TWI662156B - Etching solution composition for metal layer and manufacturing method of an array substrate for liquid crystal display using the same - Google Patents

Etching solution composition for metal layer and manufacturing method of an array substrate for liquid crystal display using the same Download PDF

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TWI662156B
TWI662156B TW104119236A TW104119236A TWI662156B TW I662156 B TWI662156 B TW I662156B TW 104119236 A TW104119236 A TW 104119236A TW 104119236 A TW104119236 A TW 104119236A TW I662156 B TWI662156 B TW I662156B
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metal layer
aforementioned
based metal
etching solution
copper
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TW201600643A (en
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崔漢永
金炫佑
田玹守
趙成培
金相泰
李俊雨
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南韓商東友精細化工有限公司
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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
    • 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
    • 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
    • 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
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making

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  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Weting (AREA)
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Abstract

本發明揭示一種蝕刻液組合物，係包括：金屬層氧化劑；氟化物；含氮原子的化合物；磷酸；聚乙二醇；以及剩餘量的水，其中，相對於1克上述蝕刻液組合物之聚乙二醇的重複單元的毫莫耳量用於表示環氧乙烷水準，並且蝕刻液組合物的環氧乙烷水準為0.4~2；並且揭示一種使用該組合物製造用於液晶顯示器的陣列基板的方法。 The invention discloses an etchant composition, comprising: a metal layer oxidant; a fluoride; a nitrogen atom-containing compound; phosphoric acid; polyethylene glycol; and a remaining amount of water, wherein, relative to 1 g of the above-mentioned etchant composition, The millimolar amount of the repeating unit of polyethylene glycol is used to indicate the ethylene oxide level, and the ethylene oxide level of the etchant composition is 0.4 to 2; and a method for manufacturing a liquid crystal display using the composition is disclosed. Array substrate method.

Description

蝕刻液組合物及使用其製造液晶顯示器用陣列基板的方法 Etching liquid composition and method for manufacturing array substrate for liquid crystal display using the same

本發明係關於一種用於金屬層的蝕刻液組合物及一種使用該蝕刻液組合物製造用於液晶顯示器的陣列基板的方法。 The present invention relates to an etchant composition for a metal layer and a method for manufacturing an array substrate for a liquid crystal display using the etchant composition.

隨著例如LCD、PDP和OLED特別是TFT-LCD的平板顯示器螢幕變大，已經廣泛重新考慮採用由銅或銅合金組成的單層，或者採用銅或銅合金/其它金屬、其它金屬的合金或者金屬氧化物的大於兩層的複數層，以降低配線電阻並提高與介電矽層的黏合性。例如，銅/鉬層、銅/鈦層或銅/鉬-鈦層可形成為TFT-LCD的閘線和構成資料線的源/汲配線，並且可有助於擴大顯示器螢幕。因此，需要開發具有優異蝕刻特性的組合物用於蝕刻包含銅基層的這些金屬層。 As flat-panel display screens such as LCDs, PDPs, and OLEDs, and especially TFT-LCDs have become larger, the use of single layers made of copper or copper alloys, or copper or copper alloys / other metals, alloys of other metals, or Multiple layers of metal oxides greater than two to reduce wiring resistance and improve adhesion to the dielectric silicon layer. For example, a copper / molybdenum layer, a copper / titanium layer, or a copper / molybdenum-titanium layer can be formed as a gate line and a source / drain line constituting a data line of a TFT-LCD, and can help expand a display screen. Therefore, there is a need to develop a composition having excellent etching characteristics for etching these metal layers including a copper-based layer.

作為上面提到的蝕刻組合物，通常使用過氧化氫和胺基酸類蝕刻液、過氧化氫和磷酸類蝕刻液、過氧化氫和聚乙二醇類蝕刻液等。 As the above-mentioned etching composition, hydrogen peroxide and amino acid-based etching solutions, hydrogen peroxide and phosphoric acid-based etching solutions, hydrogen peroxide and polyethylene glycol-based etching solutions, and the like are generally used.

作為一個例子，韓國專利申請公開號10-2011-0031796揭示一種包括水溶性化合物的蝕刻液，具有：A)過氧化氫(H2O2)、B)過硫酸鹽、C)具有胺基和羧基的可溶性化合物以及水。 As an example, Korean Patent Application Publication No. 10-2011-0031796 discloses an etching solution including a water-soluble compound having: A) hydrogen peroxide (H 2 O 2 ), B) persulfate, and C) having an amine group and Soluble compounds of carboxyl group as well as water.

韓國專利申請公開號10-2012-0044630揭示一種用於含銅的金屬層的蝕刻液，包括：過氧化氫、磷酸、環狀胺化合物、硫酸鹽、氟硼酸和水。 Korean Patent Application Publication No. 10-2012-0044630 discloses an etching solution for a copper-containing metal layer, including: hydrogen peroxide, phosphoric acid, a cyclic amine compound, sulfate, fluoboric acid, and water.

韓國專利申請公開號10-2012-0081764揭示一種蝕刻液，包括：A)氫氧化銨、B)過氧化氫、C)氟化物、D)多元醇和E)水。 Korean Patent Application Publication No. 10-2012-0081764 discloses an etching solution including: A) ammonium hydroxide, B) hydrogen peroxide, C) fluoride, D) polyol, and E) water.

然而，對於含銅基層的金屬層來講在CD損失、斜度(錐度)、圖案直線度、金屬殘渣、儲存穩定性、處理的片材數量等方面，上面提到的蝕刻液不足以滿足相關領域中所要求的條件。 However, for the copper-containing metal layer, in terms of CD loss, slope (taper), pattern straightness, metal residue, storage stability, number of sheets processed, etc., the above-mentioned etchant is not sufficient to meet the relevant Conditions required in the field.

(先前技術文獻) (Prior technical literature) (專利文獻) (Patent Literature)

專利文獻1：韓國專利申請公佈號10-2011-0031796。 Patent Document 1: Korean Patent Application Publication No. 10-2011-0031796.

專利文獻2：韓國專利申請公佈號10-2012-0044630。 Patent Document 2: Korean Patent Application Publication No. 10-2012-0044630.

專利文獻3：韓國專利申請公佈號10-2012-0081764。 Patent Document 3: Korean Patent Application Publication No. 10-2012-0081764.

因此作出本發明以解決上述問題，並且本發明的目的是提供一種蝕刻液組合物，其具有優異的工作安全性、優異的蝕刻速率和對大量片材的優異處理能力，特別是提供一種蝕刻液組合物，其在具有優異的蝕刻速率和對大量片 材的優異處理能力的同時還具有最佳蝕刻輪廓；以及提供一種使用該組合物製造液晶顯示器用陣列基板的方法。 Therefore, the present invention has been made to solve the above problems, and an object of the present invention is to provide an etching solution composition having excellent work safety, excellent etching rate, and excellent processing ability for a large number of sheets, and in particular, to provide an etching solution Composition which has excellent etch rate The material has excellent processing ability while having an optimal etching profile; and a method for manufacturing an array substrate for a liquid crystal display using the composition.

為了實現上述目的，本發明的一個方面提供一種蝕刻液組合物，包括：金屬層氧化劑；氟化物；含氮原子的化合物；磷酸；下述化學式1的聚乙二醇；以及剩餘量的水，其中，相對於1克前述蝕刻液組合物之下述化學式1的聚乙二醇的重複單元的毫莫耳量用於表示環氧乙烷水準，並且前述蝕刻液組合物的環氧乙烷水準為0.4~2。 To achieve the above object, one aspect of the present invention provides an etching solution composition including: a metal layer oxidant; a fluoride; a nitrogen atom-containing compound; phosphoric acid; polyethylene glycol of the following Chemical Formula 1; and a remaining amount of water, Here, the millimolar amount of the repeating unit of polyethylene glycol of the following Chemical Formula 1 with respect to 1 g of the aforementioned etching solution composition is used to indicate the ethylene oxide level, and the ethylene oxide level of the aforementioned etching solution composition is It is 0.4 ~ 2.

其中n是2~100的整數，並且R1和R2各自獨立地為氫、C1~C4的脂肪族烴基或苯基。 Wherein n is an integer of 2 to 100, and R 1 and R 2 are each independently hydrogen, an aliphatic hydrocarbon group of C1 to C4, or a phenyl group.

本發明的另一個方面提供一種製造用於液晶顯示器的陣列基板的方法，包括：a)在基板上形成閘極的步驟；b)在包括前述閘極的前述基板上形成閘絕緣體的步驟；c)在前述閘絕緣體上形成半導體層的步驟；d)在前述半導體層上形成源極/汲極的步驟；以及e)形成與前述汲極連接的像素電極的步驟；其中，步驟a)、d)或e)包括形成金屬層並且使用根據本發明的蝕刻液組合物蝕刻前述金屬層來形成電極的步驟。 Another aspect of the present invention provides a method of manufacturing an array substrate for a liquid crystal display, including: a) a step of forming a gate electrode on a substrate; b) a step of forming a gate insulator on the aforementioned substrate including the aforementioned gate; c ) A step of forming a semiconductor layer on the aforementioned gate insulator; d) a step of forming a source / drain on the aforementioned semiconductor layer; and e) a step of forming a pixel electrode connected to the aforementioned drain; wherein steps a), d ) Or e) includes the steps of forming a metal layer and etching the aforementioned metal layer using the etchant composition according to the present invention to form an electrode.

本發明的金屬層蝕刻液組合物藉由調節重複單元可增加處理的片材數量。 The metal layer etchant composition of the present invention can increase the number of sheets processed by adjusting the repeating unit.

此外，本發明的金屬層蝕刻液組合物提供優異的蝕刻速率。 In addition, the metal layer etchant composition of the present invention provides an excellent etching rate.

進一步，用於含銅基層的金屬層的蝕刻液組合物例如包含低含量的過氧化氫，因此它具有如下優點：優異的工作安全性、價格競爭力和能夠經濟地處置該蝕刻液的功效。 Further, the etchant composition for a metal layer containing a copper-based layer contains, for example, a low content of hydrogen peroxide, so it has the advantages of excellent work safety, price competitiveness, and the ability to dispose of the etchant economically.

進一步，使用本發明中的蝕刻液組合物製造用於液晶顯示器的陣列基板的方法使能夠藉由在用於液晶顯示器的陣列基板上形成具有優異蝕刻輪廓的電極來製造具有優異驅動特性的液晶顯示器用陣列基板。 Further, the method for manufacturing an array substrate for a liquid crystal display using the etchant composition in the present invention enables a liquid crystal display having excellent driving characteristics to be manufactured by forming an electrode having an excellent etching profile on an array substrate for a liquid crystal display. Use an array substrate.

以下詳細描述本發明。 The present invention is described in detail below.

本發明係關於一種蝕刻液組合物，包括：金屬層氧化劑；氟化物；含氮原子的化合物；磷酸；下述化學式1的聚乙二醇；以及剩餘量的水，其中相對於1克蝕刻液組合物之下述化學式1的聚乙二醇的重複單元的毫莫耳量用於表示環氧乙烷水準，並且上述蝕刻液組合物的環氧乙烷水準為0.4~2。 The invention relates to an etching solution composition, comprising: a metal layer oxidant; a fluoride; a compound containing a nitrogen atom; a phosphoric acid; a polyethylene glycol of the following chemical formula 1; The millimolar amount of the repeating unit of polyethylene glycol of the following chemical formula 1 of the composition is used to indicate the ethylene oxide level, and the ethylene oxide level of the above-mentioned etching solution composition is 0.4 to 2.

其中n是2~100的整數，並且R1和R2各自獨立地為氫、C1~C4的脂肪族烴基或苯基。 Wherein n is an integer of 2 to 100, and R 1 and R 2 are each independently hydrogen, an aliphatic hydrocarbon group of C1 to C4, or a phenyl group.

進一步較佳為R1和R2各自獨立地為氫或甲基。 More preferably, R 1 and R 2 are each independently hydrogen or methyl.

本發明藉由調節化學式1的重複單元可提供環氧乙烷水準為0.4~2的蝕刻液組合物，並由此改進蝕刻速率和處理的片材數量，最終可提供表現出最佳蝕刻輪廓的金屬層蝕刻液組合物。 The present invention can provide an etching solution composition having an ethylene oxide level of 0.4 to 2 by adjusting the repeating unit of Chemical Formula 1, thereby improving the etching rate and the number of sheets processed, and finally can provide an Metal layer etching solution composition.

在本發明中，環氧乙烷水準較佳為0.4~2，更佳為0.8~1.5。如果環氧乙烷水準小於0.4，對處理的片材數量的改進是不夠的，而如果它超過2，由於黏度增加而存在蝕刻速率降低的問題。 In the present invention, the ethylene oxide level is preferably 0.4 to 2, and more preferably 0.8 to 1.5. If the ethylene oxide level is less than 0.4, the improvement in the number of sheets processed is insufficient, and if it exceeds 2, there is a problem that the etching rate decreases due to an increase in viscosity.

金屬層氧化劑是用於氧化金屬層的主要組成成分，其沒有特別的限制，但可以是選自由過氧化氫、過乙酸、氧化金屬、硝酸、過硫酸鹽、氫鹵酸和鹵酸鹽等組成的組中的一種或複數種。 The metal layer oxidant is a main component for oxidizing the metal layer. It is not particularly limited, but may be selected from the group consisting of hydrogen peroxide, peracetic acid, metal oxide, nitric acid, persulfate, hydrohalic acid, and halide. One or more of the group.

氧化金屬是指被氧化的金屬，例如Fe3+、Cu2+等，並且它包括在溶液狀態下解離成Fe3+、Cu2+等的化合物。過硫酸鹽包括過硫酸銨、過硫酸鹼金屬鹽、過硫酸氫鉀複合鹽(oxone)等，並且鹵酸鹽包括氯酸鹽、過氯酸鹽、溴酸鹽、過溴酸鹽等。 The oxidized metal refers to a metal that is oxidized, such as Fe 3+ , Cu 2+ , and the like, and it includes compounds that dissociate into Fe 3+ , Cu 2+ , and the like in a solution state. Persulfate salts include ammonium persulfate, alkali metal persulfate, oxone, and the like, and halates include chlorate, perchlorate, bromate, perbromate, and the like.

金屬層蝕刻液組合物可藉由包括如下組成成分來製備：相對於組合物的總重量，1wt%~40wt%的金屬層氧化劑；0.1wt%~5wt%的氟化物；0.1wt%~10wt%的含氮原子的化合物；0.01wt%~10wt%的磷酸；化學式1的聚乙二醇 的wt%量使前述環氧乙烷水準為0.4~2；以及剩餘量的水。 The metal layer etchant composition can be prepared by including the following composition components: 1% to 40% by weight of the metal layer oxidant relative to the total weight of the composition; 0.1% to 5% by weight of fluoride; 0.1% to 10% by weight Nitrogen atom-containing compound; 0.01% to 10% by weight of phosphoric acid; polyethylene glycol of Chemical Formula 1 The amount of wt% makes the aforementioned ethylene oxide level 0.4 to 2; and the remaining amount of water.

金屬層氧化劑的含量可根據氧化劑的類型和性質進行適當的控制，並且當金屬層氧化劑的量落入上述範圍內時，可適當地調節金屬層的蝕刻速率。 The content of the metal layer oxidant may be appropriately controlled according to the type and nature of the oxidant, and when the amount of the metal layer oxidant falls within the above range, the etching rate of the metal layer may be appropriately adjusted.

本發明化學式1的聚乙二醇是環氧乙烷的加成聚合物，並且它的重複單元是環氧乙烷。相對於組合物的總重量，化學式1的聚乙二醇的wt%量是使化學式1的聚乙二醇的環氧乙烷水準為0.4~2，較佳為0.8~1.5。因此，藉由調節化學式1的重複單元，能夠製備處理的片材數量增加而不降低蝕刻速率的金屬層蝕刻液組合物。 The polyethylene glycol of Chemical Formula 1 of the present invention is an addition polymer of ethylene oxide, and its repeating unit is ethylene oxide. The weight% amount of the polyethylene glycol of the chemical formula 1 is 0.4 to 2 and preferably 0.8 to 1.5 with respect to the total weight of the composition. Therefore, by adjusting the repeating unit of Chemical Formula 1, it is possible to prepare a metal layer etchant composition in which the number of processed sheets is increased without reducing the etching rate.

包含在本發明蝕刻液組合物中的氟化物用於去除蝕刻殘渣，並且用於蝕刻鈦基金屬層。 The fluoride contained in the etching solution composition of the present invention is used to remove etching residues, and is used to etch a titanium-based metal layer.

相對於組合物的總重量，氟化物的量可為0.1wt%~5wt%，較佳為0.1wt%~2wt%。 Relative to the total weight of the composition, the amount of fluoride may be 0.1 wt% to 5 wt%, preferably 0.1 wt% to 2 wt%.

較佳為上述範圍是因為可防止蝕刻殘渣並且不引起玻璃基板或下面的矽層的蝕刻。 The above range is preferred because the etching residue is prevented and the glass substrate or the underlying silicon layer is not etched.

然而，如果氟化物的量超出上述範圍，由於不均一的蝕刻特性導致在基板內產生污漬，由於過快的蝕刻速率下層可能被損壞，並且在處理期間難以控制蝕刻速率。 However, if the amount of fluoride exceeds the above range, stains are generated in the substrate due to uneven etching characteristics, the lower layer may be damaged due to an excessively fast etching rate, and it is difficult to control the etching rate during processing.

較佳為氟化物可以是能夠解離成氟離子或多原子氟離子(polyatomic fluorine ion)的化合物。 Preferably, the fluoride may be a compound capable of dissociating into a fluoride ion or a polyatomic fluorine ion.

能夠解離成氟離子或多原子氟離子的化合物可以是選自由氟化銨、氟化鈉、氟化鉀、氟氫化鈉和氟氫化鉀組成的組中一種或複數種。 The compound capable of dissociating into a fluoride ion or a polyatomic fluoride ion may be one or more selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, sodium hydride, and potassium hydride.

包含在本發明蝕刻液組合物中的含氮原子的化合物用於增加蝕刻液的蝕刻速率和處理的片材數量。 The nitrogen atom-containing compound contained in the etching solution composition of the present invention is used to increase the etching rate of the etching solution and the number of sheets processed.

可以使用本領域已知的含氮原子的化合物而沒有限制，並且代表性地可以使用在分子中含有胺基和羧酸基的化合物。 A nitrogen atom-containing compound known in the art may be used without limitation, and a compound containing an amine group and a carboxylic acid group in a molecule may be typically used.

在分子中含有胺基和羧酸基的化合物可包括例如在羧酸基和胺基之間含有一個碳原子的α-胺基酸，並且代表性地為：一價胺基酸，例如甘胺酸、谷胺酸、穀胺醯胺、異白胺酸、脯胺酸、酪胺酸、精胺酸等；和多價胺基酸，例如亞胺基二乙酸、次氮基三乙酸、乙二醇四乙酸。含氮原子的化合物可以單獨使用或以兩種或更多種的組合使用。 The compound containing an amine group and a carboxylic acid group in the molecule may include, for example, an α-amino acid containing one carbon atom between the carboxylic acid group and the amine group, and is typically: a monovalent amino acid such as glycine Acids, glutamine, glutamine, isoleucine, proline, tyrosine, arginine, etc .; and polyvalent amino acids, such as iminodiacetic acid, nitrilotriacetic acid, ethyl Glycol tetraacetic acid. The nitrogen atom-containing compound may be used alone or in a combination of two or more.

相對於組合物的總重量，含氮原子的化合物的量為0.1wt%~10wt%，較佳為1wt%~5wt%。上述較佳範圍是因為能夠改進蝕刻液的蝕刻速率和處理的片材數量。 The amount of the nitrogen atom-containing compound relative to the total weight of the composition is 0.1 wt% to 10 wt%, preferably 1 wt% to 5 wt%. The above preferable range is because the etching rate of the etchant and the number of sheets processed can be improved.

磷酸藉由向蝕刻液提供氫離子促進金屬層氧化劑對銅的蝕刻。此外，由於與被氧化的銅離子結合形成磷酸鹽而增加了在水中的溶解性，消除了蝕刻後的金屬層殘渣。 Phosphoric acid promotes the etching of copper by the metal layer oxidant by supplying hydrogen ions to the etchant. In addition, by combining with the oxidized copper ions to form phosphate, the solubility in water is increased, and the residue of the metal layer after the etching is eliminated.

相對於組合物的總重量，磷酸的量為0.01wt%~10wt%，並且較佳為0.01wt%~1wt%。當磷酸的量滿足上述範圍時，可執行預期的功能，因為可避免由磷酸所導致的過度蝕刻金屬層和腐蝕下層的風險，並且不會引起由於磷酸的含量太低銅金屬層的蝕刻速率變低的問題。 The amount of phosphoric acid is 0.01 wt% to 10 wt%, and preferably 0.01 wt% to 1 wt% with respect to the total weight of the composition. When the amount of phosphoric acid satisfies the above range, an expected function can be performed because the risk of excessively etching the metal layer and corroding the underlying layer caused by the phosphoric acid can be avoided, and the etching rate of the copper metal layer does not change due to the too low content of phosphoric acid Low problem.

本發明中使用的水是指去離子水，使用用於半導體加 工的水，並且較佳為使用大於18MΩ/cm的水。 The water used in the present invention refers to deionized water. Water, and preferably more than 18 MΩ / cm.

除上面提到的組成成分外，本發明的蝕刻液組合物還可包括選自蝕刻控制劑、界面活性劑、螯合劑、腐蝕抑制劑和pH調節劑中的至少一種。 In addition to the above-mentioned constituents, the etchant composition of the present invention may further include at least one selected from an etching control agent, a surfactant, a chelating agent, a corrosion inhibitor, and a pH adjuster.

用本發明的蝕刻液組合物蝕刻的金屬層沒有特別限制，但本發明的蝕刻液組合物能夠較佳地用於蝕刻銅基金屬層、鉬基金屬層、鈦基金屬層或由這些層組成的複數層。 The metal layer etched with the etchant composition of the present invention is not particularly limited, but the etchant composition of the present invention can be preferably used to etch a copper-based metal layer, a molybdenum-based metal layer, a titanium-based metal layer, or consist of these layers. Plural layers.

銅基金屬層是指銅層或銅合金層，鉬基金屬層是指鉬層或鉬合金層，以及鈦基金屬層是指鈦層或鈦合金層。 The copper-based metal layer refers to a copper layer or a copper alloy layer, the molybdenum-based metal layer refers to a molybdenum layer or a molybdenum alloy layer, and the titanium-based metal layer refers to a titanium layer or a titanium alloy layer.

複數層包括：例如，鉬基金屬層/銅基金屬層的雙層，其中，銅基金屬層是下層並且鉬基金屬層是上層；銅基金屬層/鉬基金屬層的雙層，其中，鉬金屬層是下層並且銅基金屬層是上層；銅基金屬層/鉬基和鈦基金屬層的雙層；以及大於三層的複數層，其中，銅基金屬層和鉬基金屬層交錯積層，例如鉬基金屬層/銅基金屬層/鉬基金屬層，或者銅基金屬層/鉬基金屬層/銅基金屬層。 The plurality of layers include, for example, a double layer of a molybdenum-based metal layer / a copper-based metal layer, wherein the copper-based metal layer is a lower layer and a molybdenum-based metal layer is an upper layer; a double layer of a copper-based metal layer / molybdenum-based metal layer, wherein, The molybdenum metal layer is a lower layer and the copper-based metal layer is an upper layer; a copper-based metal layer / a double layer of a molybdenum-based and a titanium-based metal layer; and a plurality of layers having more than three layers, wherein the copper-based metal layer and the molybdenum-based metal layer are alternately laminated For example, a molybdenum-based metal layer / copper-based metal layer / molybdenum-based metal layer, or a copper-based metal layer / molybdenum-based metal layer / copper-based metal layer.

此外，複數層包括：例如，鈦基金屬層/銅基金屬層的雙層，其中，銅金屬層是下層並且鈦基金屬層是上層；銅基金屬層/鈦基金屬層的雙層，其中，鈦金屬層是下層並且銅基金屬層是上層；以及大於三層的複數層，其中，銅基金屬層和鈦基金屬層交錯積層，例如鈦基金屬層/銅基金屬層/鈦基金屬層，或者銅基金屬層/鈦基金屬層/銅基金屬層。 In addition, the plural layers include, for example, a double layer of a titanium-based metal layer / a copper-based metal layer, wherein the copper metal layer is a lower layer and a titanium-based metal layer is an upper layer; a double layer of a copper-based metal layer / titanium-based metal layer, wherein The titanium metal layer is a lower layer and the copper-based metal layer is an upper layer; and a plurality of layers of more than three layers, wherein the copper-based metal layer and the titanium-based metal layer are alternately laminated, for example, a titanium-based metal layer / a copper-based metal layer / a titanium-based metal Layer, or copper-based metal layer / titanium-based metal layer / copper-based metal layer.

藉由多重考慮構成上層或下層的材料或者與層的黏合性等，能夠確定複數層的層間組合結構。 By considering the materials constituting the upper layer or the lower layer or the adhesion to the layers, etc., the interlayer combination structure of a plurality of layers can be determined.

銅合金層、鉬合金層或鈦合金層是指作為合金而生產的金屬層，在該合金中，銅、鉬或鈦為主要組成成分並且根據膜性質使用其它不同的金屬。例如，鉬合金層是指以鉬為主要組成成分並且含有選自鈦(Ti)、鉭(Ta)、鉻(Cr)、鎳(Ni)、釹(Nd)和銦(In)中的一種或複數種的合金而生產的層。 The copper alloy layer, the molybdenum alloy layer, or the titanium alloy layer refers to a metal layer produced as an alloy. In the alloy, copper, molybdenum, or titanium is a main component and other different metals are used depending on the properties of the film. For example, the molybdenum alloy layer refers to molybdenum as a main component and contains one or more selected from titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In). A layer produced by a plurality of alloys.

作為本發明蝕刻液組合物的具體實施方式，過氧化氫可用作金屬層氧化劑，並且可包含氟化物、含氮原子的化合物、磷酸、化學式1的聚乙二醇以及剩餘量的水。 As a specific embodiment of the etching solution composition of the present invention, hydrogen peroxide may be used as a metal layer oxidant, and may include fluoride, a nitrogen atom-containing compound, phosphoric acid, polyethylene glycol of Chemical Formula 1, and a remaining amount of water.

過氧化氫是對銅、鉬和鈦進行氧化的主要組成成分，並且，相對於組合物的總重量，其量可為1wt%~25wt%，較佳為大於1wt%並且小於等於10wt%，更佳為大於1wt%並且小於等於5wt%。 Hydrogen peroxide is the main component for oxidizing copper, molybdenum, and titanium, and its amount may be 1 wt% to 25 wt%, preferably greater than 1 wt% and less than or equal to 10 wt%, relative to the total weight of the composition. It is preferably more than 1 wt% and less than or equal to 5 wt%.

當過氧化氫的量落入上述範圍內時，防止銅、鉬和鈦的蝕刻速率變差，可以實現適當量的蝕刻，並且可得到優異的蝕刻輪廓。 When the amount of hydrogen peroxide falls within the above range, the deterioration of the etching rates of copper, molybdenum, and titanium is prevented, an appropriate amount of etching can be achieved, and an excellent etching profile can be obtained.

然而，如果過氧化氫的量超出上述範圍，則不會發生蝕刻或者會發生過度蝕刻，因此可能發生圖案損失以及作為金屬配線的功能損失。 However, if the amount of hydrogen peroxide is out of the above range, etching will not occur or excessive etching will occur, so pattern loss and loss of function as a metal wiring may occur.

構成本發明蝕刻液組合物的組成成分較佳為具有半導體加工用純度。 It is preferable that the component which comprises the etching solution composition of this invention has purity for semiconductor processing.

進一步，本發明係關於一種製造用於液晶顯示器的陣列基板的方法，包括：a)在基板上形成閘極的步驟； b)在包括閘極的基板上形成閘絕緣體的步驟；c)在閘絕緣體上形成半導體層的步驟；d)在半導體層上形成源極/汲極的步驟；以及e)形成與汲極連接的像素電極的步驟；其中，步驟a)、d)或e)包括形成金屬層並且使用根據本發明的蝕刻液組合物蝕刻金屬層來形成電極的步驟。 Further, the present invention relates to a method for manufacturing an array substrate for a liquid crystal display, including: a) a step of forming a gate electrode on the substrate; b) a step of forming a gate insulator on a substrate including a gate electrode; c) a step of forming a semiconductor layer on the gate insulator; d) a step of forming a source / drain electrode on the semiconductor layer; and e) forming a connection to the drain electrode A step of a pixel electrode; wherein step a), d) or e) includes a step of forming a metal layer and etching the metal layer using the etchant composition according to the present invention to form an electrode.

由上述方法生產的液晶顯示器用陣列基板因為包括具有優異蝕刻輪廓的電極而具有優異的驅動特性。 The array substrate for a liquid crystal display produced by the above method has excellent driving characteristics because it includes an electrode having an excellent etching profile.

液晶顯示器用陣列基板可以是薄膜電晶體(TFT)陣列基板。 The array substrate for a liquid crystal display may be a thin film transistor (TFT) array substrate.

在下文中藉由提供的實施方式對本發明進行更詳細的描述。然而，下述實施例用於更詳細地說明本發明，本發明的範圍不受下述實施例的限制。下述實施例在本發明的範圍內可由本領域技術中具有通常知識者適當地進行修改。 The invention is described in more detail below by means of the embodiments provided. However, the following examples are used to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following embodiments can be appropriately modified by those having ordinary skill in the art within the scope of the present invention.

(實施例) (Example)

<製備蝕刻液組合物><Preparation of Etching Liquid Composition>

實施例1~6和比較例1~6：Examples 1 to 6 and Comparative Examples 1 to 6:

藉由以下表1中描述的含量混合組成成分製備蝕刻液組合物。 An etching solution composition was prepared by mixing the constituents at the contents described in Table 1 below.

[化學式5] [Chemical Formula 5]

實驗例1：評估蝕刻液組合物對於Cu/Mo-Ti雙層的蝕刻輪廓Experimental Example 1: Evaluation of etching profile of etching solution composition for Cu / Mo-Ti double layer

使用實施例1~6和比較例1~6的蝕刻液組合物進行了Cu/Mo-Ti雙層的蝕刻。當進行蝕刻時使用溫度約為30℃的蝕刻液組合物進行100秒的蝕刻。藉由肉眼測量EPD(終點檢測(End Point Detection)，金屬蝕刻計時)獲得根據時間的蝕刻速率。使用SEM(日立公司，型號S4700)檢測了經蝕刻的Cu/Mo-Ti雙層的輪廓剖面，結果示於下表2中。 Cu / Mo-Ti double-layer etching was performed using the etching solution compositions of Examples 1 to 6 and Comparative Examples 1 to 6. When the etching is performed, etching is performed for 100 seconds using an etchant composition having a temperature of about 30 ° C. The EPD (End Point Detection, Metal Etching Timing) was measured by the naked eye to obtain an etching rate according to time. The profile section of the etched Cu / Mo-Ti double layer was examined using a SEM (Hitachi, Model S4700), and the results are shown in Table 2 below.

實驗例2：評估處理的片材數量Experimental example 2: Evaluation of the number of sheets processed

使用實施例1~6和比較例1~6的蝕刻液組合物進行了參考測試，並且向用於參考測試的蝕刻液中添加4000ppm的銅粉並完全溶解。之後，用進行參考測試的蝕刻液再次進行蝕刻，並且對蝕刻速率的減小比例進行了評估。 Reference tests were performed using the etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 6, and 4000 ppm of copper powder was added to the etchant used for the reference test and completely dissolved. After that, the etching was performed again using the etching solution that was subjected to the reference test, and the reduction rate of the etching rate was evaluated.

<評估標準> <Evaluation criteria>

○：優異(蝕刻速率的減小比例小於10%) ○: Excellent (less than 10% reduction in etching rate)

△：良好(蝕刻速率的減小比例為10%~20%) △: Good (reduction rate of etching rate is 10% to 20%)

×：差(蝕刻速率的減小比例大於20%) ×: Poor (reduction rate of etching rate is greater than 20%)

Claims (5)

一種蝕刻液組合物，係包括：過氧化氫；氟化物；含氮原子的化合物；磷酸；下述化學式1的聚乙二醇；以及剩餘量的水；相對於前述蝕刻液組合物的總重量，包括：1wt%~25wt%的前述過氧化氫；0.1wt%~5wt%的前述氟化物；0.1wt%~10wt%的前述含氮原子的化合物；0.01wt%~10wt%的前述磷酸；前述化學式1的聚乙二醇的wt%量是使前述環氧乙烷水準為0.4~2；以及剩餘量的水其中相對於1克前述蝕刻液組合物之下述化學式1的聚乙二醇的重複單元的毫莫耳量用於表示環氧乙烷水準，並且前述蝕刻液組合物的環氧乙烷水準為0.4~2；其中前述含氮原子的化合物是胺基酸；其中n是2~100的整數，並且R1和R2各自獨立地為氫、C1~C4的脂肪族烴基或苯基。An etchant composition comprising: hydrogen peroxide; a fluoride; a compound containing a nitrogen atom; phosphoric acid; polyethylene glycol of the following chemical formula 1; and a remaining amount of water relative to the total weight of the aforementioned etchant composition Including: 1 wt% to 25 wt% of the aforementioned hydrogen peroxide; 0.1 wt% to 5 wt% of the aforementioned fluoride; 0.1 wt% to 10 wt% of the aforementioned nitrogen atom-containing compound; 0.01 wt% to 10 wt% of the aforementioned phosphoric acid; The wt% amount of the polyethylene glycol of Chemical Formula 1 is such that the foregoing ethylene oxide level is 0.4 to 2; and the remaining amount of water relative to 1 g of the polyethylene glycol of the following Chemical Formula 1 of the aforementioned etching solution composition The millimolar amount of the repeating unit is used to indicate the ethylene oxide level, and the ethylene oxide level of the aforementioned etching solution composition is 0.4 to 2; wherein the aforementioned nitrogen atom-containing compound is an amino acid; Wherein n is an integer of 2 to 100, and R 1 and R 2 are each independently hydrogen, an aliphatic hydrocarbon group of C1 to C4, or a phenyl group. 如請求項1所記載的蝕刻液組合物，其中R1和R2各自獨立地為氫或甲基。The etching solution composition according to claim 1, wherein R 1 and R 2 are each independently hydrogen or methyl. 如請求項1所記載的蝕刻液組合物，其中前述蝕刻液組合物用於蝕刻銅基金屬層、鉬基金屬層、鈦基金屬層或該等的複數層。The etching solution composition according to claim 1, wherein the etching solution composition is used to etch a copper-based metal layer, a molybdenum-based metal layer, a titanium-based metal layer, or a plurality of these layers. 如請求項3所記載的蝕刻液組合物，其中前述複數層是銅基金屬層/鉬金屬層、銅基金屬層/鈦基金屬層，或銅基金屬層/鉬-鈦基合金層。The etching solution composition according to claim 3, wherein the plurality of layers are a copper-based metal layer / molybdenum metal layer, a copper-based metal layer / titanium-based metal layer, or a copper-based metal layer / molybdenum-titanium alloy layer. 一種製造用於液晶顯示器的陣列基板的方法，包括：a)在基板上形成閘極的步驟；b)在包括前述閘極的前述基板上形成閘絕緣體的步驟；c)在前述閘絕緣體上形成半導體層的步驟；d)在前述半導體層上形成源極/汲極的步驟；以及e)形成與前述汲極連接的像素電極的步驟；其中，步驟a)、d)或e)包括形成金屬層並且使用如請求項1至4中任一項所記載的蝕刻液組合物蝕刻前述金屬層來形成電極的步驟。A method of manufacturing an array substrate for a liquid crystal display, comprising: a) a step of forming a gate electrode on a substrate; b) a step of forming a gate insulator on the aforementioned substrate including the gate electrode; c) forming on the aforementioned gate insulator A step of forming a semiconductor layer; d) a step of forming a source / drain on the aforementioned semiconductor layer; and e) a step of forming a pixel electrode connected to the aforementioned drain; wherein step a), d) or e) includes forming a metal And forming the electrode by etching the aforementioned metal layer using the etchant composition as described in any one of claims 1 to 4.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040118814A1 (en) * 2002-12-12 2004-06-24 Seong-Su Kim Etching solution for multiple layer of copper and molybdenum and etching method using the same
TW201012971A (en) * 2008-09-26 2010-04-01 Techno Semichem Co Ltd Cu or Cu/Mo or Cu/Mo alloy electrode etching liquid in liquid crystal display system
TW201207525A (en) * 2010-08-02 2012-02-16 Dongwoo Fine Chem Co Ltd Method of fabricating an array substrate for a liquid crystal display

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
KR101529733B1 (en) * 2009-02-06 2015-06-19 동우 화인켐 주식회사 Manufacturing method of an array substrate for liquid crystal display
KR101674680B1 (en) 2009-09-21 2016-11-10 동우 화인켐 주식회사 Manufacturing method of an array substrate for liquid crystal display
WO2012015089A1 (en) * 2010-07-30 2012-02-02 동우 화인켐 주식회사 Method for preparing array substrate for liquid crystal display device
KR20120044630A (en) 2010-10-28 2012-05-08 주식회사 동진쎄미켐 Etchant composition for copper-containing metal film and etching method using the same
KR101873583B1 (en) 2011-01-12 2018-07-03 동우 화인켐 주식회사 Manufacturing method of an array substrate for liquid crystal display
CN103668206A (en) * 2012-09-19 2014-03-26 东友精细化工有限公司 Etching solution combination for copper/titanium layers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040118814A1 (en) * 2002-12-12 2004-06-24 Seong-Su Kim Etching solution for multiple layer of copper and molybdenum and etching method using the same
TW201012971A (en) * 2008-09-26 2010-04-01 Techno Semichem Co Ltd Cu or Cu/Mo or Cu/Mo alloy electrode etching liquid in liquid crystal display system
TW201207525A (en) * 2010-08-02 2012-02-16 Dongwoo Fine Chem Co Ltd Method of fabricating an array substrate for a liquid crystal display

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