CN110707160B - Method for preparing SiC antireflection film of solar cell by tubular direct PECVD - Google Patents
Method for preparing SiC antireflection film of solar cell by tubular direct PECVD Download PDFInfo
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- CN110707160B CN110707160B CN201910962753.3A CN201910962753A CN110707160B CN 110707160 B CN110707160 B CN 110707160B CN 201910962753 A CN201910962753 A CN 201910962753A CN 110707160 B CN110707160 B CN 110707160B
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 title claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 230000008021 deposition Effects 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 22
- 238000005137 deposition process Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 16
- 229910000077 silane Inorganic materials 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 4
- 210000002268 wool Anatomy 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000031700 light absorption Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 7
- 229910004205 SiNX Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000003667 anti-reflective effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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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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- 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
- C23C16/44—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 method of coating
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- C30B33/08—Etching
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Abstract
The invention discloses a method for preparing a SiC antireflection film of a solar cell by tubular direct PECVD, which comprises the following steps: texturing is carried out on a silicon wafer, and an SiC antireflection film is deposited on the obtained silicon wafer in a furnace tube of tubular PECVD equipment; and cooling, and taking out the silicon wafer to finish the preparation of the SiC antireflection film. The method disclosed by the invention has the advantages that the tubular PECVD equipment is utilized, the process steps and the process parameters are improved, the deposition of the SiC antireflection film can be realized by being compatible with the existing production line equipment under the condition of not changing the equipment, the utilization rate of an old production line or old equipment is favorably improved, the mass production threshold is low, the investment cost of the industrial equipment and the preparation cost are low, and the like, and the prepared SiC antireflection film has better performances such as lower light absorption rate and higher conductivity, so that the solar cell with high photoelectric conversion efficiency is favorably prepared, and the method has very important significance for realizing the wide application of the solar cell.
Description
Technical Field
The invention belongs to the field of preparation of solar cell antireflection films, and relates to a method for preparing a solar cell SiC antireflection film by tubular direct PECVD.
Background
Reducing the reflectance is an important means to improve the conversion efficiency of solar cells, and among them, the antireflective film is the most effective means to reduce the reflectance. SiN is commonly used as an optical antireflection film in the photovoltaic industry, but with the improvement of the efficiency of a cell and the improvement of the reliability requirement of a market assembly, the defects of the SiN film are gradually reflected, specifically: (1) the absorption peak value of the SiN film is located in a range of 500-600 nm, so that the SiN film can absorb sunlight, wherein incident light absorbed in the SiN film accounts for 2-3% of the total incident light capacity, however, sunlight in the range of 500-600 nm is a region with the most intensive solar spectral capacity, which is a spectral region most required to be utilized by the solar cell, and if the sunlight in the range of 500-600 nm is absorbed by the SiN film, the utilization rate of the solar cell to the sun is reduced, and the conversion efficiency of the solar cell is further reduced; (2) the conductivity of the SiN film is low, so that the SiN film is not beneficial to resisting the erosion effect of sodium ions, the sodium ions easily penetrate through the EVA and SiN antireflection film to erode PN junctions in a silicon material, and the reliability of the photovoltaic module is poor; meanwhile, the conductivity of the SiN film is in a direct proportion relation with the refractive index, but the increase of the refractive index can improve the light absorption coefficient of the film, so that more incident light is absorbed in the film, and the conversion efficiency of the battery is reduced.
In contrast to SiN films, SiC antireflective films have the following advantages: (1) the SiC antireflection film has a wider forbidden bandwidth which reaches 3eV, only short-wave incident light with the wavelength of below 400nm can be absorbed by the SiC antireflection film, and the incident light with the wavelength of below 400nm is not utilized by the photovoltaic cell, namely, the light absorption of the SiC antireflection film does not influence the conversion efficiency of the photovoltaic cell. (2) The conductivity of the SiC antireflection film is 10-100 times that of the SiN film, so that the PID effect can be better resisted, and the direct contradiction between the PID resistance and the battery efficiency can be solved. However, in the prior art, the deposition temperature is low (lower than 250 ℃) and the deposition time is long (as long as 45min) when the SiC antireflection film is prepared by adopting the 13.56MHz plasma enhanced chemical vapor deposition technology, so that the production efficiency is not improved, the production cost is increased, and batch production cannot be realized; meanwhile, because the scheme adopts a remote plasma method, and the equipment adopted by the existing remote plasma method is not common equipment on a production line, the preparation of the SiC antireflection film cannot be realized by the existing production line equipment, and the cost of new equipment is additionally increased, so that the production cost is higher; in addition, the PECVD equipment adopted by the existing remote plasma method cannot ensure that the SiC antireflection film has excellent antireflection effect and also has good passivation effect. Therefore, how to obtain the preparation method of the high-performance SiC antireflection film with low mass production threshold and low operation cost has great significance for improving the utilization rate of the solar cell on visible light and the photoelectric conversion efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing a SiC antireflection film of a solar cell by tubular direct PECVD, which has low mass production threshold and low operation cost.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for preparing a solar cell SiC antireflection film by tubular direct PECVD comprises the following steps:
s1, texturing the silicon wafer;
s2, placing the silicon wafer subjected to texturing in the step S1 in a furnace tube of a tubular PECVD device, and depositing a SiC antireflection film on the surface of the silicon wafer, wherein the steps are as follows:
s2-1, depositing the SiC antireflection film by taking methane, silane and hydrogen as raw materials at the deposition temperature of 150-400 ℃;
s2-2, depositing the SiC antireflection film by taking methane, silane and hydrogen as raw materials at the deposition temperature of 200-450 ℃;
s2-3, performing hydrogen injection treatment on the SiC antireflection film at the deposition temperature of 200-450 ℃ by taking ammonia gas as a raw material;
and S3, cooling, and taking out the silicon wafer to finish the preparation of the SiC antireflection film.
In the step S2-1, the volume ratio of hydrogen in the raw material is 10% to 90%; the deposition process parameters in the deposition process are as follows: the flow rate of methane is 850 mL/min-7650 mL/min, the flow rate of hydrogen is 850 mL/min-7650 mL/min, the flow rate of silane is 200 mL/min-500 mL/min, the power frequency is 40 KHz-400 KHz, the power is 7500W-10000W, the pressure is 160 Pa-240 Pa, and the time is 200 s-400 s.
In the step S2-2, the volume ratio of hydrogen in the raw material is 10% to 90%; the deposition process parameters in the deposition process are as follows: the flow rate of methane is 850 mL/min-7650 mL/min, the flow rate of hydrogen is 850 mL/min-7650 mL/min, the flow rate of silane is 200 mL/min-500 mL/min, the power frequency is 40 KHz-400 KHz, the power is 7500W-10000W, the pressure is 160 Pa-240 Pa, and the time is 800 s-1000 s.
In a further improvement of the above method, in step S2-3, the deposition process parameters during the hydrogen injection treatment process are: the flow rate of ammonia gas is 4000 mL/min-6000 mL/min, the power frequency is 40 KHz-400 KHz, the power is 7500W-10000W, the pressure is 160 Pa-240 Pa, and the time is 400 s-600 s.
In the above method, further improvement, in step S1, the agent used for making the wool is potassium hydroxide solution; the concentration of the potassium hydroxide solution is 8 wt% -10 wt%; the temperature for making the wool is 80 +/-5 ℃; the texturing time is 300 +/-50 s.
In a further improvement of the above method, in step S1, the silicon wafer is a monocrystalline silicon wafer.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for preparing a solar cell SiC antireflection film by tubular direct PECVD, which is characterized in that tubular PECVD equipment is utilized, process steps and process parameters are improved, the deposition of the solar cell SiC antireflection film can be realized by being compatible with the existing production line equipment under the condition of not changing the equipment, the utilization rate of an old production line or old equipment is favorably improved, and the method has the advantages of low mass production threshold, low investment cost of the equipment, low preparation cost and the like.
(2) In the invention, SiC antireflection films are deposited at the temperature of 150-400 ℃, 200-450 ℃ and 200-450 ℃ in sequence, and SiC films with different refractive indexes are deposited step by step, so that the antireflection and passivation effects can be improved; meanwhile, the content of C in the SiC film can be controlled by adjusting the growth temperature, so that the appearance color of the film is adjusted, the higher the temperature is in the actual treatment process, the higher the content of C is, the blacker the film is, and the preparation method can be suitable for the preparation requirement of black components.
(3) According to the invention, by optimizing the volume ratio of hydrogen in the raw material to be 10-90%, the compactness of the film can be increased by supplementing hydrogen, and the reaction rate is enhanced, so that the passivation effect of the film is improved, the minority carrier lifetime of the silicon wafer body is favorably prolonged, and the conversion efficiency of the battery is improved.
(4) In the invention, the frequency in the deposition process is optimized to be 40 KHz-400 KHz, which belongs to the common frequency of the PECVD antireflective film deposition equipment of the solar cell production line, is suitable for the existing equipment, can be applied to the existing production line and is put into mass production.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the processes used were conventional processes, the equipment used were conventional equipment, and the data obtained were average values of three or more experiments.
Example 1:
a method for preparing a solar cell SiC antireflection film by tubular direct PECVD comprises the following steps:
(1) texturing a monocrystalline silicon piece in a groove type machine, wherein the solution used for texturing is a potassium hydroxide solution, the concentration of the potassium hydroxide solution is 8 wt%, the treatment temperature is 80 ℃, and the treatment time is 300 s; and cleaning the silicon wafer with deionized water and drying.
(2) Putting the silicon wafer subjected to texturing in the step (1) into a graphite boat, and depositing a SiC antireflection film by using tubular PECVD, wherein the method specifically comprises the following steps:
(2.1) using methane, silane and hydrogen as raw materials, and depositing the SiC antireflection film at the deposition temperature of 300 ℃, wherein the volume ratio of the hydrogen in the raw materials is 70%, and the deposition process parameters in the deposition process are as follows: the flow rate of methane is 7500mL/min, the flow rate of hydrogen is 3200mL/min, the flow rate of silane is 280mL/min, the frequency of a power supply is 40KHz, the power is 10000W, the pressure is 220Pa, and the time is 400 s.
(2.2) using methane, silane and hydrogen as raw materials, and depositing the SiC antireflection film at the deposition temperature of 350 ℃, wherein the volume ratio of the hydrogen in the raw materials is 70%, and the deposition process parameters in the deposition process are as follows: the flow rate of alkane is 7500mL/min, the flow rate of hydrogen is 3200mL/min, the flow rate of silane is 400mL/min, the frequency of a power supply is 40KHz, the power is 9800W, the pressure is 220Pa, and the time is 250 s.
(2.3) performing hydrogen injection treatment on the SiC antireflection film at the deposition temperature of 350 ℃ by taking ammonia gas as a raw material to enhance the passivation effect, wherein the deposition process parameters in the hydrogen injection treatment process are as follows: the flow rate of the ammonia gas is 5500mL/min, the power frequency is 40KHz, the power is 8500W, the pressure is 200Pa, and the time is 400 s.
(3) And (3) after the deposition of the SiC antireflection film in the step (2) is finished, cooling, taking out the graphite boat, and taking out the silicon wafer to finish the preparation of the SiC antireflection film.
Preparing a silicon wafer for preparing the SiC antireflection film into a solar cell, and carrying out electrical property test on the cell, wherein the electrical property test result is as follows: 22.07% efficiency, 678.4mV open circuit voltage, 9.723A short circuit current and 81.73% fill factor.
Comparative example:
a preparation method of a conventional SiNx antireflection film comprises the following steps:
(1) texturing a monocrystalline silicon piece in a groove type machine, wherein the solution used for texturing is a potassium hydroxide solution, the concentration of the potassium hydroxide solution is 8 wt%, the treatment temperature is 80 ℃, and the treatment time is 300 s; and cleaning with deionized water and drying after treatment.
(2) Placing the silicon wafer subjected to texturing in the step (1) into a graphite boat, and depositing a SiNx antireflection film by using tubular PECVD.
(2.1) depositing the SiNx antireflection film by taking ammonia and silane as raw materials at the deposition temperature of 500 ℃, wherein the deposition process parameters in the deposition process are as follows: the flow rate of ammonia gas is 5000mL/min, the flow rate of silane is 750mL/min, the power frequency is 40KHz, the power is 7350W, the pressure is 220Pa, and the time is 600 s.
(2.2) depositing the SiNx antireflection film by taking ammonia and silane as raw materials at the deposition temperature of 550 ℃, wherein the deposition process parameters in the deposition process are as follows: the flow rate of ammonia is 7500mL/min, the flow rate of silane is 1000mL/min, the power frequency is 40KHz, the power is 6000W-8000W, the pressure is 220Pa, and the time is 900 s.
(3) And cooling, taking out the graphite boat, and taking out the silicon wafer to finish the preparation of the SiNx antireflection film.
And manufacturing the silicon wafer for preparing the SiNx antireflection film into a solar cell, and testing the electrical property of the cell. Results of electrical property testing: efficiency 22.04%, open circuit voltage 679.1mV, short circuit current 9.702A, and fill factor 81.73%.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (6)
1. A method for preparing a solar cell SiC antireflection film by tubular direct PECVD is characterized by comprising the following steps:
s1, texturing the silicon wafer;
s2, placing the silicon wafer subjected to texturing in the step S1 in a furnace tube of a tubular PECVD device, and depositing a SiC antireflection film on the surface of the silicon wafer, wherein the steps are as follows:
s2-1, depositing the SiC antireflection film by taking methane, silane and hydrogen as raw materials at the deposition temperature of 150-400 ℃; the volume ratio of hydrogen in the raw material is 10-90%;
s2-2, depositing the SiC antireflection film by taking methane, silane and hydrogen as raw materials at the deposition temperature of 200-450 ℃; the volume ratio of hydrogen in the raw material is 10-90%;
s2-3, depositing the SiC antireflection film by taking ammonia gas as a raw material at the deposition temperature of 200-450 ℃ and performing hydrogen injection treatment on the SiC antireflection film;
and S3, cooling, and taking out the silicon wafer to finish the preparation of the SiC antireflection film.
2. The method according to claim 1, wherein in step S2-1, the deposition process parameters during the deposition process are: the flow rate of methane is 850 mL/min-7650 mL/min, the flow rate of hydrogen is 850 mL/min-7650 mL/min, the flow rate of silane is 200 mL/min-500 mL/min, the power frequency is 40 KHz-400 KHz, the power is 7500W-10000W, the pressure is 160 Pa-240 Pa, and the time is 200 s-400 s.
3. The method according to claim 2, wherein in step S2-2, the deposition process parameters during the deposition process are: the flow rate of methane is 850 mL/min-7650 mL/min, the flow rate of hydrogen is 850 mL/min-7650 mL/min, the flow rate of silane is 200 mL/min-500 mL/min, the power frequency is 40 KHz-400 KHz, the power is 7500W-10000W, the pressure is 160 Pa-240 Pa, and the time is 800 s-1000 s.
4. The method according to claim 3, wherein in step S2-3, the deposition process parameters during the hydrogen injection treatment are: the flow rate of ammonia gas is 4000 mL/min-6000 mL/min, the power frequency is 40 KHz-400 KHz, the power is 7500W-10000W, the pressure is 160 Pa-240 Pa, and the time is 400 s-600 s.
5. The method according to any one of claims 1 to 4, wherein in the step S1, the agent for making the wool is potassium hydroxide solution; the concentration of the potassium hydroxide solution is 8 wt% -10 wt%; the temperature for making the wool is 80 +/-5 ℃; the texturing time is 300 +/-50 s.
6. The method according to claim 5, wherein in the step S1, the silicon wafer is a single crystal silicon wafer.
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