TWI614550B - Manufacturing method of array substrate for liquid crystal display and etching liquid compositions for multi film thereof - Google Patents

Manufacturing method of array substrate for liquid crystal display and etching liquid compositions for multi film thereof Download PDF

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TWI614550B
TWI614550B TW103128514A TW103128514A TWI614550B TW I614550 B TWI614550 B TW I614550B TW 103128514 A TW103128514 A TW 103128514A TW 103128514 A TW103128514 A TW 103128514A TW I614550 B TWI614550 B TW I614550B
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weight
molybdenum
copper
etching
item
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TW201508383A (en
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李恩遠
李智娟
權五柄
崔容碩
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東友精細化工有限公司
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • 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

Abstract

本發明涉及液晶顯示裝置用陣列基板的製備方法及其多層膜用蝕刻液組合物，其方法包括：步驟a），在基板上形成柵極配線，步驟b），在包含上述柵極配線的基板上形成柵極絕緣層，步驟c），在上述柵極絕緣層上形成半導體層，步驟d），在上述半導體層上形成源極和汲極，以及步驟e），形成與上述汲極相連接的圖元電極，其中，上述步驟a）或步驟d）包括通過對包含鉬類金屬膜或銅類金屬膜的膜進行蝕刻來形成各電極的步驟，上述鉬合金膜為鈮或鎢中的一種以上與鉬的合金，用於蝕刻的上述蝕刻液組合物包括：占組合物總重量中的重量百分比為A）過氧化氫5.0重量百分比～25.0重量百分比；B）氟化合物0.01重量百分比～1.0重量百分比；C）唑類化合物0.1重量百分比～5重量百分比；D）在一個分子內具有氮原子和羧基的水溶性化合物0.1重量百分比～5.0重量百分比；E）磷酸鹽化合物0.1重量百分比～5.0重量百分比；F）多元醇類表面活性劑0.001重量百分比～5.0重量百分比；以及G）水剩餘量，除了上述成分之外，上述蝕刻液組合物不包含有機酸或有機酸鹽、無機酸或無機酸鹽或脂環族胺。The invention relates to a method for preparing an array substrate for a liquid crystal display device, and an etching solution composition for a multilayer film. The method includes: a) forming a gate wiring on the substrate; and step b) on a substrate including the gate wiring. Forming a gate insulating layer, step c), forming a semiconductor layer on the gate insulating layer, step d), forming a source and a drain on the semiconductor layer, and step e) forming a connection with the drain Element electrode, wherein step a) or step d) includes a step of forming each electrode by etching a film containing a molybdenum-based metal film or a copper-based metal film, and the molybdenum alloy film is one of niobium or tungsten The above etching solution composition for the above alloy with molybdenum for etching includes: the weight percentage of the total weight of the composition is A) 5.0 weight percent to 25.0 weight percent of hydrogen peroxide; B) 0.01 weight percent to 1.0 weight of fluorine compound Percentage; C) 0.1 to 5 weight percent of azole compounds; D) Water-soluble compound with nitrogen atom and carboxyl group in one molecule 0.1 to 5.0 weight percent E) 0.1% to 5.0% by weight of the phosphate compound; F) 0.001% to 5.0% by weight of the polyhydric alcohol surfactant; and G) the remaining amount of water, in addition to the above components, the above etching solution composition Contains no organic or organic acid salts, inorganic acids or inorganic acid salts, or alicyclic amines.

Description

液晶顯示裝置用陣列基板的製備方法及其多層膜用蝕刻液組合物Method for preparing array substrate for liquid crystal display device and etching solution composition for multilayer film 【0001】[0001]

本發明關於一種液晶顯示裝置用陣列基板的製備方法及其多層膜用蝕刻液組合物。The invention relates to a method for preparing an array substrate for a liquid crystal display device and an etching solution composition for a multilayer film.

【0002】[0002]

作為驅動半導體裝置及平板顯示裝置的電路，代表性的就是薄膜電晶體（thin film transistor，TFT）。在薄膜電晶體的製備過程中，通常在基板的上部形成金屬膜作為柵極和資料配線材料，在該金屬膜的選擇性區域上形成光刻膠後，將該光刻膠作為掩模來蝕刻上述金屬膜。As a circuit for driving a semiconductor device and a flat panel display device, a thin film transistor (TFT) is representative. In the process of preparing a thin film transistor, a metal film is usually formed on the upper part of the substrate as a gate and data wiring material. After a photoresist is formed on a selective area of the metal film, the photoresist is used as a mask for etching. The above metal film.

【0003】[0003]

通常，作為柵極及資料配線材料，使用導電性好且電阻小的含銅的銅膜或銅合金膜和與這些膜的表面黏合力優秀的金屬氧化物膜。近年來，為了提高薄膜電晶體的性能，作為金屬氧化物膜，使用含有鎵氧化物和銦氧化物、鋅氧化物或它們的混合物的膜。Generally, as a gate electrode and a data wiring material, a copper-containing copper film or a copper alloy film having good conductivity and low resistance, and a metal oxide film having excellent surface adhesion with these films are used. In recent years, in order to improve the performance of a thin film transistor, as a metal oxide film, a film containing gallium oxide, indium oxide, zinc oxide, or a mixture thereof has been used.

【0004】[0004]

一方面，在大韓民國公開公報第10-2010-0090538號中，記載了銅類金屬膜的蝕刻用組合物，該組合物包含過氧化氫（H2 O2 ）、有機酸及磷酸鹽類化合物等。當使用上述蝕刻用組合物蝕刻銅-鉬膜時，能夠形成直線性良好的錐形輪廓，但在一次蝕刻鉬-鈮（Mo-Nb）的鉬類金屬膜及銅類金屬膜的情況下，蝕刻速度變慢，會出現鉬-鈮（Mo-Nb）的鉬類金屬膜無法被蝕刻或者發生殘渣等蝕刻性能極其低下的問題。並且，在大韓民國公開公報第10-2010-0035250號中，記載了在過氧化氫等中必備地包含有硫酸銨和環己胺的組合物，當使用上述組合物蝕刻銅/鉬-鈮（Mo-Nb）的鉬類金屬膜時，無法實現對銅膜或鉬膜的充分的蝕刻速度，蝕刻特性也會嚴重低下。On the other hand, in the Republic of Korea Publication No. 10-2010-0090538, a composition for etching a copper-based metal film is described. The composition includes hydrogen peroxide (H 2 O 2 ), an organic acid, a phosphate compound, and the like. . When the copper-molybdenum film is etched by using the above-mentioned etching composition, a linear and conical profile can be formed. However, when the molybdenum-based metal film and copper-based metal film of molybdenum-niobium (Mo-Nb) are etched at one time, The etching rate becomes slow, and there is a problem that the molybdenum-based metal film of molybdenum-niobium (Mo-Nb) cannot be etched or the etching performance such as residues is extremely low. Moreover, in the Republic of Korea Publication No. 10-2010-0035250, a composition containing ammonium sulfate and cyclohexylamine in the presence of hydrogen peroxide and the like is described. When the above composition is used to etch copper / molybdenum-niobium (Mo -Nb) In the case of a molybdenum-based metal film, a sufficient etching rate for a copper film or a molybdenum film cannot be achieved, and the etching characteristics are severely deteriorated.

現有技術文獻
專利文獻
（專利文獻1）大韓民國公開公報第10-2010-0090538號
（專利文獻2）大韓民國公開公報第10-2010-0035250號Prior Art Document Patent Document (Patent Document 1) Republic of Korea Publication No. 10-2010-0090538 (Patent Document 2) Republic of Korea Publication No. 10-2010-0035250

【0005】[0005]

本發明是為了解決上述問題而提出的，本發明的目的在於提供一種使用蝕刻液的液晶顯示裝置用陣列基板的製備方法，上述蝕刻液能夠對鉬-鈮（Mo-Nb）等的鉬類金屬膜及銅類金屬膜進行一次蝕刻。The present invention has been made in order to solve the above problems, and an object of the present invention is to provide a method for preparing an array substrate for a liquid crystal display device using an etchant, which can be used for molybdenum-based metals such as molybdenum-niobium (Mo-Nb). The film and the copper-based metal film are etched once.

【0006】[0006]

並且，本發明的目的在於提供一種在對鉬-鈮（Mo-Nb）等的鉬類金屬膜及銅類金屬膜進行一次蝕刻的情況下，也能夠提高蝕刻速度和加快工序速度，避免產生殘渣，並且隨著銅濃度而保持一定的側面蝕刻（Side Etch）（μm）變化量的蝕刻液組合物。In addition, an object of the present invention is to provide a method capable of increasing the etching speed and the process speed, and avoiding the occurrence of residues, even when a molybdenum-based metal film such as molybdenum-niobium (Mo-Nb) and a copper-based metal film are etched once. And an etching solution composition with a constant side etch (μm) variation in accordance with the copper concentration.

【0007】[0007]

為了達到上述目的，本發明提供液晶顯示裝置用陣列基板的製備方法，上述液晶顯示裝置用陣列基板的製備方法包括：步驟a），在基板上形成柵極配線，步驟b），在包含上述柵極配線的基板上形成柵極絕緣層，步驟c），在上述柵極絕緣層上形成半導體層，步驟d），在上述半導體層上形成源極和汲極，以及步驟e），形成與上述汲極相連接的圖元電極，上述液晶顯示裝置用陣列基板的製備方法的特徵在於，上述步驟a）或步驟d）包括：通過對包含鉬類金屬膜或銅類金屬膜的膜進行蝕刻，來形成各電極的步驟，上述鉬合金膜為鈮（Nb）或鎢（W）中的一種以上與鉬的合金，在用於蝕刻的上述蝕刻液組合物中，各組分在組合物總重量中的重量百分比範圍為：A）過氧化氫（H2 O2 ）5.0重量百分比～25.0重量百分比；B）氟類化合物0.01重量百分比～1.0重量百分比；C）唑類化合物0.1重量百分比～5重量百分比；D）在一個分子內具有氮原子和羧基的水溶性化合物0.1重量百分比～5.0重量百分比；E）磷酸鹽類化合物0.1重量百分比～5.0重量百分比；F）多元醇類表面活性劑0.001重量百分比～5.0重量百分比；以及G）水剩餘量，除了上述成分之外，上述蝕刻液組合物不包含有機酸或有機酸鹽、無機酸或無機酸鹽或脂環族胺。In order to achieve the above object, the present invention provides a method for preparing an array substrate for a liquid crystal display device. The method for preparing the array substrate for a liquid crystal display device includes: step a), forming a gate wiring on the substrate, and step b) Forming a gate insulating layer on the substrate of the electrode wiring, step c), forming a semiconductor layer on the gate insulating layer, step d), forming a source and a drain on the semiconductor layer, and step e) The pixel electrode connected to the drain electrode, and the method for manufacturing the above-mentioned array substrate for a liquid crystal display device is characterized in that the step a) or step d) includes: etching a film containing a molybdenum-based metal film or a copper-based metal film, The step of forming each electrode, the molybdenum alloy film is an alloy of one or more of niobium (Nb) or tungsten (W) with molybdenum, and in the above etching solution composition for etching, each component is in the total weight of the composition The weight percentage range is: A) 5.0% by weight to 25.0% by weight of hydrogen peroxide (H 2 O 2 ); B) 0.01% by weight to 1.0% by weight of fluorine compounds C) 0.1 to 5 weight percent of azole compounds; D) 0.1 to 5.0 weight percent of water-soluble compounds having nitrogen atoms and carboxyl groups in one molecule; E) 0.1 to 5.0 weight percent of phosphate compounds F) Polyol surfactants from 0.001% to 5.0% by weight; and G) the remaining amount of water, in addition to the above components, the etching solution composition does not contain organic acids or organic acid salts, inorganic acids or inorganic acid salts Or cycloaliphatic amine.

【0008】[0008]

本發明提供鈮（Nb）或鎢（W）中的一種以上與鉬的合金和銅類金屬膜的蝕刻液組合物，其中，各組分在組合物總重量中的重量百分比範圍為：A）過氧化氫（H2 O2 ）5.0重量百分比～25.0重量百分比；B）氟類化合物0.01重量百分比～1.0重量百分比；C）唑類化合物0.1重量百分比～5重量百分比；D）在一個分子內具有氮原子和羧基的水溶性化合物0.1重量百分比～5.0重量百分比；E）磷酸鹽類化合物0.1重量百分比～5.0重量百分比；F）多元醇類表面活性劑0.001重量百分比～5.0重量百分比；以及G）水剩餘量，除了上述成分之外，上述蝕刻液組合物不包含有機酸或有機酸鹽、無機酸或無機酸鹽或脂環族胺。The present invention provides an etchant composition of one or more of niobium (Nb) or tungsten (W) with an alloy of molybdenum and a copper-based metal film, wherein the weight percentage of each component in the total weight of the composition is: A) over Hydrogen oxide (H 2 O 2 ) 5.0% by weight to 25.0% by weight; B) 0.01% by weight to 1.0% by weight of fluorine compounds; C) 0.1% by weight to 5% by weight of azole compounds; D) Nitrogen in one molecule Atom and carboxyl water-soluble compounds 0.1 to 5.0% by weight; E) 0.1 to 5.0% by weight of phosphate compounds; F) 0.001 to 5.0% by weight of polyol surfactants; and G) Water remaining Amount, in addition to the above-mentioned components, the above-mentioned etchant composition does not contain an organic acid or an organic acid salt, an inorganic acid or an inorganic acid salt, or an alicyclic amine.

【0009】[0009]

根據本發明的蝕刻液組合物，在對鉬-鈮（Mo-Nb）等的鉬類金屬膜及銅類金屬膜進行一次蝕刻的情況下，也能夠提高蝕刻速度和加快工序速度，避免產生殘渣，並且隨著銅濃度而保持一定的側面蝕刻（Side Etch）（μm）變化量。According to the etchant composition of the present invention, even when a molybdenum-based metal film such as molybdenum-niobium (Mo-Nb) and a copper-based metal film are etched at one time, the etching speed and the process speed can be increased, and residues can be avoided And maintain a certain amount of change in side etch (μm) with copper concentration.

【0061】[0061]

無no

【0010】[0010]

第1圖是在使用實施例2的蝕刻液組合物蝕刻銅/鉬鈮（Cu/MoNb）雙層膜質的金屬膜後，利用掃描電子顯微鏡（SEM，Hitach S-4700）來觀察圖像的結果。FIG. 1 is a result of observing an image using a scanning electron microscope (SEM, Hitach S-4700) after etching a copper / molybdenum-niobium (Cu / MoNb) double-layer metal film using the etchant composition of Example 2 .

第2圖是在使用比較例4的蝕刻液組合物蝕刻銅/鉬鈮（Cu/MoNb）雙層膜質的金屬膜後，利用掃描電子顯微鏡（SEM，Hitach S-4700）來觀察圖像的結果。FIG. 2 is a result of observing an image using a scanning electron microscope (SEM, Hitach S-4700) after etching a copper / molybdenum-niobium (Cu / MoNb) double-layered metal film using an etchant composition of Comparative Example 4 .

第3圖是在使用比較例5的蝕刻液組合物蝕刻銅/鉬鈮（Cu/MoNb）雙層膜質的金屬膜後，利用掃描電子顯微鏡（SEM，Hitach S-4700）來觀察圖像的結果。FIG. 3 is a result of observing an image using a scanning electron microscope (SEM, Hitach S-4700) after etching a copper / molybdenum-niobium (Cu / MoNb) double-layered metal film using an etchant composition of Comparative Example 5 .

第4圖是在使用比較例7的蝕刻液組合物蝕刻銅/鉬鈮（Cu/MoNb）雙層膜質的金屬膜後，利用掃描電子顯微鏡（SEM，Hitach S-4700）來觀察圖像的結果。FIG. 4 is a result of observing an image using a scanning electron microscope (SEM, Hitach S-4700) after etching a copper / molybdenum-niobium (Cu / MoNb) double-layered metal film using an etchant composition of Comparative Example 7 .

第5圖是在使用比較例9的蝕刻液組合物蝕刻銅/鉬鈮（Cu/MoNb）雙層膜質的金屬膜後，利用掃描電子顯微鏡（SEM，Hitach S-4700）來觀察圖像的結果。FIG. 5 is a result of observing an image using a scanning electron microscope (SEM, Hitach S-4700) after etching a copper / molybdenum-niobium (Cu / MoNb) double-layered metal film using an etchant composition of Comparative Example 9 .

第6圖是在使用比較例10的蝕刻液組合物蝕刻銅/鉬鈮（Cu/MoNb）雙層膜質的金屬膜後，利用掃描電子顯微鏡（SEM，Hitach S-4700）來觀察圖像的結果。FIG. 6 is a result of observing an image using a scanning electron microscope (SEM, Hitach S-4700) after etching a copper / molybdenum-niobium (Cu / MoNb) double-layered metal film using an etchant composition of Comparative Example 10 .

【0011】[0011]

本發明涉及蝕刻液組合物及利用該組合物的液晶顯示裝置用陣列基板的製備方法，上述蝕刻液組合物在由用於形成薄膜電晶體陣列配線的銅/鉬合金構成的雙層膜膜質中，能夠以優秀的蝕刻特性，對上部銅金屬膜和鈮（Nb）或鎢（W）中的一種以上與鉬的合金的鉬合金膜進行一次蝕刻。The invention relates to an etchant composition and a method for preparing an array substrate for a liquid crystal display device using the same. The above-mentioned etchant composition is in a double-layer film composed of a copper / molybdenum alloy for forming a thin film transistor array wiring It can etch the upper copper metal film and the molybdenum alloy film of one or more of niobium (Nb) or tungsten (W) with an alloy of molybdenum with excellent etching characteristics.

【0012】[0012]

具體而言，本發明提供液晶顯示裝置用陣列基板的製備方法，上述液晶顯示裝置用陣列基板的製備方法包括：步驟a），在基板上形成柵極配線，步驟b），在包含上述柵極配線的基板上形成柵極絕緣層，步驟c），在上述柵極絕緣層上形成半導體層，步驟d），在上述半導體層上形成源極和汲極，以及步驟e），形成與上述汲極相連接的圖元電極，上述液晶顯示裝置用陣列基板的製備方法的特徵在於，上述步驟a）或步驟d）包括：通過對包含作為鈮（Nb）或鎢（W）中的一種以上與鉬的合金的鉬類金屬膜或銅類金屬膜的膜進行蝕刻，來形成各電極的步驟，用於蝕刻的上述蝕刻液組合物包括：A）過氧化氫（H2 O2 ）；B）氟類化合物；C）唑類化合物；D）在一個分子內具有氮原子和羧基的水溶性化合物；E）磷酸鹽類化合物；F）多元醇類表面活性劑；以及G）水。Specifically, the present invention provides a method for preparing an array substrate for a liquid crystal display device. The method for preparing the array substrate for a liquid crystal display device includes: step a), forming a gate wiring on the substrate, step b), and including the gate electrode. A gate insulating layer is formed on the wiring substrate, step c), a semiconductor layer is formed on the gate insulating layer, step d), a source and a drain are formed on the semiconductor layer, and step e) is formed with the drain The electrode element electrode connected to the electrode, the method for manufacturing the above-mentioned array substrate for a liquid crystal display device, wherein the step a) or the step d) includes: by including one or more of niobium (Nb) or tungsten (W) and The step of forming a molybdenum-based metal film or a copper-based metal film of an alloy of molybdenum to form each electrode. The above-mentioned etching solution composition for etching includes: A) hydrogen peroxide (H 2 O 2 ); B) Fluorine compounds; C) azole compounds; D) water-soluble compounds with nitrogen and carboxyl groups in one molecule; E) phosphate compounds; F) polyol surfactants; and G) water .

【0013】[0013]

尤其，用於本發明的蝕刻液組合物的特徵在於，除了上述A）至G）成分以外，不包括有機酸或有機酸鹽、無機酸或無機酸鹽或脂環族胺。在以往，為了提高銅的蝕刻速度或者為了營造有利於銅類金屬膜的蝕刻的環境，而必備地添加了除了上述D）成分以外的有機酸或有機酸鹽、硫酸鹽等無機酸或無機酸鹽、環胺化合物等的脂環族胺，而通過對這種包含有機酸或有機酸鹽、無機酸或無機酸鹽或脂環族胺等的以往的蝕刻液組合物進行試驗後，確認了其會導致鉬類金屬膜，尤其作為鈮（Nb）或鎢（W）中的一種與鉬的合金的鉬類金屬膜的蝕刻效率急劇下降。進一步地，本發明的蝕刻液組合物在沒有如上所述的有機酸或有機酸鹽、無機酸或無機酸鹽或脂環族胺的條件下，也表現出非常優秀的銅類金屬膜蝕刻速度和蝕刻特性，對於鉬類金屬膜也表現出了非常優秀的蝕刻特性。In particular, the etchant composition used in the present invention is characterized in that it does not include organic acids or organic acid salts, inorganic acids or inorganic acid salts, or alicyclic amines in addition to the components A) to G) described above. In the past, in order to increase the etching speed of copper or to create an environment favorable for the etching of copper-based metal films, it is necessary to add inorganic acids or inorganic acids such as organic acids or organic acid salts and sulfates in addition to the component D). A cycloaliphatic amine such as a salt, a cyclic amine compound, and the like, and a conventional etching solution composition including an organic acid or an organic acid salt, an inorganic acid or an inorganic acid salt, or an alicyclic amine was confirmed by testing. This causes a sharp decrease in the etching efficiency of a molybdenum-based metal film, especially a molybdenum-based metal film that is an alloy of molybdenum (Nb) or tungsten (W) with molybdenum. Further, the etching solution composition of the present invention also exhibits a very excellent copper-based metal film etching rate without the above-mentioned organic acid or organic acid salt, inorganic acid or inorganic acid salt, or alicyclic amine. And etching characteristics, it also shows very excellent etching characteristics for molybdenum-based metal films.

【0014】[0014]

在本發明中，銅類金屬膜是在膜的組成成分中包含有銅的，上述銅類金屬膜表示純銅、銅的氮化物、銅的氧化物或銅的合金。上述銅合金表示選自包括純銅、銅的氮化物、銅的氧化物的組的一種和選自包括鋁（Al）、鎂（Mg）、鈣（Ca）、鈦（Ti）、銀（Ag）、鉻（Cr）、錳（Mn）、鐵（Fe）、鋯（Zr）、鈮（Nb）、鉬（Mo）、鈀（Pd）、鉿（Hf）、鉭（Ta）及鎢（W）的組中的一種以上的金屬的合金。In the present invention, the copper-based metal film includes copper in the composition of the film, and the copper-based metal film represents pure copper, copper nitride, copper oxide, or copper alloy. The above-mentioned copper alloy represents one selected from the group consisting of pure copper, copper nitride, and copper oxide, and selected from the group consisting of aluminum (Al), magnesium (Mg), calcium (Ca), titanium (Ti), and silver (Ag). , Chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta), and tungsten (W) An alloy of more than one metal in the group.

【0015】[0015]

並且，較佳地，上述鉬合金膜是鈮（Nb）或鎢（W）中的一種與鉬的合金。And, preferably, the above molybdenum alloy film is an alloy of one of niobium (Nb) or tungsten (W) and molybdenum.

【0016】[0016]

以下，將對本發明的構成進行詳細說明。Hereinafter, the configuration of the present invention will be described in detail.

【0017】[0017]

1.蝕刻液組合物Etching solution composition

【0018】[0018]

包含在本發明的蝕刻液組合物中的A）過氧化氫（H2 O2 ）是對以包含鉬合金膜和形成於上述鉬合金膜上的銅金屬膜為特徵的銅類金屬膜的蝕刻產生影響的主氧化劑，較佳地，上述A）過氧化氫（ H2 O2 ）在組合物總重量中的比重為5.0重量百分比～25.0重量百分比。當上述A）過氧化氫（H2 O2 ）的含量不足5.0重量百分比時，銅類金屬膜及鉬合金膜的蝕刻力不足，進而無法實施充分的蝕刻；當上述A）過氧化氫（H2 O2 ）的含量超過25.0重量百分比時，蝕刻速度整體上會加快，進而導致工序控制的難度增加，根據銅離子增加的發熱穩定性大幅降低。A) Hydrogen peroxide (H 2 O 2 ) contained in the etchant composition of the present invention is an etching of a copper-based metal film including a molybdenum alloy film and a copper metal film formed on the above-mentioned molybdenum alloy film. The main oxidant that has an effect, preferably, the specific gravity of the above A) hydrogen peroxide (H 2 O 2 ) in the total weight of the composition is 5.0% by weight to 25.0% by weight. When the content of the above A) hydrogen peroxide (H 2 O 2 ) is less than 5.0% by weight, the etching force of the copper-based metal film and the molybdenum alloy film is insufficient, so that sufficient etching cannot be performed; when the above A) hydrogen peroxide (H When the content of 2 O 2 ) exceeds 25.0% by weight, the etching rate as a whole will be accelerated, which will further increase the difficulty of process control, and the thermal stability due to the increase of copper ions will be greatly reduced.

【0019】[0019]

包含在本發明的蝕刻液組合物中的B）氟類化合物，表示分解於水而產生氟（F）離子的化合物。上述B）氟類化合物是對鉬合金膜的蝕刻速度產生影響的輔助氧化劑，用於調節鉬合金膜的蝕刻速度。The B) fluorine-based compound contained in the etchant composition of the present invention means a compound that decomposes in water to generate fluorine (F) ions. The B) fluorine-based compound is an auxiliary oxidant that affects the etching rate of the molybdenum alloy film, and is used to adjust the etching rate of the molybdenum alloy film.

【0020】[0020]

較佳地，上述B）氟類化合物的含量在組合物總重量中的比重為0.01重量百分比～1.0重量百分比，用於去除在同時對銅膜和鉬膜進行蝕刻的溶液中必然產生的殘渣。當上述B）氟類化合物的含量不足0.01重量百分比時，會產生蝕刻殘渣。當上述B）含氟化合物的含量超過1.0重量百分比時，導致玻璃基板的蝕刻率變大。Preferably, the specific gravity of the content of the above-mentioned B) fluorine compound in the total weight of the composition is 0.01% by weight to 1.0% by weight. When the content of the B) fluorine-based compound is less than 0.01% by weight, etching residues may be generated. When the content of the above-mentioned B) fluorine-containing compound exceeds 1.0% by weight, the etching rate of the glass substrate becomes large.

【0021】[0021]

氟類化合物是在本領域中使用的物質，但只要是在溶液內可分解為氟離子或多原子氟離子的化合物，就沒有特殊限制，較佳地，氟類化合物是選自包括氟化氫（HF）、氟化鈉（NaF）、氟化銨（NH4F）、氟硼酸銨（NH4BF4）、氟化氫銨（NH4F∙HF）、氟化鉀（KF）、氟氫化鉀（KHF2）、氟化鋁（AlF3）及氟硼酸（HBF4）的組的一種或兩種以上。尤其，較佳地，使用氟化氫銨（ammonium bifluoride：NH4F∙HF）。The fluorine-based compound is a substance used in the art, but as long as it is a compound that can be decomposed into a fluorine ion or a polyatomic fluorine ion in a solution, there is no particular limitation. Preferably, the fluorine-based compound is selected from the group including hydrogen fluoride (HF ), Sodium fluoride (NaF), ammonium fluoride (NH4F), ammonium fluoborate (NH4BF4), ammonium bifluoride (NH4F ∙ HF), potassium fluoride (KF), potassium hydride (KHF2), aluminum fluoride (AlF3 ) And fluoboric acid (HBF4) in one or two or more groups. In particular, ammonium bifluoride (NH4F · HF) is preferably used.

【0022】[0022]

包含在本發明的蝕刻液組合物中的蝕刻液組合物中的C）唑類化合物用於調節銅類金屬的蝕刻速度，減少圖案的臨界尺寸損失（CD Loss），進而提高工序上的收穫率。上述C）唑類化合物的含量在組合物總重量中的比重為0.1重量百分比～5重量百分比。當上述C）唑類化合物的含量不足0.1重量百分比時，銅的蝕刻速度過快，進而導致臨界尺寸損失過大。當上述C）唑類化合物的含量超過5重量百分比時，銅的蝕刻速度變慢，鉬合金膜的蝕刻速度也變慢，進而導致工序時間的浪費，鉬合金的殘渣殘留的可能性增加。The C) azole compound contained in the etchant composition of the etchant composition of the present invention is used to adjust the etching rate of copper-based metals, reduce the critical dimension loss (CD Loss) of the pattern, and thereby improve the yield in the process. . The specific gravity of the content of the C) azole compound in the total weight of the composition is 0.1 to 5 weight percent. When the content of the above-mentioned C) azole compound is less than 0.1% by weight, the etching rate of copper is too fast, and the critical dimension loss is excessively large. When the content of the above-mentioned C) azole compound exceeds 5 weight percent, the etching rate of copper becomes slower, and the etching rate of the molybdenum alloy film also becomes slower, thereby causing waste of process time and increasing the possibility of residues of molybdenum alloy residues.

【0023】[0023]

上述C）唑類化合物若是使用於本領域的，就不受特殊限制。例如，較佳地，唑類化合物是碳數為1～30的唑類化合物。更較佳地，能夠獨立或混合使用選自包括***類化合物、氨基四氮唑類化合物、咪唑類化合物、吲哚類化合物、嘌呤類化合物、吡唑類化合物、吡啶類化合物、嘧啶類化合物、吡咯類化合物、吡咯烷類化合物、吡咯啉類化合物等的組的一種或兩種以上。The above C) azole compounds are not particularly limited if they are used in the art. For example, it is preferable that the azole compound is a azole compound having 1 to 30 carbon atoms. More preferably, it can be used independently or in a mixture selected from the group consisting of triazole compounds, aminotetrazole compounds, imidazole compounds, indole compounds, purine compounds, pyrazole compounds, pyridine compounds, pyrimidine compounds , Pyrrole-based compounds, pyrrolidine-based compounds, pyrroline-based compounds, and the like, one or two or more groups.

【0024】[0024]

包含在本發明的蝕刻液組合物中的D）在一個分子內具有氮原子和羧基的水溶性化合物，用於防止在保管蝕刻液組合物時可能發生的過氧化氫水的自主分解反應，防止在蝕刻大量基板時發生的蝕刻特性變化。通常，在使用過氧化氫水的蝕刻液組合物的情況下，保管過程中過氧化氫水發生自主分解，進而導致保管期限短，還具有容器***的危險要素。但是，在包含有上述D）在一個分子內具有氮原子和羧基的水溶性化合物的情況下，過氧化氫水的分解速度降低近10倍，有利於保管期限的延長和穩定性保障。尤其，在銅層中，大量殘存著蝕刻液組合物內的銅離子的情況下，形成鈍化（passivation）膜而氧化變黑後，經常發生無法再進行蝕刻的情況，而當添加了該化合物時，能夠防止出現這種現象。較佳地，上述D）在一個分子內具有氮原子和羧基的水溶性化合物的含量為0.1重量百分比～5.0重量百分比。當上述D）在一個分子內具有氮原子和羧基的水溶性化合物的含量不足上述範圍時，在蝕刻大量的基板（約500張）後，形成鈍化膜，很難獲得足夠的工序餘量。並且，當上述D）在一個分子內具有氮原子和羧基的水溶性化合物的含量超過上述範圍時，鉬合金的蝕刻速度變慢，在銅鉬膜或銅鉬合金膜的情況下，錐角變小。D) The water-soluble compound having a nitrogen atom and a carboxyl group in one molecule contained in the etchant composition of the present invention is used to prevent an autonomous decomposition reaction of hydrogen peroxide water that may occur when the etchant composition is stored, and to prevent Changes in etching characteristics that occur when a large number of substrates are etched. Generally, in the case of an etching solution composition using hydrogen peroxide water, the hydrogen peroxide water undergoes spontaneous decomposition during storage, thereby leading to a short storage period and a risk factor of container explosion. However, in the case where the above-mentioned D) water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is included, the decomposition rate of hydrogen peroxide water is reduced by nearly 10 times, which is beneficial to the extension of the storage period and the stability guarantee. In particular, when a large amount of copper ions in the etchant composition are left in the copper layer, after a passivation film is formed and the oxide is blackened, it is often impossible to perform etching. When this compound is added, Can prevent this phenomenon. Preferably, the content of the above-mentioned D) water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is 0.1% by weight to 5.0% by weight. When the content of the above-mentioned D) water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is less than the above range, a large number of substrates (about 500 sheets) are etched to form a passivation film, and it is difficult to obtain a sufficient process margin. In addition, when the content of the water-soluble compound having a nitrogen atom and a carboxyl group in one of the above D) exceeds the above range, the etching rate of the molybdenum alloy becomes slow, and in the case of a copper-molybdenum film or a copper-molybdenum alloy film, the taper angle becomes small.

【0025】[0025]

較佳地，上述D）在一個分子內具有氮原子和羧基的水溶性化合物選自包括丙氨酸（alanine）、氨基丁酸（aminobutyric acid）、谷氨酸（glutamic acid）、甘氨酸（glycine）、亞氨基二乙酸（iminodiacetic acid）、次氨基三乙酸（nitrilotriacetic acid）及肌氨酸（sarcosine）的組的一種或兩種以上。Preferably, the above D) water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is selected from the group consisting of alanine, aminobutyric acid, glutamic acid, and glycine , Iminodiacetic acid, nitrilotriacetic acid, and sarcosine in one or two or more groups.

【0026】[0026]

包含在本發明的蝕刻液組合物中的E）磷酸鹽類化合物是使圖案的錐形輪廓變得良好的成分。若本發明的蝕刻液組合物中不含上述E）磷酸鹽類化合物，則蝕刻輪廓將變不合格。較佳地，上述磷酸鹽類化合物的含量在組合物總重量中的比重為0.1重量百分比～5.0重量百分比。當上述E）磷酸鹽類化合物的含量不足上述範圍時，蝕刻輪廓將變不合格。當上述E）磷酸鹽類化合物的含量超過上述範圍時，將發生鉬合金膜的蝕刻速度變慢的問題。The E) phosphate-based compound contained in the etchant composition of the present invention is a component that improves the tapered contour of the pattern. If the above-mentioned E) phosphate-based compound is not contained in the etching solution composition of the present invention, the etching contour becomes unacceptable. Preferably, the specific gravity of the content of the phosphate compound in the total weight of the composition is 0.1% by weight to 5.0% by weight. When the content of the E) phosphate-based compound is less than the above range, the etching contour becomes unacceptable. When the content of the E) phosphate-based compound exceeds the above range, a problem occurs in that the etching rate of the molybdenum alloy film becomes slow.

【0027】[0027]

上述E）磷酸鹽類化合物只要是選自在磷酸中一個或兩個氫被置換為鹼性金屬或鹼土金屬的鹽，沒有特殊限制，但是，較佳地，上述E）磷酸鹽類化合物選自包括磷酸鈉（sodium phosphate）、磷酸鉀（potassium phosphate）及磷酸銨（ammonium phosphate）的組的一種或兩種以上。The above E) phosphate-based compound is not particularly limited as long as it is a salt selected from one or two hydrogens in phosphoric acid to be replaced with an alkaline metal or alkaline earth metal. However, preferably, the above E) phosphate-based compound is selected from the group consisting of One or two or more groups of sodium phosphate, potassium phosphate, and ammonium phosphate.

【0028】[0028]

包含在本發明的蝕刻液組合物中的F）多元醇類表面活性劑通過降低表面張力來增加蝕刻的均勻性。並且，上述F）多元醇類表面活性劑在蝕刻銅膜後，包覆蝕刻液中溶解的銅離子，進而遏制銅離子的活躍度，遏制過氧化氫的分解反應。如此，當降低銅離子的活躍度時，使用蝕刻液期間，能夠穩定地推進工序。上述F）多元醇類表面活性劑的含量在組合物總重量中的比重為0.001重量百分比～5.0重量百分比。當上述F）多元醇類表面活性劑的含量不足上述範圍時，蝕刻均勻性降低，並且過氧化氫的分解會加速。當上述F）多元醇類表面活性劑的含量超過上述範圍時，將產生大量泡沫。The F) polyol-based surfactant contained in the etchant composition of the present invention increases the uniformity of etching by reducing the surface tension. In addition, after the F) polyol-based surfactant etches the copper film, it covers the copper ions dissolved in the etching solution, thereby suppressing the activity of copper ions and the decomposition reaction of hydrogen peroxide. In this way, when the activity of copper ions is reduced, the process can be stably advanced while using the etchant. The specific gravity of the content of the above-mentioned polyol surfactants in the total weight of the composition is 0.001% by weight to 5.0% by weight. When the content of the F) polyol-based surfactant is less than the above range, the etching uniformity is reduced and the decomposition of hydrogen peroxide is accelerated. When the content of the F) polyol-based surfactant exceeds the above range, a large amount of foam will be generated.

【0029】[0029]

較佳地，上述F）多元醇類表面活性劑選自包括丙三醇（glycerol）、乙二醇（ethylene glycol）、二甘醇（diethylene glycol）、三甘醇（triethylene glycol）及聚乙二醇（polyethylene glycol）等的組的一種或兩種以上。Preferably, the F) polyhydric alcohol surfactant is selected from the group consisting of glycerol, ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol. Alcohol (polyethylene glycol) and other groups of one or two or more.

【0030】[0030]

較佳地，包含在本發明的銅鉬合金膜蝕刻液組合物中的G）水，以剩餘量的形式包含其中，確保能夠滿足組合物總重量為100重量百分比。上述水不受特別限制，較佳地，使用脫離子水。並且，較佳地，使用表示上述水中的離子被去除的程度的水的比電阻值為18MΩ•cm以上的脫離子水。Preferably, G) water contained in the copper-molybdenum alloy film etching solution composition of the present invention is contained in the form of a remaining amount to ensure that the total weight of the composition can be 100% by weight. The water is not particularly limited, and deionized water is preferably used. In addition, it is preferable to use deionized water having a specific resistance value of 18 MΩ · cm or more, which indicates the degree to which ions in the water have been removed.

【0031】[0031]

並且，除了前述的成分之外，還可添加常規的添加劑，添加劑有金屬離子螯合劑及防腐劑等。並且，上述添加劑不受此限定，為了進一步發揮本發明的效果，可選擇並添加本領域公開的其他各種添加劑。Moreover, in addition to the aforementioned components, conventional additives may be added, such as metal ion chelating agents and preservatives. In addition, the aforementioned additives are not limited thereto, and in order to further exert the effects of the present invention, various other additives disclosed in the art may be selected and added.

【0032】[0032]

在本發明中使用的A）過氧化氫（H2 O2 ）、B）氟類化合物、C）唑類化合物、D）一個分子內具有氮原子和羧基的水溶性化合物、E）磷酸鹽類化合物、F）多元醇類表面活性劑等可借助常規公知的方法而製備，較佳地，本發明的蝕刻液組合物具有半導體工序用的純度。A) Hydrogen peroxide (H 2 O 2 ), B) fluorine compounds, C) azole compounds, D) water-soluble compounds having a nitrogen atom and a carboxyl group in one molecule, E) phosphates Compounds, F) polyhydric alcohol surfactants and the like can be prepared by conventionally known methods. Preferably, the etchant composition of the present invention has purity for semiconductor processes.

【0033】[0033]

本發明的蝕刻液組合物在蝕刻銅類金屬膜時，能夠體現蝕刻均勻性及直線性優秀的錐形輪廓。本發明的蝕刻液組合物在蝕刻時不產生殘渣，可避免電氣短路或佈線不合格、亮度降低等問題。因此，本發明的蝕刻液組合物非常適用於具有大畫面、高亮度的電路的液晶顯示裝置用陣列基板的製備。When the etchant composition of the present invention is used to etch a copper-based metal film, it can reflect a tapered contour with excellent etching uniformity and linearity. The etching solution composition of the present invention does not generate residues during etching, and can avoid problems such as electrical short circuits, unsatisfactory wiring, and reduced brightness. Therefore, the etching solution composition of the present invention is very suitable for preparing an array substrate for a liquid crystal display device having a large screen and a high-brightness circuit.

【0034】[0034]

本發明的蝕刻液組合物能夠一次蝕刻由銅類金屬構成的液晶顯示裝置的柵極電極和柵極配線及源極/汲極和數據配線層。The etchant composition of the present invention can etch the gate electrode and gate wiring, and the source / drain and data wiring layers of a liquid crystal display device made of a copper-based metal at one time.

【0035】[0035]

尤其，本發明的蝕刻液組合物，其特徵在於，以15～30

Figure TWI614550BD00001
/sec的速度蝕刻鉬類金屬膜，以70～120
Figure TWI614550BD00002
/sec的速度蝕刻銅類金屬膜。在LGD蝕刻工序中，當蝕刻速度（Etch rate）緩慢時，蝕刻工序時間（Process Time）增加，進而很難確保批量生產性，因此，如何確保上述範圍的蝕刻速度顯得非常重要。In particular, the etching solution composition of the present invention is characterized in that
Figure TWI614550BD00001
etch molybdenum-based metal film at a speed of 70 to 120
Figure TWI614550BD00002
/ sec. The copper-based metal film is etched. In the LGD etching process, when the etching rate (Etch rate) is slow, the process time increases, which makes it difficult to ensure mass productivity. Therefore, it is very important to ensure the etching rate in the above range.

【0036】[0036]

2.液晶顯示裝置用陣列基板的製備方法2. Preparation method of array substrate for liquid crystal display device

【0037】[0037]

本發明提供液晶顯示裝置用陣列基板的製備方法，該液晶顯示裝置用陣列基板的製備方法包括：步驟a），在基板上形成柵極配線，步驟b），在包含上述柵極配線的基板上形成柵極絕緣層，步驟c），在上述柵極絕緣層上形成半導體層，步驟d），在上述半導體層上形成源極和汲極，以及步驟e），形成與上述汲極相連接的圖元電極，上述液晶顯示裝置用陣列基板的製備方法的特徵在於，上述步驟a）或步驟d）包括：通過對包含鉬類金屬膜或銅類金屬膜的膜進行蝕刻，來形成各電極的步驟，在用於蝕刻的上述蝕刻液組合物中，各組分在組合物總重量中的重量百分比範圍為：A）過氧化氫5.0重量百分比～25.0重量百分比；B）氟類化合物0.01重量百分比～1.0重量百分比；C）唑類化合物0.1重量百分比～5重量百分比；D）在一個分子內具有氮原子和羧基的水溶性化合物0.1重量百分比～5.0重量百分比；E）磷酸鹽類化合物0.1重量百分比～5.0重量百分比；F）多元醇類表面活性劑0.001重量百分比～5.0重量百分比；以及G）水剩餘量。The invention provides a method for preparing an array substrate for a liquid crystal display device. The method for preparing an array substrate for a liquid crystal display device includes: step a), forming a gate wiring on the substrate, and step b) on a substrate including the gate wiring. Forming a gate insulating layer, step c), forming a semiconductor layer on the gate insulating layer, step d), forming a source and a drain on the semiconductor layer, and step e), forming a connection with the drain The pixel electrode, the method for manufacturing the above-mentioned array substrate for a liquid crystal display device, wherein the step a) or step d) includes: etching a film containing a molybdenum-based metal film or a copper-based metal film to form each electrode. Step: In the above etching solution composition used for etching, the weight percentage of each component in the total weight of the composition ranges from: A) 5.0 weight percent to 25.0 weight percent of hydrogen peroxide; B) 0.01 weight percent of fluorine compounds ～ 1.0% by weight; C) 0.1% to 5% by weight of azole compounds; D) Water-solubility with nitrogen atom and carboxyl group in one molecule It was 0.1 weight percent to 5.0 weight percent; E) a phosphate-based compound 0.1 weight percent to 5.0 weight percent; F.) Polyhydric alcohol surfactant 0.001 weight percent to 5.0 weight percent; and G) the remaining amount of water.

【0038】[0038]

上述液晶顯示裝置用陣列基板能夠是薄膜電晶體（TFT）陣列基板。The array substrate for a liquid crystal display device can be a thin film transistor (TFT) array substrate.

【0039】[0039]

並且，上述配線形成方法包括：In addition, the wiring forming method includes:

【0040】[0040]

Ⅰ）在基板上形成鉬合金膜的步驟；Ⅰ) forming a molybdenum alloy film on the substrate;

【0041】[0041]

Ⅱ）在上述鉬合金膜的上部形成銅類金屬膜的步驟；Ii) a step of forming a copper-based metal film on the upper part of the above molybdenum alloy film;

【0042】[0042]

Ⅲ）在上述銅類金屬膜上選擇性地保留光反應物質的步驟；以及III) a step of selectively retaining a photoreactive substance on the copper-based metal film; and

【0043】[0043]

Ⅳ）使用本發明的蝕刻液組合物，對銅類金屬膜及鉬合金膜進行一次蝕刻的步驟。IV) A step of performing one-time etching on the copper-based metal film and the molybdenum alloy film using the etching solution composition of the present invention.

【0044】[0044]

在本發明的配線形成方法中，較佳地，上述光反應物質為一般的光刻膠物質，能夠借助通常的曝光及顯像工序而選擇性地保留。In the wiring forming method of the present invention, it is preferable that the photo-reactive substance is a general photoresist substance and can be selectively retained by a normal exposure and development process.

【0045】[0045]

較佳地，上述鉬合金膜為鈮（Nb）或鎢（W）中的一種以上與鉬的合金。Preferably, the molybdenum alloy film is an alloy of one or more of niobium (Nb) or tungsten (W) with molybdenum.

【0046】[0046]

以下，將利用實施例及比較例對本發明進行更詳細的說明。然而，下述實施例及比較例僅僅是用於例示本發明，本發明不受此限制，而且能夠實施各種修改及變更。Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the following examples and comparative examples are merely for illustrating the present invention, and the present invention is not limited thereto, and various modifications and changes can be implemented.

【0047】[0047]

實施例1至實施例3及比較例1至比較例10蝕刻液組合物的製備Preparation of Etchant Compositions of Examples 1 to 3 and Comparative Examples 1 to 10

【0048】[0048]

按照下表1顯示的組成，製備了實施例1至實施例3及比較例1至比較例10的蝕刻液組合物。The etching solution compositions of Examples 1 to 3 and Comparative Examples 1 to 10 were prepared according to the compositions shown in Table 1 below.

【0049】[0049]

【表1】【Table 1】

（單位：重量百分比）

Figure TWI614550BD00003
(Unit: weight percent)
Figure TWI614550BD00003

【0050】[0050]

試驗例：蝕刻液組合物的特性評估Test example: Evaluation of the characteristics of the etching solution composition

【0051】[0051]

在玻璃基板（100mm×100mm）上沉積鉬合金膜，在上述膜上沉積銅膜後，通過光刻（photolithography）工序在基板上形成具有規定的圖案的光刻膠，分別使用實施例1至實施例3及比較例1至比較例10的組合物，針對銅類金屬膜實施蝕刻工序。在試驗中，使用了噴射式蝕刻方式的實驗裝備（型號：ETCHER（TFT），SEMES公司），在實施蝕刻工序時，蝕刻液組合物的溫度設置為約30℃左右，但適當溫度可根據其他工序條件和其他要素而按需變更。蝕刻時間可隨著蝕刻溫度而發生變化，通常實施80秒鐘左右。通過剖面SEM（Hitachi公司產品，型號S-4700），來檢查在上述蝕刻工序中完成蝕刻的銅類金屬膜的屬性，其結果記載於下表2。A molybdenum alloy film is deposited on a glass substrate (100mm × 100mm), a copper film is deposited on the film, and a photoresist having a predetermined pattern is formed on the substrate through a photolithography process. Examples 1 to 1 are used respectively. In the compositions of Example 3 and Comparative Examples 1 to 10, an etching step was performed on the copper-based metal film. In the test, experimental equipment (type: ETCHER (TFT), SEMES) of the spray etching method was used. When the etching process was performed, the temperature of the etching solution composition was set to about 30 ° C, but the appropriate temperature can be determined according to other Process conditions and other factors are changed as needed. The etching time may vary depending on the etching temperature, and is usually performed for about 80 seconds. The properties of the copper-based metal film which was etched in the above-mentioned etching step were examined by a cross-section SEM (Hitachi's product, model S-4700). The results are shown in Table 2 below.

【0052】[0052]

【表2】【Table 2】

Figure TWI614550BD00004
Figure TWI614550BD00004

○：良
△：一般
X：不良
Unetch：未蝕刻○: Good △: Fair
X: bad
Unetch: Unetched

【0053】[0053]

在LCD蝕刻工序中，當蝕刻速度（Etch rate）緩慢時，工序時間（Process Time）就會增加，進而難以確保批量生產性，因此，應確保銅蝕刻速度（Cu Etch rate）70～120

Figure TWI614550BD00005
/sec、鉬鈮蝕刻速度（Mo-Nb）15～30
Figure TWI614550BD00006
/sec以上。並且，應保持一定的根據銅濃度的側面蝕刻（Side Etch）（μm）變化量。側面蝕刻（Side Etch）是指在蝕刻後測定的光刻膠末端和下部金屬末端之間的距離。當側面蝕刻變化量大時，薄膜電晶體驅動時信號傳遞速度發生變化，進而導致薄膜電晶體-液晶顯示器（TFT-LCD）特性發生變化，因此，較佳地，側面蝕刻變化量應最小化。在本評估中，假設了當側面蝕刻變化量滿足±0.1μm的條件時能夠繼續將蝕刻液組合物用於蝕刻工序，並實施了實驗。In the LCD etching process, when the etching rate (Etch rate) is slow, the process time increases, which makes it difficult to ensure mass productivity. Therefore, the copper etching rate (Cu Etch rate) should be 70 to 120.
Figure TWI614550BD00005
/ sec, Mo-Nb etching speed (Mo-Nb) 15 ～ 30
Figure TWI614550BD00006
/ sec or more. In addition, a certain amount of change in side etch (μm) according to copper concentration should be maintained. Side Etch refers to the distance between the photoresist end and the lower metal end measured after etching. When the amount of change in the side etching is large, the signal transmission speed changes when the thin film transistor is driven, which causes the characteristics of the thin film transistor-liquid crystal display (TFT-LCD) to change. Therefore, the amount of change in the side etching should preferably be minimized. In this evaluation, it is assumed that the etching solution composition can continue to be used in the etching process when the side etching change amount satisfies the condition of ± 0.1 μm, and experiments were performed.

【0054】[0054]

從表2中可知，實施例1至實施例3的本發明的蝕刻液組合物均表現出良好的蝕刻特性。並且，從第1圖可知，以實施例2的蝕刻液組合物蝕刻的銅類金屬膜，其蝕刻輪廓（Profile）及直線性優秀，並且未殘留有蝕刻殘渣。As can be seen from Table 2, the etching solution compositions of the present invention in Examples 1 to 3 all showed good etching characteristics. In addition, it can be seen from FIG. 1 that the copper-based metal film etched with the etchant composition of Example 2 has an excellent etching profile and linearity, and no etching residues remain.

【0055】[0055]

相比之下，在過氧化氫含量小於適當含量範圍的比較例1中，銅（Cu）及鉬鈮（Mo-Nb）蝕刻速度過慢，表現出未蝕刻（Unetch）的現象，在中性氟化銨含量小於適當含量範圍的比較例2中，銅蝕刻速度（Cu Etch rate）處於可滿足水準，但鉬鈮（Mo-Nb）出現未蝕刻（Unetch）的現象。在氨基噻唑的含量大於適當含量範圍的比較例3中，銅、鉬鈮均表現出未蝕刻的現象。In contrast, in Comparative Example 1 in which the hydrogen peroxide content is less than the appropriate content range, the etching rate of copper (Cu) and molybdenum niobium (Mo-Nb) is too slow, showing an unetched phenomenon, which is neutral. In Comparative Example 2 in which the ammonium fluoride content was less than an appropriate content range, the copper etching rate (Cu Etch rate) was at a satisfactory level, but molybdenum niobium (Mo-Nb) was not etched. In Comparative Example 3 in which the content of aminothiazole was larger than the appropriate content range, both copper and molybdenum and niobium showed no etching.

【0056】[0056]

一方面，不同於實施例2，在組合中包含有乙醇酸的比較例4的情況下，銅蝕刻速度（Cu Etch rate）從100

Figure TWI614550BD00007
/sec的速度提高到120
Figure TWI614550BD00008
/sec的速度，有利於銅蝕刻（Cu Etch），但從第2圖中可知，鉬鈮（Mo-Nb）表現出殘留著殘渣未蝕刻（Unetch）的現象，在包含有有機酸的情況下，不利於鉬鈮蝕刻（Mo-Nb Etch）。On the one hand, unlike Example 2, in the case of Comparative Example 4 in which glycolic acid is included in the combination, the copper etching rate (Cu Etch rate) is from 100
Figure TWI614550BD00007
/ sec speed increased to 120
Figure TWI614550BD00008
The speed per second is good for copper etching (Cu Etch), but from the second figure, it can be seen that molybdenum niobium (Mo-Nb) shows the phenomenon of residual unetching (Unetch), and it contains organic acids. , Is not conducive to molybdenum niobium etching (Mo-Nb Etch).

【0057】[0057]

並且，不同於實施例2，在組合中包含有硫酸銨的比較例5的情況下，銅蝕刻速度從100

Figure TWI614550BD00009
/sec提高到110
Figure TWI614550BD00010
/sec，在比較例6中，銅蝕刻速度從100
Figure TWI614550BD00011
/sec提高到130
Figure TWI614550BD00012
/sec，進而有利於銅蝕刻，但從第3圖中可知，在銅和鉬鈮表面部能夠觀察到侵蝕現象，並表現出殘留著鉬鈮殘渣的未蝕刻（Unetch）現象，由此可知，在包含有硫酸鹽的情況下，將對蝕刻輪廓造成不利影響。And, unlike Example 2, in the case of Comparative Example 5 in which ammonium sulfate was included in the combination, the copper etching rate was from 100
Figure TWI614550BD00009
/ sec increased to 110
Figure TWI614550BD00010
/ sec, in Comparative Example 6, the copper etching speed is from 100
Figure TWI614550BD00011
/ sec increased to 130
Figure TWI614550BD00012
/ sec, which is beneficial to copper etching, but from Figure 3, it can be seen that the corrosion phenomenon can be observed on the surface of copper and molybdenum-niobium, and the unetching phenomenon of molybdenum-niobium residues remains, which shows that In the case where sulfate is contained, the etching profile will be adversely affected.

【0058】[0058]

補充地，不同於實施例2，在組合中包含有1.0%環已胺的比較例7的情況下，銅蝕刻速度從100

Figure TWI614550BD00013
/sec下降到90
Figure TWI614550BD00014
/sec，而且鉬鈮蝕刻速度從20
Figure TWI614550BD00015
/sec顯著下降到5
Figure TWI614550BD00016
/sec，從第4圖中可知，鉬鈮表現出了殘留著殘渣的未蝕刻（Unetch）的現象，如比較例8所示，環已胺的濃度增加到4.0%時，鉬鈮未蝕刻（Unetch），由此可知，在包含有環已胺的情況下，不利於鉬鈮的蝕刻。Additionally, different from Example 2, in the case of Comparative Example 7 in which 1.0% cyclohexylamine was included in the combination, the copper etching rate was from 100
Figure TWI614550BD00013
/ sec drops to 90
Figure TWI614550BD00014
/ sec, and the molybdenum-niobium etch rate is from 20
Figure TWI614550BD00015
/ sec drops significantly to 5
Figure TWI614550BD00016
/ sec, it can be seen from the fourth figure that molybdenum and niobium show an unetched phenomenon with residue remaining. As shown in Comparative Example 8, when the concentration of cyclohexanamine is increased to 4.0%, molybdenum and niobium are not etched ( Unetch), which shows that, when cyclohexanamine is contained, it is not good for the etching of molybdenum and niobium.

【0059】[0059]

不同於實施例2，在組合中包含有1.0%硫酸銨、1.0%環已胺的比較例9中，從第5圖中可知，在銅和鉬鈮表面部能夠觀察到侵蝕現象，並且表現出殘留著鉬鈮殘渣的未蝕刻（Unetch）現象，由此可知，將對蝕刻輪廓造成不利的影響。Different from Example 2, in Comparative Example 9 containing 1.0% ammonium sulfate and 1.0% cyclohexanamine in the combination, it can be seen from FIG. 5 that the erosion phenomenon can be observed on the surface of copper and molybdenum-niobium, and it shows that The unetched phenomenon of molybdenum and niobium residues remains, and it can be seen that the etching contour will be adversely affected.

【0060】[0060]

並且，在大韓民國公開公報第10-2010-0035250號中，記載了在過氧化氫等中必備地包含有硫酸銨和環已胺的組合物，如比較例10，當使用上述組合物蝕刻銅/鉬-鈮（Mo-Nb）時，從第6圖中可知，在銅和鉬鈮表面部能夠觀察到侵蝕現象，無法實現對鉬鈮的充分的蝕刻速度，蝕刻特性也會嚴重低下。Furthermore, in the Republic of Korea Publication No. 10-2010-0035250, a composition containing ammonium sulfate and cyclohexylamine in the presence of hydrogen peroxide and the like is described. As in Comparative Example 10, when the above composition is used to etch copper / In the case of molybdenum-niobium (Mo-Nb), it can be seen from FIG. 6 that the erosion phenomenon can be observed on the surface of copper and molybdenum-niobium, and a sufficient etching rate for molybdenum-niobium cannot be achieved, and the etching characteristics are severely deteriorated.

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Claims (10)

【第1項】[Item 1] 一種液晶顯示裝置用陣列基板的製備方法，其方法包括：步驟a），在一基板上形成一柵極配線，步驟b），在包含該柵極配線的該基板上形成一柵極絕緣層，步驟c），在該柵極絕緣層上形成一半導體層，步驟d），在該半導體層上形成一源極和一汲極，以及步驟e），形成與該汲極相連接的一圖元電極，其中，
上述步驟a）或步驟d）包括：通過對包含鉬類金屬膜或銅類金屬膜的膜進行蝕刻，來形成各電極的步驟，
上述鉬合金膜為鈮或鎢中的一種以上與鉬的合金，
用於蝕刻的上述蝕刻液組合物包括：占組合物總重量中的重量百分比為：A）過氧化氫5.0重量百分比～25.0重量百分比；B）氟化合物0.01重量百分比～1.0重量百分比；C）唑類化合物0.1重量百分比～5重量百分比；D）在一個分子內具有氮原子和羧基的水溶性化合物0.1重量百分比～5.0重量百分比；E）磷酸鹽化合物0.1重量百分比～5.0重量百分比；F）多元醇類表面活性劑0.001重量百分比～5.0重量百分比；以及G）水剩餘量，除了上述成分之外，上述蝕刻液組合物不包含有機酸或有機酸鹽、無機酸或無機酸鹽或脂環族胺。A method for preparing an array substrate for a liquid crystal display device includes the following steps: a) forming a gate wiring on a substrate, and step b) forming a gate insulating layer on the substrate including the gate wiring, Step c), forming a semiconductor layer on the gate insulating layer, step d), forming a source and a drain on the semiconductor layer, and step e), forming a picture element connected to the drain Electrode, where
The above step a) or step d) includes: a step of forming each electrode by etching a film containing a molybdenum-based metal film or a copper-based metal film,
The above molybdenum alloy film is an alloy of one or more of niobium or tungsten with molybdenum,
The above-mentioned etching solution composition used for etching includes: the weight percentage of the total weight of the composition is: A) 5.0 weight percent to 25.0 weight percent of hydrogen peroxide; B) 0.01 weight percent to 1.0 weight percent of fluorine compounds; C) azole 0.1% to 5% by weight of a class compound; D) 0.1% to 5.0% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule; E) 0.1% to 5.0% by weight of a phosphate compound; F) a polyol 0.001% to 5.0% by weight of surfactants; and G) the remaining amount of water, in addition to the above components, the above-mentioned etching solution composition does not contain organic acids or organic acid salts, inorganic acids or inorganic acid salts or alicyclic amines . 【第2項】[Item 2] 如申請專利範圍第1項所述的液晶顯示裝置用陣列基板的製備方法，其中，該液晶顯示裝置用陣列基板為薄膜電晶體陣列基板。The method for manufacturing an array substrate for a liquid crystal display device according to item 1 of the scope of application for a patent, wherein the array substrate for a liquid crystal display device is a thin film transistor array substrate. 【第3項】[Item 3] 如申請專利範圍第1項所述的液晶顯示裝置用陣列基板的製備方法，其中，用於蝕刻的上述蝕刻液組合物，以15～30
Figure TWI614550BC00001
/sec的速度蝕刻鉬類金屬膜，以70～120
Figure TWI614550BC00002
/sec的速度蝕刻銅類金屬膜。The method for preparing an array substrate for a liquid crystal display device according to item 1 of the scope of patent application, wherein the etching solution composition used for etching is in a range of 15 to 30.
Figure TWI614550BC00001
etch molybdenum-based metal film at a speed of 70 to 120
Figure TWI614550BC00002
/ sec. The copper-based metal film is etched. 【第4項】[Item 4] 一種由鈮或鎢中的一種以上與鉬的合金及銅類金屬膜構成的多層膜用蝕刻液組合物，其中，包括：
占組合物總重量中的重量百分比為：
A）過氧化氫5.0重量百分比～25.0重量百分比；
B）氟化合物0.01重量百分比～1.0重量百分比；
C）唑類化合物0.1重量百分比～5重量百分比；
D）在一個分子內具有氮原子和羧基的水溶性化合物0.1重量百分比～5.0重量百分比；
E）磷酸鹽化合物0.1重量百分比～5.0重量百分比；
F）多元醇類表面活性劑0.001重量百分比～5.0重量百分比；以及
G）水剩餘量，
除了上述成分之外，上述蝕刻液組合物不包含有機酸或有機酸鹽、無機酸或無機酸鹽或脂環族胺。An etching solution composition for a multilayer film composed of one or more of niobium or tungsten with an alloy of molybdenum and a copper-based metal film, including:
The weight percentage of the total weight of the composition is:
A) 5.0% by weight to 25.0% by weight of hydrogen peroxide;
B) 0.01% by weight to 1.0% by weight of the fluorine compound;
C) 0.1 to 5 weight percent of azole compounds;
D) a water-soluble compound having a nitrogen atom and a carboxyl group in a molecule of 0.1 to 5.0% by weight;
E) 0.1% to 5.0% by weight of the phosphate compound;
F) Polyol surfactants from 0.001% by weight to 5.0% by weight; and
G) the amount of water remaining,
In addition to the above components, the above-mentioned etchant composition does not include an organic acid or an organic acid salt, an inorganic acid or an inorganic acid salt, or an alicyclic amine. 【第5項】[Item 5] 如申請專利範圍第4項所述的由鈮或鎢中的一種以上與鉬的合金及銅類金屬膜構成的多層膜用蝕刻液組合物，其中，以15～30
Figure TWI614550BC00003
/sec的速度蝕刻鉬類金屬膜，以70～120
Figure TWI614550BC00004
/sec的速度蝕刻銅類金屬膜。The etching solution composition for a multilayer film composed of one or more of niobium or tungsten, an alloy of molybdenum, and a copper-based metal film as described in item 4 of the scope of patent application, wherein
Figure TWI614550BC00003
etch molybdenum-based metal film at a speed of 70 to 120
Figure TWI614550BC00004
/ sec. The copper-based metal film is etched. 【第6項】[Item 6] 如申請專利範圍第4項所述的由鈮或鎢中的一種以上與鉬的合金及銅類金屬膜構成的多層膜用蝕刻液組合物，其中，上述B）氟化合物為選自由氟化氫、氟化鈉、氟化銨、氟硼酸銨、氟化氫銨、氟化鉀、氟氫化鉀、氟化鋁及氟硼酸組成的組中的一種以上。The etching solution composition for a multilayer film composed of one or more of niobium or tungsten with an alloy of molybdenum and a copper-based metal film according to item 4 of the scope of the patent application, wherein the above-mentioned B) fluorine compound is selected from the group consisting of hydrogen fluoride and fluorine One or more selected from the group consisting of sodium chloride, ammonium fluoride, ammonium fluoborate, ammonium hydrogen fluoride, potassium fluoride, potassium fluoride, potassium fluoride, aluminum fluoride, and fluoboric acid. 【第7項】[Item 7] 如申請專利範圍第4項所述的由鈮或鎢中的一種以上與鉬的合金及銅類金屬膜構成的多層膜用蝕刻液組合物，其中，上述C）唑類化合物為選自由***類化合物、氨基四唑類化合物、咪唑類化合物、吲哚類化合物、嘌呤類化合物、吡唑類化合物、吡啶類化合物、嘧啶類化合物、吡咯類化合物、吡咯烷類化合物及吡咯啉類化合物組成的組中的一種以上。The etching solution composition for a multilayer film composed of one or more of niobium or tungsten with an alloy of molybdenum and a copper-based metal film as described in item 4 of the scope of patent application, wherein the above-mentioned C) azole compound is selected from the group consisting of triazole Compounds, aminotetrazole compounds, imidazole compounds, indole compounds, purine compounds, pyrazole compounds, pyridine compounds, pyrimidine compounds, pyrrole compounds, pyrrolidine compounds, and pyrroline compounds More than one in the group. 【第8項】[Item 8] 如申請專利範圍第4項所述的由鈮或鎢中的一種以上與鉬的合金及銅類金屬膜構成的多層膜用蝕刻液組合物，其中，上述D）在一個分子內具有氮原子和羧基的水溶性化合物為選自由丙氨酸、氨基丁酸、谷氨酸、甘氨酸、亞氨基二乙酸、氨三乙酸及肌氨酸組成的組中的一種以上。The etching solution composition for a multilayer film composed of one or more of niobium or tungsten, an alloy of molybdenum, and a copper-based metal film as described in item 4 of the scope of the patent application, wherein D) above has a nitrogen atom and The carboxyl water-soluble compound is one or more selected from the group consisting of alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, aminotriacetic acid, and sarcosine. 【第9項】[Item 9] 如申請專利範圍第4項所述的由鈮或鎢中的一種以上與鉬的合金及銅類金屬膜構成的多層膜用蝕刻液組合物，其中，上述E）磷酸鹽化合物為選自由磷酸鈉、磷酸鉀及磷酸銨組成的組中的一種以上。The etching solution composition for a multilayer film composed of one or more of niobium or tungsten with an alloy of molybdenum and a copper-based metal film according to item 4 of the scope of patent application, wherein the above-mentioned E) phosphate compound is selected from the group consisting of sodium phosphate , Potassium phosphate, and ammonium phosphate. 【第10項】[Item 10] 如申請專利範圍第4項所述的由鈮或鎢中的一種以上與鉬的合金及銅類金屬膜構成的多層膜用蝕刻液組合物，其中，上述F）多元醇類表面活性劑為選自由丙三醇、乙二醇、二甘醇、三甘醇及聚乙二醇組成的組中的一種以上。The etching solution composition for a multilayer film composed of one or more of niobium or tungsten, an alloy of molybdenum, and a copper-based metal film as described in item 4 of the scope of the patent application, wherein the above-mentioned F) polyol-based surfactant is selected One or more selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.
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