CN114133876B - Alkali polishing auxiliary agent for small tower-shaped silicon chip and application thereof - Google Patents

Alkali polishing auxiliary agent for small tower-shaped silicon chip and application thereof Download PDF

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CN114133876B
CN114133876B CN202111298362.XA CN202111298362A CN114133876B CN 114133876 B CN114133876 B CN 114133876B CN 202111298362 A CN202111298362 A CN 202111298362A CN 114133876 B CN114133876 B CN 114133876B
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polishing
silicon wafer
agent
alkali
adjuvant
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CN114133876A (en
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张新鹏
张鹏伟
冯萍
李侠
殷政
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Xi'an Lanqiao New Energy Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09GPOLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00Polishing compositions
    • C09G1/04Aqueous dispersions
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604Chemical etching
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804Processes 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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention belongs to the technical field of crystalline silicon polishing. An alkali polishing assistant for small tower silicon wafers comprises an assistant A and an assistant B; the adjuvant A comprises the following components in percentage by mass: 0.1-0.5% of silane coupling agent, 2-5% of ethanol, 0.05-0.2% of gelatin, 1-3% of n-butyl alcohol, 0.05-0.2% of sodium dodecyl benzene sulfonate, 0.01-0.05% of perfluoroalkyl polyoxyethylene ether and the balance of deionized water; the adjuvant B comprises the following components in percentage by mass: 0.5-1% of silane coupling agent, 0.1-0.4% of alkyl trimethyl ammonium bromide, 0.01-0.1% of perfluoroalkyl polyoxyethylene ether, 2-5% of ethanol, 1-3% of ammonium persulfate and the balance of deionized water. The alkali polishing auxiliary agent can effectively protect a non-polished surface from being corroded in the alkali polishing process, the alkali corrosion amount of the polished surface is controllable, and the polished silicon wafer pyramid base is small in size, uniform in surface and high in flatness.

Description

Alkali polishing auxiliary agent for small tower-shaped silicon chip and application thereof
Technical Field
The invention belongs to the technical field of crystalline silicon polishing, and particularly relates to a small tower-shaped silicon wafer alkali polishing auxiliary agent and application thereof.
Background
Solar photovoltaic power generation is an important component in a future energy structure, and in a plurality of solar cell routes, a topcon cell is considered to be one of the most promising solar efficient cell technologies in the future due to high power generation efficiency, low cost, low attenuation, simple process flow, good compatibility with the existing perc cell production line and easy upgrading. The mainstream topcon process at present adopts an acid polishing mode, and the method uses a large amount of nitric acid and hydrofluoric acid, so that the cost is high and the environmental protection pressure is high. The alkali polishing technology can effectively solve the problems of cost and environmental protection of acid polishing, but the alkali polishing technology needs a certain amount of corrosion of the silicon wafer, and the corresponding tower base after surface pyramid corrosion is large. The large size of the pyramid base can cause the decrease of the adhesive force of the slurry to the silicon wafer in the screen printing process, the poor contact between the slurry and the silicon wafer, the poor appearance and the reduction of the efficiency, so that the pyramid base with smaller size needs to be formed. Furthermore, the non-polished surface cannot be etched because it is necessary to maintain the pyramid structure, and therefore the silicon dioxide on the front surface needs to be protected from etching in an alkaline solution.
Disclosure of Invention
The invention aims to solve the technical problem of providing the small-tower-shaped silicon wafer alkali polishing auxiliary agent which can effectively protect a non-polished surface from being corroded in the alkali polishing process, the alkali corrosion amount of the polished surface is controllable, and the polished silicon wafer pyramid base has small size, uniform surface and high flatness.
The technical scheme of the invention is as follows:
an alkali polishing assistant for small tower silicon chips comprises an assistant A and an assistant B; the adjuvant A comprises the following components in percentage by mass: 0.1-0.5% of silane coupling agent, 2-5% of ethanol, 0.05-0.2% of gelatin, 1-3% of n-butyl alcohol, 0.05-0.2% of sodium dodecyl benzene sulfonate, 0.01-0.05% of perfluoroalkyl polyoxyethylene ether and the balance of deionized water; the adjuvant B comprises the following components in percentage by mass: 0.5-1% of silane coupling agent, 0.1-0.4% of alkyl trimethyl ammonium bromide, 0.01-0.1% of perfluoroalkyl polyoxyethylene ether, 2-5% of ethanol, 1-3% of ammonium persulfate and the balance of deionized water.
Further, the water is deionized water with the resistivity larger than 15M omega.
The application of the small-pyramid-shaped silicon wafer alkali polishing auxiliary agent in two-step polishing to obtain the small-size pyramid-shaped silicon wafer.
Further, the specific method comprises the following steps:
s1, soaking a silicon wafer in hydrofluoric acid and then performing two-step polishing;
s2, mixing the auxiliary agent A with an alkali aqueous solution to prepare a polishing agent A, and carrying out primary corrosion on the surface of the silicon wafer by using the polishing agent A;
and S3, mixing the auxiliary agent B with an alkali aqueous solution to prepare a polishing agent A, and carrying out secondary corrosion on the surface of the silicon wafer subjected to primary corrosion by using the polishing agent B to obtain the silicon wafer with the small-size pyramid-based structure on the surface.
Further, in the step S1, the concentration of the hydrofluoric acid is 45-50%, the usage volume ratio of the hydrofluoric acid on the silicon wafer is 10-30% (v/v%), and the soaking time is 15-60S.
Further, in the step S2, the alkali is NaOH or KOH, the concentration of the alkali in the polishing agent a is 1 to 4% (v/v%), and the concentration of the adjuvant a in the polishing agent a is 0.5 to 1% (v/v%).
Furthermore, the temperature of the first corrosion is 60-80 ℃, and the corrosion time is 6-9min.
Further, in the step S3, the base is NaOH or KOH, the concentration of the base in the polishing agent B is 2 to 8% (v/v%), and the concentration of the adjuvant B in the polishing agent B is 0.5 to 1% (v/v%).
Further, the temperature of the secondary corrosion is 60-80 ℃, and the corrosion time is 1-6min.
Further, the pyramid base size of the silicon wafer obtained by two-step polishing is 1-10 μm.
The invention has the following beneficial effects:
the polishing auxiliary agent disclosed by the invention is added with a component capable of adsorbing the surface of silicon dioxide, so that the corrosion effect of alkali on the silicon dioxide in the polishing process is inhibited, the non-polished surface of the silicon wafer is protected from being corroded through chemical adsorption and physical adsorption, the corrosion amount of the polished surface is controllable, the size of the pyramid base after corrosion is small, and the uniformity and the flatness of the polished surface after corrosion are high. The polishing auxiliary agent comprises an auxiliary agent A and an auxiliary agent B, both of which comprise a silane coupling agent, and silicon hydroxyl groups hydrolyzed by the silane coupling agent can be condensed with silicon dioxide surface hydroxyl groups and adsorbed to the silicon oxide surface through chemical bonds, so that long-chain carbon chains are grafted on the silicon oxide surface to prevent alkali from corroding the silicon oxide. The auxiliary agent B comprises alkyl trimethyl ammonium bromide, the surface of the soaked silicon wafer is negatively charged, and the alkyl trimethyl ammonium bromide serving as a cationic surfactant can be adsorbed on the surface of the silicon wafer through coulomb force to protect the silicon wafer from being corroded.
The polishing auxiliary agent is applied to two-step polishing of silicon wafers, and uniform and flat silicon wafers with small pyramid base size can be obtained. The silicon wafer is polished by utilizing the anisotropy of alkali in the polishing process, so that the uniformity and the flatness of a polished surface can be improved, and the surface roughness is reduced. The first step of etching is carried out by using the assistant A, the etching amount can be controlled within the range of 0.05-0.2wt%, and the pyramid structure on the surface of the silicon wafer is reserved. And (4) carrying out low-step corrosion by using the auxiliary agent B, removing the pyramid structure to enable the surface to be smooth, and enabling the size of the polished pyramid base to be small.
Drawings
FIG. 1 is a graph showing the morphology of a silicon wafer before polishing in a two-step polishing process in accordance with example 1 of the present invention;
FIG. 2 shows the morphology of a silicon wafer after the first etching step in the two-step polishing of example 1 of the present invention;
FIG. 3 shows the silicon wafer morphology after etching for 1min in the second step, which is applied in two-step polishing in example 1 of the present invention;
FIG. 4 shows the silicon wafer morphology after the second etching step for 1.5min, in which the embodiment 1 of the present invention is applied to the two-step polishing;
FIG. 5 shows the silicon wafer morphology after the second etching step for 2min, in which example 1 of the present invention is applied to two-step polishing;
FIG. 6 shows the silicon wafer morphology after the second etching step for 3min, in which the embodiment 1 of the present invention is applied to two-step polishing;
FIG. 7 shows the silicon wafer morphology after the second etching step for 4min, in the case of the application of embodiment 1 of the present invention to two-step polishing;
FIG. 8 shows the silicon wafer morphology after the second etching step for 6min, as applied to the two-step polishing in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.
The water used in the embodiments of the present invention is deionized water having a resistivity greater than 15M Ω.
Example 1
An alkali polishing assistant for small tower silicon chips comprises an assistant A and an assistant B; comprises an adjuvant A and an adjuvant B; the adjuvant A comprises the following components in percentage by mass: 0.25% of silane coupling agent, 3% of ethanol, 0.15% of gelatin, 2% of n-butyl alcohol, 0.15% of sodium dodecyl benzene sulfonate, 0.25% of perfluoroalkyl polyoxyethylene ether and the balance of deionized water; the adjuvant B comprises the following components in percentage by mass: 0.75% of silane coupling agent, 0.3% of alkyl trimethyl ammonium bromide, 0.5% of perfluoroalkyl polyoxyethylene ether, 3% of ethanol, 2% of ammonium persulfate and the balance of deionized water.
The application of the small tower-shaped silicon wafer alkali polishing auxiliary agent in two-step polishing of silicon wafers comprises the following steps:
s1, soaking a silicon wafer for 30s by using 49% hydrofluoric acid, and performing two-step polishing after soaking by using a volume ratio of 15% (v/v%);
s2, mixing an auxiliary agent A with a NaOH solution with the concentration of 3% (v/v%) to prepare a polishing agent A, wherein the concentration of the auxiliary agent is 0.8% (v/v%), and carrying out primary corrosion on the surface of the silicon wafer by using the polishing agent A, the corrosion temperature is 75 ℃, and the corrosion time is 8min;
s3, mixing the auxiliary agent B with 6% (v/v%) NaOH solution to obtain a polishing agent B, wherein the concentration of the auxiliary agent B is 0.8% (v/v%), performing secondary corrosion on the surface of the silicon wafer subjected to primary corrosion by using the polishing agent B, the corrosion temperature is 75 ℃, the corrosion time is 1-6min, and the pyramid-based structure size on the surface of the silicon wafer is controllable within the range of 1-10 mu m.
The surface topography of the silicon wafer before polishing is shown in figure 1, and the surface of the monocrystalline silicon wafer after texture surface making has a pyramid structure with the size of 2-4 mu m. The surface appearance of the silicon wafer after the first-step corrosion is shown in fig. 2, and the pyramid structure is well reserved on the surface of the silicon wafer. The surface appearance of the silicon wafer after the second step of corrosion for 1min is shown in figure 3, and the pyramid base size on the surface of the silicon wafer is about 1 μm. The surface topography of the silicon wafer after the second etching for 1.5min is shown in FIG. 4, and the pyramid base size on the surface of the silicon wafer is about 1-2 μm. The surface topography of the silicon wafer after the second etching for 2min is shown in FIG. 5, and the pyramid base size on the surface of the silicon wafer is about 2-3 μm. The surface topography of the silicon wafer after 3min of the second step of etching is shown in FIG. 6, and the pyramid base size on the surface of the silicon wafer is about 3-4 μm. The surface topography of the silicon wafer after the second etching for 4min is shown in FIG. 7, and the pyramid base size on the surface of the silicon wafer is about 5-6 μm. The surface topography of the silicon wafer after the second etching for 6min is shown in FIG. 8, and the pyramid base size on the surface of the silicon wafer is about 8-10 μm.
Example 2
An alkali polishing assistant for small tower silicon chips comprises an assistant A and an assistant B; the adjuvant A comprises the following components in percentage by mass: 0.1-0.5% of silane coupling agent, 2-5% of ethanol, 0.05-0.2% of gelatin, 1-3% of n-butyl alcohol, 0.05-0.2% of sodium dodecyl benzene sulfonate, 0.01-0.05% of perfluoroalkyl polyoxyethylene ether and the balance of deionized water; the adjuvant B comprises the following components in percentage by mass: 0.5-1% of silane coupling agent, 0.1-0.4% of alkyl trimethyl ammonium bromide, 0.01-0.1% of perfluoroalkyl polyoxyethylene ether, 2-5% of ethanol, 1-3% of ammonium persulfate and the balance of deionized water.
The application of the small tower-shaped silicon wafer alkali polishing auxiliary agent in two-step polishing of silicon wafers comprises the following steps:
s1, soaking a silicon wafer for 15s by using 49% hydrofluoric acid, and performing two-step polishing after soaking by using the hydrofluoric acid with the volume ratio of 10% (v/v%);
s2, mixing the adjuvant A with a KOH solution with the concentration of 1% (v/v%) to prepare a polishing agent A, wherein the concentration of the adjuvant is 0.5% (v/v%), and carrying out primary corrosion on the surface of the silicon wafer by using the polishing agent A at the corrosion temperature of 60 ℃ for 9min;
s3, mixing the assistant B with a KOH solution with the concentration of 8% (v/v%) to prepare a polishing agent B, wherein the concentration of the assistant B is 1% (v/v%), performing secondary corrosion on the surface of the silicon wafer subjected to primary corrosion by using the polishing agent B, the corrosion temperature is 70 ℃, the corrosion time is 5min, and the obtained surface of the silicon wafer has a pyramid-based structure with the size of 7-8 microns.
Example 3
An alkali polishing assistant for small tower silicon chips comprises an assistant A and an assistant B; the adjuvant A comprises the following components in percentage by mass: 0.1-0.5% of silane coupling agent, 2-5% of ethanol, 0.05-0.2% of gelatin, 1-3% of n-butyl alcohol, 0.05-0.2% of sodium dodecyl benzene sulfonate, 0.01-0.05% of perfluoroalkyl polyoxyethylene ether and the balance of deionized water; the adjuvant B comprises the following components in percentage by mass: 0.5-1% of silane coupling agent, 0.1-0.4% of alkyl trimethyl ammonium bromide, 0.01-0.1% of perfluoroalkyl polyoxyethylene ether, 2-5% of ethanol, 1-3% of ammonium persulfate and the balance of deionized water.
The application of the small tower-shaped silicon wafer alkali polishing auxiliary agent in two-step polishing of silicon wafers comprises the following steps:
s1, soaking a silicon wafer for 30s by using 49% hydrofluoric acid, and performing two-step polishing after soaking by using a volume ratio of 30% (v/v%);
s2, mixing an auxiliary agent A with a NaOH solution with the concentration of 4% (v/v%) to prepare a polishing agent A, wherein the concentration of the auxiliary agent is 1% (v/v%), and carrying out primary corrosion on the surface of the silicon wafer by using the polishing agent A, the corrosion temperature is 80 ℃, and the corrosion time is 9min;
s3, mixing the auxiliary agent B with a KOH solution with the concentration of 2 percent (v/v percent) to prepare a polishing agent B, wherein the concentration of the auxiliary agent B is 0.5 percent (v/v percent), performing secondary corrosion on the surface of the silicon wafer subjected to primary corrosion by using the polishing agent B, the corrosion temperature is 60 ℃, the corrosion time is 1min, and the surface of the obtained silicon wafer has a pyramid-based structure with the size of about 1-2 mu m.
Comparative example
The method for alkali polishing the small tower-shaped silicon chip comprises the following steps:
s1, soaking a silicon wafer for 30s by using 49% hydrofluoric acid, and polishing after soaking by using 15% (v/v%) of a volume ratio;
s2, using 6% (v/v%) NaOH solution as a polishing agent, and corroding the surface of the silicon wafer by using the polishing agent at the corrosion temperature of 75 ℃ for 4min, wherein the pyramid base size on the surface of the silicon wafer after corrosion is about 9-10 microns.
The alkali polishing auxiliary agent can effectively protect a non-polished surface from being corroded in the alkali polishing process, the alkali corrosion amount of the polished surface is controllable, and the polished silicon wafer pyramid base is small in size, uniform in surface and high in flatness.

Claims (8)

1. An application of an alkali polishing auxiliary agent for a small-size pyramid-based silicon wafer in two-step polishing to obtain a small-size pyramid-based silicon wafer is characterized by comprising the following steps:
s1, soaking a silicon wafer in hydrofluoric acid and then performing two-step polishing;
s2, mixing the auxiliary agent A with an alkali aqueous solution to prepare a polishing agent A, and carrying out primary corrosion on the surface of the silicon wafer by using the polishing agent A;
s3, mixing the auxiliary agent B with an alkali aqueous solution to prepare a polishing agent B, and carrying out secondary corrosion on the surface of the silicon wafer subjected to primary corrosion by using the polishing agent B to obtain a silicon wafer with a small-size pyramid-based structure on the surface;
the adjuvant A comprises the following components in percentage by mass: 0.1-0.5% of silane coupling agent, 2-5% of ethanol, 0.05-0.2% of gelatin, 1-3% of n-butyl alcohol, 0.05-0.2% of sodium dodecyl benzene sulfonate, 0.01-0.05% of perfluoroalkyl polyoxyethylene ether and the balance of deionized water; the adjuvant B comprises the following components in percentage by mass: 0.5-1% of silane coupling agent, 0.1-0.4% of alkyl trimethyl ammonium bromide, 0.01-0.1% of perfluoroalkyl polyoxyethylene ether, 2-5% of ethanol, 1-3% of ammonium persulfate and the balance of deionized water.
2. Use according to claim 1, wherein the water is deionized water having a resistivity greater than 15 Μ Ω.
3. The use according to claim 1, wherein in step S1, the concentration of hydrofluoric acid is 45-50%, the usage volume ratio of hydrofluoric acid on the silicon wafer is 10-30%, and the soaking time is 15-60S.
4. Use according to claim 1, characterised in that in step S2 the base is NaOH or KOH, the concentration of base in polishing agent a is between 1 and 4% and the concentration of adjuvant a in polishing agent a is between 0.5 and 1%.
5. The use according to claim 4, wherein the temperature of the first etching is 60-80 ℃ and the etching time is 6-9min.
6. Use according to claim 1, characterised in that in step S3 the base is NaOH or KOH, the concentration of base in polishing agent B is between 2 and 8% and the concentration of adjuvant B in polishing agent B is between 0.5 and 1%.
7. Use according to claim 6, characterized in that the secondary etching is carried out at a temperature of 60-80 ℃ and for a period of 1-6min.
8. Use according to any one of claims 1 to 7, wherein the silicon wafer obtained by the two-step polishing has a pyramid base size of 1 to 10 μm.
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