WO2022213460A1 - 一种集成隧穿氧化层的非晶硅制备方法 - Google Patents
一种集成隧穿氧化层的非晶硅制备方法 Download PDFInfo
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- WO2022213460A1 WO2022213460A1 PCT/CN2021/096255 CN2021096255W WO2022213460A1 WO 2022213460 A1 WO2022213460 A1 WO 2022213460A1 CN 2021096255 W CN2021096255 W CN 2021096255W WO 2022213460 A1 WO2022213460 A1 WO 2022213460A1
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- 229910021417 amorphous silicon Inorganic materials 0.000 title claims abstract description 50
- 230000005641 tunneling Effects 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 55
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 235000012431 wafers Nutrition 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 238000009489 vacuum treatment Methods 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 238000002161 passivation Methods 0.000 abstract description 15
- 238000011068 loading method Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 229910004205 SiNX Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical group ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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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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Definitions
- the invention belongs to the technical field of solar cells, and particularly relates to a method for preparing amorphous silicon with an integrated tunnel oxide layer.
- a conventional way to solve this influencing factor is to use local contact.
- This structure reduces the effective contact area between the silicon base and the metal electrode, and the uncontacted area is blocked by passivation layers or other masking layers, such as PERC, PERL and other battery structures. .
- passivation layers or other masking layers such as PERC, PERL and other battery structures.
- Another option to reduce contact recombination is to use selectively passivated contacts, a structure consisting of a material placed between a silicon base and a metal electrode, which effectively inhibits the recombination of charge carriers through defects at the silicon surface. At the same time, it also plays a role in contact. Since the recombination loss of this passivation contact is very low, it can be used as a passivation layer on the whole surface, avoiding the use of a separate passivation layer and local metal contact. Selectively passivated contact structures have the potential to simplify the solar cell fabrication process and increase efficiency.
- N-TOPCon cells are based on the theory of selective contact passivation, and the structure includes an ultra-thin oxide layer (electron tunneling layer) and a phosphorus-doped polysilicon layer (SiOx/doped-poly Si).
- TOPCon batteries have different process routes due to different equipment and processes.
- the difficulty of the industrialized TOPCon process lies in the balance of yield, production capacity, efficiency and cost. Whether the factory can gain advantages in technology and cost in the future, the formulation of the process route is particularly important.
- the present invention provides a method for preparing amorphous silicon with an integrated tunnel oxide layer.
- the present invention provides the following technical solutions:
- a method for preparing amorphous silicon with an integrated tunnel oxide layer comprising the following steps:
- Oxidation keep the pressure stable, and after heating until the furnace tube temperature is stable, oxygen is introduced to carry out SiO2 growth; the stable temperature range is 550-620 °C, the flow rate of O2 is in the range of 5-30slm, and the time is 5-30 minute;
- Amorphous silicon growth After the temperature and pressure are stabilized, SiH 4 is introduced to grow amorphous silicon; the stable temperature range is 550-600 ° C, the flow rate of SiH 4 is 80-1000 sccm, the pressure range is 250-600 mtorr, and the time is 10 ⁇ 150 minutes;
- step (1) the internal temperature of the furnace tube is 450-600° C., and the N 2 flow range is 1-30 slm.
- step (2) the stable temperature range is 560-600°C.
- step (2) the O 2 flow range is 10-20 slm, and the time is 8-15 minutes.
- step (3) vacuum is applied to make the furnace tube atmosphere less than 100 mtorr.
- step (4) the N 2 flow range is 100-10000 sccm, the back pressure pressure is 250-1000 mtorr, and the holding time is 0.5-10 min.
- step (4) the N 2 flow range is 200-1000 sccm, the back pressure pressure is 250-600 mtorr, and the holding time is 0.5-5 min.
- the SiH 4 flow range is 200-500 sccm
- the pressure is 300-500 mtorr
- the time is 20-60 minutes.
- step (7) the cooling temperature range is 400-550°C.
- the present invention uses a method of growing amorphous silicon with an integrated ultra-thin oxide layer, that is, the growth of the ultra-thin tunnel oxide layer and the growth of amorphous silicon are performed in the same process, and there is no Q-time time, which can reduce the process steps.
- the present invention uses an amorphous silicon growth method with an integrated ultra-thin oxide layer, which does not involve additional loading and unloading processes, does not increase the risk of scratches and contamination, and is more excellent than the separate method of oxidation and amorphous silicon growth. passivation results.
- FIG. 1 is a flow chart of a method for preparing amorphous silicon with an integrated tunnel oxide layer according to the present invention.
- a and/or B can mean that A exists alone, A and B exist at the same time, and B exists alone.
- the terms “first”, “second”, “third”, etc. involved in this application are only to distinguish similar objects, and do not represent a specific order for the objects.
- a method for preparing amorphous silicon with an integrated tunnel oxide layer comprising the following steps:
- Oxidation keep the pressure stable, heat to the furnace tube temperature of 560 ° C, after the temperature is stable, feed oxygen to carry out SiO 2 growth; O 2 flow range 10slm, time 10 minutes;
- Amorphous silicon growth after the temperature and pressure are stabilized, SiH 4 is introduced to conduct amorphous silicon growth; SiH 4 flow range is 200sccm, pressure is 300mtorr, and time is 40 minutes;
- Cooling and releasing the boat after the temperature is lowered, the boat is taken out from the furnace tube after breaking the vacuum, and the cooling temperature range is 400 °C;
- a method for preparing amorphous silicon with an integrated tunnel oxide layer comprising the following steps:
- SiH 4 is introduced to conduct amorphous silicon growth; SiH 4 flow range is 1000sccm, pressure 400mtorr, and time 10 minutes;
- Cooling and releasing the boat after the temperature is lowered, the boat is taken out from the furnace tube after breaking the vacuum, and the cooling temperature range is 450°C;
- a method for preparing amorphous silicon with an integrated tunnel oxide layer comprising the following steps:
- Oxidation keep the pressure stable, after heating until the furnace tube temperature is stable, oxygen is introduced to carry out SiO2 growth; the stable temperature range is 600°C, the O2 flow range is 15slm, and the time is 15 minutes;
- Amorphous silicon growth after the temperature and pressure are stabilized, SiH 4 is introduced to grow amorphous silicon; the flow range of SiH 4 is 500sccm, the pressure is 500mtorr, and the time is 30 minutes;
- Cooling and releasing the boat after the temperature is lowered, the boat is taken out from the furnace tube after breaking the vacuum, and the cooling temperature range is 550°C;
- a method for preparing amorphous silicon with an integrated tunnel oxide layer comprising the following steps:
- Oxidation keep the pressure stable, and after heating until the furnace tube temperature is stable, oxygen is introduced to carry out SiO2 growth; the stable temperature range is 550°C, the O2 flow range is 5slm, and the time is 30 minutes;
- Amorphous silicon growth after the temperature and pressure are stabilized, SiH 4 is introduced to conduct amorphous silicon growth; SiH 4 flow range is 80sccm, pressure is 250mtorr, and time is 150 minutes;
- Cooling and releasing the boat after the temperature is lowered, the boat is taken out from the furnace tube after breaking the vacuum, and the cooling temperature range is 400 °C;
- Contact quality in crystalline silicon cells can be characterized by J0 and PL values.
- the monitor film is an N-type polished film. After the oxidation and amorphous silicon processes are completed on the back side (using the method for preparing amorphous silicon with an integrated tunnel oxide layer as described in Example 1 above), double-sided phosphorous expansion is performed, and a cleaning machine is used to remove it. After double-sided PSG, double-sided SiNx film was plated. Finally, after sintering, WCT120 and PL machines were used to test J 0 and PL values.
- a single crystal silicon wafer (CZ Si) prepared by a single-throw N-type Czochralski method with a thickness of 1.175 ⁇ m and a resistivity of 1 to 3 ⁇ cm.
- the reflectivity of the treated silicon wafer is about 30-40%;
- the silicon wafer is put into the phosphorus diffusion equipment for phosphorus doping treatment.
- the conventional phosphorus doping method in the prior art is adopted, and the phosphorus doping temperature is 790° C.
- the source is POCl3, the gas source volume is 800-1000sccm, and the passage time is 20-25min;
- the above is the preparation method of the amorphous silicon process monitoring sheet with integrated tunnel oxide layer, in which, except for the preparation method of amorphous silicon integrated with tunnel oxide layer of the present invention, other processing methods are conventional in the prior art .
- step (3) the conventional method is used to carry out the tunneling oxide layer and the growth of amorphous silicon, and after the tunneling oxide layer is completed After the growth of the silicon wafer, the temperature of the silicon wafer is cooled, and then the growth of amorphous silicon is carried out.
- the normal pressure oxidation process is usually used in the conventional process. The oxidation under normal pressure usually has a fast growth rate, poor controllability, and is greatly affected by the environment.
- Vacuum degree keep the vacuum degree at 100-700 Torr, reduce the growth rate of the oxide layer, and at the same time, it is less affected by environmental cleanliness under vacuum, and can obtain a high-quality thin oxide layer.
- the conventional oxidation process flow is: chip loading (oxidation furnace tube carrier) - tube inlet - heating - oxygen oxidation (atmospheric pressure) - cooling - tube cooling - unloading - chip loading (amorphous silicon furnace tube carrier) - The process of entering the tube - heating up and vacuuming - growing amorphous silicon - cooling down and breaking the vacuum - exiting the tube and cooling - unloading is complicated, and the carrier needs to be switched.
- Tables 1 and 2 are the passivation results of the monitor wafers prepared by the integrated and non-integrated processes, respectively.
- Table 1 Table of passivation results of amorphous silicon with integrated oxide layer
- Table 2 Table of passivation results prepared by oxide layer and amorphous silicon layer respectively
- the sample prepared by the method of the present invention has a longer minority carrier lifetime, a smaller current density value, a larger filling factor, a larger open circuit voltage, and different furnace tubes.
- the difference of the test data of the position monitoring sheet is small, which shows that the sample prepared by the method of the present invention has good uniformity.
- the sample prepared by the method of the invention can be tested with a minority carrier lifetime of more than 2000 ⁇ s, indicating that it has good passivation performance; and the higher the minority carrier lifetime, the smaller the recombination, and the higher the battery efficiency.
- amorphous silicon passivation result of the integrated oxide layer of the present invention is better than the passivation result of the oxide layer and the amorphous silicon prepared separately.
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Abstract
Description
position | Lifetime_(μs) | Jo_(fA/cm 2) | I-Voc_(V) | I-FF_(%) | PL |
1 | 2314.57 | 11.96 | 0.7103 | 84.8 | 68894 |
2 | 2370.49 | 10.96 | 0.7104 | 85.16 | 69475 |
3 | 2720.07 | 11.58 | 0.7116 | 85.51 | 69362 |
4 | 2245.47 | 10.77 | 0.7111 | 84.26 | 70013 |
5 | 3315.86 | 10.08 | 0.7134 | 86.02 | 69740 |
position | Lifetime_(μs) | Jo_(fA/cm 2) | I-Voc_(V) | I-FF_(%) | PL |
1 | 732.24 | 32.08 | 0.6846 | 83.94 | 58585 |
2 | 1449.31 | 19.98 | 0.6983 | 84.96 | 70892 |
3 | 2124.98 | 14.17 | 0.7076 | 85.13 | 72199 |
4 | 869.78 | 29.46 | 0.6878 | 84.31 | 58662 |
5 | 800.79 | 33.79 | 0.6858 | 82.85 | 47286 |
Claims (9)
- 一种集成隧穿氧化层的非晶硅制备方法,其特征是,包括以下步骤:(1)进舟:将完成表面抛光的硅片装入舟中,将舟推进入炉管中,进舟过程中通入N 2;进舟完成后,停止通入N 2,对炉管进行抽真空处理,保持真空度在100-700Torr;(2)氧化:保持压力稳定,加热至炉管温度稳定后,通入氧气,进行SiO 2生长;稳定温度范围为550-620℃,通入O 2流量范围5-30slm,时间为5~30分钟;(3)抽真空:完成氧化后,打开阀抽真空,使炉管氛围为1000mtorr以下状态;(4)回压:通入N 2回压,保持一段时间;(5)非晶硅生长:温度压力稳定后,通入SiH 4,进行非晶硅生长;稳定温度范围550-600℃,通入SiH 4流量范围80~1000sccm,压力范围250~600mtorr,时间10~150分钟;(6)通入N 2,排出管内剩余SiH 4;(7)降温出舟:温度降低后,破真空后将舟从炉管中取出;(8)卸片:将硅片从舟上取下。
- 根据权利要求1所述的一种集成隧穿氧化层的非晶硅制备方法,其特征是,步骤(1)中,炉管内部温度为450~600℃,N 2流量范围1~30slm。
- 根据权利要求1所述的一种集成隧穿氧化层的非晶硅制备方法,其特征是,步骤(2)中,稳定温度范围560~600℃。
- 根据权利要求1所述的一种集成隧穿氧化层的非晶硅制备方法,其特征是,步骤(2)中,O 2流量范围10~20slm,时间8~15分钟。
- 根据权利要求1所述的一种集成隧穿氧化层的非晶硅制备方法,其特征是,步骤(3)中,抽真空,使炉管氛围为小于100mtorr状态。
- 根据权利要求1所述的一种集成隧穿氧化层的非晶硅制备方法,其特征是,步骤(4)中,N 2流量范围100~10000sccm,回压压力范围250~1000mtorr,保持时间0.5~10min。
- 根据权利要求1所述的一种集成隧穿氧化层的非晶硅制备方法,其特征是,步骤(4)中,N 2流量范围200~1000sccm,回压压力范围250~600mtorr,保持时间0.5~5min。
- 根据权利要求1所述的一种集成隧穿氧化层的非晶硅制备方法,其特征是,步骤(5)中,SiH 4流量范围200~500sccm,压力300~500mtorr,时间20~60分钟。
- 根据权利要求1所述的一种集成隧穿氧化层的非晶硅制备方法,其特征是,步骤(7)中,降温温度范围400~550℃。
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