SiON film can be greatly improved.
The SiON film layer is reasonably split and spliced with the annealing process, so that internal defects when the SiON film layer is too thick can be reduced. Firstly, the vacuum annealing in the first step and the second step can sufficiently eliminate stress defects of the SiON dielectric film in the preparation process, and the NH3 annealing can further passivate Si/SiON interface states, but the annealing time needs to be accurately controlled; the annealing in the third step is performed by adding N2O for annealing, and the ionized oxygen in the N2O can be further diffused to the Si/SiON interface through pores, so that the interface state is reduced to the greatest extent; and fifthly, vacuum annealing is carried out after SiN for a short time, so that passivation of Si/SiON interface or body is realized through hydrogen in the SiN dielectric film, the annealing temperature is controlled to be 440-460 ℃, si-H bonds are broken when the annealing temperature is lower than 440 ℃, and H overflows when the annealing temperature is higher than 460 ℃.
Detailed Description
Examples
An annealing enhancement back passivation method for a P-type crystalline silicon double-sided battery comprises the following steps:
first SiON film deposition + anneal. When SiON film layer is deposited, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, the pulse switching ratio is 1:16, and the time of the SiH4/NH 3/N2O=2.5/1/2.5 is 35s; during annealing, vacuum annealing is firstly carried out for 50s, no gas is introduced during the vacuum annealing, the annealing temperature is 490 ℃, and the power, the pressure and the duty ratio are all zero; then using NH3 for annealing, wherein the time is controlled at 300s, the NH3 flow is 7000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13.
Second SiON film deposition + anneal. When SiON film layer is deposited, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, the pulse switching ratio is 1:16, and the time is 30s when SiH4/NH 3/N2O=2.5/1/2.5 is introduced; during annealing, vacuum annealing is firstly carried out for 50s, no gas is introduced during the vacuum annealing, the annealing temperature is 490 ℃, and the power, the pressure and the duty ratio are all zero; then using NH3 for annealing, wherein the time is controlled at 200s, the NH3 flow is 7000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13.
Third SiON film deposition + anneal. When SiON film layer is deposited, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, the pulse switching ratio is 1:16, and the time is 10s when SiH4/NH 3/N2O=2.5/1/2.5 is introduced; during annealing, vacuum annealing is firstly carried out for 80 seconds, no gas is introduced during the vacuum annealing, the annealing temperature is 490 ℃, and the power, the pressure and the duty ratio are all zero; then using N2O for annealing, wherein the time is controlled between 30s, the flow rate of the N2O is 4000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13; and finally, NH3 annealing, wherein the time is controlled to be 100s, the flow rate of NH3 is 7000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13.
The SiN film layer is a three-layer film, the pressure is 1700mTorr when the first SiN film layer close to the SiON film layer is deposited, the temperature is 490 ℃, the power is 12000W, and the pulse switching ratio is 1:17.5, siN film SiH 4/NH3=1/4, and the process time is 400s; the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, and the pulse switching ratio is 1 when the second SiN film layer is deposited: 17.5 SiN film SiH 4/NH3=1/7, process time is 270s, the pressure is 1700mTorr, temperature is 490 ℃, power is 12000W, and pulse switching ratio is 1:17.5 SiN film SiH 4/NH3=1/10, process time 150s.
And SiN post-annealing. Vacuum annealing is used for 100s, no gas is introduced during vacuum annealing, the annealing temperature is 450 ℃, and the power, the pressure and the duty ratio are all zero.
Comparative example 1
SiON film deposition + annealing. When SiON film layer is deposited, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, the pulse switching ratio is 1:16, and the time is 60s when SiH4/NH 3/N2O=2.5/1/2.5 is introduced; and (3) annealing by using NH3, wherein the time is controlled at 600s, the NH3 flow is 7000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13.
The SiN film layer is a three-layer film, the pressure is 1700mTorr when the first SiN film layer close to the SiON film layer is deposited, the temperature is 490 ℃, the power is 12000W, and the pulse switching ratio is 1:17.5, siN film SiH 4/NH3=1/4, and the process time is 400s; the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, and the pulse switching ratio is 1 when the second SiN film layer is deposited: 17.5, siN film SiH 4/NH3=1/7, the process time is 270s; the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, and the pulse switching ratio is 1 when the second SiN film layer is deposited: 17.5 SiN film SiH 4/NH3=1/10, process time 150s.
Comparative example 2:
SiON film deposition + annealing. When SiON film layer is deposited, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, the pulse switching ratio is 1:16, and the time is 70s when SiH4/NH 3/N2O=2.5/1/2.5 is introduced; and (3) annealing by using NH3, wherein the time is controlled at 600s, the NH3 flow is 7000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13.
The SiN film layer is a three-layer film, the pressure is 1700mTorr when the first SiN film layer close to the SiON film layer is deposited, the temperature is 490 ℃, the power is 12000W, and the pulse switching ratio is 1:17.5, siN film SiH 4/NH3=1/4, and the process time is 400s; the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, and the pulse switching ratio is 1 when the second SiN film layer is deposited: 17.5, siN film SiH 4/NH3=1/7, the process time is 270s; the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, and the pulse switching ratio is 1 when the second SiN film layer is deposited: 17.5 SiN film SiH 4/NH3=1/10, process time 150s.
Comparative example 3:
first SiON film deposition + anneal. When SiON film layer is deposited, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, the pulse switching ratio is 1:16, and the time of the SiH4/NH 3/N2O=2.5/1/2.5 is 35s; during annealing, vacuum annealing is firstly carried out for 50s without introducing any gas during the vacuum annealing,
the annealing temperature is 490 ℃, and the power, the pressure and the duty ratio are all zero; then using NH3 for annealing, wherein the time is controlled at 300s, the NH3 flow is 7000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13.
Second SiON film deposition + anneal. When SiON film layer is deposited, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, the pulse switching ratio is 1:16, and the time is 30s when SiH4/NH 3/N2O=2.5/1/2.5 is introduced; during annealing, vacuum annealing is firstly carried out for 50s, no gas is introduced during the vacuum annealing, the annealing temperature is 490 ℃, and the power, the pressure and the duty ratio are all zero; then using NH3 for annealing, wherein the time is controlled at 200s, the NH3 flow is 7000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13.
Third SiON film deposition + anneal. When SiON film layer is deposited, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, the pulse switching ratio is 1:16, and the time is 10s when SiH4/NH 3/N2O=2.5/1/2.5 is introduced; during annealing, vacuum annealing is firstly carried out for 80 seconds, no gas is introduced during the vacuum annealing, the annealing temperature is 490 ℃, and the power, the pressure and the duty ratio are all zero; then using N2O for annealing, wherein the time is controlled between 30s, the flow rate of the N2O is 4000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13; and finally, NH3 annealing, wherein the time is controlled to be 100s, the flow rate of NH3 is 7000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13.
The SiN film layer is a three-layer film, the pressure is 1700mTorr when the first SiN film layer close to the SiON film layer is deposited, the temperature is 490 ℃, the power is 12000W, and the pulse switching ratio is 1:17.5, siN film SiH 4/NH3=1/4.5, and the process time is 400s; the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, and the pulse switching ratio is 1 when the second SiN film layer is deposited: 17.5 SiN film SiH 4/NH3=1/7, process time is 270s, the pressure is 1700mTorr, temperature is 490 ℃, power is 12000W, and pulse switching ratio is 1:17.5 SiN film SiH 4/NH3=1/10, process time 150s.
Comparative example 4
First SiON film deposition + anneal. When SiON film layer is deposited, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, the pulse switching ratio is 1:16, and the time of the SiH4/NH 3/N2O=2.5/1/2.5 is 35s; during annealing, vacuum annealing is firstly carried out for 50s without introducing any gas during the vacuum annealing,
the annealing temperature is 490 ℃, and the power, the pressure and the duty ratio are all zero; then using NH3 for annealing, wherein the time is controlled at 300s, the NH3 flow is 7000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13.
Second SiON film deposition + anneal. When SiON film layer is deposited, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, the pulse switching ratio is 1:16, and the time is 30s when SiH4/NH 3/N2O=2.5/1/2.5 is introduced; during annealing, vacuum annealing is firstly carried out for 50s, no gas is introduced during the vacuum annealing, the annealing temperature is 490 ℃, and the power, the pressure and the duty ratio are all zero; then using NH3 for annealing, wherein the time is controlled at 200s, the NH3 flow is 7000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13.
Third SiON film deposition + anneal. When SiON film layer is deposited, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, the pulse switching ratio is 1:16, and the time is 10s when SiH4/NH 3/N2O=2.5/1/2.5 is introduced; during annealing, vacuum annealing is firstly carried out for 80 seconds, no gas is introduced during the vacuum annealing, the annealing temperature is 490 ℃, and the power, the pressure and the duty ratio are all zero; then using N2O for annealing, wherein the time is controlled between 30s, the flow rate of the N2O is 4000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13; and finally, NH3 annealing, wherein the time is controlled to be 100s, the flow rate of NH3 is 7000sccm, the pressure is 1700mTorr, the temperature is 490 ℃, the power is 10000W, and the pulse switching ratio is 1:13.
The SiN film layer is a three-layer film, the pressure is 1700mTorr when the first SiN film layer close to the SiON film layer is deposited, the temperature is 490 ℃, the power is 12000W, and the pulse switching ratio is 1:17.5, siN film SiH 4/NH3=1/5.5, and the process time is 400s; the pressure is 1700mTorr, the temperature is 490 ℃, the power is 12000W, and the pulse switching ratio is 1 when the second SiN film layer is deposited: 17.5 SiN film SiH 4/NH3=1/7, process time is 270s, the pressure is 1700mTorr, temperature is 490 ℃, power is 12000W, and pulse switching ratio is 1:17.5 SiN film SiH 4/NH3=1/10, process time 150s.
And SiN post-annealing. Vacuum annealing is used for 100s, no gas is introduced during vacuum annealing, the annealing temperature is 450 ℃, and the power, the pressure and the duty ratio are all zero.
Table 1 shows the differences between the preparation methods of examples and comparative examples 1 to 4, and Table 2 shows the mass production efficiencies of the corresponding examples and comparative examples 1 to 4, and the specific data are as follows:
table 1 preparation method variability of examples and comparative examples 1 to 4
TABLE 2 conversion efficiency Difference between examples and comparative examples 1-4
As shown in the data of the tables 1 and 2, the SiON dielectric film is deposited by adopting the three-step deposition and the three-step annealing of the patent of the invention, the problem that the single-step deposition is poor along with the conversion efficiency of SiON film thickness is solved to a great extent, and the conversion efficiency is further improved by superposing the SiN chemical composition ratio adjustment and the post annealing close to the SiON film layer.
Claims (5)
1. The annealing enhancement back passivation method for the P-type crystalline silicon double-sided battery is characterized by comprising the following steps of: the method comprises the following steps of
Step one, first SiON film deposition and first annealing, wherein the thickness of a first SiON film formed after the first SiON film deposition is 10-12nm, and the annealing adopts vacuum annealing and NH 3 Annealing, wherein the first total annealing time is 250-400s, and the ratio of the first total annealing time to the thickness of the first SiON film layer in seconds is 30-35 in terms of nano-value;
step two, second SiON film deposition and second annealing, and a second SiON film layer is formed after the second SiON film depositionThe thickness is 8-10nm, and vacuum annealing and NH are adopted for annealing 3 Annealing, wherein the second total annealing time is 150-300s, and the ratio of the second total annealing time to the second SiON film thickness is 30-35 in terms of nano-value;
thirdly, depositing a second SiON film layer and annealing the second SiON film layer, wherein the thickness of a third SiON film layer formed after the third SiON film layer is 3-5nm, and the annealing adopts vacuum annealing and N annealing 2 O+NH 3 Annealing, wherein the third total annealing time is 200-300s, and the ratio of the third total annealing time to the third SiON film thickness is 60-80 in terms of seconds; the total thickness of the three SiON film layers is 25-30nm;
step four, a SiN film layer deposition structure, wherein the SiN film layer adopts three layers of deposition, and gas SiH is deposited when the first SiN film layer is deposited 4 With NH 3 The ratio is 1/3.5-1/4.5, the deposition time is 350-400s, the second layer is deposited with SiH 4 With NH 3 The ratio of the SiH to the third layer is 1/6.5-1/7.5, the deposition time is 250-300s, and the third layer is deposited with SiH 4 With NH 3 The ratio is 1/9.5-1/10.5, the deposition time is 100-200s, and the total thickness of three SiN film layers is 60-70nm;
fifth, annealing is carried out for the fourth time, vacuum annealing is adopted for the SiN film layer, the annealing temperature is 440-460 ℃, and the annealing time is 100-200s.
2. The annealing and back passivation enhancing method for the P-type crystalline silicon double-sided battery according to claim 1, wherein the method comprises the following steps: when the SiON film layer is deposited in the first step, the pressure is 1500-2000mTorr, the power is 10000-12000W, the temperature is 450-500 ℃, the pulse switching ratio is 1:16, and SiH is introduced 4 /NH 3 /N 2 The O volume ratio is 1/1/2.0-2.5/1/5.0, and the time is 30-35s; no gas is introduced during vacuum annealing, the annealing temperature is 450-500 ℃, the power, the pressure and the duty ratio are all zero, the duration is 50-100s, and the NH is that 3 During annealing, NH 3 The flow is 5000-7000sccm, the pressure is 1500-2000mTorr, the temperature is 450-500 ℃, the power is 10000-12000W, the pulse switching ratio is 1:13-1:16, and the duration is 200-300s.
3. An annealing enhancement back for P-type crystalline silicon double-sided cell as claimed in claim 1The passivation method is characterized in that: when SiON film is deposited in the second step, the pressure is 1500-2000mTorr, the power is 10000-12000W, the temperature is 450-500 ℃, the pulse switching ratio is 1:16, and SiH is introduced 4 /NH 3 /N 2 The volume ratio of O is 1/1/2-2.5/1/5.0, the time is 25-30s, no gas is introduced during vacuum annealing, the annealing temperature is 450-500 ℃, the power, the pressure and the duty ratio are all zero, the duration is 50-100s, and the NH is that 3 During annealing, the duration is 100-200s, NH 3 The flow is 5000-7000sccm, the pressure is 1500-2000mTorr, the temperature is 450-500 ℃, the power is 10000-12000W, and the pulse switching ratio is 1:13-1:16.
4. The annealing and back passivation enhancing method for the P-type crystalline silicon double-sided battery according to claim 1, wherein the method comprises the following steps: when the SiON film layer is deposited in the third step, the pressure is 1500-2000mTorr, the power is 10000-12000W, the temperature is 450-500 ℃, the pulse switching ratio is 1:16, and SiH is introduced 4 /NH 3 /N 2 The volume ratio of O is 1/1/2-2.5/1/5.0, the time is 10-15s, no gas is introduced during vacuum annealing, the annealing temperature is 450-500 ℃, the power, the pressure and the duty ratio are all zero, and the duration is 50-100s; n (N) 2 The time length is 25-50s during O annealing 2 The O flow is 3500-4500sccm, the pressure is 1500-2000mTorr, the temperature is 450-500 ℃, the power is 10000-12000W, and the pulse switching ratio is 1:13-1:16; NH (NH) 3 During annealing, the duration is 100-200s, NH 3 The flow is 5000-7000sccm, the pressure is 1500-2000mTorr, the temperature is 450-500 ℃, the power is 10000-12000W, and the pulse switching ratio is 1:13-1:16.
5. The annealing and back passivation enhancing method for the P-type crystalline silicon double-sided battery according to claim 1, wherein the method comprises the following steps: in the fourth step, when the first SiN film layer is deposited, the pressure is 1500-2000mTorr, the temperature is 450-500 ℃, the power is 10000-12000W, and the pulse switching ratio is 1:15-1:17.5; when the second SiN film layer is deposited and the third SiN film layer is deposited, the pressure is 1500-2000mTorr, the temperature is 450-500 ℃, the power is 10000-12000W, and the pulse switching ratio is 1:15-1:17.5.
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