WO2020155424A1 - 蚀刻液组合物 - Google Patents

蚀刻液组合物 Download PDF

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Publication number
WO2020155424A1
WO2020155424A1 PCT/CN2019/083773 CN2019083773W WO2020155424A1 WO 2020155424 A1 WO2020155424 A1 WO 2020155424A1 CN 2019083773 W CN2019083773 W CN 2019083773W WO 2020155424 A1 WO2020155424 A1 WO 2020155424A1
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Prior art keywords
film
solution composition
etching solution
titanium
etching
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PCT/CN2019/083773
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English (en)
French (fr)
Inventor
郝起林
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Priority to US16/492,131 priority Critical patent/US11136504B2/en
Publication of WO2020155424A1 publication Critical patent/WO2020155424A1/zh
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • 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
    • 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
    • C23F1/20—Acidic compositions for etching aluminium 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/60—Wet etching
    • H10P50/66—Wet etching of conductive or resistive materials
    • H10P50/663—Wet etching of conductive or resistive materials by chemical means only
    • H10P50/667—Wet etching of conductive or resistive materials by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/621—Providing a shape to conductive layers, e.g. patterning or selective deposition

Definitions

  • This application relates to the technical field of display panels, and in particular to an etching solution composition that can be used in the display panel manufacturing process.
  • OLED display devices are widely used in the display field because of their self-luminous, simple structure, ultra-light and thin, fast response speed, wide viewing angle, low power consumption and flexible display.
  • the production cost of OLEDs is required to be further reduced.
  • the cost of OLED is affected by equipment purchase costs and operating costs.
  • the etching process of OLEDs often requires simultaneous etching of multiple metal films.
  • the metal titanium film and titanium alloy film which are the main etching objects, have strong corrosion resistance, so the etching rate in wet etching is relatively difficult to control, which limits the application of wet etching. Therefore, at present, the dry etching process is mainly used to simultaneously etch multiple metal films.
  • the cost of the dry etching process is high, resulting in the high cost of OLED products.
  • the purpose of this application is to provide an etching solution composition, which is used in the touch panel process (Touch process) to use a wet etching process instead of a dry etching process to etch the titanium film/aluminum film/titanium film multilayer metal film to reduce Equipment cost and production cost and improve production efficiency.
  • an etching solution composition for wet etching a titanium-containing film.
  • the etching solution composition uses hydrofluoric acid as the main oxidant, and includes a co-oxidant that forms a dense oxide film on the surface of the titanium film during the etching process, an alkali metal salt that inhibits the accumulation and adsorption of titanium film ions during the etching process, and a solvent.
  • the etching solution composition comprises 0.5-3% hydrofluoric acid, 30-55% co-oxidant, 1-5% alkali metal salt, and the total weight percentage is 100%. % Of solvent.
  • the etching solution composition includes 2 to 3% of hydrofluoric acid, such as 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6% , 2.7%, 2.8%, 2.9%.
  • the etching solution composition includes 1 to 3% of alkali metal salt, such as 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6% , 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%.
  • alkali metal salt such as 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6% , 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%.
  • the co-oxidant is a mixture of at least two acids.
  • the co-oxidant is a mixture of a halogen-containing acid and an oxygen-containing acid.
  • the halogen-containing acid is one or a mixture of perbromic acid and perchloric acid.
  • the oxygen-containing acid is nitric acid.
  • the etching solution composition includes 1 to 5% of nitric acid and 30 to 50% of perchloric acid by weight.
  • the etching solution composition includes 2 to 3% nitric acid, such as 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2. %, 2.8%, 2.9%.
  • the etching solution composition includes 35-45% perchloric acid, such as 36%, 37%, 38%, 39%, 40%, 41% , 42%, 43%, 44%.
  • the solvent is deionized water.
  • the alkali metal salt is sodium nitrate.
  • an etchant composition which comprises 0.5-3% hydrofluoric acid, 0.5-5% nitric acid, and 30-50% perchloric acid relative to the total weight of the etchant composition. , 1 ⁇ 5% sodium nitrate, and deionized water to make the total weight percentage 100%.
  • an etching solution composition which comprises, relative to the total weight of the etching solution composition: 2 to 3% hydrofluoric acid, 1 to 3% sodium nitrate, and 2 to 3% nitric acid, 35 ⁇ 45% perchloric acid, and deionized water to make the total weight percentage 100%.
  • an application of the above-mentioned etching solution composition in wet etching of a titanium-containing film is provided.
  • the application of etching titanium-containing film in TFT array substrates refers to a film that includes a titanium film (Ti) in its constituent components, and includes a single-layer film or a multi-layer film including a double-layer film or more.
  • the titanium-containing film may be, but is not limited to, a single-layer titanium film or a titanium alloy film or a multilayer film composed of a single-layer film of a titanium film or a titanium alloy film and an aluminum film.
  • the titanium alloy film is mainly composed of a titanium film, and may include alloy forms of other metals such as Nd, Cu, Pd, Ni, Ma, and various forms of titanium nitride, oxide or carbide, but not limited to this. .
  • the titanium-containing film may be a multilayer film of aluminum film/titanium film, titanium film/aluminum film/titanium film, titanium film/aluminum film, or aluminum film/titanium film/aluminum film.
  • a multi-layer titanium-containing film film such as aluminum film/titanium film, titanium film/aluminum film/titanium film, Titanium film/aluminum film or a multilayer film of aluminum film/titanium film/aluminum film
  • the etching solution composition described in the present application can be used in the touch panel manufacturing process to use a wet etching process instead of a dry etching process to etch a titanium film/aluminum film/titanium film multilayer metal film to reduce equipment costs and production costs And improve production efficiency.
  • Figure 1 shows the polarization curve of titanium electrode passivation at different potentials for different time to form oxide film in 1.0 mol/L HClO 4 solution
  • Figure 2 shows the polarization curves of titanium electrodes in a mixed solution of 0.1 mol/L NaF and 0.1 mol/L NaClO 4 at different sweep speeds.
  • the "above” or “below” of the first feature of the second feature may include the first and second features in direct contact, or may include the first and second features Not in direct contact but through other features between them.
  • “above”, “above” and “above” the second feature of the first feature include the first feature being directly above and obliquely above the second feature, or it simply means that the level of the first feature is higher than the second feature.
  • the “below”, “below” and “below” the first feature of the second feature include the first feature directly below and obliquely below the second feature, or it simply means that the level of the first feature is smaller than the second feature.
  • an etching solution composition for wet etching a titanium-containing film.
  • the etching solution composition includes a main oxidant, a co-oxidant, an alkali metal salt, and a solvent.
  • the main oxidant is hydrofluoric acid (HF), which functions to oxidize the titanium film to perform wet etching when etching a single-layer film or a multilayer film.
  • HF hydrofluoric acid
  • the content of the hydrofluoric acid is 0.5-3%, preferably 1-2%.
  • the etching rate of the aluminum film in the titanium-containing film is reduced, and the etching rate of the titanium film or titanium alloy film becomes too fast, which will cause the etching angle to become polygonal.
  • the subsequent non-metallic film covering causes collapse or voids.
  • the co-oxidants are nitric acid and perchloric acid.
  • the content of the nitric acid is 1 to 5%, preferably 2 to 3%.
  • the content of the perchloric acid is 30-50%, preferably 35-45%.
  • the nitric acid (HNO 3 ) functions to oxidize the surfaces of the titanium film and the aluminum film during the etching process to form a dense oxide film, thereby slowing down the etching rate.
  • HNO 3 nitric acid
  • the content of nitric acid exceeds 5%, the oxide film formed by the titanium film/aluminum film is too dense and the etching speed is reduced, which results in poor etching uniformity in the substrate, which may cause streaking The problem.
  • the content of the hydrofluoric acid is less than 1%, the etching rate is too fast, which may cause undercutting of the aluminum film.
  • Figure 1 shows the polarization curve (scanning 50 mV/s) measured in 1.0 mol/L HClO 4 solution for titanium electrode passivation at different potentials for different time to form oxide film.
  • Figure 1 shows that the anodic oxygen evolution reaction will cause the transformation of the oxide on the surface of the titanium film.
  • HClO 4 perchloric acid
  • the alkali metal salt is sodium nitrate (NANO 3 ).
  • NANO 3 sodium nitrate
  • the content of the sodium nitrate is 1 to 5%, preferably 1 to 3%.
  • Figure 2 is the superposition of the polarization curves of the titanium electrode in a mixed solution of 0.1 mol/L NaF and 0.1 mol/L NaClO 4 with different sweep speeds.
  • the polarization current is significantly larger than that in the 0.1mol/L sodium perchlorate in the bottom solution, indicating the addition of fluoride ions It does not change the blunt process of the titanium electrode surface.
  • Fluoride ions and the titanium film on the surface of the titanium electrode form a complex TiF 6 2- . When fluoride ions are present, it will accelerate the dissolution of the titanium film.
  • the sodium nitrate plays a role in accelerating the reaction rate of the titanium film during the etching process, while inhibiting the accumulation of titanium film ions and preventing re-adsorption, and is used to adjust the etching rate to achieve uniform etching.
  • the solvent is water, preferably deionized water.
  • an etching solution composition which comprises 0.5-3% hydrofluoric acid, 0.5-5% nitric acid, and 30-50% high chlorine relative to the total weight of the etching solution composition. Acid, 1 ⁇ 5% sodium nitrate, and deionized water to make the total weight percentage 100%. More preferably, relative to the total weight of the etching solution composition, the etching solution composition includes: 2 ⁇ 3% hydrofluoric acid, 1 ⁇ 3% sodium nitrate, 2 ⁇ 3% nitric acid, 35 ⁇ 45% % Perchloric acid, and deionized water to make the total weight percentage 100%.
  • This embodiment also provides the application of the above-mentioned etching solution composition in the wet etching of a titanium-containing film.
  • etching titanium-containing film in TFT array substrates.
  • the titanium-containing film refers to a film that includes a titanium film (Ti) in its constituent components, and includes a single-layer film or a multi-layer film including a double-layer film or more.
  • the titanium-containing film may be, but is not limited to, a single-layer film of a titanium film or a titanium alloy film, or a multilayer film composed of a single-layer film of a titanium film or a titanium alloy film and an aluminum film.
  • the titanium alloy film is mainly composed of a titanium film, which may include alloy forms of other metals such as Nd, Cu, Pd, Ni, Ma, and various forms such as nitrides, oxides, or carbides of the titanium film, but is not limited to this.
  • the titanium-containing film may be a multilayer film of aluminum film/titanium film, titanium film/aluminum film/titanium film, titanium film/aluminum film, or aluminum film/titanium film/aluminum film.
  • the equipment investment cost of the dry etching equipment is about 150 million yuan, and the equipment is modified to wet etching using the etching solution composition described in this application.
  • the investment fee is only about 20 million yuan.
  • the operating cost of wet etching equipment is slightly lower than that of dry etching equipment.
  • a multi-layer titanium-containing film film such as aluminum film/titanium film, titanium film/aluminum film/titanium film, Titanium film/aluminum film or a multilayer film of aluminum film/titanium film/aluminum film
  • the etching solution composition described in the present application can be used in the touch panel manufacturing process to use a wet etching process instead of a dry etching process to etch a titanium film/aluminum film/titanium film multilayer metal film to reduce equipment costs and production costs And improve production efficiency.
  • the main body of this application can be manufactured and used in industry and has industrial applicability.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Weting (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

一种蚀刻液组合物，以氢氟酸为主氧化剂，并包括在蚀刻过程中在钛膜表面形成致密氧化膜的助氧化剂，在蚀刻过程中抑制钛膜离子聚集吸附的碱金属盐，以及溶剂。

Description

蚀刻液组合物 技术领域
本申请涉及显示面板技术领域，特别涉及显示面板制程种能所使用的蚀刻液组合物。
 背景技术
有机电致发光二极管(OLED)显示装置因具有自发光、结构简单、超轻薄、响应速度快、宽视角、低功耗及可实现柔性显示等特性，被广泛应用于显示领域。随着市场对OLED需求的不断增强，要求OLED的生产成本进一步降低。目前，OLED的成本受设备采购成本和运营成本的影响。
 技术问题
由于OLED对线宽要求较为严格，同时OLED的蚀刻制程多要求同时蚀刻多种金属膜。目前市场较少有能满足同时蚀刻多种金属膜需求的蚀刻液组合物。此外，作为主要蚀刻对象的金属钛膜及钛合金膜的抗腐蚀性强，因而在湿法蚀刻中的蚀刻速率较难以控制，限制了湿法蚀刻的应用。因此，目前主要采用干法蚀刻制程进行多种金属膜的同时蚀刻。然而，干法蚀刻制程的成本高，导致OLED产品的成本居高不下。
因而，需要一种新的蚀刻液组合物，可以满足对线宽和多金属膜层的需求，实现使用湿法蚀刻代替干法蚀刻，从而达到降低设备采购成本和运营成本的要求。
 技术解决方案
本申请的目的在于提供一种蚀刻液组合物，用于在触摸面板制程（Touch制程）中使用湿法蚀刻制程替代干法蚀刻制程蚀刻钛膜/铝膜/钛膜多层金属膜，以降低设备成本和生产成本并提高生产效率。
为了达到上述目的，根据本申请的一方面，提供一种蚀刻液组合物，用于湿法蚀刻含钛膜薄膜。所述蚀刻液组合物以氢氟酸为主氧化剂，并包括在蚀刻过程中在钛膜表面形成致密氧化膜的助氧化剂，在蚀刻过程中抑制钛膜离子聚集吸附的碱金属盐，以及溶剂。
在一实施例中，所述蚀刻液组合物按重量百分比包括：0.5~3%的氢氟酸，30~55%的助氧化剂，1~5 %的碱金属盐，以及使总重量百分比为100％的溶剂。
在一优选实施例中，相对于蚀刻液组合物总重量，所述蚀刻液组合物包括2~3%的氢氟酸，例如2.1%，2.2%，2.3%，2.4%，2.5%，2.6%，2.7%，2.8%，2.9%。
在一优选实施例中，相对于蚀刻液组合物总重量，所述蚀刻液组合物包括1~3%的碱金属盐，例如1.1%，1.2%，1.3%，1.4%，1.5%，1.6%，1.7%，1.8%，1.9%，2.0%，2.1%，2.2%，2.3%，2.4%，2.5%，2.6%，2.7%，2.8%，2.9%。
在一实施例中，所述助氧化剂为至少两种酸的混合。
在一实施例中，所述助氧化剂为含卤酸与含氧酸的混合。
在一实施例中，所述含卤酸为高溴酸、高氯酸中的一种或几种混合。
在一实施例中，所述含含氧酸为硝酸。
在一实施例中，所述蚀刻液组合物按重量百分比包括1~5%的硝酸和30~50%的高氯酸。
在一优选实施例中，相对于蚀刻液组合物总重量，所述蚀刻液组合物包括2~3%的硝酸，例如2.1%，2.2%，2.3%，2.4%，2.5%，2.6%，2.7%，2.8%，2.9%。
在一优选实施例中，相对于蚀刻液组合物总重量，所述蚀刻液组合物包括35~45%的高氯酸，例如36%，37%，38%，39%，40%，41%，42%，43%，44%。
在一实施例中，所述溶剂为去离子水。
在一实施例中，所述碱金属盐为硝酸钠。
在一优选实施例中，提供一种蚀刻液组合物，按相对于蚀刻液组合物总重量包括：0.5~3%的氢氟酸，0.5~5 %的硝酸，30~50 %的高氯酸，1~5 %的硝酸钠，以及使总重量百分比为100％的去离子水。
在一优选实施例中，提供一种蚀刻液组合物，按相对于蚀刻液组合物总重量包括：2~3%的氢氟酸，1~3%的硝酸钠，2~3%的硝酸，35~45%的高氯酸，以及使总重量百分比为100％的去离子水。
根据本申请的另一方面，提供上述蚀刻液组合物在含钛膜薄膜湿法蚀刻中的应用。例如，在TFT阵列基板中蚀刻含钛膜薄膜的应用。所述含钛膜薄膜是指构成成分中包括钛膜（Ti）的薄膜，包括单层膜或双层膜以上的多层膜。所述含钛膜薄膜可以是但不限于，单层钛膜或钛合金膜或者，钛膜或钛合金膜的单层膜与铝膜所构成的多层膜。
所述钛合金膜以钛膜为主成分，可以包括Nd，Cu，Pd，Ni，Ma等其他金属的合金形式，以及钛的氮化物、氧化物或碳化物等多种形态，但不限于此。
在本申请一实施例中，所述含钛膜薄膜可以为铝膜/钛膜、钛膜/铝膜/钛膜、钛膜/铝膜或铝膜/钛膜/铝膜的多层膜。
 有益效果
在本申请中，通过各组分的合理选择及组分间的协同作用，获得了一种可以同时蚀刻多层含钛膜薄膜（例如铝膜/钛膜、钛膜/铝膜/钛膜、钛膜/铝膜或铝膜/钛膜/铝膜的多层膜）的蚀刻液组合物。因此，本申请所述的蚀刻液组合物可以用于在触摸面板制程中使用湿法蚀刻制程替代干法蚀刻制程蚀刻钛膜/铝膜/钛膜多层金属膜，以降低设备成本和生产成本并提高生产效率。
 附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为钛电极在不同电位下钝化不同时间形成氧化膜在1.0 mol/L的HClO 4溶液中测得的极化曲线；
图2为钛电极在0.1mol/L的NaF与0.1mol/L的NaClO 4混合溶液中不同扫速的极化曲线。
本发明的实施方式
下面详细描述本发明的实施方式，所述实施方式的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施方式是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。
在本发明中，除非另有明确的规定和限定，第一特征在第二特征之“上”或之“下”可以包括第一和第二特征直接接触，也可以包括第一和第二特征不是直接接触而是通过它们之间的另外的特征接触。而且，第一特征在第二特征“之上”、“上方”和“上面”包括第一特征在第二特征正上方和斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”包括第一特征在第二特征正下方和斜下方，或仅仅表示第一特征水平高度小于第二特征。
下文的公开提供了许多不同的实施方式或例子用来实现本发明的不同结构。为了简化本发明的公开，下文中对特定例子的部件和设置进行描述。当然，它们仅仅为示例，并且目的不在于限制本发明。此外，本发明可以在不同例子中重复参考数字和/或参考字母，这种重复是为了简化和清楚的目的，其本身不指示所讨论各种实施方式和/或设置之间的关系。此外，本发明提供了的各种特定的工艺和材料的例子，但是本领域普通技术人员可以意识到其他工艺的应用和/或其他材料的使用。
在本实施例中提供一种蚀刻液组合物，用于湿法蚀刻含钛膜薄膜。所述蚀刻液组合物包括主氧化剂、助氧化剂、碱金属盐，以及溶剂。
所述主氧化剂为氢氟酸（HF），在蚀刻单层膜或多层膜时起到使钛膜氧化而进行湿式蚀刻的作用。对于蚀刻液组合物总重量，所述氢氟酸的含量为0.5~3%，优先1~2%。
经实验表明，蚀刻过程中仅氢氟酸被分解，其氢离子参与蚀刻反应，故过程中需控制氢氟酸的比例。当氢氟酸过少时，硝酸将参与腐蚀金属铝膜。如果所述氢氟酸的含量低于0.5%，则所述蚀刻液组合物的蚀刻能力不足，可能导致蚀刻速度降低和蚀刻轮廓不良。此外，如果所述氢氟酸的含量超过4%，则使得含钛膜薄膜中的铝膜的蚀刻速度降低，而钛膜或钛合金膜的蚀刻速度变得过快，会导致蚀刻角成多边型，后续非金属膜覆盖产生坍塌或空洞。
所述助氧化剂为硝酸和高氯酸。对于蚀刻液组合物总重量，所述硝酸的含量为1~5%，优先为2~3%。所述高氯酸的含量为30~50 %，优选35~45%。
所述硝酸（HNO 3）在蚀刻过程中起到使钛膜和铝膜表面氧化，形成致密氧化膜，从而减缓蚀刻速率的作用。经实验表明，如果所述硝酸的含量超过5 %，则会因钛膜/铝膜形成氧化膜过于致密而导致蚀刻速度降低，由此导致基板内的蚀刻均一性变得不良，因此可能产生斑纹的问题。如果所述氢氟酸的含量低于1%，则会因蚀刻速率过快，而导致铝膜的底切问题。
请参见图1，图1为钛电极在不同电位下钝化不同时间形成氧化膜在1.0 mol/L的HClO 4溶液中测得的极化曲线(扫描50 mV/s)。图1表明，阳极析氧反应将引起钛膜表面氧化物的转变，随着析氧反应和钛膜表面过氧化物的形成，在氧化物表面的最外层形成一层很薄的绝缘层，从而产生钝化层。该氧化物稳定不可逆，减缓腐蚀速率。因此，所述高氯酸（HClO 4）在蚀刻过程中用于起到使钛膜表面形成致密的氧化膜的作用，以延缓钛膜的腐蚀速度。
经实验表明，在所述高氯酸的含量低于30 %的情况下，存在由于基板内蚀刻速度不均而产生的斑纹的问题。而在所述高氯酸的含量高于50 %的情况下，会在蚀刻的过程中产生大量的反应气泡，同时钛膜表面的氧化膜过于致密而导致蚀刻速率下降。
所述碱金属盐为硝酸钠（NANO 3）。对于蚀刻液组合物总重量，所述硝酸钠的含量为1~5%，优选1~3%。
请参见图2，图2是钛电极在0.1mol/L的NaF与0.1mol/L的NaClO 4混合溶液中不同扫速的极化曲线的叠加。如图2所示，在底液0.1mol/L的高氯酸钠中加入氟化钠之后，极化电流明显比在底液0.1mol/L高氯酸钠中的大，说明氟离子的加入并不改变钛电极表面致钝的过程。氟离子与钛电极表面的钛膜生成络合物TiF 6 2-，当有氟离子存在时，会加速钛膜的溶解。因此，所述硝酸钠在蚀刻过程中起到加速钛膜的反应速率，同时抑制钛膜离子聚集，防止再吸附的作用，用于调节蚀刻速度从而实现均匀蚀刻。
经实验表明，在所述硝酸钠的含量低于1 %的情况下，存在基板内蚀刻均一性降低的问题。在所述硝酸钠的含量高于5%的情况下，则会因蚀刻速度加大而导致钛膜与铝膜反应速率不一致。
所述溶剂为水，优选去离子水。
因此，在本实施例中，提供一种蚀刻液组合物，按相对于蚀刻液组合物总重量包括：0.5~3%的氢氟酸，0.5~5 %的硝酸，30~50 %的高氯酸，1~5 %的硝酸钠，以及使总重量百分比为100％的去离子水。更为优选地，按相对于蚀刻液组合物总重量，所述蚀刻液组合物包括：2~3%的氢氟酸，1~3%的硝酸钠，2~3%的硝酸，35~45%的高氯酸，，以及使总重量百分比为100％的去离子水。
本实施例还提供上述蚀刻液组合物在含钛膜薄膜湿法蚀刻中的应用。例如，在TFT阵列基板中蚀刻含钛膜薄膜的应用。所述含钛膜薄膜是指构成成分中包括钛膜（Ti）的薄膜，包括单层膜或双层膜以上的多层膜。所述含钛膜薄膜可以是但不限于，钛膜或钛合金膜的单层膜，或者，钛膜或钛合金膜的单层膜与铝膜所构成的多层膜。所述钛合金膜以钛膜为主成分，可以包括Nd，Cu，Pd，Ni，Ma等其他金属的合金形式，以及钛膜的氮化物、氧化物或碳化物等多种形态，但不限于此。所述含钛膜薄膜可以为铝膜/钛膜、钛膜/铝膜/钛膜、钛膜/铝膜或铝膜/钛膜/铝膜的多层膜。
以触控面板生产工厂为例进行计算，在45K产能的情况下，干法蚀刻设备的设备投资费约1.5亿元人民币，而修改为使用本申请所述蚀刻液组合物的湿法蚀刻，设备投资费仅约2千万元人民币。同时，湿法蚀刻设备的运营费用也略低于干法蚀刻设备的运营费用。
在本申请中，通过各组分的合理选择及组分间的协同作用，获得了一种可以同时蚀刻多层含钛膜薄膜（例如铝膜/钛膜、钛膜/铝膜/钛膜、钛膜/铝膜或铝膜/钛膜/铝膜的多层膜）的蚀刻液组合物。因此，本申请所述的蚀刻液组合物可以用于在触摸面板制程中使用湿法蚀刻制程替代干法蚀刻制程蚀刻钛膜/铝膜/钛膜多层金属膜，以降低设备成本和生产成本并提高生产效率。
本申请已由上述相关实施例加以描述，然而上述实施例仅为实施本申请的范例。必需指出的是，已公开的实施例并未限制本申请的范围。相反地，包含于权利要求书的精神及范围的修改及均等设置均包括于本申请的范围内。
 工业实用性
本申请的主体可以在工业中制造和使用，具备工业实用性。

Claims (13)

  1. 一种蚀刻液组合物，按重量百分比包括：
    氢氟酸         2~3 %，
    硝酸             2~3%，
    高氯酸         35~45%，
    硝酸钠         1~3 %，以及，
    使总重量百分比为100％的溶剂。
  2. 如权利要求1所述的蚀刻液组合物，其中，所述溶剂为去离子水。
  3. 一种蚀刻液组合物，用于湿法蚀刻含钛膜薄膜，其特征在于，所述蚀刻液组合物以氢氟酸为主氧化剂，并包括在蚀刻过程中在钛膜表面形成致密氧化膜的助氧化剂，在蚀刻过程中抑制钛膜离子聚集吸附的碱金属盐，以及溶剂。
  4. 如权利要求3所述的蚀刻液组合物，其特征在于，所述蚀刻液组合物按重量百分比包括：0.5~3 %的氢氟酸，30~55%的助氧化剂，1~5 %的碱金属盐，以及使总重量百分比为100％的溶剂。
  5. 如权利要求4所述的蚀刻液组合物，其特征在于，所述助氧化剂为至少两种酸的混合。
  6. 如权利要求5所述的蚀刻液组合物，其特征在于，所述助氧化剂为含卤酸与含氧酸的混合。
  7. 如权利要求6所述的蚀刻液组合物，其特征在于，所述含卤酸为高溴酸、高氯酸中的一种或几种混合。
  8. 如权利要求6所述的蚀刻液组合物，其特征在于，所述含含氧酸为硝酸。
  9. 如权利要求7所述的蚀刻液组合物，其特征在于，所述蚀刻液组合物按重量百分比包括1~5%的硝酸和30~50%的高氯酸。
  10. 如权利要求3所述的蚀刻液组合物，其特征在于，所述溶剂为去离子水。
  11. 如权利要求3所述的蚀刻液组合物，其特征在于，所述碱金属盐为硝酸钠。
  12. 权利要求3所述的蚀刻液组合物在中的含钛膜薄膜湿法蚀刻中的应用。
  13. 如权利要求12所述的应用，其中，所述含钛膜薄膜为一单层钛膜，或包含至少一层钛膜的多层膜。
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