WO2021159577A1 - 蚀刻液、添加剂及金属布线的制作方法 - Google Patents

蚀刻液、添加剂及金属布线的制作方法 Download PDF

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Publication number
WO2021159577A1
WO2021159577A1 PCT/CN2020/079565 CN2020079565W WO2021159577A1 WO 2021159577 A1 WO2021159577 A1 WO 2021159577A1 CN 2020079565 W CN2020079565 W CN 2020079565W WO 2021159577 A1 WO2021159577 A1 WO 2021159577A1
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Prior art keywords
acid
etching solution
etching
additive
metal wiring
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PCT/CN2020/079565
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English (en)
French (fr)
Inventor
吴豪旭
张月红
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Tcl华星光电技术有限公司
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Priority to US16/652,286 priority Critical patent/US20210404068A1/en
Publication of WO2021159577A1 publication Critical patent/WO2021159577A1/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
    • C23F1/02—Local etching
    • 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
    • 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
    • C23F1/26—Acidic compositions for etching refractory metals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/067—Etchants

Definitions

  • This application relates to the technical field of etching solutions, and in particular to a manufacturing method of etching solutions, additives and metal wiring.
  • Etching is a technique in which materials are removed using chemical reaction or physical impact; etching techniques are divided into wet etching and dry etching. Among them, wet etching uses chemical reagents to achieve the purpose of etching through chemical reactions. The effect of etching can directly affect the accuracy and quality of the high-density thin wire image.
  • liquid crystal display devices Liquid Crystal Display
  • metal wiring uses aluminum or aluminum alloy.
  • aluminum or aluminum alloy materials are prone to signal delay and other problems due to their high resistivity, which affects the display. Effect.
  • the copper material can meet the wiring requirements of large-size panels because of its lower resistivity; molybdenum has high adhesion to glass and other substrates, is difficult to diffuse to the silicon semiconductor film, and has barrier properties; therefore, The copper/molybdenum film layer becomes the metal layer structure of the gate, source, drain of the thin film transistor in the liquid crystal display device, and the gate line and data line connected to the thin film transistor, and the related
  • the development of etching solutions is also particularly important.
  • the present application provides an etching solution, an additive, and a manufacturing method of metal wiring.
  • the etching solution does not contain fluoride, is environmentally friendly, and has the advantages of moderate etching rate, suitable etching angle, low line width loss, and no metal residue.
  • an embodiment of the present application provides an etching solution
  • the main components of the etching solution include 5-30% hydrogen peroxide, 0.1-5% hydrogen peroxide stabilizer, and the total weight of the etching solution. 5 ⁇ 25% chelating agent, 0.1 ⁇ 1% surfactant and 0.1 ⁇ 5% inorganic acid oxidizer, the balance is deionized water.
  • the hydrogen peroxide stabilizer includes at least one of phenylurea, polyacrylamide, and inorganic salt.
  • the chelating agent includes citric acid, tartaric acid, malonic acid, benzoic acid, diglycolic acid, maleic acid, hydroxybutyric acid, lactic acid, malic acid, succinic acid, iso At least one of propanolamine and propylene glycol.
  • the surfactant is an alcohol amine substance; the alcohol amine substance includes any one or two of polyethylene glycol and polyacrylamide.
  • the inorganic acid oxidizer includes at least one of nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid.
  • the embodiments of the present application also provide an additive, which is added to the etching solution when the above-mentioned etching solution is repeatedly used, and the main components of the additive include 5-20% of the total weight of the additive.
  • the organic acid includes at least one of citric acid, malonic acid, malic acid and succinic acid;
  • the etching inhibitor is a benzoxazole compound.
  • the hydrogen peroxide stabilizer includes at least one of phenylurea, polyacrylamide, and inorganic salt.
  • the chelating agent includes citric acid, tartaric acid, malonic acid, benzoic acid, diglycolic acid, maleic acid, hydroxybutyric acid, lactic acid, malic acid, succinic acid, isopropyl At least one of alcoholamine and propylene glycol.
  • the surfactant is an alcohol amine substance; the alcohol amine substance includes any one or two of polyethylene glycol and polyacrylamide.
  • the inorganic acid oxidizer includes at least one of nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid.
  • an embodiment of the present application also provides a method for manufacturing metal wiring, including the following steps:
  • the etching solution as described above is used to etch the part of the metal layer that is not covered by the anti-etching coating to form metal wiring.
  • the metal layer etched away exists in the etching solution in the form of metal ions
  • the manufacturing method also includes the following steps:
  • the main components of the additive include 5-20% of the total weight of the additive, an organic acid, 0.3-3% of an etching inhibitor, and the balance is deionized water.
  • the organic acid includes at least one of citric acid, malonic acid, malic acid, and succinic acid.
  • the etching inhibitor is a benzoxazole compound.
  • adding an additive to the etching solution containing the metal ion includes the following steps:
  • the metal layer includes a copper metal layer or a copper-molybdenum metal layer.
  • the hydrogen peroxide stabilizer includes at least one of phenylurea, polyacrylamide, and inorganic salt.
  • the chelating agent includes citric acid, tartaric acid, malonic acid, benzoic acid, diglycolic acid, maleic acid, hydroxybutyric acid, lactic acid, malic acid, and succinic acid. At least one of acid, isopropanolamine, and propylene glycol.
  • the surfactant is an alcohol amine substance; the alcohol amine substance includes any one or two of polyethylene glycol and polyacrylamide.
  • the inorganic acid oxidizer includes at least one of nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid.
  • the etching solution provided by the embodiments of the application does not contain fluoride.
  • etching the metal layer copper/molybdenum film layer
  • it has the advantages of moderate etching rate, suitable etching angle, small line width loss and no metal residue, which is beneficial to improve the product It is of high quality and environmentally friendly, which is conducive to reducing the cost of waste liquid treatment.
  • the additives provided in the embodiments of the present application can be added to the etching solution during repeated use, which can greatly increase the service life of the etching solution and greatly reduce production costs. At the same time, the harm to operators is greatly reduced, and the processing cost of etching liquid waste is greatly reduced, which meets the needs of industrial production lines.
  • FIG. 1 is a scanning electron microscope image of a copper/molybdenum wiring obtained by etching a copper/molybdenum film layer by using an etching solution according to an embodiment of the application.
  • FIG. 2 is a scanning electron microscope image of another copper/molybdenum wiring obtained by etching the copper/molybdenum film layer by using an etching solution according to an embodiment of the application.
  • FIG. 3 is a scanning electron microscope image of copper/molybdenum wiring obtained by etching the copper/molybdenum film layer by using an etching solution containing 500 ppm copper ions according to an embodiment of the application.
  • FIG. 4 is a scanning electron microscope image of copper/molybdenum wiring obtained by etching the copper/molybdenum film layer by using an etching solution containing 6000 ppm copper ions according to an embodiment of the application.
  • FIG. 5 is a scanning electron microscope image of copper/molybdenum wiring obtained by etching the copper/molybdenum film layer after adding additives to an etching solution containing 6000 ppm copper ions according to an embodiment of the application.
  • FIG. 6 is a schematic flowchart of a manufacturing method of metal wiring provided by an embodiment of the application.
  • the embodiment of the application provides a fluoride-free etching solution for etching copper/molybdenum film layers; the main components of the etching solution include hydrogen peroxide (hydrogen peroxide), 0.1% of the total weight of the etching solution. ⁇ 5% hydrogen peroxide stabilizer, 5 ⁇ 25% chelating agent, 0.1 ⁇ 1% surfactant and 0.1 ⁇ 5% inorganic acid oxidizer, the balance is deionized water.
  • the etching solution provided in this embodiment does not contain environmentally destructive azole etching inhibitors.
  • the copper/molybdenum film layer refers to a laminated layer formed by a copper layer (which may be copper or a copper alloy) and a molybdenum layer.
  • hydrogen peroxide is the main oxidant of copper and molybdenum; the hydrogen peroxide stabilizer includes at least one of phenylurea, polyacrylamide, and inorganic salts.
  • a suitable hydrogen peroxide stabilizer can prevent the violent chain reaction of hydrogen peroxide in the etching solution, prevent the hydrogen peroxide from decomposing hydrogen peroxide ions too quickly, so that the hydrogen peroxide can function smoothly and fully, which is beneficial to ensure the etching rate Moderate, and improve the etching life.
  • the chelating agent includes at least one of citric acid, tartaric acid, malonic acid, benzoic acid, diglycolic acid, maleic acid, hydroxybutyric acid, lactic acid, malic acid, succinic acid, isopropanolamine, and propylene glycol.
  • the chelating agent can effectively control the etching rate of the etching solution, chelate copper/molybdenum ions, help the etching of copper and molybdenum, and facilitate the removal of molybdenum residues, and obtain a good wiring cross-sectional shape.
  • the surfactant is an alcohol amine substance; the alcohol amine substance includes any one or two of polyethylene glycol and polyacrylamide. Surfactant can activate the etching interface, which is beneficial to the etching process, and it is not easy to produce residue.
  • the inorganic acid oxidizer includes at least one of nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid.
  • Inorganic acid oxidants can oxidize metals and chelate and dissolve them, which is conducive to the complete elimination of metal substances and is not easy to produce residues.
  • the method for configuring the etching solution is: sequentially adding quantitative water, hydrogen peroxide, chelating agent, hydrogen peroxide stabilizer, inorganic acid oxidizer and surfactant into the container, and stirring for 60 to 180 minutes Until the mixing is uniform; and during the above configuration process, the temperature needs to be controlled at 15 ⁇ 30°C.
  • the mass fraction of hydrogen peroxide (hydrogen peroxide) in the etching solution is 7.8%
  • the mass fraction of hydrogen peroxide stabilizer is 0.1%
  • the mass fraction of chelating agent is 16%
  • the mass fraction of surfactant is 0.1%
  • the mass fraction of inorganic acid oxidizer is 2.2%
  • the mass fraction of deionized water is 73.8%.
  • Fig. 1 is a scanning electron microscope image of copper/molybdenum wiring obtained by etching a copper/molybdenum film layer by using an etching solution provided in an embodiment of the present application, specifically a side-view scanning electron microscope image.
  • the etching angle when the etching solution in the embodiment of the present application is used for etching is suitable, which is 30°-50°.
  • FIG. 2 is a scanning electron microscope diagram of a copper/molybdenum wiring obtained by etching a copper/molybdenum film layer using an etching solution provided by an embodiment of the present application with a top view angle of about 30°. The layers are the same, but the viewing angle is different. It can be seen from FIG. 2 that there is no metal residue in the part that is not covered with the anti-etching coating.
  • the etching solution provided in this embodiment does not contain fluoride.
  • the etching rate is moderate and will not damage the substrate glass. It also has a suitable etching angle (Taper) (30° ⁇ 50°), The advantages of small line loss (CD Loss) and no metal residues are conducive to improving product quality; moreover, it is environmentally friendly and is conducive to reducing waste liquid treatment costs.
  • the copper/molybdenum film etching solution is used repeatedly (that is, the etching solution is recycled for etching, during the etching process, the etched copper exists in the etching solution in the form of copper ions), the copper ion concentration in the etching solution Larger (such as 4000ppm ⁇ 6000ppm, where ppm is parts per million), due to the decomposition of hydrogen peroxide and the lack of chelating agent (copper ion chelating agent), the pH value of the solution will increase, which will easily cause etching performance at this time Poor, many problems such as slow etching, residual molybdenum layer, and substandard etching angle, have caused a significant increase in the cost of industrial production and use.
  • the etching solution provided by the embodiment of the application can meet the requirements of factory line use when the copper ion concentration is less than 6000ppm.
  • the copper ion concentration is greater than 6000ppm, if the etching is continued, the etching rate will be too slow, the etching angle is not good, and the molybdenum Layer residue and other issues.
  • this application also provides an additive.
  • the embodiments of the present application also provide an additive, which is added to the etching solution when the above-mentioned etching solution is used repeatedly, and can correct the etching rate, etching angle, and metal residue of the etching solution at a higher copper ion concentration;
  • the main components of the additive include 5-20% of the total weight of the additive, and 0.3-3% of the etching inhibitor.
  • the balance is deionized water.
  • the organic acids include citric acid, malonic acid, malic acid and amber. At least one of the acids; the etching inhibitor is a benzoxazole compound.
  • the configuration method of the additives provided in the embodiments of the present application is as follows: add quantitative water, organic acid, and etching inhibitor to the container in sequence, and stir for 60 ⁇ 180min until the mixing is uniform; during the above configuration process, the temperature needs to be controlled at 15 ⁇ 30°C.
  • the mass fraction of the organic acid in the additive is 8%
  • the mass fraction of the etching inhibitor is 0.6%
  • the mass fraction of deionized water is 91.4%.
  • the concentration of copper ions in the etching solution exceeds the preset concentration
  • additives are added to the etching solution; the addition method is that when the copper ion concentration increases by 1000 ppm, the etching solution containing copper ions is added to the etching solution to account for the total Additives of 0.1 ⁇ 2% by weight.
  • the preset concentration is less than or equal to 6000 ppm, which can be 4000 ppm, or 6000 ppm or other values, which are set according to actual conditions. It should be noted that the method of adding additives can also be adjusted according to actual production conditions. For example, when the copper ion concentration increases by 500 ppm, the additive is added once, and there is no limitation here.
  • this application uses an etching solution containing 500ppm copper ions, an etching solution containing 6000ppm copper ions, and an etching solution containing 6000ppm copper ions under other conditions.
  • the same copper/molybdenum film layer was etched in the same period of time.
  • the etching temperature was 35°C and the pH value of the etching solution was 4.4.
  • the copper was etched by scanning electron microscope.
  • Figure 3 is the use of 500ppm copper ion etching solution to the copper/molybdenum film layer etching of copper/molybdenum wiring scan
  • Figure 4 is a scanning electron microscope image of copper/molybdenum wiring obtained by etching the copper/molybdenum film layer with an etching solution containing 6000ppm copper ions
  • the etching angles of the copper/molybdenum wiring in Figure 3, Figure 4 and Figure 5 are respectively 48°31', 25°59' and 46°36'; it can be seen from Figures 3 and 4 that when the copper ion in the etching solution After the concentration is increased, the etching angle is greatly reduced; from Fig. 3 and Fig. 5, it can be seen that after adding the additives, the etching angle is corrected, and the difference between the etching angle and the etching angle of the etching solution containing 500 ppm copper ions is small.
  • the single-sided line width loss of the copper/molybdenum wiring in Figures 3, 4, and 5 is 1456 nm, 1066 nm, and 1419 nm, respectively; it can be seen from Figures 3 and 4 that when the copper ion concentration in the etching solution increases , The single-sided line width loss is reduced, which makes the line width difference obtained by etching larger; from Figure 3 and Figure 5, it can be seen that after the addition of additives, the single-sided line width loss can be corrected, and it is compared with the single-sided line of the etching solution containing 500ppm copper ions. The wide loss difference is small.
  • Figures 3, 4, and 5 are effect diagrams obtained by etching in the same time period, the etching rate can be evaluated from the amount of line width loss on one side. It can be seen from Figures 3 and 4 that when the etching solution is After the copper ion concentration increases, the etching rate decreases, and it can be seen from FIGS. 3 and 5 that the etching rate returns to the level of FIG. 3 after adding additives. Therefore, the additives provided by the present application can effectively correct the etching characteristics of the etching solution.
  • the additives provided in this embodiment are added during the repeated use of the etching solution, so that the etching characteristics can be corrected, that is, the etching rate is stable and moderate, and the etching angle is stable at 30° ⁇ 50 at different copper ion concentrations.
  • the addition of additives makes the service life of the etching solution reach 12000ppm (the copper ion concentration in the etching solution), which greatly improves the service life of the etching solution, thereby It greatly reduces the amount of new etching solution used and the amount of etching solution waste produced, greatly reducing production costs while greatly reducing the harm to operators, and greatly reducing the processing cost of etching solution waste, which satisfies the industry Production line demand.
  • an embodiment of the present application also provides a method for manufacturing metal wiring, specifically a method for manufacturing copper/molybdenum wiring.
  • the manufacturing method includes the following steps:
  • Step S601 Provide a substrate covered with a metal layer.
  • the material of the substrate includes glass; the metal layer includes a copper metal layer or a copper/molybdenum film layer.
  • Step S602 Disposing an anti-etching coating on the part of the metal layer on the side away from the substrate.
  • the material of the anti-etching coating includes a photoresist material, which is not limited here.
  • Step S603 Use the etching solution in the foregoing embodiment to etch the part of the metal layer that is not covered by the anti-etching coating to form a metal wiring.
  • the composition of the etching solution includes 7.8% hydrogen peroxide (hydrogen peroxide), 0.1% hydrogen peroxide stabilizer, 16% chelating agent, 0.1% surfactant, and 2.2% inorganic Acid oxidizer and 73.8% deionized water.
  • the etching temperature is 35°C
  • the pH value of the etching solution is 4.4.
  • the etched metal layer exists in the etching solution in the form of metal ions; the method for manufacturing the metal wiring further includes the following steps:
  • the concentration of metal ions (copper ions) in the etching solution when the concentration of metal ions exceeds the preset concentration, add additives to the etching solution containing metal ions to allow the etching solution to be used repeatedly; among them, the main components of the additives include additives 5-20% of the total weight of organic acid, 0.3-3% of etching inhibitor, and the balance is deionized water; wherein the organic acid includes at least one of citric acid, malonic acid, malic acid and succinic acid;
  • the etching inhibitor is a benzoxazole compound.
  • the preset concentration is less than 6000 ppm, which can be 4000 ppm, or 6000 ppm or other values, which are set according to actual conditions.
  • the components of the additive include 8% organic acid, 0.6% etching inhibitor, and 91.4% deionized water based on the total weight of the additive.
  • adding additives to the etching solution containing metal ions includes the following steps:
  • an additive that accounts for 0.1 to 2% of the total weight of the etching solution is added to the etching solution containing metal ions.
  • the method of adding additives can also be adjusted according to actual production conditions. For example, when the copper ion concentration increases by 500 ppm, the additives are added once, and there is no limitation here.
  • the etching rate is stable and moderate, the etching angle is stable at 30° ⁇ 50°, the line width loss is small and stable, and there is no metal residue, which is beneficial to improve Product quality;
  • the addition of additives can greatly increase the service life of the etching solution, which can greatly reduce the use of new etching solution and the amount of waste etching solution produced, which greatly reduces production costs and greatly harms operators. It reduces and greatly reduces the processing cost of etching liquid waste liquid, and meets the needs of industrial production lines.

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Abstract

公开一种蚀刻液、添加剂及金属布线的制作方法，所述蚀刻液的主要成分包括占所述蚀刻液总重量的5~30%的过氧化氢、0.1~5%的过氧化氢稳定剂、5~25%的螯合剂、0.1~1%的表面活性剂和0.1~5%的无机酸氧化剂，余量为去离子水；所述添加剂在反复使用所述蚀刻液时添加至所述蚀刻液中。

Description

蚀刻液、添加剂及金属布线的制作方法
本申请要求于2020年02月13日提交中国专利局、申请号为202010090863.8、发明名称为“蚀刻液、添加剂及金属布线的制作方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及蚀刻液技术领域，尤其涉及一种蚀刻液、添加剂及金属布线的制作方法。
 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。蚀刻的效果能直接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（LCD，Liquid Crystal Display）的金属配线中使用的是铝或铝合金，但是随着液晶显示装置的大型化以及高分辨率化，铝或铝合金材料由于电阻率大，容易产生信号延迟等问题，从而影响显示效果。而铜材料因其具有更低的电阻率，可以满足大尺寸面板的布线要求；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，铜/钼膜层成为液晶显示装置中薄膜晶体管的栅极（Gate）、源极（Source）、漏极（Drain）以及与薄膜晶体管连接的栅极线和数据线等金属层结构，而相关的蚀刻液的开发也显得尤为重要。
现有的过氧化氢基铜/钼膜层蚀刻液为了提高蚀刻速度常常含有氟化物，而氟化物对环境不友好；另外，氟化物的存在不利于操作人员的身体健康；且其腐蚀能力强，往往会造成对基板玻璃的腐蚀；除此之外，蚀刻产线中的废水存在大量的氟化物对环境也存在威胁，使得对废液的处理成本大大增加。
基于此，对现有的含氟化物的铜/钼膜层蚀刻液的改进很有必要。
 技术问题
本申请提供一种蚀刻液、添加剂及金属布线的制作方法，所述蚀刻液不含氟化物，对环境友好，且具有蚀刻速率适中、蚀刻角度适宜、线宽损失小以及无金属残留等优势。
 技术解决方案
第一方面，本申请实施例提供一种蚀刻液，所述蚀刻液的主要成分包括占所述蚀刻液总重量的5~30%的过氧化氢、0.1~5%的过氧化氢稳定剂、5~25%的螯合剂、0.1~1%的表面活性剂和0.1~5%的无机酸氧化剂，余量为去离子水。
在本申请实施例所提供的蚀刻液中，所述过氧化氢稳定剂包括苯基脲、聚丙烯酰胺和无机盐中的至少一种。
在本申请实施例所提供的蚀刻液中，所述螯合剂包括柠檬酸、酒石酸、丙二酸、苯甲酸、二乙醇酸、马来酸、羟基丁酸、乳酸、苹果酸、琥珀酸、异丙醇胺和丙二醇中的至少一种。
在本申请实施例所提供的蚀刻液中，所述表面活性剂为醇胺类物质；所述醇胺类物质包括聚乙二醇和聚丙烯酸胺中的任意一种或两种。
在本申请实施例所提供的蚀刻液中，所述无机酸氧化剂包括硝酸、磷酸、盐酸和硫酸中的至少一种。
第二方面，本申请实施例还提供一种添加剂，在反复使用以上所述的蚀刻液时添加至所述蚀刻液中，所述添加剂的主要成分包括占所述添加剂总重量的5~20%的有机酸、0.3~3%的蚀刻抑制剂，余量为去离子水；
其中，所述有机酸包括柠檬酸、丙二酸、苹果酸和琥珀酸中的至少一种；所述蚀刻抑制剂为苯并唑类化合物。
在本申请实施例所提供的添加剂中，所述过氧化氢稳定剂包括苯基脲、聚丙烯酰胺和无机盐中的至少一种。
在本申请实施例所提供的添加剂中，所述螯合剂包括柠檬酸、酒石酸、丙二酸、苯甲酸、二乙醇酸、马来酸、羟基丁酸、乳酸、苹果酸、琥珀酸、异丙醇胺和丙二醇中的至少一种。
在本申请实施例所提供的添加剂中，所述表面活性剂为醇胺类物质；所述醇胺类物质包括聚乙二醇和聚丙烯酸胺中的任意一种或两种。
在本申请实施例所提供的添加剂中，所述无机酸氧化剂包括硝酸、磷酸、盐酸和硫酸中的至少一种。
第三方面，本申请实施例还提供一种金属布线的制作方法，包括以下步骤：
提供覆盖有金属层的基板；
在所述金属层远离所述基板的一侧部分设置防蚀刻涂层；
采用如以上所述的蚀刻液对所述金属层中未被所述防蚀刻涂层覆盖的部分进行蚀刻，形成金属布线。
在本申请实施例所提供的金属布线的制作方法中，蚀刻掉的金属层以金属离子的形式存在于所述蚀刻液中；
所述制作方法还包括以下步骤：
检测所述蚀刻液中所述金属离子的浓度；
当所述金属离子浓度超过预设浓度时，向含有所述金属离子的所述蚀刻液中加入添加剂，以使所述蚀刻液反复使用；
所述添加剂的主要成分包括占所述添加剂总重量的5~20%的有机酸、0.3~3%的蚀刻抑制剂，余量为去离子水。
在本申请实施例所提供的金属布线的制作方法中，所述有机酸包括柠檬酸、丙二酸、苹果酸和琥珀酸中的至少一种。
在本申请实施例所提供的金属布线的制作方法中，所述蚀刻抑制剂为苯并唑类化合物。
在本申请实施例所提供的金属布线的制作方法中，所述向含有所述金属离子的所述蚀刻液中加入添加剂，包括以下步骤：
所述蚀刻液中的所述金属离子的浓度每升高1000ppm时，向含有所述金属离子的所述蚀刻液中加入占所述蚀刻液总重量的0.1~2%的添加剂。
在本申请实施例所提供的金属布线的制作方法中，所述金属层包括铜金属层或铜钼金属层。
在本申请实施例所提供的金属布线的制作方法中，所述过氧化氢稳定剂包括苯基脲、聚丙烯酰胺和无机盐中的至少一种。
在本申请实施例所提供的金属布线的制作方法中，所述螯合剂包括柠檬酸、酒石酸、丙二酸、苯甲酸、二乙醇酸、马来酸、羟基丁酸、乳酸、苹果酸、琥珀酸、异丙醇胺和丙二醇中的至少一种。
在本申请实施例所提供的金属布线的制作方法中，所述表面活性剂为醇胺类物质；所述醇胺类物质包括聚乙二醇和聚丙烯酸胺中的任意一种或两种。
在本申请实施例所提供的金属布线的制作方法中，所述无机酸氧化剂包括硝酸、磷酸、盐酸和硫酸中的至少一种。
 有益效果
本申请实施例提供的蚀刻液不含氟化物，在蚀刻金属层（铜/钼膜层）时，具有蚀刻速率适中、蚀刻角度适宜、线宽损失小以及无金属残留等优势，有利于提高产品质量，并且对环境友好，有利于降低废液处理成本；另外，本申请实施例提供的添加剂，在蚀刻液反复使用的过程中添加到其中可以大大提高蚀刻液的使用寿命，在大幅降低生产费用的同时对操作人员的危害大大降低，且大幅度降低了蚀刻液废液的处理成本，满足了工业产线需求。
 附图说明
下面结合附图，通过对本申请的具体实施方式详细描述，将使本申请的技术方案及其它有益效果显而易见。
图1为本申请实施例提供的一种采用蚀刻液对铜/钼膜层蚀刻得到的铜/钼布线的扫描电镜图。
图2为本申请实施例提供的另一种采用蚀刻液对铜/钼膜层蚀刻得到的铜/钼布线的扫描电镜图。
图3为本申请实施例提供的采用含500ppm铜离子的蚀刻液对铜/钼膜层蚀刻得到的铜/钼布线的扫描电镜图。
图4为本申请实施例提供的采用含6000ppm铜离子的蚀刻液对铜/钼膜层蚀刻得到的铜/钼布线的扫描电镜图。
图5为本申请实施例提供的在含6000ppm铜离子的蚀刻液中加入添加剂后对铜/钼膜层蚀刻得到的铜/钼布线的扫描电镜图。
图6为本申请实施例提供的一种金属布线的制作方法的流程示意图。
 本发明的实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
本申请实施例提供了一种不含氟化物的蚀刻液，用于蚀刻铜/钼膜层；蚀刻液的主要成分包括占蚀刻液总重量的5~30%的过氧化氢（双氧水）、0.1~5%的过氧化氢稳定剂、5~25%的螯合剂、0.1~1%的表面活性剂和0.1~5%的无机酸氧化剂，余量为去离子水。本实施例提供的蚀刻液不含环境破坏型的唑类蚀刻抑制剂。
具体的，铜/钼膜层是指铜层(可以是铜或铜合金)与钼层形成的叠层。
具体的，过氧化氢为铜、钼的主要氧化剂；过氧化氢稳定剂包括苯基脲、聚丙烯酰胺和无机盐中的至少一种。合适的过氧化氢稳定剂可以阻止蚀刻液中过氧化氢剧烈的连锁反应，阻止过氧化氢过快的分解出过氧氢离子，从而使得过氧化氢平稳充分的发挥作用，有利于保证蚀刻速率适中，并提高蚀刻寿命。
具体的，螯合剂包括柠檬酸、酒石酸、丙二酸、苯甲酸、二乙醇酸、马来酸、羟基丁酸、乳酸、苹果酸、琥珀酸、异丙醇胺和丙二醇中的至少一种。螯合剂可以有效的调控蚀刻液的蚀刻速率，螯合铜/钼离子，有助于对铜和钼的蚀刻，以及有利于钼的残渣的去除，得到良好的布线截面形状。
具体的，表面活性剂为醇胺类物质；醇胺类物质包括聚乙二醇和聚丙烯酸胺中的任意一种或两种。表面活性剂可以使蚀刻界面活化，有利于蚀刻进行，不易产生残留。
具体的，无机酸氧化剂包括硝酸、磷酸、盐酸和硫酸中的至少一种。无机酸氧化剂可以起到氧化金属并进行螯合溶解的作用，有利于金属物质的完全消除，不易产生残留。
具体的，本申请实施例提供的蚀刻液的配置方法为：在容器中依次加入定量的水、过氧化氢、螯合剂、过氧化氢稳定剂、无机酸氧化剂和表面活性剂，搅拌60~180min直至混合均匀；且上述配置过程中，温度需控制在15~30℃。在一实施例中，蚀刻液中过氧化氢（双氧水）的质量分数为7.8%、过氧化氢稳定剂的质量分数为0.1%、螯合剂的质量分数为16%、表面活性剂的质量分数为0.1%、无机酸氧化剂的质量分数为2.2%、去离子水的质量分数为73.8%。
图1为采用本申请实施例提供的蚀刻液对铜/钼膜层蚀刻得到的铜/钼布线的扫描电镜图，具体为侧视扫描电镜图，图中从下至上依次为基板玻璃、铜/钼布线以及防蚀刻涂层，由图1可知，采用本申请实施例中的蚀刻液进行蚀刻时的蚀刻角度适宜，为30°~50°。图2为采用本申请实施例提供的蚀刻液对铜/钼膜层蚀刻得到的铜/钼布线的约30°俯视视角的扫描电镜图，图2中的各膜层与图1中的各膜层相同，仅视角不同，由图2可知，未覆盖防蚀刻涂层的部分无金属残留。
本实施例中提供的蚀刻液不含氟化物，在蚀刻铜/钼膜层时，蚀刻速率适中，不会对基板玻璃产生破坏，还具有蚀刻角度(Taper)适宜(30°~50°)、线宽损失（CD Loss)小以及无金属残留等优势，有利于提高产品质量；并且，对环境友好，有利于降低废液处理成本。
铜/钼膜层蚀刻液在反复使用（即循环使用蚀刻液进行蚀刻，在蚀刻过程中，被蚀刻掉的铜以铜离子的形式存在于蚀刻液中）过程中，蚀刻液中的铜离子浓度较大（例如4000ppm~6000ppm，其中，ppm为百万分率）后，由于过氧化氢的分解以及螯合剂（铜离子螯合剂）的不足，溶液的PH值升高，此时容易造成蚀刻表现不佳，如蚀刻过慢、钼层残留和蚀刻角度不达标等诸多问题，使得工业生产使用时成本大幅上升。例如，本申请实施例提供的蚀刻液在铜离子浓度小于6000ppm下可以满足厂线上使用，当铜离子浓度大于6000ppm以后，如果继续进行蚀刻，会出现蚀刻速率过慢、蚀刻角度不好和钼层残留等问题。为了解决上述问题，本申请还提供了一种添加剂。
具体的，本申请实施例还提供了一种添加剂，在反复使用上述蚀刻液时添加至蚀刻液中，可以矫正蚀刻液在更高铜离子浓度下的蚀刻速率、蚀刻角度和金属残留等问题；添加剂的主要成分包括占添加剂总重量的5~20%的有机酸、0.3~3%的蚀刻抑制剂，余量为去离子水；其中，有机酸包括柠檬酸、丙二酸、苹果酸和琥珀酸中的至少一种；蚀刻抑制剂为苯并唑类化合物。
具体的，本申请实施例提供的添加剂的配置方法为：在容器中依次加入定量的水、有机酸和蚀刻抑制剂，搅拌60~180min直至混合均匀；上述配置过程中，温度需控制在15~30℃。在一实施例中，添加剂中的有机酸的质量分数为8%、蚀刻抑制剂的质量分数为0.6%以及去离子水的质量分数为91.4%。
具体的，当蚀刻液中的铜离子的浓度超过预设浓度后，向蚀刻液中加入添加剂；添加方式为铜离子浓度每升高1000ppm时，向含有铜离子的蚀刻液中加入占蚀刻液总重量的0.1~2%的添加剂。其中，预设浓度小于或等于6000ppm，可以是4000ppm，也可以是6000ppm或其他值，根据实际情况设定。需要说明的是，添加剂的添加方式也可以根据实际生产情况进行调整，例如铜离子浓度每升高500ppm时，添加一次添加剂，此处不做限制。
具体的，为了评价本申请实施例提供的蚀刻液和添加剂的效果，本申请在其他条件相同的情况下分别采用含500ppm铜离子的蚀刻液、含6000ppm铜离子的蚀刻液以及在含6000ppm铜离子的蚀刻液中加入添加剂后的蚀刻液分别对相同的铜/钼膜层在相同的时间段内进行蚀刻，其中，蚀刻温度为35℃，蚀刻液PH值4.4，蚀刻后利用扫描电子显微镜对铜/钼膜层的蚀刻特征进行观察，结果分别如图3、图4和图5所示，图3为采用含500ppm铜离子的蚀刻液对铜/钼膜层蚀刻得到的铜/钼布线的扫描电镜图；图4为采用含6000ppm铜离子的蚀刻液对铜/钼膜层蚀刻得到的铜/钼布线的扫描电镜图；图5为在含6000ppm铜离子的蚀刻液中加入添加剂后对铜/钼膜层蚀刻得到的铜/钼布线的扫描电镜图。
其中，图3、图4和图5中铜/钼布线的蚀刻角度分别为48°31’、25°59’和46°36’；由图3和图4可知，当蚀刻液中的铜离子浓度增大后，蚀刻角度大大减小；由图3和图5可知，在加入添加剂后，蚀刻角度得以矫正，且与含500ppm铜离子的蚀刻液的蚀刻角度相差较小。并且，图3、图4和图5中铜/钼布线的单侧线宽损失分别为1456纳米、1066纳米和1419纳米；由图3和图4可知，当蚀刻液中的铜离子浓度增大后，单侧线宽损失减小，使得蚀刻得到的线宽差异较大；由图3和图5可知，在加入添加剂后，单侧线宽损失得以矫正，且与含500ppm铜离子的蚀刻液的单侧线宽损失相差较小。另外，由于图3、图4和图5是在相同的时间段内蚀刻得到的效果图，可以由单侧的线宽损失量评价蚀刻速率，由图3和图4可知，当蚀刻液中的铜离子浓度增大后，蚀刻速率降低，而由图3和图5可知，加入添加剂后，蚀刻速率恢复至图3的水平。因此，本申请提供的添加剂可以有效的矫正蚀刻液的蚀刻特性。
本实施例中，在蚀刻液反复使用的过程中添加本实施例提供的添加剂，使得蚀刻特性得以矫正，即在不同铜离子浓度下均能保证蚀刻速率稳定适中、蚀刻角度稳定在30°~50°以及线宽损失较小且稳定，使得形成的金属布线差异小；添加剂的加入使蚀刻液的使用寿命达到12000ppm（蚀刻液中的铜离子浓度）以上，大大提高了蚀刻液的使用寿命，从而大大减少了新的蚀刻液的使用量以及产生的蚀刻液废液量，在大幅降低生产费用的同时对操作人员的危害大大降低，且大幅度降低了蚀刻液废液的处理成本，满足了工业产线需求。
如图6所示，本申请实施例还提供了一种金属布线的制作方法，具体为铜/钼布线的制作方法，制作方法包括以下步骤：
步骤S601：提供覆盖有金属层的基板。
具体的，基板的材料包括玻璃；金属层包括铜金属层或铜/钼膜层。
步骤S602：在金属层远离基板的一侧部分设置防蚀刻涂层。
具体的，防蚀刻涂层的材料包括光阻材料，此处不做限制。
步骤S603：采用上述实施例中的蚀刻液对金属层中未被防蚀刻涂层覆盖的部分进行蚀刻，形成金属布线。
具体的，蚀刻液的成分包括占蚀刻液总重量的7.8%的过氧化氢（双氧水）、0.1%的过氧化氢稳定剂、16%的螯合剂、0.1%的表面活性剂和2.2%的无机酸氧化剂以及73.8%的去离子水。蚀刻温度为35℃，蚀刻液的PH值为4.4。
在一实施例中，蚀刻掉的金属层以金属离子的形式存在于蚀刻液中；金属布线的制作方法还包括以下步骤：
检测蚀刻液中金属离子（铜离子）的浓度；当金属离子浓度超过预设浓度时，向含有金属离子的蚀刻液中加入添加剂，以使蚀刻液反复使用；其中，添加剂的主要成分包括占添加剂总重量的5~20%的有机酸、0.3~3%的蚀刻抑制剂，余量为去离子水；其中，有机酸包括柠檬酸、丙二酸、苹果酸和琥珀酸中的至少一种；蚀刻抑制剂为苯并唑类化合物。
具体的，预设浓度小于6000ppm，可以是4000ppm，也可以是6000ppm或其他值，根据实际情况设定。
具体的，添加剂的成分包括占添加剂总重量的8%的有机酸、0.6%的蚀刻抑制剂以及91.4%的去离子水。
具体的，向含有金属离子的蚀刻液中加入添加剂，包括以下步骤：
蚀刻液中的金属离子的浓度每升高1000ppm时，向含有金属离子的蚀刻液中加入占蚀刻液总重量的0.1~2%的添加剂。当然，添加剂的添加方式也可以根据实际生产情况进行调整，例如铜离子浓度每升高500ppm时，添加一次添加剂，此处不做限制。
本实施例中，采用以上实施例提供的蚀刻剂和添加剂制作金属布线时，蚀刻速率稳定适中，蚀刻角度稳定在30°~50°，线宽损失较小且稳定，无金属残留，有利于提高产品质量；另外，添加剂的加入可以大大提高蚀刻液的使用寿命，从而可以大大减少新的蚀刻液的使用量以及产生的蚀刻液废液量，在大幅降低生产费用的同时对操作人员的危害大大降低，且大幅度降低了蚀刻液废液的处理成本，满足了工业产线需求。
在上述实施例中，对各个实施例的描述都各有侧重，某个实施例中没有详述的部分，可以参见其他实施例的相关描述。
以上对本申请实施例所提供的一种蚀刻液、添加剂及金属布线的制作方法进行了详细介绍，本文中应用了具体个例对本申请的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本申请的技术方案及其核心思想；本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例的技术方案的范围。

Claims (20)

  1. 一种蚀刻液，所述蚀刻液的主要成分包括占所述蚀刻液总重量的5~30%的过氧化氢、0.1~5%的过氧化氢稳定剂、5~25%的螯合剂、0.1~1%的表面活性剂和0.1~5%的无机酸氧化剂，余量为去离子水。
  2. 如权利要求1所述的蚀刻液，其中，所述过氧化氢稳定剂包括苯基脲、聚丙烯酰胺和无机盐中的至少一种。
  3. 如权利要求1所述的蚀刻液，其中，所述螯合剂包括柠檬酸、酒石酸、丙二酸、苯甲酸、二乙醇酸、马来酸、羟基丁酸、乳酸、苹果酸、琥珀酸、异丙醇胺和丙二醇中的至少一种。
  4. 如权利要求1所述的蚀刻液，其中，所述表面活性剂为醇胺类物质；所述醇胺类物质包括聚乙二醇和聚丙烯酸胺中的任意一种或两种。
  5. 如权利要求1所述的蚀刻液，其中，所述无机酸氧化剂包括硝酸、磷酸、盐酸和硫酸中的至少一种。
  6. 一种添加剂，在反复使用如权利要求1所述的蚀刻液时添加至所述蚀刻液中，所述添加剂的主要成分包括占所述添加剂总重量的5~20%的有机酸、0.3~3%的蚀刻抑制剂，余量为去离子水；
    其中，所述有机酸包括柠檬酸、丙二酸、苹果酸和琥珀酸中的至少一种；所述蚀刻抑制剂为苯并唑类化合物。
  7. 如权利要求6所述的添加剂，其中，所述过氧化氢稳定剂包括苯基脲、聚丙烯酰胺和无机盐中的至少一种。
  8. 如权利要求6所述的添加剂，其中，所述螯合剂包括柠檬酸、酒石酸、丙二酸、苯甲酸、二乙醇酸、马来酸、羟基丁酸、乳酸、苹果酸、琥珀酸、异丙醇胺和丙二醇中的至少一种。
  9. 如权利要求6所述的添加剂，其中，所述表面活性剂为醇胺类物质；所述醇胺类物质包括聚乙二醇和聚丙烯酸胺中的任意一种或两种。
  10. 如权利要求6所述的添加剂，其中，所述无机酸氧化剂包括硝酸、磷酸、盐酸和硫酸中的至少一种。
  11. 一种金属布线的制作方法，包括以下步骤：
    提供覆盖有金属层的基板；
    在所述金属层远离所述基板的一侧部分设置防蚀刻涂层；
    采用如权利要求1所述的蚀刻液对所述金属层中未被所述防蚀刻涂层覆盖的部分进行蚀刻，形成金属布线。
  12. 如权利要求11所述的金属布线的制作方法，其中，蚀刻掉的金属层以金属离子的形式存在于所述蚀刻液中；
    所述制作方法还包括以下步骤：
    检测所述蚀刻液中所述金属离子的浓度；
    当所述金属离子浓度超过预设浓度时，向含有所述金属离子的所述蚀刻液中加入添加剂，以使所述蚀刻液反复使用；
    所述添加剂的主要成分包括占所述添加剂总重量的5~20%的有机酸、0.3~3%的蚀刻抑制剂，余量为去离子水。
  13. 如权利要求12所述的金属布线的制作方法，其中，所述有机酸包括柠檬酸、丙二酸、苹果酸和琥珀酸中的至少一种。
  14. 如权利要求12所述的金属布线的制作方法，其中，所述蚀刻抑制剂为苯并唑类化合物。
  15. 如权利要求12所述的金属布线的制作方法，其中，所述向含有所述金属离子的所述蚀刻液中加入添加剂，包括以下步骤：
    所述蚀刻液中的所述金属离子的浓度每升高1000ppm时，向含有所述金属离子的所述蚀刻液中加入占所述蚀刻液总重量的0.1~2%的添加剂。
  16. 如权利要求11所述的金属布线的制作方法，其中，所述金属层包括铜金属层或铜钼金属层。
  17. 如权利要求11所述的金属布线的制作方法，其中，所述过氧化氢稳定剂包括苯基脲、聚丙烯酰胺和无机盐中的至少一种。
  18. 如权利要求11所述的金属布线的制作方法，其中，所述螯合剂包括柠檬酸、酒石酸、丙二酸、苯甲酸、二乙醇酸、马来酸、羟基丁酸、乳酸、苹果酸、琥珀酸、异丙醇胺和丙二醇中的至少一种。
  19. 如权利要求11所述的金属布线的制作方法，其中，所述表面活性剂为醇胺类物质；所述醇胺类物质包括聚乙二醇和聚丙烯酸胺中的任意一种或两种。
  20. 如权利要求11所述的金属布线的制作方法，其中，所述无机酸氧化剂包括硝酸、磷酸、盐酸和硫酸中的至少一种。
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