TW200951205A - Cleaning and etching composition for glass substrate of liquid crystal display device and etching method for glass substrate using the same - Google Patents
Cleaning and etching composition for glass substrate of liquid crystal display device and etching method for glass substrate using the same Download PDFInfo
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- TW200951205A TW200951205A TW098112289A TW98112289A TW200951205A TW 200951205 A TW200951205 A TW 200951205A TW 098112289 A TW098112289 A TW 098112289A TW 98112289 A TW98112289 A TW 98112289A TW 200951205 A TW200951205 A TW 200951205A
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- 238000005530 etching Methods 0.000 title claims abstract description 66
- 239000011521 glass Substances 0.000 title claims abstract description 65
- 239000000758 substrate Substances 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 11
- 238000004140 cleaning Methods 0.000 title abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 150000004673 fluoride salts Chemical class 0.000 claims abstract description 12
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- -1 succinyl amine Chemical class 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 3
- 239000010452 phosphate Substances 0.000 claims 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims 2
- 239000011698 potassium fluoride Substances 0.000 claims 2
- 229910052707 ruthenium Inorganic materials 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 150000003973 alkyl amines Chemical class 0.000 claims 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 235000010755 mineral Nutrition 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 235000003270 potassium fluoride Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 13
- 238000002834 transmittance Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 230000007547 defect Effects 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Chemical class 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005326 engraved glass Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XBSVWZGULSYIEG-UHFFFAOYSA-N ethenyl hypofluorite Chemical class FOC=C XBSVWZGULSYIEG-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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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
-
- 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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
- H01L21/302—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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Surface Treatment Of Glass (AREA)
- Weting (AREA)
- Liquid Crystal (AREA)
- Detergent Compositions (AREA)
Abstract
Description
200951205 六、發明說明： 【明所屬标領3 發明領域 本發明涉及可以同時清洗及蝕刻液晶顯示裝置用玻螭 基板的組成物，具體地涉及包含氟化物鹽、無機酸、表面 活性劑及水的蝕刻液組成物。 L· ity· Ί 發明背景 液晶顯示裝置（liquid crystal display device， LCD device)由於提供基於卓越的解析度的鮮明的影像、耗電 少、可較薄地製作顯示晝面的特性，在平板顯示裝置中最 受到關注。 液晶顯示裝置使用於包括手機、筆記本型PC的移動用 設備及電視，隨著上述設備的薄型、輕量的要求，在構成 LCD裝置的構成因素中減輕重量最大的玻璃基板的重量的 技術變得重要，隨之玻璃基板的蝕刻成為重要的問題。 現有的玻璃基板蝕刻方法（韓國專利登記第815856號) 是利用強毒性、發煙性的氫氟酸(HF)的方法，由此生成了 氫氟石夕酸(HAiF6)。現在’以中國和臺灣為首的各國通過環 境規制逐漸禁止氫氟酸的使用。另外，如過去利用氮氣酸 蝕刻玻璃基板時’蝕刻速度過快，或難以維持坡璃基板的 膜均勻度、光透射性及色再現性等。 作為氧化劑’也有對使用過硫酸鹽的玻螭基板#刻液 (韓國專利登記第248113號、第415261號）的研究，但是過硫 3 200951205 酸鹽的情況下，由於具有自己分解的性質，所以餘刻液保 官安全性降低，存在需要進行低溫保管的問題。 另外’作為黏度調節劑，也有對罐酸、乙二醇、甘醇 等的玻璃基板_液(韓國專利登記第677G52號）的研究，但 是黏度調節劑的添加導致_液_度上升，_大型玻 璃時，存在產生由斑點引起的不良的問題。 【日月内容―】 發明概要 本發明的目的在於，提供一種保管安全性優秀的玻璃 基板的清洗及_組成物及⑽方法，為了廢水處理及工 序上的安全性，不使用氫氟酸，並且容易地調節蝕刻速度， 從而沒有不良地調節玻璃厚度，並維持玻璃基板的瞑均勻 度、光透射性及色再現性。 本發明提供一種蝕刻液組成物，相對於整體蝕刻液組 成物重量包含0.1〜30重量％的氟化物鹽、1〇〜6〇重量％的 無機酸、0.001〜3重量％的表面活性劑、及使組成物總重量 成為100重量％的量的水。 另外，提供一種在液晶顯示裝置製造中包括利用上述 蝕刻液組成物同時清洗及蝕刻玻璃基板的步驟的液晶顯示 裝置用玻璃基板茲刻方法。 若使用根據本發明的一實施例的蝕刻液，則保管安全 性優秀’可以同時進行清洗和蝕刻，容易調節蝕刻速度， 可以製造希望厚度的玻璃基板，可以確保玻璃基板的犋均 勻度、光透射性及色再現性。另外，通過不使用氫氣酸， 200951205 序上的安全性。 可以確保廢水 圖式簡單說啊 苐1圖是用枯 卜 之後由P t、更用氯氟酸的現有的触刻液餘刻玻璃基板BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition capable of simultaneously cleaning and etching a glass substrate for a liquid crystal display device, and particularly to a composition comprising a fluoride salt, a mineral acid, a surfactant, and water. Etching liquid composition. L• ity· 发明 In the liquid crystal display device (LCD device), a liquid crystal display device (LCD device) is provided in a flat panel display device because it provides a clear image based on excellent resolution, consumes less power, and can produce a thinner display surface. Most concerned. The liquid crystal display device is used in a mobile device including a mobile phone or a notebook PC, and a television. With the thin and lightweight requirements of the above-described device, the technology for reducing the weight of the glass substrate having the largest weight among the constituent elements of the LCD device becomes Importantly, the etching of the glass substrate is an important problem. A conventional glass substrate etching method (Korean Patent Registration No. 815856) is a method using a highly toxic and smoky hydrofluoric acid (HF), thereby producing hydrofluorite acid (HAiF6). Now countries such as China and Taiwan have gradually banned the use of hydrofluoric acid through environmental regulations. Further, when the glass substrate is etched by nitrogen gas in the past, the etching rate is too fast, or it is difficult to maintain the film uniformity, light transmittance, color reproducibility, and the like of the glass substrate. As an oxidizing agent, there is also a study on a sulphate substrate using a persulfate (Korean Patent Registration No. 248113, No. 415261), but in the case of a persulfate 3 200951205 acid salt, since it has its own decomposition property, The safety of the remaining liquid security officer is lowered, and there is a problem that it is necessary to perform low temperature storage. In addition, as a viscosity modifier, there is also a study on a glass substrate _ liquid (Korean Patent Registration No. 677G52) of can acid, ethylene glycol, glycol, etc., but the addition of a viscosity modifier causes _ liquid _ degree to rise, _ large In the case of glass, there is a problem that defects are caused by spots. [Summary of the Sun and the Moon] - SUMMARY OF THE INVENTION An object of the present invention is to provide a method for cleaning and constituting a glass substrate having excellent safety, and a method for (10), which does not use hydrofluoric acid for waste water treatment and process safety, and The etching speed is easily adjusted so that the glass thickness is not poorly adjusted, and the uniformity of the glass substrate, the light transmittance, and the color reproducibility are maintained. The present invention provides an etching liquid composition comprising 0.1 to 30% by weight of a fluoride salt, 1 to 6 % by weight of a mineral acid, 0.001 to 3% by weight of a surfactant, and/or a surfactant, based on the weight of the entire etching liquid composition. The total weight of the composition was made into water in an amount of 100% by weight. Further, there is provided a method for etching a glass substrate for a liquid crystal display device comprising the step of simultaneously cleaning and etching a glass substrate by using the above-described etching liquid composition in the production of a liquid crystal display device. When the etching liquid according to an embodiment of the present invention is used, the storage safety is excellent, the cleaning and etching can be performed at the same time, the etching speed can be easily adjusted, the glass substrate of a desired thickness can be manufactured, and the uniformity and light transmission of the glass substrate can be ensured. Sex and color reproducibility. In addition, by not using hydrogen acid, the safety of the 200951205 order. It can be ensured that the waste water pattern is simple. 苐1 is a glass substrate after the use of P t and more chlorofluorofluoric acid.
電子顯微鏡對玻璃基板的厚度和表面進行測 置、拍攝的照片。 J 、J 弟2圖是表级。口 *月人用根據設想的比較例2的I虫刻液钮刻 玻璃基板之後A photograph of the thickness and surface of a glass substrate measured and photographed by an electron microscope. J, J brother 2 is a table level. Mouth *monthly after using the I insect engraving button of Comparative Example 2 to engrave the glass substrate
田命描電子顯微鏡對玻璃基板的厚度和表面 進行測量、拍攝的照片。 第3圖是本微 破璃基板之後^ 用根據設想的比較例3的㈣液姓刻 谁- 3，旦 掃描電子顯微鏡對玻璃基板的厚度和表面 進仃測量、拍攝的照片。 弟4圖是本絡 坡螭基板之後 人用根據設想的比較例4的蝕刻液蝕刻 進行測旦、杯由如描電子顯微鏡對玻璃基板的厚度和表面 '、里柏攝的照片。 破螭基板8之後^^月人用根據設想的比較例5的蝕刻液蝕刻 進行二量、私ί掃描電子顯微鏡對玻璃基板的厚度和表面 ?白躡的照片。 第6圖是本發 坡螭基板之後由*用根據設想的比較例6的蝕刻液蝕刻 進行^量、掃插電子顯微鏡對玻璃基板的厚度和表面 相躡的照片。 第7圖是用祀# + 板之後由掃描電^ y發明的實施例1祕刻液餘刻玻璃基 量、拍攝的^。顯U鏡對玻板的厚度和表面進行測 弟8圖是用押^ 板之後由掃描發明的實施例2的⑽液钱刻玻璃基 包顯微鏡對玻璃基板的厚度和表面進行測 5 200951205 量、拍攝的照片。 【實施方式】 較佳實施例之詳細說明 以下’對本發明進行更詳細的說明。 本發明的钮刻液組成物相對於整體钱刻液組成物重量 包含0.1〜30重量％的氟化物鹽（Flu〇ride salt)、丨〇〜6〇重量％ 的無機酸(Inorganic acid)、〇_〇〇1〜3重量％的表面活性劑、 及使組成物總重量成為100重量％的量的水。本發明的蝕刻 液組成物相對於整體蝕刻液組成物重量還可以包含〇 〇〇1 〜5重量％的银刻抑制劑。 氟化物鹽是蝕刻玻璃基板膜的主成分，可以使用具有 半導體工序用純度的材料。作為氟化物鹽，是包含氟陰離 子F的化合物’可以使用氟化銨NH/、氟化氫銨NH4Hf2、 氣化钟KF、或氟化經LiF等’不特別限定。在本發明的一實 施例中，氟化物鹽相對於整體蝕刻液組成物重量可以包含 0.1〜30重量％，若氟化物鹽的含量不到01重量％，則蝕刻 速度降低，若超過30重量％ ’則由過度蝕刻引起玻璃基板 表面的均勻度降低。 無機酸具有促進玻璃基板的清洗和蝕刻的功能，可以 使用具有半導體功序用純度的材料。作為無機酸可以使用 確酸(Nitric acid)或硫酸(Sulfuric acid)等。在本發明的一實 施例中’無機酸相對於整體蝕刻液組成物重量包含1〇〜6〇 重量％ ’若無機酸的含量不到10重量％，則蝕刻速度降低， 若超過6〇重量％ ’則由過度#刻引起破縣板表面的均句 200951205 度(uniformity)降低。 ^』巧“1為了抑制蝕刻主成分的氟化物的性能來調 即钮刻速度’具有在㈣條件下降減化物的關能力的 功能。蝕刻抑制劑可以使用磷酸鹽(Phosphate)及硼酸鹽 (Boric salt)等 、 岐鹽可以使用[m]h2po4、[M]2HP〇4 或（4)3P04(M-NH4、K：或Na)，作為删酸鹽可以仍使用石朋 酸(Bode acid)。上述餘刻抑制劑可以單獨或混合使用，不 特別限定。在本發明的一實施例中 不包含姓刻抑制劑，The photo of the thickness and surface of the glass substrate was measured by an electron microscope. Fig. 3 is a photograph of the thickness and surface of the glass substrate measured by the scanning electron microscope after the micro-glass substrate was photographed with the (4) liquid of the comparative example 3 according to the assumption. Fig. 4 is a photograph of the thickness and surface of the glass substrate and the surface of the glass substrate by the etching of the etching solution of Comparative Example 4, which was carried out by the human body after the substrate. After the substrate 8 was broken, a photo of the thickness and surface of the glass substrate was measured by etching with an etching solution according to the envisaged Comparative Example 5. Fig. 6 is a photograph of the thickness and surface contrast of the glass substrate by etching with an etching solution according to the presumed Comparative Example 6 after the substrate of the present invention. Fig. 7 is a photograph of the glass base of the etched liquid of Example 1 invented by the scanning electrons after the 祀# + plate, and photographed. The U-mirror is used to measure the thickness and surface of the glass plate. The thickness of the glass substrate and the surface of the glass substrate are measured by the (10) liquid-engraved glass-based package microscope of Example 2 of the invention. Photo taken. [Embodiment] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail. The button engraving composition of the present invention comprises 0.1 to 30% by weight of a fluoride salt (Flu〇ride salt), 丨〇6 to 6% by weight of a mineral acid (Inorganic acid), 〇 with respect to the weight of the whole body engraving composition. _〇〇1 to 3% by weight of the surfactant, and water in an amount such that the total weight of the composition is 100% by weight. The etching liquid composition of the present invention may further contain 银1 to 5% by weight of a silver etching inhibitor with respect to the weight of the entire etching liquid composition. The fluoride salt is a main component of the etching glass substrate film, and a material having a purity for a semiconductor process can be used. The fluoride salt is a compound containing fluorine anion F. The ammonium fluoride NH/, ammonium hydrogen fluoride NH4Hf2, vaporization clock KF, or fluorinated LiF or the like can be used without particular limitation. In an embodiment of the invention, the fluoride salt may comprise 0.1 to 30% by weight based on the weight of the entire etchant composition, and if the fluoride salt content is less than 01% by weight, the etching rate is reduced, if more than 30% by weight. 'The uniformity of the surface of the glass substrate is reduced by over-etching. The inorganic acid has a function of promoting cleaning and etching of the glass substrate, and a material having a purity for semiconductor work can be used. As the inorganic acid, Nitric acid, Sulfuric acid or the like can be used. In one embodiment of the present invention, the 'inorganic acid contains 1 to 6 〇% by weight based on the weight of the entire etchant composition.' If the content of the inorganic acid is less than 10% by weight, the etching rate is lowered, and if it exceeds 6% by weight 'The average sentence of 200951205 degrees (uniformity) is reduced by the excessive ##. ^"Q" "1 in order to suppress the performance of the fluoride of the main component of the etching to adjust the button speed" has the function of reducing the ability to reduce the reduction in (4) conditions. The etching inhibitor can use phosphate (Phosphate) and borate (Boric For salt and the like, [m]h2po4, [M]2HP〇4 or (4)3P04 (M-NH4, K: or Na) can be used, and as the acid salt, Bode acid can still be used. The above-mentioned residual inhibitor may be used singly or in combination, and is not particularly limited. In one embodiment of the present invention, no surname inhibitor is included.
或相對於整體_液組成物重量包含議丨〜5重量％，若以 超過5重量％的量使用敍刻抑制劑，則钱刻速度過度降低而 工序時間變長，從而生產性降低。優選的㈣抑制劑的含 置相對於整體蝕刻液組成物重量為〇·5〜2重量％。 表面活性劑降低蝕刻液的表面張力（Surface tension)和 接觸角（Contact angle)，具有在蝕刻玻璃基板時去除顆粒， 提高膜均勻度的功能。根據本發明的一實施例的表面活性 劑可以由碳原子數為4個以上22個以下構成，優選構成為碳 原子數12個以上18個以下，但不特別限定。 根據本發明的一實施例的表面活性劑使用單獨的陰離 子表面活性劑或非離子表面活性劑、或者陰離子表面活性 劑/非離子表面活性劑的組合。陰離子表面活性劑可以使用 氟代烷基或烴系列。氟代烷基可以使用氟代烷基磺醯胺、 I代烧基績酸鹽、全氟烧基續酸鹽、氟代烧基碟酸鹽系列， 不特別限定。作為烴系列可以使用院基項醯胺、或烧基石黃 酸鹽、烷基磷酸鹽系列，不特別限定。作為非離子表面活 200951205 性劑可以使用氟代氧化乙烯（fluoro oxyethylene)衍生物系 列或聚環氧乙烧(Poly oxyethylene)衍生物系列。 在本發明的一實施例中，表面活性劑相對於整體蝕刻 液組成物重量可以包含0.001〜3重量％，若以不到0.001重 置％使用表面活性劑，則不能降低蝕刻液的表面張力和接 觸角’若以超過3重量％的量使用，則泡沫發生加重，玻璃 基板蝕刻時以障礙要素作用來增加不良發生率。 並且，根據本發明的一實施例的姓刻液是水溶液，必 、I 3對上述必需成分的重量比之和的殘餘的水，使整體 重量比成為100%。這時使用的水可以是超純水。 A以下舉出本實施例更詳細地說明本發明。預先明示下面 實施例所示的構成最終是為了幫助理解發明，在任何情況下 ^不是將本發_技術範_制為實施觸示的方式。 [貫施例 '比較例] 根射述们所示的組成（重量％)製造了触刻液組成 。作為氟化鹽使用氟化氫銨，無機酸〗使用硫酸，2使用 硝酸。作為姓刻抑制劑使用了哪酸。In addition, when the amount of the composition is more than 5% by weight, the use of the scoring inhibitor is excessively lowered, and the process time is prolonged, and the productivity is lowered. The preferred (iv) inhibitor is present in an amount of from 5% to 2% by weight based on the weight of the overall etchant composition. The surfactant lowers the surface tension and the contact angle of the etching liquid, and has a function of removing particles during etching of the glass substrate and improving film uniformity. The surfactant according to an embodiment of the present invention may be composed of 4 or more and 22 or less carbon atoms, and preferably has 12 or more and 18 or less carbon atoms, but is not particularly limited. The surfactant according to an embodiment of the present invention uses a separate anionic surfactant or a nonionic surfactant, or a combination of an anionic surfactant/nonionic surfactant. As the anionic surfactant, a fluoroalkyl group or a hydrocarbon series can be used. The fluoroalkyl group may be, for example, a fluoroalkylsulfonamide, a methicone, a perfluoroalkyl sulfonate or a fluoroalkyl discate, and is not particularly limited. As the hydrocarbon series, a hospital-based guanamine, a pyroline salt, or an alkyl phosphate series can be used, and it is not particularly limited. As the nonionic surface active 200951205, a fluoro oxyethylene derivative series or a poly oxyethylene derivative series can be used. In an embodiment of the present invention, the surfactant may comprise 0.001 to 3% by weight based on the weight of the entire etchant composition. If the surfactant is used at less than 0.001% by reset, the surface tension of the etchant cannot be lowered. When the contact angle is used in an amount of more than 3% by weight, the foam is aggravated, and when the glass substrate is etched, the barrier element acts to increase the incidence of defects. Further, according to an embodiment of the present invention, the surname is an aqueous solution, and the residual water of the weight ratio of I 3 to the above-mentioned essential components is made such that the overall weight ratio becomes 100%. The water used at this time may be ultrapure water. A The present invention will be described in more detail below with reference to the examples. The configuration shown in the following embodiments is clarified in advance to help understand the invention, and in any case, is not a way of implementing the invention. [Comparative Example] Comparative Example The composition (% by weight) shown by the root shots produced a composition of a etchant. As the fluoride salt, ammonium hydrogen fluoride is used, inorganic acid is sulfuric acid, and 2 is nitric acid. Which acid is used as the surname inhibitor.
200951205 [試驗例] 為了對上述製造的實施例及本發明人設想的比較例的 蝕刻液確認性能，以噴塗方式進行了蝕刻。在〇.5mm玻璃 基板上喷塗上述蝕刻液20分鐘蝕刻之後，利用超純水進行 水洗大約1分鐘，使用氮氣使其乾燥。200951205 [Test Example] In order to confirm the performance of the etching liquid of the above-described produced examples and the comparative examples of the inventors of the present invention, etching was performed by spraying. The etching liquid was sprayed on a 55 mm glass substrate for 20 minutes, and then washed with ultrapure water for about 1 minute, and dried with nitrogen gas.
在結束钮刻之後，玻璃基板的厚度和表面由掃描電子 顯微鏡測量，其結果照片示於第1至8圖。表面張力用張力 計(Tension meter)測量，接觸角由接觸角測量儀測量，泡沐 ’肖滅時間是用氮氣產生泡泳1分鐘之後測量了所產生的泡 沐全部消滅的時間。上述測量結果示於下述表2。After the end of the button, the thickness and surface of the glass substrate were measured by a scanning electron microscope, and the results are shown in Figures 1 to 8. The surface tension was measured with a Tension meter, and the contact angle was measured by a contact angle meter. The bubble time was measured by the time when the bubble was completely destroyed by nitrogen for 1 minute. The above measurement results are shown in Table 2 below.
[表2] 玻璃蝕刻速度 (_/分） 玻璃基板缺陷 有/無 表面張力 (mN/m25°C) 接觸角 泡沫消滅時間 (秒）[Table 2] Glass etching rate (_/min) Glass substrate defect With/without Surface tension (mN/m25°C) Contact angle Foam elimination time (seconds)
根據上述表2的結果，使用包含氫氟酸的比較例丄的敍 刻液來姓刻時出現了玻璃基板的缺陷。 另外，如比較例2’若無機酸的含量少’則蝕刻速度慢。 在無機酸為5〇重量％以上時，溫度高為抑左右（比較例* 及5)時速度加快，但是表面張力也升高，所以在玻 填基板產生了缺陷。 這時，通過表面活性劑添加來降低表面張力（實施州 200951205 及2)，則在相同的蝕刻速度下也沒有玻璃基板的缺陷，所 以可以縮短工序時間。 根據實施例1及2的結果，特別是混合使用陰離子表面 活性劑和非離子表面活性劑時，可知表面張力和接觸角更 加減小。 在添加表面活性劑的實施例1及2的情況下，泡沫消滅 時間示出20秒以下，可知沒有由泡沫產生引起的玻璃基板 I虫刻障礙。 【圖式簡單說明3 第1圖是用使用氫氟酸的現有的蝕刻液蝕刻玻璃基板 之後由掃描電子顯微鏡對玻璃基板的厚度和表面進行測 量、拍攝的照片。 第2圖是本發明人用根據設想的比較例2的蝕刻液蝕刻 玻璃基板之後由掃描電子顯微鏡對玻璃基板的厚度和表面 進行測量、拍攝的照片。 第3圖是本發明人用根據設想的比較例3的蝕刻液蝕刻 玻璃基板之後由掃描電子顯微鏡對玻璃基板的厚度和表面 進行測量、拍攝的照片。 第4圖是本發明人用根據設想的比較例4的蝕刻液蝕刻 玻璃基板之後由掃描電子顯微鏡對玻璃基板的厚度和表面 進行測量、拍攝的照片。 第5圖是本發明人用根據設想的比較例5的蝕刻液蝕刻 玻璃基板之後由掃描電子顯微鏡對玻璃基板的厚度和表面 進行測量、拍攝的照片。 10 200951205 第6圖是本發明人用根據設想的比較例6的蝕刻液蝕刻 玻璃基板之後由掃描電子顯微鏡對玻璃基板的厚度和表面 進行測量、拍攝的照片。 第7圖是用根據本發明的實施例1的蝕刻液蝕刻玻璃基 板之後由掃描電子顯微鏡對玻璃基板的厚度和表面進行測 量、拍攝的照片。 第8圖是用根據本發明的實施例2的蝕刻液蝕刻玻璃基 板之後由掃描電子顯微鏡對玻璃基板的厚度和表面進行測 量、拍攝的照片。 【主要元件符號說明】 (無）According to the results of the above Table 2, the defect of the glass substrate occurred when the surrogate of the comparative example containing hydrofluoric acid was used. Further, as in Comparative Example 2', if the content of the inorganic acid was small, the etching rate was slow. When the inorganic acid is 5% by weight or more, the temperature is increased when the temperature is high (Comparative Examples * and 5), but the surface tension is also increased, so that defects occur in the glass-filled substrate. At this time, by reducing the surface tension by the addition of the surfactant (Implementation State 200951205 and 2), there is no defect of the glass substrate at the same etching rate, so that the process time can be shortened. According to the results of Examples 1 and 2, in particular, when an anionic surfactant and a nonionic surfactant were used in combination, it was found that the surface tension and the contact angle were further reduced. In the case of Examples 1 and 2 in which a surfactant was added, the foam elimination time was 20 seconds or less, and it was found that there was no glass substrate I trouble caused by foam generation. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph of a glass substrate which has been etched by a conventional etching solution using hydrofluoric acid, and which has been measured and photographed by a scanning electron microscope. Fig. 2 is a photograph of the thickness and surface of the glass substrate measured by a scanning electron microscope after the inventors etched the glass substrate with the etching liquid of Comparative Example 2 as envisaged. Fig. 3 is a photograph of the thickness and surface of the glass substrate measured by a scanning electron microscope after the inventors etched the glass substrate with the etching liquid of Comparative Example 3 as envisaged. Fig. 4 is a photograph of the thickness and surface of the glass substrate measured by a scanning electron microscope after the inventors etched the glass substrate with the etching liquid of Comparative Example 4 as envisaged. Fig. 5 is a photograph of the thickness and surface of the glass substrate measured by a scanning electron microscope after the inventors etched the glass substrate with the etching liquid of Comparative Example 5 as envisaged. 10 200951205 Fig. 6 is a photograph of the thickness and surface of the glass substrate measured by a scanning electron microscope after the inventors etched the glass substrate with the etching liquid of Comparative Example 6 as envisaged. Fig. 7 is a photograph of the thickness and surface of the glass substrate measured by a scanning electron microscope after etching the glass substrate with the etching liquid of Example 1 of the present invention. Fig. 8 is a photograph of the thickness and surface of the glass substrate measured by a scanning electron microscope after etching the glass substrate with the etching liquid of Example 2 of the present invention. [Main component symbol description] (none)
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| CN108033686A (en) * | 2017-12-14 | 2018-05-15 | 天津美泰真空技术有限公司 | A kind of etching liquid for thinning glass substrate |
| CN107902914A (en) * | 2017-12-14 | 2018-04-13 | 天津美泰真空技术有限公司 | A kind of glass substrate thinning technique etching solution |
| CN108840577B (en) * | 2018-08-20 | 2021-05-14 | 郑州恒昊光学科技有限公司 | Glass etching solution, preparation method thereof and method for preparing anti-glare glass by using glass etching solution |
| CN109052979A (en) * | 2018-10-18 | 2018-12-21 | 江苏金琥珀光学科技股份有限公司 | Etching solution and the processing technology that low haze glare proof glass is realized using the etching solution |
| CN111847894B (en) * | 2020-07-08 | 2023-03-14 | 郑州恒昊光学科技有限公司 | Preparation process of glass with scratch-resistant crystal diamond flash point effect |
| CN114620939B (en) * | 2020-12-09 | 2023-03-14 | Oppo广东移动通信有限公司 | Shell assembly, preparation method thereof and electronic equipment |
| KR20220126436A (en) * | 2021-03-09 | 2022-09-16 | 주식회사 이엔에프테크놀로지 | Etchant composition for display substrate |
| CN116240023A (en) * | 2022-12-08 | 2023-06-09 | 湖北兴福电子材料股份有限公司 | Silicon oxide high-selectivity etching solution |
| CN116639883B (en) * | 2023-05-30 | 2024-05-24 | 郑州恒昊光学科技有限公司 | Manufacturing method of rime-like ice flower effect mobile phone glass rear shell |
| CN118562505A (en) * | 2024-07-31 | 2024-08-30 | 浙江奥首材料科技有限公司 | High-wettability buffer oxide etching solution, and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4620934A (en) * | 1984-04-26 | 1986-11-04 | Allied Corporation | Soluble fluorinated cycloalkane sulfonate surfactant additives for NH4 |
| KR100248113B1 (en) * | 1997-01-21 | 2000-03-15 | 이기원 | Cleaning and etching compositions for electrical display device and substrate |
| US6284721B1 (en) * | 1997-01-21 | 2001-09-04 | Ki Won Lee | Cleaning and etching compositions |
| KR101299131B1 (en) * | 2006-05-10 | 2013-08-22 | 주식회사 동진쎄미켐 | Etching composition for tft lcd |
| CN101054265B (en) * | 2007-05-09 | 2010-05-19 | 信利半导体有限公司 | Glass etching liquid for flat panel display |
-
2008
- 2008-04-15 KR KR1020080034529A patent/KR20090109198A/en not_active Application Discontinuation
-
2009
- 2009-04-14 TW TW098112289A patent/TWI479012B/en active
- 2009-04-14 CN CN200910134360XA patent/CN101560058B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101560058A (en) | 2009-10-21 |
| KR20090109198A (en) | 2009-10-20 |
| CN101560058B (en) | 2012-03-21 |
| TWI479012B (en) | 2015-04-01 |
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