CN116313904A - TOPCON battery texturing stability monitoring method - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000012544 monitoring process Methods 0.000 title claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 59
- 239000010703 silicon Substances 0.000 claims abstract description 59
- 239000003814 drug Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000004364 calculation method Methods 0.000 claims abstract description 4
- 235000012431 wafers Nutrition 0.000 claims description 56
- 238000004140 cleaning Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 210000002268 wool Anatomy 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 25
- 238000001514 detection method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002310 reflectometry Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000013585 weight reducing agent Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67242—Apparatus for monitoring, sorting or marking
- H01L21/67253—Process monitoring, e.g. flow or thickness monitoring
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L22/00—Testing or measuring during manufacture or treatment; Reliability measurements, i.e. testing of parts without further processing to modify the parts as such; Structural arrangements therefor
- H01L22/10—Measuring as part of the manufacturing process
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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
- H01L31/04—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention relates to the technical field of solar cells, and particularly discloses a TOPCON battery texturing stability monitoring method. Texturing the surface of the silicon wafer to obtain a textured surface with pyramid morphology; measuring a value of the bottom side length a of the pyramid morphology and a value of the ratio R of the raised surface area; judging the stability of the texturing process according to the value a and the value R, and when a is more than or equal to 4.0 mu m and less than or equal to 7.0 mu m,
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a TOPCON battery texturing stability monitoring method.
Background
TOPCon battery, tunnel Oxide Passivated Contact battery, is a novel passivation contact technology, can effectively reduce surface recombination and metal contact recombination, and is a development trend of high-efficiency battery at present. The conventional TOPCO battery process flow mainly comprises the following steps: alkali texturing, boron diffusion, back winding diffusion borosilicate glass removal and cleaning, alkali polishing, ultra-thin oxide layer deposition, polysilicon, phosphorus doping, front surface dephosphorization silica glass, front surface winding plating, aluminum oxide passivation, silicon nitride antireflection, screen printing, sintering and testing, wherein the process time is about 9.5 hours.
In the TOPCON battery production process, firstly, the surface of a silicon wafer needs to be textured, and the texturing effect directly influences the absorption of sunlight by the battery and the passivation effect of a coating film in the subsequent process, so that the battery efficiency is influenced. The current method for judging whether the texturing process is stable in the TOPCO battery production process is to judge according to the battery efficiency of the final battery, so that the time is long, the cost is high, the specific process with abnormality cannot be focused, and a large amount of complicated investigation work is needed in the later period. Although weight reduction and reflectivity are also studied as indexes for evaluating the quality of the texturing process, monitoring of the reflectivity and the weight reduction cannot guarantee stability of the efficiency of the final battery, and the accuracy of the method is required to be further verified.
Disclosure of Invention
In view of the above, the invention provides a method for monitoring the stability of TOPCO battery texturing, which discovers key parameters affecting the quality of the texturing process through a large number of experiments, and monitors the key parameters rapidly, thus having high accuracy, simple operation and low cost, and not affecting the normal production of TOPCO battery.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a TOPCON battery texturing stability monitoring method comprises the following steps:
texturing the surface of the silicon wafer to obtain a textured surface with pyramid morphology;
measuring a value of the bottom side length a of the pyramid morphology and a value of the ratio R of the raised surface area;
judging the stability of the texturing process according to the value a and the value R, and when a is more than or equal to 4.0 mu m and less than or equal to 7.0 mu m,
The texturing process is stable; otherwise, adjusting the texturing liquid medicine or/and the technological conditions;
wherein, the calculation formula of the R value is the texturing surface area of the silicon wafer/the silicon wafer area.
Through a great deal of researches, the inventor finds that in the TOPCON battery production process, the surface texture of the silicon wafer is complicated in reaction process due to the use of various chemical liquid medicines and additives, the production process is easy to be abnormal, and the abnormality is mainly caused by the micro-sized texture on the surface of the silicon wafer, and is not visible to naked eyes under normal conditions, so that problems cannot be found in time, waste of production resources is caused, and the battery yield is low. Through a great deal of creative research, the inventor finds that after the surface texturing treatment of the silicon wafer, when the ratio of the texturing surface area of the silicon wafer to the silicon wafer area and the bottom edge length of the pyramid meet a specific relation, the qualified rate of the surface texturing of the silicon wafer is greatly improved, and the rapid and accurate monitoring of the texturing stability is realized. Compared with the prior art that the quality of a final battery is adopted to judge whether the surface texturing of the silicon wafer is stable, the monitoring method provided by the invention has the advantages of short time, simple and convenient operation and low cost, and does not influence the normal production of TOPCON batteries; compared with the method for judging whether the texturing process is stable or not through detecting the weight loss and the reflectivity, the monitoring method provided by the invention is better in accuracy.
Optionally, after the surface of the silicon wafer of the preset batch is textured, selecting a preset number of silicon wafers, and measuring an a value and an R value of the silicon wafers to judge the stability of the textured surface on line within a preset time interval. The monitoring efficiency can be improved by detecting the silicon wafers subjected to the texturing of the preset batch; and the accuracy of monitoring is improved by selecting the preset number of silicon wafers for testing.
Optionally, the a value and the R value are measured by using a three-dimensional interference microscope, specifically: more than 3 points are selected on the wool making surface, and the points are respectively tested and averaged. The method of taking average value through multipoint test improves the accuracy of monitoring.
Optionally, after texturing every 10-60 batches of silicon wafers, selecting 5-20 silicon wafers, and respectively measuring an a value and an R value of the selected silicon wafers.
Further alternatively, in the step of texturing the surface of the silicon wafer, the silicon wafer with the resistivity of 1.5-1.7Ω & cm is selected. By limiting the resistivity of the silicon wafer, the difference of photoelectric conversion efficiency of the battery caused by the difference of the silicon wafer is reduced, and the monitoring accuracy is improved.
Optionally, the pre-cleaning and the post-cleaning are both carried out by adopting a method comprising the steps of KOH with the mass concentration of 1.0-2.0% and H with the mass concentration of 5.0-6.0% 2 O 2 Cleaning the mixture for 100 to 140 seconds at the temperature of between 65 and 70 ℃;
the alkali texturing is to react an aqueous solution containing KOH with the mass concentration of 1.5-2.0% and a texturing additive with the mass concentration of 0.3-0.5% at the temperature of 80-85 ℃ for 400-440 s;
the pickling is to adopt aqueous solution containing 4.5 to 5.5 percent of HCl and 2.5 to 3.0 percent of HF with mass concentration to clean for 100 to 140 seconds at the temperature of between 65 and 70 ℃;
the slow pulling is carried out in water, the slow pulling temperature is 70-80 ℃, and the slow pulling time is 130-170 s;
the drying is carried out at 70-85 ℃ for 130-170 s;
the one-time cleaning is carried out for 100-140 s at 20-35 ℃.
Still further alternatively, the texturing additive is an aqueous solution comprising the following components in mass concentration: 0.5 to 10 percent of nucleating agent, 1 to 10 percent of suede catalyst, 0.01 to 0.05 percent of surfactant and 0.05 to 0.5 percent of defoaming agent.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to better illustrate the present invention, the following examples are provided for further illustration.
Example 1
60 pieces of 182 x 182mm silicon wafers with the resistance value of 1.5-1.7 omega cm are selected for grouping, and are divided into 12 groups, each group of serial numbers S1-S12 and S1/3/5/7/9/11 are tracked by adopting a conventional process method, the final battery performance is tested, and S2/4/6/8/10/12 is tracked by adopting the method. Each group of 5 tablets, numbered S1-1/2/3/4/5, S2-1/2/3/4/5, S3-1/2/3/4/5. The alkali wool making groove 225 of the wool making equipment is put into production in succession in a maintenance period: after maintenance, 1 st batch is put into S1 and S2, 60 th batch is put into S3 and S4, 110 th batch is put into S5 and S6, 160 th batch is put into S7 and S8, 200 th batch is put into S9 and S10, and 225 th batch is put into S11 and S12.
TOPCon cells were produced according to the following procedure: the preparation method comprises the steps of surface texturing of a silicon wafer, boron diffusion, back-side winding diffusion borosilicate glass removal and cleaning, alkali polishing, ultra-thin oxide layer deposition, polysilicon, phosphorus doping, front-side dephosphorization silica glass, front-side winding plating, aluminum oxide passivation, silicon nitride antireflection, screen printing, sintering and testing. This process is a conventional process.
The surface texturing of the silicon wafer comprises the following steps:
(1) Cleaning the silicon wafer: with KOH having a mass concentration of 1.5% and 5.5% H 2 O 2 Is washed at 68℃for 120s.
(2) And (3) washing the silicon wafer treated in the step (1) once: washing at 30 deg.c for 100-140 s.
(3) Alkali texturing is carried out on the silicon wafer treated in the step (2): reacting for 420s at 82 ℃ by adopting an aqueous solution containing KOH with the mass concentration of 1.8% and a texturing additive with the mass concentration of 0.5%; the texturing additive is an aqueous solution comprising the following components in mass concentration: 5% of nucleating agent, 5% of suede catalyst, 0.03% of surfactant and 0.3% of defoaming agent.
(4) And (3) performing secondary water washing on the silicon wafer treated in the step (3): washing at 30 deg.c for 100-140 s.
(5) Post-cleaning the silicon wafer treated in the step (4): with KOH having a mass concentration of 1.5% and 5.5% H 2 O 2 Is washed at 68 ℃ for 120s;
(6) And (3) washing the silicon wafer treated in the step (5) for three times: cleaning at 30 ℃ for 100-140 s,
(7) Pickling the silicon wafer treated in the step (6): washing with aqueous solution containing HCl with mass concentration of 5.0% and HF with mass concentration of 2.8% at 68 ℃ for 120s;
(8) And (3) performing four times of water washing on the silicon wafer treated in the step (7): washing at 30 deg.c for 100-140 s.
(9) Slowly lifting the silicon wafer processed in the step (8): in water, the slow-pulling temperature is 75 ℃, and the slow-pulling time is 150s
(10) Drying the silicon wafer treated in the step (9): oven dried at 80deg.C for 150s.
By tracking the battery performance of six groups S1/3/5/7/9/11 with six groups S2/4/6/8/10/12
The corresponding relation between the value and the value a is used for verifying whether the method has correlation or not, and the detection and calculation results are shown in the table 1.
TABLE 1
By analyzing the experimental data, the bottom side length a and the bottom side length a of the pyramid on the napped surface
Under the condition of meeting the requirements, the battery of the TOPCO battery is producedThe efficiency is more than 22.5 percent, and the requirements are met; when a or->
When there is an unsatisfactory battery efficiency of the TOPCON battery produced is unsatisfactory. The TOPCON battery texturing stability monitoring method provided by the invention can fully reflect the process stability of the texturing process and ensure the battery conversion efficiency.
Example 2
In the embodiment, the method for monitoring the texture-making stability of the TOPCON battery is applied to TOPCON battery production, 30 silicon wafers are selected for texture-making process treatment in every 30 batches of production batches, and then the treated silicon wafers are detected. When the surface structure is pyramid-shaped, a is more than or equal to 4.0 μm and less than or equal to 7.0 μm,
And when the TOPCO battery is detected to be qualified, the wool making process is judged to be stable, and TOPCO battery production is continued. If the detection is unqualified, judging that the surface of the silicon wafer is unqualified, and replacing the texturing liquid medicine and then carrying out production.
The production process flow of the TOPCON battery and the silicon wafer surface texturing step are the same as those of the embodiment 1, and are not repeated.
In the maintenance period of the alkali wool making groove 225 of the wool making equipment, in the 191 th batch production process, the condition of unqualified detection occurs, and the wool making liquid medicine is replaced in time and then is produced. After 225 batches of production were completed, the qualification rate of the TOPCO battery was 98.1% according to the battery performance detection result.
Comparative example 1
The production of TOPCON batteries is performed in a conventional manner in this comparative example, and the production process flow is the same as that of example 2, and will not be repeated. And in the production process, the stability monitoring of the surface texturing step of the silicon wafer is not carried out. After the production of 225 batches of TOPCO batteries is completed, the conversion efficiency qualification rate of the TOPCO batteries is 92.3% according to battery performance detection results.
Comparative example 2
The production of TOPCON batteries is performed in a conventional manner in this comparative example, and the production process flow is the same as that of example 2, and will not be repeated. In the production process, the stability of the silicon wafer surface texturing step is monitored through weight reduction and reflectivity, and when the weight reduction is 0.25-0.35 g and the reflectivity is less than or equal to 11%, the stability of the silicon wafer surface texturing step is judged, and the production is continued. If the detection is unqualified, judging that the surface of the silicon wafer is unqualified, and replacing the texturing liquid medicine and then carrying out production. After the production of 225 batches of TOPCO batteries is completed, the conversion efficiency qualification rate of the TOPCO batteries is 94.5% according to battery performance detection results.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (8)
1. The TOPCON battery texturing stability monitoring method is characterized by comprising the following steps of:
texturing the surface of the silicon wafer to obtain a textured surface with pyramid morphology;
measuring a value of the bottom side length a of the pyramid morphology and a value of the ratio R of the raised surface area;
judging the stability of the texturing process according to the value a and the value R, and when a is more than or equal to 4.0 mu m and less than or equal to 7.0 mu m,
The texturing process is stable; otherwise, adjusting the texturing liquid medicine or/and the technological conditions;
wherein, the calculation formula of the R value is the texturing surface area of the silicon wafer/the silicon wafer area.
2. The method for monitoring the stability of the TOPCON battery texturing as claimed in claim 1, wherein after the surface of the preset batch of silicon wafers is textured, a preset number of silicon wafers are selected, and the a value and the R value of the silicon wafers are measured for on-line judging the stability of the texturing within a preset time interval.
3. The method for monitoring the stability of the TOPCON battery texturing according to claim 1 or 2, wherein a value and an R value are measured by a three-dimensional interference microscope, specifically: more than 3 points are selected on the wool making surface, and the points are respectively tested and averaged.
4. The method for monitoring the texture surface stability of the TOPCON battery according to claim 2, wherein after the texture surface of each 10-60 batches of silicon wafers is performed, 5-20 silicon wafers are selected, and the a value and the R value of the selected silicon wafers are respectively measured.
5. The method for monitoring the texture-making stability of the TOPCON battery according to claim 1, wherein in the step of texture-making the surface of the silicon wafer, the silicon wafer with the resistivity of 1.5-1.7Ω & cm is selected.
6. The method for monitoring the texture-making stability of the TOPCON battery according to claim 1, wherein the step of texture-making on the surface of the silicon wafer comprises the steps of pre-cleaning, primary washing, alkali texture-making, secondary washing, post-cleaning, tertiary washing, acid cleaning, quaternary washing, slow-pulling and drying.
7. The method for monitoring the texture surface stability of the TOPCON battery according to claim 6, wherein the pre-cleaning and the post-cleaning are carried out by adopting a method comprising the steps of KOH with a mass concentration of 1.0-2.0% and H with a mass concentration of 5.0-6.0% 2 O 2 Cleaning the mixture for 100 to 140 seconds at the temperature of between 65 and 70 ℃;
the alkali texturing is to react an aqueous solution containing KOH with the mass concentration of 1.5-2.0% and a texturing additive with the mass concentration of 0.3-0.5% at the temperature of 80-85 ℃ for 400-440 s;
the pickling is to adopt aqueous solution containing 4.5 to 5.5 percent of HCl and 2.5 to 3.0 percent of HF with mass concentration to clean for 100 to 140 seconds at the temperature of between 65 and 70 ℃;
the slow pulling is carried out in water, the slow pulling temperature is 70-80 ℃, and the slow pulling time is 130-170 s;
the drying is carried out at 70-85 ℃ for 130-170 s;
the one-time cleaning is carried out for 100-140 s at 20-35 ℃.
8. The method for monitoring the stability of TOPCon battery texturing as claimed in claim 7, wherein the texturing additive is an aqueous solution comprising the following components in mass concentration: 0.5 to 10 percent of nucleating agent, 1 to 10 percent of suede catalyst, 0.01 to 0.05 percent of surfactant and 0.05 to 0.5 percent of defoaming agent.
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