CN110820048B - Metal ion-assisted non-nitric acid polishing method - Google Patents

Metal ion-assisted non-nitric acid polishing method Download PDF

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CN110820048B
CN110820048B CN201911186539.XA CN201911186539A CN110820048B CN 110820048 B CN110820048 B CN 110820048B CN 201911186539 A CN201911186539 A CN 201911186539A CN 110820048 B CN110820048 B CN 110820048B
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metal ion
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cleaning
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CN110820048A (en
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常洪进
刘宇琛
万鹏
侯成成
管自生
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Nanjing Naxin New Material Co ltd
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    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/08—Etching
    • C30B33/10—Etching in solutions or melts
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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    • C30B29/02—Elements
    • C30B29/06—Silicon
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    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment 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
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604—Chemical etching
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
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    • H—ELECTRICITY
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    • 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
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Abstract

The invention relates to the technical field of monocrystalline silicon solar cells, and discloses a metal ion-assisted non-nitric acid polishing method, which comprises the following steps: s1: preparing a polishing solution: dissolving 1.5-5 ml/L of silver nitrate solution, 0.1-5% of organic acid, 0.5-5% of ammonium bifluoride and 10-40% of hydrogen peroxide in the balance of deionized water in sequence, and uniformly mixing; s2: heating and polishing: heating the polishing solution obtained in the step S1 to 55-70 ℃, and putting the single crystal texturing sheet into the polishing solution for polishing within 90-360 seconds; s3: cleaning: and cleaning the polished monocrystal flocking sheet in the step S2. The metal ion-assisted non-nitric acid polishing method can solve the problems of low reflectivity, poor stability and high consumption at present.

Description

Metal ion-assisted non-nitric acid polishing method
Technical Field
The invention relates to the technical field of monocrystalline silicon solar cells, in particular to a metal ion-assisted non-nitric acid polishing method.
Background
The core of the local contact back Passivation (PERC) solar cell is that the back of a silicon wafer is covered by aluminum oxide and silicon nitride to play the roles of passivating the surface and improving long-wave response, thereby improving the conversion efficiency of the cell. The uniformity of the reflectivity of the etched silicon wafer determines the uniformity of the back passivation coating film and also determines the uniformity of the laser aperture ratio and size, so that the etching plays a significant role in the whole production process of the PERC battery.
At present, a chain machine hydrofluoric acid/nitric acid mixed acid back polishing process is mainly used, and the steps are as follows: floating a silicon wafer on etching liquid consisting of hydrofluoric acid/nitric acid, removing phosphosilicate glass (PSG) on the back and the edge, and polishing the back; removing the porous silicon and neutralizing the acid liquor on the surface of the silicon wafer by NaOH aqueous solution; and thirdly, removing the phosphorosilicate glass on the front side of the silicon wafer by hydrofluoric acid aqueous solution. The prior acid polishing process has three problems: the reflectivity is difficult to improve at 30-35 percent, and the stability is poor; consumption of hydrofluoric acid/nitric acid in the etching process is large, and waste liquid is difficult to treat and expensive: and the generated waste liquid has great harm to the environment.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a metal ion-assisted non-nitric acid polishing method, which has the advantage of improving the reflecting surface and solves the problems of low reflectivity, poor stability and high consumption at present.
(II) technical scheme
In order to realize the purpose of improving the reflecting surface, the invention provides the following technical scheme: a metal ion-assisted non-nitric acid polishing method comprises the following steps:
s1: preparing a polishing solution: dissolving 1.5-5 ml/L of silver nitrate solution, 0.1-5% of organic acid, 0.5-5% of ammonium bifluoride and 10-40% of hydrogen peroxide in the balance of deionized water in sequence, and uniformly mixing;
s2: heating and polishing: heating the polishing solution obtained in the step S1 to 55-70 ℃, and putting the single crystal texturing sheet into the polishing solution for polishing within 90-360 seconds;
s3: cleaning: and cleaning the polished monocrystal flocking sheet in the step S2.
Preferably, the organic acids include citric acid, acetic acid, glycolic acid, malic acid, lactic acid and oxalic acid.
(III) advantageous effects
Compared with the prior art, the invention provides a metal ion-assisted non-nitric acid polishing method, which has the following beneficial effects:
according to the metal ion-assisted non-nitric acid polishing method, the components used by the polishing solution are safe and stable, pollution is not easily caused, the reflection capacity of the surface of a silicon wafer can be obviously improved on the premise of controlling the weight reduction of the silicon wafer, appropriate reaction time can be obtained, the single crystal texturing sheet obtained after polishing is microscopically uniform and flatter, and meanwhile, the consumption of the polishing solution is low.
Drawings
FIG. 1 is a schematic view of a textured microstructure of a single-crystal texturing sheet in a metal ion-assisted non-nitric acid polishing method according to the present invention before polishing;
FIG. 2 is a schematic view of a textured microstructure of a single-crystal textured sheet polished under different organic acids in a metal ion-assisted non-nitric acid polishing method provided by the invention;
FIG. 3 is a comparison graph of wavelength-reflectance curves before and after polishing of a single-crystal texturing sheet in a stoichiometric ratio in a metal ion-assisted non-nitric acid polishing method provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1-3, a metal ion assisted non-nitric polishing method comprises the following steps:
s1: preparing a polishing solution: 0.5% of citric acid, 3ml/L of silver nitrate solution, 2% of ammonium bifluoride and 30% of hydrogen peroxide are dissolved in the balance of deionized water in sequence and are uniformly mixed, HF 2-in the ammonium bifluoride has a faster etching rate, the citric acid has a good metal ion chelation effect, and hydroxyl on alpha carbon has more active property under the combined action of three adjacent carboxyl groups, has stronger reducibility, is easy to dissolve in water and is suitable for an acidic environment, and the two are matched for use, so that the polishing solution has an ideal effect in the polishing process;
s2: heating and polishing: heating the polishing solution obtained in the step S1 to 65 ℃, and putting the single-crystal flocking sheet into the polishing solution for polishing for less than 150S;
s3: cleaning: and cleaning the polished monocrystal flocking sheet in the step S2.
Example 2
Referring to fig. 1-3, a metal ion assisted non-nitric polishing method comprises the following steps:
s1: preparing a polishing solution: dissolving 0.5% of citric acid, 3ml/L of silver nitrate solution, 2% of ammonium bifluoride and 30% of hydrogen peroxide in the balance of deionized water in sequence, and uniformly mixing;
s2: heating and polishing: heating the polishing solution obtained in the step S1 to 65 ℃, and putting the single-crystal flocking sheet into the polishing solution for polishing for less than 150S;
s3: cleaning: and cleaning the polished monocrystal flocking sheet in the step S2.
Example 3
Referring to fig. 1-3, a metal ion assisted non-nitric polishing method comprises the following steps:
s1: preparing a polishing solution: dissolving 0.5% of glycolic acid, 3ml/L of silver nitrate solution, 2% of ammonium bifluoride and 30% of hydrogen peroxide in the balance of deionized water in sequence, and uniformly mixing;
s2: heating and polishing: heating the polishing solution obtained in the step S1 to 65 ℃, and putting the single-crystal flocking sheet into the polishing solution for polishing for less than 150S;
s3: cleaning: and cleaning the polished monocrystal flocking sheet in the step S2.
Example 4
Referring to fig. 1-3, a metal ion assisted non-nitric polishing method comprises the following steps:
s1: preparing a polishing solution: dissolving 0.5% of malic acid, 3ml/L of silver nitrate solution, 2% of ammonium bifluoride and 30% of hydrogen peroxide in the balance of deionized water in sequence, and uniformly mixing;
s2: heating and polishing: heating the polishing solution obtained in the step S1 to 65 ℃, and putting the single-crystal flocking sheet into the polishing solution for polishing for less than 150S;
s3: cleaning: and cleaning the polished monocrystal flocking sheet in the step S2.
Example 5
Referring to fig. 1-3, a metal ion assisted non-nitric polishing method comprises the following steps:
s1: preparing a polishing solution: dissolving 0.5% of lactic acid, 3ml/L of silver nitrate solution, 2% of ammonium bifluoride and 30% of hydrogen peroxide in the balance of deionized water in sequence, and uniformly mixing;
s2: heating and polishing: heating the polishing solution obtained in the step S1 to 65 ℃, and putting the single-crystal flocking sheet into the polishing solution for polishing for less than 150S;
s3: cleaning: and cleaning the polished monocrystal flocking sheet in the step S2.
Example 6
Referring to fig. 1-3, a metal ion assisted non-nitric polishing method comprises the following steps:
s1: preparing a polishing solution: dissolving 0.5% of oxalic acid, 3ml/L of silver nitrate solution, 2% of ammonium bifluoride and 30% of hydrogen peroxide in the balance of deionized water in sequence, and uniformly mixing;
s2: heating and polishing: heating the polishing solution obtained in the step S1 to 65 ℃, and putting the single-crystal flocking sheet into the polishing solution for polishing for less than 150S;
s3: cleaning: and cleaning the polished monocrystal flocking sheet in the step S2.
Comparative example one:
the conventional method for polishing hydrofluoric acid and nitric acid at present comprises the following steps: hydrofluoric acid and nitric acid were dissolved in 1L of deionized water to obtain 1000g of acidic polishing solution.
TABLE 1 comparison of reflectivity results for groups of treated monocrystalline silicon wafers
Group of Reflectivity of light
Example one 43％
Example two 38％
EXAMPLE III 41％
Example four 46％
EXAMPLE five 44％
EXAMPLE six 40％
Comparative example 1 35％
As can be seen from table 1, compared with the conventional hydrofluoric acid/nitric acid back-polishing system, different organic acids (citric acid, acetic acid, glycolic acid, malic acid, lactic acid, oxalic acid) can be matched with silver nitrate, hydrogen peroxide, and ammonium bifluoride to achieve the purpose of improving the reflectivity of the back-polished silicon wafer, and the high reflectivity of the back surface can better improve the uniformity of the back passivation coating film and the uniformity of the laser aperture ratio and size, thereby achieving the effect of improving the electrochemical performance of the PERC battery.
In summary, the metal ion-assisted non-nitric acid polishing method has the advantages that the components used by the polishing solution are safe and stable, pollution is not easily caused, the reflection capability of the surface of a silicon wafer can be obviously improved under the premise of controlling the weight reduction of the silicon wafer by the polishing solution, the proper reaction time can be obtained, the single crystal texturing sheet obtained after polishing is microscopically uniform and flatter, and meanwhile, the consumption of the polishing solution is low.
It is to be noted that the term "comprises," "comprising," or any other variation thereof is intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (2)

1. A metal ion-assisted non-nitric acid polishing method is characterized by comprising the following steps:
s1: preparing a polishing solution: dissolving 1.5-5 ml/L of silver nitrate solution, 0.1-5% of organic acid, 0.5-5% of ammonium bifluoride and 10-40% of hydrogen peroxide in the balance of deionized water in sequence, and uniformly mixing;
s2: heating and polishing: heating the polishing solution obtained in the step S1 to 55-70 ℃, and putting the single crystal texturing sheet into the polishing solution for polishing for 90-360 seconds;
s3: cleaning: and cleaning the polished monocrystal flocking sheet in the step S2.
2. The metal ion-assisted non-nitric polishing method of claim 1, wherein: the organic acids include citric acid, acetic acid, glycolic acid, malic acid, lactic acid, and oxalic acid.
CN201911186539.XA 2019-11-28 2019-11-28 Metal ion-assisted non-nitric acid polishing method Expired - Fee Related CN110820048B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1402309A (en) * 2001-08-20 2003-03-12 中国科学院半导体研究所 Proces for polishing indium phosphide single crystal wafer
CN108250976A (en) * 2016-12-28 2018-07-06 安集微电子（上海）有限公司 A kind of chemical mechanical polishing liquid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1402309A (en) * 2001-08-20 2003-03-12 中国科学院半导体研究所 Proces for polishing indium phosphide single crystal wafer
CN108250976A (en) * 2016-12-28 2018-07-06 安集微电子（上海）有限公司 A kind of chemical mechanical polishing liquid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Synthesis of Silicon Nanowire Arrays by Metal-Assisted Chemical Etching in Aqueous NH4HF2 Solution;S. Naama et al.;《Journal of Nano Research》;20121227;第21卷;参见第110页第2段 *
单面抛光在PERC电池中应用的研究;赵保星等;《太阳能技术产品与工程》;20170817(第6期);第23-26页 *

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