CN114929836A - Buffer etching solution for non-metal oxide film - Google Patents
Buffer etching solution for non-metal oxide film Download PDFInfo
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- CN114929836A CN114929836A CN202180007457.3A CN202180007457A CN114929836A CN 114929836 A CN114929836 A CN 114929836A CN 202180007457 A CN202180007457 A CN 202180007457A CN 114929836 A CN114929836 A CN 114929836A
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- etching solution
- oxide film
- metal oxide
- buffered
- formula
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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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
- H01L21/02—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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture 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
- H01L21/30—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
Abstract
The invention discloses a buffer etching solution for a non-metal oxide film, which comprises hydrofluoric acid, ammonium fluoride, a penetrating agent, water and a composite modifier, wherein the composite modifier is composed of a compound shown in a formula (I) and a compound shown in a formula (II) which are added in a molar ratio of 2-8: 1; n (C) n F 2n+1 ) 3 In the formula, n is an integer selected from 2-10; NH (NH) 2 ‑C(C m H 2m+1 ) 2 ‑CH 2 OH (II), wherein n is an integer selected from 1 to 6; the etching solution has stronger selective etching capability on silicon dioxide and high etching speed, and basically does not generate over-etching phenomenon on polycrystalline silicon and glass substrates.
Description
Technical Field
The invention relates to the technical field of etching solution, in particular to a buffer etching solution for a non-metal oxide film.
Background
In integrated circuit fabrication processes, silicon dioxide layers can be used as gate oxides in mos devices, protective layers for devices, and isolation of electrical properties, insulating materials, dielectric films for capacitors, and the like. For example, in the OLED manufacturing process, an ILD film (silicon dioxide + silicon nitride) and a GI film (silicon dioxide + silicon nitride) inevitably need to be evaporated, the silicon dioxide film needs to be selectively etched after the yellow light process, and the conventional chemical solution generally adopts a buffered combination of hydrofluoric acid and ammonium fluoride, but during the actual use process, the polysilicon and glass substrate often over-etch, and cannot effectively penetrate into the silicon dioxide layer in the micro-hole, and the selective etching capability of the silicon dioxide is poor, resulting in incomplete etching.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an improved buffer etching solution for a non-metal oxide film, which has stronger selective etching capability on silicon dioxide and high etching speed, and basically does not generate over-etching phenomenon on polysilicon and glass substrates.
In order to solve the technical problem, the technical scheme of the invention is as follows: a buffer etching solution for a non-metal oxide film comprises hydrofluoric acid, ammonium fluoride, a penetrating agent, water and a composite modifier, wherein the composite modifier is composed of a compound shown in a formula (I) and a compound shown in a formula (II) which are added in a molar ratio of 2-8: 1;
N(C n F 2n+1 ) 3 in the formula, n is an integer selected from 2-10;
NH 2 -C(C m H 2m+1 ) 2 -CH 2 OH (II), wherein n is an integer selected from 1 to 6.
According to some preferred and specific aspects of the present invention, the compound represented by formula (i) is a combination of one or more selected from the group consisting of perfluorotriethylamine, perfluorotripropylamine, and perfluorotributylamine.
According to a preferred and specific aspect of the present invention, the compound of formula (ii) is isobutanolamine.
According to some preferred aspects of the present invention, the composite modifier is composed of perfluorotriethylamine and isobutanol amine which are fed in a molar ratio of 3-5: 1.
According to some preferred aspects of the invention, the composite modifier accounts for 0.001-0.1% of the etching solution by mass percentage. Further, the composite modifier accounts for 0.005-0.08% of the etching solution by mass percentage.
According to some preferred aspects of the present invention, the water is high purity water having an electric resistance of 18M Ω · cm or less.
According to the invention, the purity of the hydrofluoric acid and the purity of the ammonium fluoride are both UP grade and above in electronic grade chemicals.
According to some preferred aspects of the present invention, the ammonium fluoride accounts for 1% to 40% of the etching solution by mass%.
According to some preferred aspects of the invention, the etching solution comprises, by mass percent: 0.5 to 5 percent of hydrofluoric acid, 5 to 25 percent of ammonium fluoride, 0.001 to 1 percent of penetrating agent, 0.004 to 0.06 percent of perfluorinated triethylamine, 0.001 to 0.02 percent of isobutanol amine and the balance of water.
In some embodiments of the invention, the osmotic agent comprises an osmotic agent JFC series, a low-foaming osmotic agent series, a fast osmotic agent series, or an osmotic agent OE-35.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention innovatively provides the buffer etching solution for the non-metal oxide film, which has strong selective etching capability on silicon dioxide and high etching speed, and basically does not generate over-etching phenomenon on polysilicon and glass base materials.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not noted are generally those in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art. The penetrant JFC is purchased from Haian petrochemical industry, the purity level of hydrofluoric acid is UP grade, the purity level of ammonium fluoride is UP grade, and the resistance of pure water is 18M omega cm.
Example 1
In the buffered etching solution for a non-metal oxide film of the present embodiment, in terms of mass percentage, the etching solution includes: 1% of hydrofluoric acid, 8% of ammonium fluoride, 0.005% of penetrating agent JFC, 0.004% of perfluorinated triethylamine, 0.001% of isobutanol amine and the balance of water.
The preparation method of the buffer etching solution for the non-metal oxide film comprises the following steps: mixing the components according to the formula amount, dispersing and filtering, wherein the filtrate is the buffer etching solution for the non-metal oxide film.
Example 2
In the buffered etching solution for a non-metal oxide film of the present embodiment, in terms of mass percentage, the etching solution includes: 2% of hydrofluoric acid, 10% of ammonium fluoride, 0.002% of penetrating agent JFC, 0.01% of perfluorinated triethylamine, 0.003% of isobutanol amine and the balance of water.
The preparation method is the same as example 1.
Example 3
In the buffered etching solution for a non-metal oxide film of the present embodiment, in terms of mass percentage, the etching solution includes: 5% of hydrofluoric acid, 15% of ammonium fluoride, 0.005% of penetrating agent JFC, 0.04% of perfluorinated triethylamine, 0.01% of isobutanol amine and the balance of water.
The preparation method is the same as example 1.
Example 4
In the buffered etching solution for a non-metal oxide film of the present embodiment, in terms of mass percentage, the etching solution includes: 3% of hydrofluoric acid, 10% of ammonium fluoride, 0.005% of penetrating agent JFC, 0.05% of perfluorinated triethylamine, 0.01% of isobutanol amine and the balance of water.
The preparation method is the same as example 1.
Comparative example 1
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: the addition amount of water is adjusted correspondingly without adding perfluorinated triethylamine and isobutanolamine.
Comparative example 2
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: the addition amount of the isobutanolamine is correspondingly adjusted to be 0.005 percent without adding perfluorinated triethylamine.
Comparative example 3
Basically, the method is the same as the embodiment 1, and the differences are that: the addition amount of perfluorotriethylamine was adjusted to 0.005% without isobutanol amine.
Examples of the experiments
The etching solutions prepared in examples 1 to 4 and comparative examples 1 to 3 were used to perform an etching experiment on a polysilicon substrate, a glass substrate, and a silicon dioxide layer, respectively, at an etching temperature of 25 ℃ for 2min, and the results are shown in table 1:
TABLE 1
Peeling of the polysilicon substrate: does not fall off: @ or; and (3) dropping trace: #; the shedding is obvious: and &; residual amount of silica layer: good: no residue is left; o: trace residue is left; very good: and the residue is obvious.
As can be seen from the above table, the etching solution of the present invention has highly selective etching to the silicon oxide film layer in the manufacturing process, the etching rate is efficient and controllable, and no step appears after etching; the etching solution does not etch the contact layer ILD film and the GI film layer, the efficiency of the etching rate of the polysilicon substrate and the glass substrate is less than the maximum degree, the over-etching of the polysilicon substrate and the glass substrate is avoided, and meanwhile, the etching solution can quickly wet micropores and completely etch the silicon dioxide layer.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (10)
1. A buffer etching solution for a non-metal oxide film comprises hydrofluoric acid, ammonium fluoride, a penetrating agent and water, and is characterized in that the etching solution also comprises a composite modifier, wherein the composite modifier is composed of a compound shown in a formula (I) and a compound shown in a formula (II) which are fed in a molar ratio of 2-8: 1;
N(C n F 2n+1 ) 3 in the formula, n is an integer selected from 2-10;
NH 2 -C(C m H 2m+1 ) 2 -CH 2 OH (II), wherein n is an integer selected from 1 to 6.
2. The buffered etching solution for a non-metal oxide film according to claim 1, wherein the compound represented by formula (I) is one or more selected from the group consisting of perfluorotriethylamine, perfluorotripropylamine, and perfluorotributylamine.
3. The buffered etchant for a non-metal oxide film according to claim 1, wherein the compound represented by formula (II) is isobutanolamine.
4. The buffered etching solution for a non-metal oxide film as defined in claim 1, wherein the composite modifier comprises perfluorotriethylamine and isobutanol amine at a molar ratio of 3-5: 1.
5. The buffered etching solution for a non-metal oxide film according to claim 1, wherein the composite modifier accounts for 0.001 to 0.1% of the etching solution in terms of mass percentage.
6. The buffered etching solution for a non-metal oxide film according to claim 5, wherein the composite modifier accounts for 0.005 to 0.08 percent of the etching solution in terms of mass percentage.
7. The buffered etchant for a non-metal oxide film according to claim 1, wherein the water is high purity water having a resistance of 18M Ω -cm or less.
8. The buffered etchant for a non-metal oxide film according to claim 1, wherein the purity of the hydrofluoric acid and the purity of the ammonium fluoride are both UP grade and higher in electronic grade chemicals.
9. The buffered etching solution for a non-metal oxide film according to claim 1, wherein the ammonium fluoride accounts for 1 to 40 mass% of the etching solution.
10. The buffered etching solution for a non-metal oxide film according to claim 1, wherein the etching solution comprises, in terms of mass%, in the following amount: 0.5 to 5 percent of hydrofluoric acid, 5 to 25 percent of ammonium fluoride, 0.001 to 1 percent of penetrating agent, 0.004 to 0.06 percent of perfluorinated triethylamine, 0.001 to 0.02 percent of isobutanol amine and the balance of water.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2021/136060 WO2023102726A1 (en) | 2021-12-07 | 2021-12-07 | Buffer etching solution for nonmetal oxide film |
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| CN114929836A true CN114929836A (en) | 2022-08-19 |
| CN114929836B CN114929836B (en) | 2023-06-27 |
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| KR20050034890A (en) * | 2003-10-10 | 2005-04-15 | 삼성전자주식회사 | Method for manufacturing shallow trench isolation in semiconductor device preventable void |
| CN103756680A (en) * | 2013-12-31 | 2014-04-30 | 浙江凯圣氟化学有限公司 | Method for preparing BOE (Buffer Oxide Etch) etching liquid |
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| CN103992043A (en) * | 2014-05-15 | 2014-08-20 | 奇瑞汽车股份有限公司 | Preparation method of hydrophobing agent |
| CN107250914A (en) * | 2015-02-26 | 2017-10-13 | 富士胶片株式会社 | Upper layer film formation composition and the pattern formation method of the upper layer film formation composition and the manufacture method of electronic device are used |
| CN108384548A (en) * | 2018-02-24 | 2018-08-10 | 苏州晶瑞化学股份有限公司 | A kind of nonmetal oxide film buffered etch liquid |
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| JPS63283028A (en) * | 1986-09-29 | 1988-11-18 | Hashimoto Kasei Kogyo Kk | Treating agent for fine working surface |
| KR101349975B1 (en) * | 2011-11-17 | 2014-01-15 | 주식회사 이엔에프테크놀로지 | Etchant composition for molybdenium alloy layer and indium oxide layer |
| WO2018047011A2 (en) * | 2016-09-12 | 2018-03-15 | Premium Genetics (Uk) Ltd. | Method and system for hydrophobic coating of microfluidic chips |
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2021
- 2021-12-07 WO PCT/CN2021/136060 patent/WO2023102726A1/en unknown
- 2021-12-07 CN CN202180007457.3A patent/CN114929836B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1334492A (en) * | 2000-07-07 | 2002-02-06 | 富士胶片株式会社 | Method for making lithographic plate |
| KR20050034890A (en) * | 2003-10-10 | 2005-04-15 | 삼성전자주식회사 | Method for manufacturing shallow trench isolation in semiconductor device preventable void |
| CN103756680A (en) * | 2013-12-31 | 2014-04-30 | 浙江凯圣氟化学有限公司 | Method for preparing BOE (Buffer Oxide Etch) etching liquid |
| CN103756681A (en) * | 2013-12-31 | 2014-04-30 | 浙江凯圣氟化学有限公司 | BOE (buffer oxide etchant) composition |
| CN103992043A (en) * | 2014-05-15 | 2014-08-20 | 奇瑞汽车股份有限公司 | Preparation method of hydrophobing agent |
| CN107250914A (en) * | 2015-02-26 | 2017-10-13 | 富士胶片株式会社 | Upper layer film formation composition and the pattern formation method of the upper layer film formation composition and the manufacture method of electronic device are used |
| CN108384548A (en) * | 2018-02-24 | 2018-08-10 | 苏州晶瑞化学股份有限公司 | A kind of nonmetal oxide film buffered etch liquid |
| CN111471463A (en) * | 2020-04-24 | 2020-07-31 | 湖北兴福电子材料有限公司 | Etching solution for silicon dioxide film |
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| Publication number | Publication date |
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| CN114929836B (en) | 2023-06-27 |
| WO2023102726A1 (en) | 2023-06-15 |
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