WO2020062590A1 - 一种铜钼合金膜的化学蚀刻用组合物 - Google Patents

一种铜钼合金膜的化学蚀刻用组合物 Download PDF

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Publication number
WO2020062590A1
WO2020062590A1 PCT/CN2018/119835 CN2018119835W WO2020062590A1 WO 2020062590 A1 WO2020062590 A1 WO 2020062590A1 CN 2018119835 W CN2018119835 W CN 2018119835W WO 2020062590 A1 WO2020062590 A1 WO 2020062590A1
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Prior art keywords
etching
acid
composition
copper
hydrogen peroxide
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PCT/CN2018/119835
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English (en)
French (fr)
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赵大成
康威
陈思宇
郑春怀
鄢艳华
张文涛
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惠州市宙邦化工有限公司
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Publication of WO2020062590A1 publication Critical patent/WO2020062590A1/zh

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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
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition

Definitions

  • the invention relates to the field of etching technology, in particular to a composition for chemical etching of a copper-molybdenum alloy film.
  • Etching is the technique of removing material using a chemical reaction or physical impact. Etching technology is divided into wet etching and dry etching. Among them, wet etching uses chemical reagents to achieve the purpose of etching through chemical reactions.
  • a multilayer film containing copper and a copper-molybdenum alloy containing copper as a main component is formed on a substrate such as glass by a film formation process such as a sputtering method, and then subjected to an etching step of etching using a resist or the like as a mask.
  • a film formation process such as a sputtering method
  • an etching step of etching using a resist or the like as a mask By forming an electrode pattern, a wiring having good electrical conductivity and thermal conductivity is prepared.
  • the present invention provides a copper-molybdenum alloy film etching solution with long service life, no residue in etching, high etching efficiency and high precision, little corrosion to the substrate, and environmental friendliness.
  • the invention provides a composition for chemical etching of a copper-molybdenum alloy film.
  • the total weight of the composition for etching is 100%, and the composition includes the following components:
  • hydrogen peroxide is used as the main oxidant of the copper-molybdenum alloy.
  • the addition of hydrogen peroxide in the range of 5% to 15% can ensure that the etching is effectively performed, and at the same time, the etching rate can be controlled to maintain it in a suitable range, which is easier. Control the amount of etching to avoid over-etching; add organic acid to promote the dissolution of copper that is oxidized by peroxyhydroxide. If the amount of organic acid is less than 0.5%, it will easily produce etching residues during the etching process. ; By adding a hydrogen peroxide stabilizer, the decomposition rate of hydrogen peroxide can be reduced, and the service life of the composition can be prolonged.
  • the chelating agent is used to form a chelate complex with metal ions generated during the etching process, thereby deactivating it, thereby suppressing the decomposition reaction of hydrogen peroxide in the etching solution. If the addition amount is less than 2.0%, it cannot be compared with that generated during the etching process. The metal ions are completely chelated, and the production cost is increased if the amount is greater than 7.0%; at the same time, in order to adjust the metal etching rate, the present invention also adds The etching additive is used to slow down the etching rate.
  • the added etching additive is mainly a corrosion inhibitor, which makes it easy to control the etching rate of the prepared etching composition.
  • the addition amount is less than 0.001% and the corrosion inhibition effect cannot be achieved.
  • the addition amount is greater than 0.5%. It can suppress the etching activity, reduce the etching rate, and affect the accuracy of the etching.
  • the addition of surfactant is to ensure the wettability and permeability of the substrate for the etching composition, and effectively improve the etching rate.
  • the addition amount is less than 0.03%.
  • the present invention uses hydrogen peroxide as the main oxidant.
  • hydrogen peroxide stabilizers and chelating agents By adding hydrogen peroxide stabilizers and chelating agents, the decomposition of hydrogen peroxide during the etching process is suppressed, the etching reaction process is mild and the service life is extended.
  • the following components are included:
  • the present invention uses hydrogen peroxide as the main oxidant, and suppresses the decomposition of hydrogen peroxide during the etching process by adding hydrogen peroxide stabilizers and chelating agents, so that the etching reaction process is mild and the service life is prolonged.
  • Organic acids and phosphate esters react with copper and molybdenum generated during the etching process, so that no etching residues are generated during the etching process, and the stability of the etching composition is improved by using pH adjusters and surfactants as auxiliary agents And the wettability and permeability to the substrate, improve its applicability.
  • the following components are included:
  • the chemical etching composition prepared according to the above weight percentage does not generate etching residue at all during the etching process, effectively inhibits the etching of the glass substrate, and efficiently and accurately etches the copper-molybdenum alloy film under mild working conditions.
  • the operation is very convenient and easy to control, and the service life can reach more than 8000ppm.
  • organic acid is one or more of tartaric acid, isoleucine, valine, salicylic acid, and glycolic acid.
  • Organic acids can promote the dissolution of copper that has been subjected to hydrogen peroxide oxidation.
  • the organic acids selected have good stability and moderate acidity to ensure a mild reaction process.
  • the hydrogen peroxide stabilizer is an aminocarboxylic acid type hydrogen peroxide stabilizer, an organic phosphonic acid compound, an organic phosphonate, a poly (poly) carboxylic acid type hydrogen peroxide stabilizer, diethylamine pentaacetic acid, One or more of phenylurea, 8-hydroxyquinoline, and polyacrylamine.
  • the hydrogen peroxide stabilizer used in the present invention is a complex stabilizer. It forms a chelate compound with heavy metal ions generated during the etching process, thereby reducing or eliminating the decomposition of heavy metal ions by hydrogen peroxide, which prevents the catalytic decomposition of metal ions.
  • the ability is greater than that of adsorption stabilizers, it has a certain chelating and shielding effect on metal ions, and can inhibit the catalytic damage of metal ions to a certain extent.
  • the metal chelating agent is ethylenediaminetetraacetic acid, aminotriacetic acid, diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, gluconic acid and their corresponding One or more of salt and phytic acid.
  • a metal chelator is added to assist the hydrogen peroxide stabilizer to chelate with other metal ions such as magnesium ions, calcium ions, ferrous ions, etc., and reduce the influence of other metal ions on the stability of the etching composition.
  • the etching additive is 5-aminotetrazole, 3-amino-1,2,4-triazole, benzotriazole, hydroxymethylbenzotriazole, imidazole, benzimidazole, polyhydroxy One or more of benzoic acid and thiourea.
  • Etching additives can effectively prevent side corrosion, make the etched lines straight without burrs, and add stability to the etching rate, stabilize the concentration of the etching solution to prevent crystallization, increase the complexation capacity of copper, increase the dissolution capacity, and effectively extend the service life. .
  • the phosphoric acid-based substance is one or two of monobutyl phosphite, monobutyl phosphate, diethyl phosphite, and diethyl phosphate.
  • the added phosphoric acid can react with the molybdenum generated during the etching process to solve the problem of molybdenum residue, and make the etching surface smooth without molybdenum residue.
  • the pH adjusting agent is any one of sodium hydroxide, potassium hydroxide, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, and isopropanolamine. Adding a pH adjuster to form a buffer system ensures that the overall pH value of the etching composition is in a relatively stable state and ensures an etching rate.
  • the surfactant is one or more of polysorbate 80, PE-100, 188-A, and fatty alcohol polyoxyethylene ether. Adding a surfactant can effectively improve the wettability and permeability of the etching composition to the substrate and increase the etching rate.
  • the selected surfactant is a common reagent on the market, which is easy to obtain and has low cost.
  • the present invention uses hydrogen peroxide as the main oxidant. By controlling the amount of hydrogen peroxide added to ensure that the etching is effectively performed, it also controls the etching rate to maintain within a suitable range to ensure the efficiency of the etching. Etching additives effectively prevent side corrosion, making the etched lines straight without burrs, and the accuracy of the lines obtained by etching is high;
  • the service life is long; the oxidant hydrogen peroxide is easily decomposed into water and oxygen during the etching process, reducing the etching ability of the etching composition, making it short in service life and increasing the cost of etching.
  • the present invention adds a hydrogen peroxide stabilizer Forms a chelate with heavy metal ions generated during the etching process, thereby reducing or eliminating the decomposition of heavy metal ions by hydrogen peroxide, to a certain extent, can inhibit the catalytic damage of metal ions, slow down the decomposition rate of hydrogen peroxide, and add etching additives to stabilize Etching speed, stable etching solution concentration to prevent crystallization, increase the complexing capacity of copper and increase the dissolving capacity, thereby effectively extending the service life, so that the service life of the composition for etching can reach more than 8000 ppm;
  • the present invention promotes the dissolution of the copper hydroxide oxidized by adding an organic acid, and the selected organic acid has good stability and ensures the continuous dissolution of the oxidized copper during the etching process. And cooperate with the addition of phosphoric acid and molybdenum generated during the etching process to solve the problem of residual molybdenum, make the etching surface smooth without etching residue, and make the etching surface smooth without burrs;
  • the reaction conditions are mild, and the operation is convenient and easy to control.
  • the present invention can control the etching while maintaining the etching within a suitable range, thereby making it easy to control the amount of etching.
  • the invention can be poured only at the site where the etching is required, and the operation is convenient.
  • the addition of a pH adjuster, a hydrogen peroxide stabilizer, a chelating agent and the like makes the composition for etching stable, and the etching can be performed at normal temperature.
  • the reaction has mild reaction conditions and also improves the controllability of the etching process.
  • a composition for chemical etching of a copper-molybdenum alloy film, based on the total weight of the etching composition being 100%, comprising the following components:
  • the organic acid is isoleucine
  • the hydrogen peroxide stabilizer is polyacrylic acid amine
  • the metal chelator is ethylenediaminetetraacetic acid
  • the etching additive is thiourea
  • the surfactant is PE-100
  • the phosphate ester substance is phosphate monophosphate.
  • Butyl ester, and the pH adjuster was sodium hydroxide.
  • a composition for chemical etching of a copper-molybdenum alloy film, based on the total weight of the etching composition being 100%, comprising the following components:
  • the organic acid is salicylic acid
  • the hydrogen peroxide stabilizer is DTPA
  • the metal chelator is gluconic acid
  • the etching additive is 3-amino-1,2,4-triazole
  • the surfactant is 188-A
  • the phosphate ester is The substance is monobutyl phosphite
  • the pH adjuster is triethanolamine.
  • a composition for chemical etching of a copper-molybdenum alloy film, based on the total weight of the etching composition being 100%, comprising the following components:
  • the organic acid is tartaric acid
  • the hydrogen peroxide stabilizer is DTPA
  • the metal chelator is ammonia triacetic acid
  • the etching additive is 3-amino-1,2,4-triazole
  • the surfactant is polysorbate 80
  • the phosphate ester is monobutyl phosphite
  • the pH adjuster is ethanolamine.
  • a composition for chemical etching of a copper-molybdenum alloy film, based on the total weight of the etching composition being 100%, comprising the following components:
  • the organic acid is salicylic acid
  • the hydrogen peroxide stabilizer is phenylurea
  • the metal chelator is phytic acid
  • the etching additive is benzotriazole
  • the surfactant is 188-A
  • the phosphate is diethyl phosphate.
  • Ester pH adjuster is diethanolamine.
  • a composition for chemical etching of a copper-molybdenum alloy film, based on the total weight of the etching composition being 100%, comprising the following components:
  • the organic acid is tartaric acid
  • the hydrogen peroxide stabilizer is DTPA
  • the metal chelator is ethylenediaminetetraacetic acid
  • the etching additive is p-hydroxybenzoic acid
  • the surfactant is PE-100
  • the phosphate ester is monobutyl phosphite.
  • the pH adjuster is ethanolamine.
  • a composition for chemical etching of a copper-molybdenum alloy film, based on the total weight of the etching composition being 100%, comprising the following components:
  • the organic acid is isoleucine
  • the hydrogen peroxide stabilizer is polyacrylamine
  • the metal chelator is aminotriacetic acid
  • the etching additive is imidazole
  • the surfactant is PE-100
  • the phosphate ester is not added
  • the pH adjuster Sodium hydroxide is isoleucine
  • a composition for chemical etching of a copper-molybdenum alloy film, based on the total weight of the etching composition being 100%, comprising the following components:
  • the organic acid is valine
  • the hydrogen peroxide stabilizer is phenylurea
  • the metal chelator is gluconic acid
  • the etching additive is not added
  • the surfactant is polysorbate 80
  • the phosphate ester substance is monobutyl phosphite.
  • the pH adjuster is potassium hydroxide.
  • a composition for chemical etching of a copper-molybdenum alloy film, based on the total weight of the etching composition being 100%, comprising the following components:
  • the organic acid is not added, the hydrogen peroxide stabilizer is DTPA, the metal chelator is ammonia triacetic acid, the etching additive is 3-amino-1,2,4-triazole, the surfactant is polysorbate 80, and the phosphate ester
  • the substance is monobutyl phosphite, and the pH adjuster is ethanolamine.
  • the etching solution compositions prepared by using the above-mentioned Examples 1 to 5 and Comparative Examples 1 to 3 are used for copper-containing and alloy metal films of electrodes such as TFT-LCD displays.
  • a barrier film made of a molybdenum-based material and a copper / molybdenum-based multilayer film made of copper or a material containing copper as a main component are sequentially laminated on a glass substrate by sputtering, and a desired resist is formed by exposure and development. Coating pattern.
  • Cu / Mo As an example, a layered metal structure is used to etch a glass substrate at 32 ° C with an etching solution. The etching time can be adjusted according to the film thickness of the metal thin film. Generally, it is 1-5 minutes.
  • the etching composition prepared by the present invention has a long service life, a small deviation in the etching cone angle, a high etching rate, and effectively inhibits the etching of the glass substrate. There is no residue remaining after etching, and the etching surface has a high accuracy .

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Abstract

一种铜钼合金膜的化学蚀刻用组合物，以蚀刻用组合物的总重量为100％计，包含下述组分：过氧化氢5％～15％，有机酸0.5％～5％，过氧化氢稳定剂0.1％～5％，金属螯合剂2.0％～7.0％，蚀刻添加剂0.001％～0.5％，表面活性剂0.03％～0.1％，磷酸酯类物质0.005％～0.05，pH调节剂3.0％～7.0％，余量为去离子水。所述化学蚀刻用组合物具有高效高精度蚀刻、使用寿命长、蚀刻过程中不会产生蚀刻残渣且反应条件温和，工作操作方便等优点。

Description

一种铜钼合金膜的化学蚀刻用组合物 技术领域
本发明涉及蚀刻技术领域，具体为一种铜钼合金膜的化学蚀刻用组合物。
背景技术
蚀刻是将材料使用化学反应或物理撞击作用而移除的技术。蚀刻技术分为湿蚀刻和干蚀刻，其中，湿蚀刻是采用化学试剂，经由化学反应达到蚀刻的目的。
近年来，人们对液晶显示器的需求量不断增加的同时，对产品的质量和画面精度也提出了更高的要求，而蚀刻的效果能直接导致电路板制造工艺的好坏，影响高密度细导线图像的精度和质量。以往的液晶显示装置的金属配线中使用了铝或铝合金，但是随着液晶显示器的大型化以及高分辨率化，与薄膜晶体管连接的栅极线和数据线会变长，这些配线的电阻也会增加，因此产生信号延迟等问题。所以，研究转向与电阻更低的材料即铜或以铜为主成分的布线组合，而钼具有与玻璃等基板的密合性高、难以产生向硅半导体膜的扩散，且兼具阻挡性。因此，将包含铜、以铜为主成分的铜钼合金的层叠膜通过溅射法等成膜工艺在玻璃等基板上成膜，然后经过将抗蚀剂等作为掩膜进行蚀刻的蚀刻工序而成为电极图案，从而制备得到导电性好、导热性好的配线。
以往的双氧水系铜钼合金用蚀刻液，为了提高蚀刻铜钼合金的速度， 常常加入氟化物和无机酸。这些蚀刻液不足之处在于加入的氟化物对环境极为不友好，腐蚀能力强，在试剂蚀刻过程中，往往难以控制蚀刻角度和蚀刻时间，对操作人员和客户端设备的危险性也较高，而无机酸主要为硫酸、磷酸，对环境污染较严重，另外目前市场上使用的蚀刻液铜溶解量一般在4000ppm～5000ppm之间，使用寿命较短。随着越来越多的生产者开始使用铜及其合金膜，对一种能够提高加工精度的蚀刻液的需求大大增加。因此，研发一种不含氟化物和无机酸，对环境友好，使用寿命长，且对基底腐蚀小的铜钼合金膜蚀刻液，为本技术领域迫切需要解决的技术问题。
发明内容
针对上述技术缺陷，本发明提供一种使用寿命长，蚀刻无残渣，蚀刻效率高且精度高，对基底腐蚀小且对环境友好的铜钼合金膜蚀刻液。
本发明提供一种铜钼合金膜的化学蚀刻用组合物，以蚀刻用组合物的总重量为100％计，包含下述组分：
Figure PCTCN2018119835-appb-000001
Figure PCTCN2018119835-appb-000002
本发明以过氧化氢作为铜钼合金的主要氧化剂，过氧化氢的添加量在5％～15％范围内可保证蚀刻有效进行，同时也能控制蚀刻速率维持在适宜的范围内，从而更容易控制蚀刻量，避免蚀刻过度；添加有机酸促进被过氧化氢氧化的铜溶解，有机酸的添加量少于0.5％则在蚀刻过程中容易产生蚀刻残渣，添加量大于5％则影响蚀刻锥角；通过添加过氧化氢稳定剂可降低过氧化氢分解的速度，延长组合物的使用寿命，添加量少于0.1％则无法降低过氧化氢分解的速度，添加量大于5％则增加生产成本；并且利用螯合剂与蚀刻过程中产生的金属离子形成螯合复合物，使其非活性化，从而抑制蚀刻液中过氧化氢的分解反应，添加量少于2.0％则无法与蚀刻过程中产生的金属离子完全螯合，添加量大于7.0％则增加生产成本；同时为了调节金属蚀刻速率，本发明还添加了蚀刻添加剂用于减缓蚀刻速率，所添加的蚀刻添加剂主要为缓蚀剂，使制备得到的蚀刻用组合物的蚀刻速率容易控制，添加量少于0.001％无法达到缓蚀效果，添加量大于0.5％则抑制蚀刻活性，降低蚀刻速率，影响蚀刻的精准度；表面活性剂的添加是为了保证蚀刻用组合物对基板的润湿性和渗透性，有效提高蚀刻速率，添加量少于0.03％则达不到提高蚀刻速率的效果，添加量大于0.1％则蚀刻反应过于激烈，导致蚀刻过程不可控；通过添加磷酸酯类物质，与蚀刻过程中产生的 钼反应，从而解决蚀刻部位钼残留的问题，添加量少于0.005％则无法有效清除残留的钼，添加量大于0.5％则增加生产成本；并添加pH调节剂作为溶液环境pH值的缓冲剂，保证过氧化氢的稳定性，避免过氧化氢过快降解从而缩短其使用寿命，添加量小于3.0％则达不到缓冲效果，添加量大于7.0％则增加生产成本；采用去离子水可避免水中的离子影响制备得到的组合物稳定性，降低其使用寿命。综合上述分析可见，本发明以过氧化氢作为主要氧化剂，通过添加过氧化氢稳定剂、螯合剂抑制蚀刻过程中过氧化氢分解，使蚀刻反应过程温和并延长使用寿命，为了解决蚀刻过程产生的杂质残留问题，添加有机酸和磷酸酯类物质分别与蚀刻过程中产生的铜及钼反应，使蚀刻过程中完全不产生蚀刻残渣，并且通过pH调节剂和表面活性剂作为辅助剂，提高蚀刻用组合物的稳定性以及对基板的润湿性及渗透性，提高其适用性。
进一步地，以蚀刻用组合物的总重量为100％计，包含下述组分：
Figure PCTCN2018119835-appb-000003
Figure PCTCN2018119835-appb-000004
本发明以过氧化氢作为主要氧化剂，通过添加过氧化氢稳定剂、螯合剂抑制蚀刻过程中过氧化氢分解，使蚀刻反应过程温和并延长使用寿命，为了解决蚀刻过程产生的杂质残留问题，添加有机酸和磷酸酯类物质分别与蚀刻过程中产生的铜及钼反应，使蚀刻过程中完全不产生蚀刻残渣，并且通过pH调节剂和表面活性剂作为辅助剂，提高蚀刻用组合物的稳定性以及对基板的润湿性及渗透性，提高其适用性。
进一步地，以蚀刻用组合物的总重量为100％计，包含下述组分：
Figure PCTCN2018119835-appb-000005
按照上述重量百分比制备得到的化学蚀刻用组合物在蚀刻过程中完全不产生蚀刻残渣，有效抑制对玻璃基板的蚀刻，在温和的工作条件下对 铜钼合金膜高效且高精度地进行蚀刻，工艺操作十分方便、易于控制，且使用寿命可达到8000ppm以上。
进一步地，所述有机酸为酒石酸、异亮氨酸、缬氨酸、水杨酸、羟基乙酸中的一种或者多种。有机酸可促进被过氧化氢氧化的铜的溶解，所选用的有机酸具有较好的稳定性，且酸性适中，保证反应过程缓和。
进一步地，所述过氧化氢稳定剂为氨羧酸型过氧化氢稳定剂、有机膦酸化合物、有机膦酸盐、聚(多)羧酸型过氧化氢稳定剂、二乙胺五乙酸、苯基脲、8-羟基喹啉、聚丙烯酸胺中的一种或多种。本发明所选用的过氧化氢稳定剂属于络合型稳定剂，通过与蚀刻过程中产生的重金属离子形成螯合物，从而降低或者消除重金属离子的过氧化氢分解，其防止金属离子的催化分解能力大于吸附型稳定剂，对金属离子有一定的螯合和屏蔽作用，在一定程度上能抑制金属离子的催化损伤。
进一步地，所述金属螯合剂为乙二胺四乙酸、氨基三乙酸、二亚乙基三胺五乙酸、二乙烯三胺五乙酸、羟乙基乙二胺三乙酸、葡萄糖酸及其对应的盐、植酸中的一种或多种。加入金属螯合剂辅助过氧化氢稳定剂，与其它金属离子如镁离子、钙离子、亚铁离子等螯合，降低其它金属离子对蚀刻用组合物稳定性的影响。
进一步地，所述蚀刻添加剂为5-氨基四氮唑、3-氨基-1，2，4-三氮唑、苯并三唑、羟甲基苯并三唑、咪唑、苯并咪唑、多羟基苯甲酸、硫脲中的一种或者多种。蚀刻添加剂可有效防止侧腐蚀，使蚀刻线条笔直没有毛刺， 且加入蚀刻用组合物中起到稳定蚀刻速度、稳定蚀刻溶液浓度防止结晶、增加铜的络合能力提高溶容量，从而有效延长使用寿命。
进一步地，所述磷酸类物质为亚磷酸单丁酯、磷酸单丁酯、亚磷酸二乙酯，磷酸二乙酯中的一种或两种。所添加的磷酸类物质可与蚀刻过程中产生的钼反应解决钼残留问题，使蚀刻表面光滑无钼残留。
进一步地，所述pH调节剂为氢氧化钠、氢氧化钾、乙醇胺、二乙醇胺、三乙醇胺、乙二胺、异丙醇胺中任意一种。加入pH调节剂形成缓冲体系保证蚀刻用组合物整体pH值处于较平稳的状态，保证蚀刻速率。
进一步地，所述表面活性剂为聚山梨酯80、PE-100、188-A、脂肪醇聚氧乙烯醚中的一种或多种。加入表面活性剂可以有效提高蚀刻用组合物对基板的润湿性和渗透性，提高蚀刻速率，所选用的表面活性剂为市面常见试剂，容易获取且成本低。
本发明铜钼合金膜的化学蚀刻用组合物，具有如下的有益效果：
第一、高效高精度蚀刻；本发明以过氧化氢作为主要氧化剂，通过控制过氧化氢添加量保证蚀刻有效进行，同时也控制蚀刻速率维持在适宜的范围内，保证蚀刻的高效性，并且加入蚀刻添加剂有效防止侧腐蚀，使蚀刻线条笔直没有毛刺，经蚀刻得到的线路精度高；
第二、使用寿命长；氧化剂过氧化氢在蚀刻过程中容易分解为水和氧气，降低蚀刻用组合物的蚀刻能力，使其使用寿命短，蚀刻成本增高，本发明通过添加过氧化氢稳定剂与蚀刻过程中产生的重金属离子形成螯合 物，从而降低或者消除重金属离子的过氧化氢分解，在一定程度上能抑制金属离子的催化损伤，减缓过氧化氢的分解速率，并添加蚀刻添加剂稳定蚀刻速度、稳定蚀刻溶液浓度防止结晶、增加铜的络合能力提高溶容量，从而有效延长使用寿命，使蚀刻用组合物使用寿命可达到8000ppm以上；
第三、蚀刻过程中不产生蚀刻残渣；本发明通过添加有机酸促进被过氧化氢氧化的铜的溶解，所选用的有机酸具有较好的稳定性，保证蚀刻过程中持续溶解被氧化的铜，并配合加入磷酸类物质与蚀刻过程中产生的钼反应解决钼残留问题，使蚀刻表面光滑无蚀刻残渣，使蚀刻表面光滑无毛刺；
第四、反应条件温和，工作操作方便易控制；本发明通过控制过氧化氢添加量在保证蚀刻有效进行的同时也控制蚀刻维持在适宜的范围内，从而使蚀刻量容易控制，使用时只需将本发明倒至所需蚀刻的部位即可，工作操作方便，并且通过pH调节剂、过氧化氢稳定剂、螯合剂等的加入使蚀刻用组合物稳定性好，在常温条件即可进行蚀刻反应，反应条件温和，也提高蚀刻过程的可控性。
具体实施方式
为了使本技术领域的人员更好地理解本发明的技术方案，下面结合实施例对本发明作进一步详细的说明。
实施例1
一种铜钼合金膜的化学蚀刻用组合物，以蚀刻用组合物的总重量为 100％计，包含下述组分：
Figure PCTCN2018119835-appb-000006
其中有机酸为异亮氨酸，过氧化氢稳定剂为聚丙烯酸胺，金属螯合剂为乙二胺四乙酸，蚀刻添加剂为硫脲，表面活性剂为PE-100，磷酸酯类物质为磷酸单丁酯，pH调节剂为氢氧化钠。
实施例2
一种铜钼合金膜的化学蚀刻用组合物，以蚀刻用组合物的总重量为100％计，包含下述组分：
Figure PCTCN2018119835-appb-000007
Figure PCTCN2018119835-appb-000008
其中有机酸为水杨酸，过氧化氢稳定剂为DTPA，金属螯合剂为葡萄糖酸，蚀刻添加剂为3-氨基-1，2，4-三氮唑，表面活性剂为188-A，磷酸酯类物质为亚磷酸单丁酯，pH调节剂为三乙醇胺。
实施例3
一种铜钼合金膜的化学蚀刻用组合物，以蚀刻用组合物的总重量为100％计，包含下述组分：
Figure PCTCN2018119835-appb-000009
其中有机酸为酒石酸，过氧化氢稳定剂为DTPA，金属螯合剂为氨三乙酸，蚀刻添加剂为3-氨基-1，2，4-三氮唑，表面活性剂为聚山梨酯80，磷酸酯类物质为亚磷酸单丁酯，pH调节剂为乙醇胺。
实施例4
一种铜钼合金膜的化学蚀刻用组合物，以蚀刻用组合物的总重量为100％计，包含下述组分：
Figure PCTCN2018119835-appb-000010
其中有机酸为水杨酸，过氧化氢稳定剂为苯基脲，金属螯合剂为植酸，蚀刻添加剂为苯并三氮唑，表面活性剂为188-A，磷酸酯类物质为磷酸二乙酯，pH调节剂为二乙醇胺。
实施例5
一种铜钼合金膜的化学蚀刻用组合物，以蚀刻用组合物的总重量为 100％计，包含下述组分：
Figure PCTCN2018119835-appb-000011
其中有机酸为酒石酸，过氧化氢稳定剂为DTPA，金属螯合剂为乙二胺四乙酸，蚀刻添加剂为对羟基苯甲酸，表面活性剂为PE-100，磷酸酯类物质为亚磷酸单丁酯，pH调节剂为乙醇胺。
对比例1
一种铜钼合金膜的化学蚀刻用组合物，以蚀刻用组合物的总重量为100％计，包含下述组分：
Figure PCTCN2018119835-appb-000012
Figure PCTCN2018119835-appb-000013
其中有机酸为异亮氨酸，过氧化氢稳定剂为聚丙烯酸胺，金属螯合剂为氨三乙酸，蚀刻添加剂为咪唑，表面活性剂为PE-100，磷酸酯类物质不添加，pH调节剂为氢氧化钠。
对比例2
一种铜钼合金膜的化学蚀刻用组合物，以蚀刻用组合物的总重量为100％计，包含下述组分：
Figure PCTCN2018119835-appb-000014
其中有机酸为缬氨酸，过氧化氢稳定剂为苯基脲，金属螯合剂为葡萄糖酸，蚀刻添加剂未添加，表面活性剂为聚山梨酯80，磷酸酯类物质为亚磷酸单丁酯，pH调节剂为氢氧化钾。
对比例3
一种铜钼合金膜的化学蚀刻用组合物，以蚀刻用组合物的总重量为100％计，包含下述组分：
Figure PCTCN2018119835-appb-000015
其中有机酸未添加，过氧化氢稳定剂为DTPA，金属螯合剂为氨三乙酸，蚀刻添加剂为3-氨基-1，2，4-三氮唑，表面活性剂为聚山梨酯80，磷酸酯类物质为亚磷酸单丁酯，pH调节剂为乙醇胺。
利用上述实施例1至5和对比例1至3制备得到的蚀刻液组合物，用于TFT-LCD显示器等电极的含铜及合金金属膜。在玻璃基板上采用溅射法 依次层叠由钼系材料形成的阻挡膜和由铜或以铜为主成分的材料形成的铜/钼系多层薄膜上，显影、曝光，形成有期望的抗蚀涂层图案。以Cu/Mo
Figure PCTCN2018119835-appb-000016
层金属结构为例玻璃基板在32℃下用蚀刻液蚀刻，蚀刻时间可根据金属薄膜的膜厚等进行调节，一般而言为1-5分钟，蚀刻结束后，进行超纯水清洗并用氮气吹干。通过对蚀刻锥角、蚀刻液残渣除去能力、CD损失均匀性、使用寿命(以蚀刻液仍保持较好性能时溶解的最高的Cu含量表示)进行评价，，实施例与对比例结果如下表所示。
实施例与对比例测试结果对比表
Figure PCTCN2018119835-appb-000017
由以上测试结果对比可见，本发明制备得到的蚀刻用组合物使用寿命长，并且蚀刻锥角偏差小，蚀刻速率高且有效抑制对玻璃基板的蚀刻，蚀刻后无残渣残留，蚀刻面光滑精度高。
上述为本发明的较佳实施例而已，并非对本发明作任何形式上的限制；凡本行业的普通技术人员均可按以上所述而顺畅地实施本发明；但是，凡熟悉本专业的技术人员在不脱离本发明技术方案范围内，可利用以上所 揭示的技术内容而作出的些许更动、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明的实质技术对以上实施例所作的任何等同变化的更动、修饰与演变等，均仍属于本发明的技术方案的保护范围之内。

Claims (10)

  1. 一种铜钼合金膜的化学蚀刻用组合物，其特征在于，以蚀刻用组合物的总重量为100％计，包含下述组分：
    过氧化氢 5％～15％
    有机酸 0.5％～5％
    过氧化氢稳定剂 0.1％～5％
    金属螯合剂 2.0％～7.0％
    蚀刻添加剂 0.001％～0.5％
    表面活性剂 0.03％～0.1％
    磷酸酯类物质 0.005％～0.05％
    pH调节剂 3.0％～7.0％
    余量为去离子水。
  2. 根据权利要求1所述的铜钼合金膜的化学蚀刻用组合物，其特征在于，以蚀刻用组合物的总重量为100％计，包含下述组分：
    过氧化氢 5％～12％
    有机酸 0.5％～3％
    过氧化氢稳定剂 0.1％～4％
    金属螯合剂 2.0％～4.0％
    蚀刻添加剂 0.001％～0.5％
    表面活性剂 0.005％～0.02％
    磷酸酯类物质 0.005％～0.02％
    pH调节剂 3.0％～5.0％
    余量为去离子水。
  3. 根据权利要求2所述的铜钼合金膜的化学蚀刻用组合物，其特征在于，以蚀刻用组合物的总重量为100％计，包含下述组分：
    过氧化氢 8％
    有机酸 3％
    过氧化氢稳定剂 0.2％
    金属螯合剂 2.8％
    蚀刻添加剂 0.005％
    表面活性剂 0.0.5％
    磷酸酯类物质 0.01％
    pH调节剂 5.0％
    余量为去离子水。
  4. 根据权利要求1至3任一项所述的铜钼合金膜的化学蚀刻用组合物，其特征在于：所述有机酸为酒石酸、异亮氨酸、缬氨酸、水杨酸、羟基乙酸中的一种或者多种。
  5. 根据权利要求4所述的铜钼合金膜的化学蚀刻用组合物，其特征在于：所述过氧化氢稳定剂为氨羧酸型过氧化氢稳定剂、有机膦酸化合物、有机膦酸盐、聚(多)羧酸型过氧化氢稳定剂、二乙胺五乙酸、苯基脲、8-羟基喹啉、聚丙烯酸胺中的一种或多种。
  6. 根据权利要求1-3、5中任意一项所述的铜钼合金膜的化学蚀刻用组合物，其特征在于：所述金属螯合剂为乙二胺四乙酸、氨基三乙酸、二亚乙基三胺五乙酸、二乙烯三胺五乙酸、羟乙基乙二胺三乙酸、葡萄糖酸及其对应的盐、植酸中的一种或多种。
  7. 根据权利要求1-3、5中任意一项所述的铜钼合金膜的化学蚀刻用组合物，其特征在于：所述蚀刻添加剂为5-氨基四氮唑、3-氨基-1，2，4-三氮唑、苯并三唑、羟甲基苯并三唑、咪唑、苯并咪唑、多羟基苯甲酸、硫脲中的一种或者多种。
  8. 根据权利要求1-3、5中任意一项所述的铜钼合金膜的化学蚀刻用组合物，其特征在于：所述磷酸类物质为亚磷酸单丁酯、磷酸单丁酯、亚磷酸二乙酯，磷酸二乙酯中的一种或两种。
  9. 根据权利要求1-3、5中任意一项所述的铜钼合金膜的化学蚀刻用组合物，其特征在于：所述pH调节剂为氢氧化钠、氢氧化钾、乙醇胺、二乙醇胺、三乙醇胺、乙二胺、异丙醇胺中任意一种。
  10. 根据权利要求1-3、5中任意一项所述的铜钼合金膜的化学蚀刻用组合物，其特征在于：所述表面活性剂为聚山梨酯80、PE-100、188-A、脂肪醇聚氧乙烯醚中的一种或多种。
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Families Citing this family (12)

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Publication number Priority date Publication date Assignee Title
CN111719156A (zh) * 2019-03-20 2020-09-29 易安爱富科技有限公司 蚀刻组合物及利用其的蚀刻方法
CN110204358B (zh) * 2019-06-26 2021-11-09 匡云叶 一种陶瓷预处理液及预处理方法
CN111074278A (zh) * 2020-01-03 2020-04-28 深圳市华星光电半导体显示技术有限公司 蚀刻液组合物及铜钼膜层的蚀刻方法
CN111155091A (zh) * 2020-02-13 2020-05-15 Tcl华星光电技术有限公司 蚀刻液、添加剂及金属布线的制作方法
CN111349938B (zh) 2020-03-23 2021-04-27 深圳市华星光电半导体显示技术有限公司 蚀刻螯合剂及其制备方法与蚀刻液组合物
CN111519190B (zh) * 2020-05-27 2022-03-18 湖北兴福电子材料有限公司 一种铜制程面板中稳定蚀刻锥角的蚀刻液及稳定方法
CN111972413B (zh) * 2020-08-05 2023-05-09 东莞东阳光科研发有限公司 一种过氧化氢消毒组合物及其制备方法
CN114107989B (zh) * 2020-08-31 2022-12-06 深圳新宙邦科技股份有限公司 一种含铜金属膜用蚀刻液
CN114250469B (zh) * 2020-09-24 2023-04-18 深圳新宙邦科技股份有限公司 一种蚀刻液组合物及其制备方法
CN113529085A (zh) * 2021-07-15 2021-10-22 深圳市华星光电半导体显示技术有限公司 蚀刻液和蚀刻方法
US20230121639A1 (en) * 2021-10-20 2023-04-20 Entegris, Inc. Selective wet etch composition and method
CN115558046A (zh) * 2022-10-10 2023-01-03 上海昶法新材料有限公司 一种造纸制浆助剂及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104480469A (zh) * 2014-12-12 2015-04-01 江阴润玛电子材料股份有限公司 一种新型tft铜钼层叠膜蚀刻液组合物及蚀刻方法
CN105648439A (zh) * 2014-11-27 2016-06-08 三菱瓦斯化学株式会社 液体组合物及使用其的蚀刻方法
KR20160114825A (ko) * 2015-03-25 2016-10-06 동우 화인켐 주식회사 구리계 금속막의 식각액 조성물 및 이를 이용한 액정표시장치용 어레이 기판의 제조방법
CN106637209A (zh) * 2016-12-29 2017-05-10 深圳市华星光电技术有限公司 一种蚀刻液组合物及该组合物的金属膜刻蚀方法
CN107090581A (zh) * 2016-02-17 2017-08-25 易安爱富科技有限公司 蚀刻液组合物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107227463B (zh) * 2013-01-14 2020-05-19 易安爱富科技有限公司 铜/钼膜或铜/钼合金膜的蚀刻液组合物
CN104498951B (zh) * 2014-12-11 2017-05-17 深圳新宙邦科技股份有限公司 一种双氧水系铜钼合金膜用蚀刻液
CN105908188A (zh) * 2016-05-23 2016-08-31 杭州格林达化学有限公司 一种用于tft铜钼叠层的双氧水系蚀刻液
CN107151795A (zh) * 2017-06-02 2017-09-12 苏州晶瑞化学股份有限公司 一种铜钼合金膜用蚀刻液

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105648439A (zh) * 2014-11-27 2016-06-08 三菱瓦斯化学株式会社 液体组合物及使用其的蚀刻方法
CN104480469A (zh) * 2014-12-12 2015-04-01 江阴润玛电子材料股份有限公司 一种新型tft铜钼层叠膜蚀刻液组合物及蚀刻方法
KR20160114825A (ko) * 2015-03-25 2016-10-06 동우 화인켐 주식회사 구리계 금속막의 식각액 조성물 및 이를 이용한 액정표시장치용 어레이 기판의 제조방법
CN107090581A (zh) * 2016-02-17 2017-08-25 易安爱富科技有限公司 蚀刻液组合物
CN106637209A (zh) * 2016-12-29 2017-05-10 深圳市华星光电技术有限公司 一种蚀刻液组合物及该组合物的金属膜刻蚀方法

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