WO2014000320A1 - Tft阵列基板铜导线的蚀刻液 - Google Patents

Tft阵列基板铜导线的蚀刻液 Download PDF

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Publication number
WO2014000320A1
WO2014000320A1 PCT/CN2012/078260 CN2012078260W WO2014000320A1 WO 2014000320 A1 WO2014000320 A1 WO 2014000320A1 CN 2012078260 W CN2012078260 W CN 2012078260W WO 2014000320 A1 WO2014000320 A1 WO 2014000320A1
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compound
array substrate
etching solution
volume content
tft array
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French (fr)
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寇浩
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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Priority to US13/583,225 priority Critical patent/US20130341558A1/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • 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
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D86/00—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates
    • H10D86/40—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates characterised by multiple TFTs
    • H10D86/441—Interconnections, e.g. scanning lines
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D86/00—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates
    • H10D86/40—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates characterised by multiple TFTs
    • H10D86/60—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates characterised by multiple TFTs wherein the TFTs are in active matrices

Definitions

  • the present invention relates to the field of etching liquids, and more particularly to an etching solution for a copper wire of a TFT array substrate. Background technique
  • Liquid crystal display has many advantages such as thin body, power saving, and no radiation, and has been widely used.
  • the existing liquid crystal display device includes a liquid crystal display panel and a backlight module (Backlight Module).
  • a liquid crystal display panel includes a CF (Color Filter) substrate, a TFT (Thin Film Transistor) array substrate, and a liquid crystal (Liquid Crystal) provided between the CF substrate and the TFT array substrate.
  • the liquid crystal molecules are controlled to change direction by powering the TFT array substrate, and the light of the backlight module is projected onto the CF substrate to generate a picture.
  • the performance characteristics and operational characteristics of the TFT array substrate are largely dependent on the materials forming the various elements of the TFT array substrate.
  • a metal wire is disposed on the TFT array substrate, and the metal wire in the TFT array substrate is formed by etching a metal layer sputtered on the TFT array substrate, and the etching process can be classified into dry etching and wet etching.
  • the metal wires conventionally applied to the TFT array substrate are aluminum wires.
  • the copper wire has a lower resistivity (about 2 ⁇ ⁇ ) and good electromigration resistance with respect to the aluminum wire, and thus is applied to the TFT array substrate to solve the problem caused by the above aluminum wire.
  • RIE reactive Ion Etch
  • copper metal forms copper fluoride (CuF x ) and copper chloride (CuCl x ), and the product is below 200 ° C. Solid, will not vaporize. Therefore, the copper metal cannot be formed into a wire pattern by dry etching like aluminum metal. Therefore, it has become more important to develop an etchant for copper metal wet etching.
  • copper and glass have poor adhesion and require a transition of the underlying metal layer.
  • copper is easily reacted with silicon to form a copper silicide (CuSi 3 ) compound by interdiffusion below 200 ° C, which results in high contact resistance, so it is also necessary to use other underlying metal layers for transition.
  • a refractory metal as a transitional bonding layer and a barrier layer, such as molybdenum ( ⁇ ), titanium (Ti) and the like. Accordingly, there is a need to develop a metal junction suitable for a copper wire of a TFT-LCD array substrate. Construct a copper wire etchant corresponding thereto.
  • the etchant has a short process window in the process of etching the metal layer, which makes the engineering control difficult and seriously affects the stability of the production and the production yield;
  • the service life is also generally short (3000 ppm), and the process window is narrowed and the performance becomes unstable in the later stage of the process, which shows defects such as large critical loss (CD loss).
  • An object of the present invention is to provide an etching solution for a copper wire of a TFT array substrate having a wide process window, a long shelf-time, and a long etching life.
  • the present invention provides an etching solution for a copper wire of a TFT array substrate, comprising: a main oxidizing agent, a secondary oxidizing agent, a chelating agent, an inhibitor, and an additive, wherein the primary oxidizing agent is hydrogen peroxide, and the secondary oxidizing agent is phosphoric acid, Sulfuric acid and nitric acid; the chelating agent is an amino compound; the inhibitor is an aminoazole compound and a carboxylic acid compound; and the additive is an amine compound containing an ammonia nitrogen and a carboxyloxy coordinating atom.
  • the volume content of the primary oxidant is 3-10%
  • the volume content of the secondary oxidant is 6-25%
  • the volume content of the chelating agent is 7-11%.
  • the inhibitor has a volume content of 3-5%
  • the additive has a volume content of 0.5-2%.
  • the amino compound contains two or more coordinating atoms.
  • the amino compound is iminodiacetic acid or triethylenetetramine.
  • the structural formula of the chelate formed by chelation of the iminodiacetic acid with copper ions or molybdenum ions is as follows
  • M is a copper ion or a molybdenum ion.
  • the amine compound is at least one of triethanolamines.
  • the aminoazole compound is an aminotetrazole compound.
  • the carboxylic acid compound is ethylenediaminetetraacetic acid or cyclohexanediaminetetraacetic acid.
  • a solvent which is deionized water, the volume content of which is the total volume of the etchant
  • the residual volume content after the volume content of the primary oxidant, secondary oxidant, chelating agent, inhibitor, and additive is subtracted from 100%.
  • the invention also provides an etching solution for a copper wire of a TFT array substrate, comprising: a main oxidizing agent, a secondary oxidizing agent, a chelating agent, an inhibitor, and an additive, wherein the primary oxidizing agent is hydrogen peroxide, and the secondary oxidizing agent is phosphoric acid, sulfuric acid, and nitric acid.
  • the chelating agent is an amino compound; the inhibitor is an aminoazole compound and a carboxylic acid compound; the additive is an amine compound containing an ammonia nitrogen and a carboxyloxy coordinating atom;
  • the volume content of the primary oxidant is 3-10%
  • the volume content of the secondary oxidant is 6-25%
  • the volume content of the chelating agent is 7-, calculated according to 100% of the total volume of the etching solution.
  • the inhibitor has a volume content of 3-5%
  • the additive has a volume content of 0.5-2%;
  • amino compound contains two or more coordinating atoms
  • amino compound is iminodiacetic acid
  • M is a copper ion
  • the amine compound is at least one of triethanolamines
  • aminoazole compound is an aminotetrazole compound
  • the carboxylic acid compound is ethylenediaminetetraacetic acid or cyclohexanediaminetetraacetic acid; further comprising a solvent, the solvent being deionized water, the volume content of which is 100% of the total etchant minus the main Residual volume content after volume content of oxidizing agents, secondary oxidizing agents, chelating agents, inhibitors and additives
  • the present invention significantly improves the short process characteristics of the copper wire etching solution by using the composition and type of the novel chelating agent and the additive, reduces the difficulty of engineering control, increases the stability of the engineering production, and improves the output. Yield; Improve shelf-time stability, shelf-time storage stability can also be maintained in the later stage of storage; increase the service life of 5000ppm), and the process window does not appear significantly narrower in the later stages of the process, and the performance is still relatively stable.
  • CD-loss critical dimension loss
  • Figure 2 is an etched photograph of the shelf life (Shelf-time) at 180% OE (Over Etching) in the last week;
  • FIG. 3 is a graph showing a relationship between a taper angle, a critical dimension loss (CD-loss), and an etching time when the etching solution has a service life of 5000 ppm;
  • CD-loss critical dimension loss
  • FIG. 5 is an etching photograph of an etching time at JET (Just Etching Time) according to an embodiment of the present invention
  • FIG. 6 is an etching photograph of an etching time at 120% OE (Over Etching) according to an embodiment of the present invention
  • Figure ⁇ is an etching photograph of an etching time of 180% OE (Over Etching) according to an embodiment of the present invention. detailed description
  • the invention provides an etching liquid for a copper wire of a TFT array substrate, mainly for a metal structure such as Cu/Mo and Cu/Mo-alloys, and the metal alloy may include Mg, Al, Ni, V, Mn or Si, etc.
  • a molybdenum layer or a molybdenum alloy layer is used as the underlying metal to enhance the adhesion and blocking effect of the underlying metal to the glass and to stabilize the electrode potential of the barrier metal layer in the etching liquid.
  • the etchant comprises: a primary oxidant, a secondary oxidant, a chelating agent, an inhibitor, and an additive, the primary oxidant is hydrogen peroxide, the secondary oxidant is phosphoric acid, sulfuric acid, and nitric acid; the chelating agent is an amino compound; the inhibitor It is an aminoazole compound and a carboxylic acid compound; the additive is an amine compound containing an ammonia nitrogen and a carboxyloxy coordinating atom.
  • the volume content of the primary oxidant is 3-10%
  • the volume content of the secondary oxidant is 6-25%
  • the volume content of the chelating agent is 7-11%.
  • the inhibitor has a volume content ranging from 3 to 5%
  • the additive has a volume content of from 0.5 to 2%.
  • the hydrogen peroxide (3 ⁇ 40 2 ) is used as the main oxidant of the etching solution, and mainly reacts with Cu and Mo to form a metal oxide; etc.; Mo0 3 and a chelating agent and other additives can effectively combine to form a stable complex, and CuO and Chelating agents, inhibitors, and additives have poor binding forces, making it difficult to form stable compounds and promote 3 ⁇ 40 2 volatilization.
  • the secondary oxidant is phosphoric acid, sulfuric acid, and nitric acid, which reacts mainly with CuO to form Cu 2+ to facilitate formation of stable compounds with chelating agents, inhibitors, and additives.
  • the metal ion etched by the chemical agent uses a "multidentate ligand" chelating agent containing a plurality of atoms. In the etching process, the chelating agent forms a "coordinating ring structure" with the metal ion.
  • the compound, and in the chelation process is generally stable with a five-membered ring and a six-membered ring, which can effectively reduce or even eliminate the hierarchical complexation phenomenon.
  • the amino compound is iminodiacetic acid or triethylenetetramine, and the structural formula of the chelate formed by the separation of the iminodiacetic acid and copper is as follows:
  • M is a copper ion or a molybdenum ion.
  • the inhibitor is an aminoazole compound and a carboxylic acid compound
  • the aminoazole compound is an aminotetrazole compound
  • the carboxylic acid compound is ethylenediaminetetraacetic acid or cyclohexanediaminetetraacetic acid
  • the inhibitor Used to control etching effects such as taper angle, ammonia contained in the molecule
  • the nitrogen and carboxyloxy coordination atoms have strong coordination ability and can basically form a complex reaction with all metal materials contained in the alloy metal.
  • the amine compound contains ammonia nitrogen and a carboxyloxycoordination atom, and is at least one of triethanolamines, which can decompose different amounts of amino groups as the etching progresses, can be combined with the etched Cu 2+ and effectively suppress the previous Decomposition of the chelate formed by Cu 2+ and chelating agent; ensuring the effective chelation of the chelating agent to the metal ion, reducing the immersion of the etching solution during the etching process and the over-etching attack on the metal layer, ensuring a wide process window And meet the required technical specifications, such as taper angle and CD-loss.
  • the etching solution comprises a solvent, which is deionized water, and the volume content thereof is 100% of the total volume of the etching solution, and the remaining volume content after subtracting the volume content of the main oxidizing agent, the secondary oxidizing agent, the chelating agent, the inhibitor and the additive .
  • the etching liquid is added in proportion, so that the etching liquid has a long etching life of about 5000 ppm.
  • the main performance of the copper wire etching solution of the invention is as follows:
  • FIG. 1 it is a copper wire etching solution etching performance summary and a process window shown in the present invention. It can be seen that JET (Just etching time) and OE (Over Etching) meeting the specification requirements are 180%, A wider process window facilitates production stability;
  • the etchant can still exhibit better performance at the end of the shelf-time
  • the etchant has a longer etch life and still exhibits good etch and a wider process window and better performance at 5000 ppm.
  • the present invention significantly improves the short process characteristics of the copper wire etching solution by using the composition and type of the novel chelating agent and the additive, reduces the difficulty of engineering control, increases the stability of the engineering production, and improves the yield. Rate; Improve shelf-time stability, maintain etch performance stability at the end of shelf-time storage; increase service life (> 5000ppm), and process window does not appear significantly narrower in the later process, and performance is still stable .
  • the TFT array substrate is sputtered with a copper film 2500A and a molybdenum alloy film 200A; the technical specification is 90% OE for the process window, and the process window after etching with the etching solution of the present invention is shown in Table 1:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Thin Film Transistor (AREA)
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Abstract

提供了一种TFT阵列基板铜导线的蚀刻液，包括：主氧化剂、次氧化剂、螯合剂、抑制剂、及添加剂，该主氧化剂为过氧化氢，该次氧化剂为磷酸、硫酸、及硝酸；该螯合剂为氨基类化合物；该抑制剂为氨基唑类化合物和羧酸类化合物；该添加剂为含氨氮及羧氧配位原子的胺类化合物。所述蚀刻液改善铜导线蚀刻液工艺窗口较短的特点，降低了工程控制难度，增加工程生产的稳定性及提高产出良率；提高shelf-time稳定性，shelf-time储存后期时也能保持蚀刻性能的稳定性；提高使用寿命（≥5000ppm），且在制程后期process window未出现明显变窄，且性能等仍较为稳定。

Description

TFT阵列基板铜导线的蚀刻液 技术领域
本发明涉及蚀刻液领域， 尤其涉及一种 TFT 阵列基板铜导线的蚀刻 液。 背景技术
液晶显示装置（LCD , Liquid Crystal Display )具有机身薄、 省电、 无 辐射等众多优点， 得到了广泛的应用。 现有液晶显示装置包括液晶显示面 板及背光模组 （ Backlight Module ) 。 通常液晶显示面板包括 CF ( Color Filter )基板、 TFT ( Thin Film Transistor)阵列基板、 及设于 CF基板与 TFT 阵列基板之间的液晶 （Liquid Crystal ) 。 通过给 TFT阵列基板供电与否来 控制液晶分子改变方向， 将背光模组的光线投射到 CF基板产生画面。
TFT阵列基板的性能特征和运行特性部分很大程度上取决于形成 TFT 阵列基板各元件的材料。 在 TFT阵列基板上布有金属导线， TFT阵列基板 中的金属导线是将溅射在 TFT阵列基板上的金属层通过蚀刻工艺制成， 该 蚀刻工艺可分为干式蚀刻和湿式蚀刻。 常规应用于 TFT阵列基板中的金属 导线为铝导线。 随着电视等液晶显示终端的大尺寸化、 高解析度以及驱动 频率高速化的发展趋势及要求， 液晶显示领域技术人员不得不面对 TFT阵 列基板中电阻及所造成的电阻 /电容时间延迟问题。 而铝导线具有较高的电 阻率 (约 4μΩ οηι)使得 TFT 阵列基板的像素电极不能够充分充电， 随着高 频寻址 (≥120Ηζ)液晶显示的广泛应用， 这一现象更加明显。
铜导线相对于铝导线具有较低的电阻率 (约 2μΩ οηι)及良好的抗电迁移 能力， 因而被应用到 TFT阵列基板上来解决上述铝导线产生的问题。 然 而， 在铜导线蚀刻制程中， 经过离子蚀刻（Reactive Ion Etch, RIE)时， 铜金 属会生成氟化铜 (CuFx)和氯化铜 (CuClx) , 该生成物在 200 °C以下为固体， 不会气化。 因此铜金属无法像铝金属那样以干式蚀刻的方式制作出导线图 案。 因此， 发展应用于铜金属湿式蚀刻的蚀刻剂变得尤为重要。
此外， 铜与玻璃具有差的粘附性， 需要用下层金属层进行过渡。 且铜 在 200 °C以下通过互扩散易与硅反应生成具有硅化铜 （CuSi3 )化合物， 产 生很高的接触电阻， 因此也需要釆用其它下层金属层进行过渡。 目前较为 常用的是釆用难熔金属作为过渡的粘结层和阻挡层， 例如钼 （Μο ) , 钛 ( Ti )等。 相应地， 需要开发出适用于 TFT-LCD阵列基板铜导线的金属结 构及与其相对应的铜导线蚀刻液。
美国专利 US20010983733 、 US2002076930A1 、 US20080079008 及 US2009286360A1 揭露了行业内已经用于量产的 Cu/Mo及 Cu/Ti金属结构。 从目前量产的铜导线制程及生产良率来看， 过氧化氢（¾02 )基体的 Cu蚀 刻液具有明显的优 但目前仍存在较为明显的缺点：
( 1 ) 蚀刻液在刻蚀金属层过程中普遍存在工艺窗口 （ process window )较短的特点， 导致工程控制难度加大且严重影响工程生产的稳定 性及生产良率；
( 2 ) 目前使用铜导线蚀刻液， 普遍存在存储期 （shelf-time ) 不稳定 状况， 在储存后期时易存在蚀刻性能不稳定， 工艺窗口降低等缺点；
( 3 )使用寿命也普遍较短（ 3000ppm) , 且在制程后期工艺窗口变窄 且性能也变得不稳定， 表现出临界尺寸损失（CD loss )较大等缺陷。 发明内容
本发明的目的在于提供一种 TFT阵列基板铜导线的蚀刻液， 其具有宽 的工艺窗口、 长的 shelf-time及长的刻蚀寿命。
为实现上述目的， 本发明提供一种 TFT阵列基板铜导线的蚀刻液， 包 括： 主氧化剂、 次氧化剂、 螯合剂、 抑制剂、 及添加剂， 该主氧化剂为过 氧化氢， 该次氧化剂为磷酸、 硫酸、 及硝酸； 该螯合剂为氨基类化合物； 该抑制剂为氨基唑类化合物和羧酸类化合物； 该添加剂为含氨氮及羧氧配 位原子的胺类化合物。
按所述蚀刻液的总体积 100%计算， 所述主氧化剂的体积含量为 3- 10% , 所述次氧化剂的体积含量为 6-25% , 所述螯合剂的体积含量为 7- 11%, 所述抑制剂的体积含量为 3-5%, 所述添加剂的体积含量为 0.5-2%。
所述氨基类化合物含有两个或两个以上的配位原子。
所述氨基类化合物为亚氨基二乙酸或三乙烯四胺。
所述亚氨基二乙酸与铜离子或钼离子螯合后生成的螯合物的结构式如
Figure imgf000003_0001
其中， M为铜离子或钼离子。
所述胺类化合物为三乙醇胺类中的至少一种。
所述氨基唑类化合物为氨基四唑化合物。
所述羧酸类化合物为乙二胺四乙酸或环已二胺四乙酸。
还包括溶剂， 其为去离子水， 其体积含量为所述蚀刻液的总体积
100%中减去主氧化剂、 次氧化剂、 螯合剂、 抑制剂及添加剂的体积含量后 的剩余体积含量。
本发明还提供一种 TFT阵列基板铜导线的蚀刻液， 包括： 主氧化剂、 次氧化剂、 螯合剂、 抑制剂、 及添加剂， 该主氧化剂为过氧化氢， 该次氧 化剂为磷酸、 硫酸、 及硝酸； 该螯合剂为氨基类化合物； 该抑制剂为氨基 唑类化合物和羧酸类化合物； 该添加剂为含氨氮及羧氧配位原子的胺类化 合物；
其中， 按所述蚀刻液的总体积 100%计算， 所述主氧化剂的体积含量 为 3-10%, 所述次氧化剂的体积含量为 6-25%, 所述螯合剂的体积含量为 7-11% , 所述抑制剂的体积含量为 3-5% , 所述添加剂的体积含量为 0.5- 2%;
其中， 所述氨基类化合物含有两个或两个以上的配位原子；
其中， 所述氨基类化合物为亚氨基二乙酸；
其中， 所述亚氨基二乙酸与铜离子螯合后生成的螯合物的结构式如 下:
Figure imgf000004_0001
其中， M为铜离子；
其中， 所述胺类化合物为三乙醇胺类中的至少一种；
其中， 所述氨基唑类化合物为氨基四唑化合物；
其中， 所述羧酸类化合物为乙二胺四乙酸或环已二胺四乙酸； 还包括溶剂， 所述溶剂为去离子水， 其体积含量为所述蚀刻液的总体 100%中减去主氧化剂、 次氧化剂、 螯合剂、 抑制剂及添加剂的体积含 量后的剩余体积含量 ( 本发明的有益效果： 本发明通过使用新型的螯合剂及添加剂的成分及 类型， 显著改善铜导线蚀刻液工艺窗口较短的特点， 降低了工程控制难 度， 增加工程生产的稳定性及提高产出良率； 提高 shelf-time 稳定性， shelf-time 储存后期时也能保持蚀刻性能的稳定性； 提高使用寿命 5000ppm) , 且在制程后期 process window未出现明显变窄， 且性能等仍较 为稳定。
为了能更进一步了解本发明的特征以及技术内容， 请参阅以下有关本 发明的详细说明与附图， 然而附图仅提供参考与说明用， 并非用来对本发 明加以限制。 附图说明
下面结合附图， 通过对本发明的具体实施方式详细描述， 将使本发明 的技术方案及其它有益效果显而易见。
附图中，
图 1 为本发明蚀刻液蚀刻金属层的雉角 （taper angle ) 、 临界尺寸损 失（ CD- loss )与蚀刻时间的关系；
图 2为存储期 ( Shelf-time )在最后一周的 180%OE ( Over Etching ) 时的蚀刻照片；
图 3为本发明蚀刻液使用寿命在 5000ppm时的雉角 （taper angle ) 、 临界尺寸损失（ CD- loss )与蚀刻时间的关系；
图 4 为本发明蚀刻液使用寿命在 5000ppm 的 180%OE ( Over Etching ) 时的蚀刻照片；
图 5为本发明一实施例蚀刻时间在 JET ( Just Etching Time ) 时的蚀刻 照片；
图 6为本发明一实施例蚀刻时间在 120%OE ( Over Etching ) 时的蚀刻 照片；
图 Ί为本发明一实施例蚀刻时间在 180%OE ( Over Etching ) 时的蚀刻 照片。 具体实施方式
为更进一步阐述本发明所釆取的技术手段及其效果， 以下结合本发明 的优选实施例及其附图进行详细描述。
本发明提供一种 TFT阵列基板铜导线的蚀刻液， 主要针对 Cu/Mo及 Cu/Mo-alloys等金属结构， 金属合金可包括 Mg、 Al、 Ni、 V、 Mn或 Si等 材料， 使用钼层或钼合金层作为下层金属， 以提高下层金属对于玻璃的粘 附性与阻挡作用并在蚀刻液内起到稳定阻挡金属层的电极电位作用。 该蚀 刻液包含： 主氧化剂、 次氧化剂、 螯合剂、 抑制剂、 及添加剂， 该主氧化 剂为过氧化氢， 该次氧化剂为磷酸、 硫酸、 及硝酸； 该螯合剂为氨基类化 合物； 该抑制剂为氨基唑类化合物和羧酸类化合物； 该添加剂为含氨氮及 羧氧配位原子的胺类化合物。
按所述蚀刻液的总体积 100%计算， 所述主氧化剂的体积含量为 3- 10% , 所述次氧化剂的体积含量为 6-25% , 所述螯合剂的体积含量为 7- 11% , 所述抑制剂的体积含量范围介于 3-5% , 所述添加剂的体积含量为 0.5-2%。
所述过氧化氢（¾02 )作为蚀刻液的主氧化剂， 其主要与 Cu及 Mo反 应生成金属氧化物等； Mo03与螯合剂及其他添加剂能够有效结合生成稳 定的络合物， 而 CuO与螯合剂、 抑制剂及添加剂结合力差， 难以形成稳定 的化合物且会促使 ¾02挥发。
所述次氧化剂为磷酸、 硫酸、 及硝酸， 其主要与 CuO进一步反应生成 Cu2+, 以便易于与螯合剂、 抑制剂及添加剂生成稳定的化合物。 化剂蚀刻出来的金属离子 ^釆用^含多个可 合原子的 "多齿配位体" 螯合剂， 在刻蚀过程中， 螯合剂会与金属离子形成 "配位环状结构" 的螯 合物， 且在螯合过程中， 一般以五元环、 六元环最为稳定， 这可以有效减 少甚至消除分级络合现象。
所述氨基类化合物为亚氨基二乙酸或三乙烯四胺， 该亚氨基二乙酸与 铜离 后生成的螯合物的结构式如下：
Figure imgf000006_0001
其中， M为铜离子或钼离子。
所述抑制剂为氨基唑类化合物和羧酸类化合物， 所述氨基唑类化合物 为氨基四唑化合物， 所述羧酸类化合物为乙二胺四乙酸或环已二胺四乙 酸， 该抑制剂用于控制雉角 （taper angle ) 等蚀刻效果， 分子中包含的氨 氮和羧氧配位原子具有强的配位能力， 基本能与合金金属所含的所有金属 材料产生络合反应。
所述胺类化合物含有氨氮及羧氧配位原子， 为三乙醇胺类中的至少一 种， 能够随蚀刻的进行而分解出不同含量的氨基， 能够与蚀刻出的 Cu2+结 合并有效抑制之前 Cu2+与螯合剂生成的螯合物的分解； 能够保证螯合剂对 金属离子的有效螯合并降低蚀刻过程中蚀刻液的浸入及对金属层的过蚀刻 攻击， 确保了拥有较宽的 process window及符合要求的技术规格， 例如 taper angle及 CD- loss等。
所述蚀刻液包含溶剂， 其为去离子水， 其体积含量为所述蚀刻液的总 体积 100%中减去主氧化剂、 次氧化剂、 螯合剂、 抑制剂及添加剂的体积 含量后的剩余体积含量。
在工程应用过程中， 当蚀刻液内部金属离子达到 2500ppm时按照比例 进行添加， 可以使蚀刻液具有长的刻蚀寿命达到 5000ppm左右。
本发明铜导线蚀刻液主要性能表现在：
一、 如图 1 所示， 其为本发明所示的铜导线蚀刻液蚀刻性能总结及 process window , 可以看出 JET(Just etching time)与符合规格要求的 OE(Over Etching)为 180%, 具有较宽的 process window便于生产的稳定 性；
二、 如图 2所示， 蚀刻液在 shelf-time后期时仍能够表现出较好的性 能；
三、 如图 3与图 4所示， 蚀刻液具有更长的蚀刻寿命， 在 5000ppm时 仍能够表现出好的蚀刻效果及较宽的 process window和较好的性能。
综上所述， 本发明通过使用新型的螯合剂及添加剂的成分及类型， 显 著改善铜导线蚀刻液工艺窗口较短的特点， 降低了工程控制难度， 增加工 程生产的稳定性及提高产出良率； 提高 shelf-time稳定性， shelf-time储存 后期时也能保持蚀刻性能的稳定性； 提高使用寿命（> 5000ppm) , 且在制 程后期 process window未出现明显变窄， 且性能等仍较为稳定。 下面以实 施例来更进一步说明本发明所达到的技术效果。
釆用 TFT阵列基板上溅射有铜薄膜 2500A, 钼合金薄膜 200A; 制定 的技术规格为 process window 为 90%OE , 釆用本发明蚀刻液蚀刻后的 process window如表 1所示：
表 1 本发明蚀刻液蚀刻金属层主要性能表现
Figure imgf000007_0001
Figure imgf000008_0001
7 , 用本发明蚀刻液样品蚀刻金属层， 当蚀刻时间分别为
Figure imgf000008_0002
180%ΟΕ 时， 蚀刻液样品均表现出良好的蚀刻效果和较好 以上所述， 对于本领域的普通技术人员来说， 可以根据本发明的技术 方案和技术构思作出其他各种相应的改变和变形， 而所有这些改变和殳形 都应属于本发明权利要求的保护范围。

Claims

权 利 要 求
1、 一种 TFT 阵列基板铜导线的蚀刻液， 包括： 主氧化剂、 次氧化 剂、 螯合剂、 抑制剂、 及添加剂， 该主氧化剂为过氧化氢， 该次氧化剂为 磷酸、 硫酸、 及硝酸； 该螯合剂为氨基类化合物； 该抑制剂为氨基唑类化 合物和羧酸类化合物； 该添加剂为含氨氮及羧氧配位原子的胺类化合物。
2、 如权利要求 1 所述的 TFT阵列基板铜导线的蚀刻液， 其中， 按所 述蚀刻液的总体积 100%计算， 所述主氧化剂的体积含量为 3-10%, 所述 次氧化剂的体积含量为 6-25%, 所述螯合剂的体积含量为 7-11%, 所述抑 制剂的体积含量为 3-5%, 所述添加剂的体积含量为 0.5-2%。
3、 如权利要求 1 所述的 TFT阵列基板铜导线的蚀刻液， 其中， 所述 氨基类化合物含有两个或两个以上的配位原子。
4、 如权利要求 3所述的 TFT阵列基板铜导线的蚀刻液， 其中， 所述 氨基类化合物为亚氨基二乙酸或三乙烯四胺。
5、 如权利要求 4所述的 TFT阵列基板铜导线的蚀刻液， 其中， 所述 亚 子或钼离子螯合后生成的螯合物的结构式如下：
Figure imgf000009_0001
其中， M为铜离子或钼离子。
6、 如权利要求 1 所述的 TFT阵列基板铜导线的蚀刻液， 其中， 所述 胺类化合物为三乙醇胺类中的至少一种。
7、 如权利要求 1 所述的 TFT阵列基板铜导线的蚀刻液， 其中， 所述 氨基唑类化合物为氨基四唑化合物。
8、 如权利要求 1 所述的 TFT阵列基板铜导线的蚀刻液， 其中， 所述 羧酸类化合物为乙二胺四乙酸或环已二胺四乙酸。
9、 如权利要求 2 所述的 TFT 阵列基板铜导线的蚀刻液， 还包括溶 剂， 所述溶剂为去离子水， 其体积含量为所述蚀刻液的总体积 100%中减 去主氧化剂、 次氧化剂、 螯合剂、 抑制剂及添加剂的体积含量后的剩余体 积含量。
10、 一种 TFT 阵列基板铜导线的蚀刻液， 包括： 主氧化剂、 次氧化 剂、 螯合剂、 抑制剂、 及添加剂， 该主氧化剂为过氧化氢， 该次氧化剂为 磷酸、 硫酸、 及硝酸； 该螯合剂为氨基类化合物； 该抑制剂为氨基唑类化 合物和羧酸类化合物； 该添加剂为含氨氮及羧氧配位原子的胺类化合物； 其中， 按所述蚀刻液的总体积 100%计算， 所述主氧化剂的体积含量 为 3-10%, 所述次氧化剂的体积含量为 6-25%, 所述螯合剂的体积含量为 7-11% , 所述抑制剂的体积含量为 3-5% , 所述添加剂的体积含量为 0.5- 2%;
其中， 所述氨基类化合物含有两个或两个以上的配位原子；
其中， 所述氨基类化合物为亚氨基二乙酸；
其中， 所述亚氨基二乙酸与铜离子螯合后生成的螯合物的结构式如
Figure imgf000010_0001
其中， M为铜离子；
其中， 所述胺类化合物为三乙醇胺类中的至少一种；
其中， 所述氨基唑类化合物为氨基四唑化合物；
其中， 所述羧酸类化合物为乙二胺四乙酸或环已二胺四乙酸； 还包括溶剂， 所述溶剂为去离子水， 其体积含量为所述蚀刻液的总体 积 100%中减去主氧化剂、 次氧化剂、 螯合剂、 抑制剂及添加剂的体积含 量后的剩余体积含量。
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