TWI632670B - Method of manufacturing array substrate for liquid crystal display - Google Patents
Method of manufacturing array substrate for liquid crystal display Download PDFInfo
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- TWI632670B TWI632670B TW103121389A TW103121389A TWI632670B TW I632670 B TWI632670 B TW I632670B TW 103121389 A TW103121389 A TW 103121389A TW 103121389 A TW103121389 A TW 103121389A TW I632670 B TWI632670 B TW I632670B
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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
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133351—Manufacturing of individual cells out of a plurality of cells, e.g. by dicing
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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
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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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
Abstract
本發明涉及一種製造液晶顯示器用陣列基板的方法，包括以下步驟：a)在基板上形成閘電極；b)在包括閘電極的基板上形成閘絕緣層；c)在閘絕緣層上形成半導體層(n+a-Si：H和a-Si：H)；d)在半導體層上形成源電極/汲電極；以及e)形成與汲電極連接的畫素電極，其中，步驟a)或d)包括通過蝕刻銅基金屬膜來形成各個電極的步驟，而且，在蝕刻銅基金屬膜中使用的蝕刻劑組合物包括作為用於增加被加工片材的數量的改進劑的檸檬酸。 The present invention relates to a method for manufacturing an array substrate for a liquid crystal display, including the following steps: a) forming a gate electrode on the substrate; b) forming a gate insulating layer on the substrate including the gate electrode; c) forming a semiconductor layer on the gate insulating layer (n + a-Si: H and a-Si: H); d) forming a source electrode / drain electrode on the semiconductor layer; and e) forming a pixel electrode connected to the drain electrode, wherein step a) or d) A step of forming each electrode by etching a copper-based metal film is included, and the etchant composition used in etching the copper-based metal film includes citric acid as an improver for increasing the number of sheets to be processed.
Description
本發明涉及一種製造液晶顯示器用陣列基板的方法。 The invention relates to a method for manufacturing an array substrate for a liquid crystal display.
一種用於驅動半導體器件和平板顯示器的典型的電子電路是薄膜電晶體(TFT)。通常，TFT的製造過程包括以下步驟：在基板上形成作為用於閘電極線和資料線的材料的金屬膜；在所述金屬膜的選擇性區域上形成光致抗蝕劑；以及使用所述光致抗蝕劑作為掩模來蝕刻該金屬膜。 A typical electronic circuit for driving semiconductor devices and flat panel displays is a thin film transistor (TFT). Generally, the manufacturing process of a TFT includes the steps of forming a metal film on a substrate as a material for a gate electrode line and a data line; forming a photoresist on a selective region of the metal film; and using the A photoresist is used as a mask to etch the metal film.
通常，將含有導電性高且電阻低的銅的銅膜或銅合金膜以及與銅膜或銅合金膜具有高介面黏合性的金屬氧化膜用作用於閘電極線和資料線的材料。近來，為了提高TFT的性能，已經使用了含有氧化銦、氧化鋅或它們與氧化鎵的混合物的金屬氧化膜。 Generally, a copper film or a copper alloy film containing copper having high conductivity and low resistance, and a metal oxide film having high interface adhesion with the copper film or copper alloy film are used as materials for the gate electrode line and the data line. Recently, in order to improve the performance of a TFT, a metal oxide film containing indium oxide, zinc oxide, or a mixture thereof with gallium oxide has been used.
同時，韓國專利申請公開10-2006-0064881公開了一種用於銅-鉬膜的蝕刻溶液，該蝕刻溶液包括過氧化氫、有機酸、唑類化合物、氟化合物和作為螯合物的亞氨基二乙酸(IDA)類化合物。當用該蝕刻溶液蝕刻銅-鉬膜時，帶輪廓具有優異的線性，並且在蝕刻後不存在鉬合金的殘渣，但是問題在於：在該蝕刻溶液貯存30天后，由此蝕刻的銅-鉬膜的片材的數量顯著地降低，所以其放熱穩定性以及其貯存穩定性極度變差，而且其對諸如MoTi/Cu/MoTi膜等的三層銅基金屬膜的蝕刻性能極度變差。 Meanwhile, Korean Patent Application Publication No. 10-2006-0064881 discloses an etching solution for a copper-molybdenum film. The etching solution includes hydrogen peroxide, an organic acid, an azole compound, a fluorine compound, and an imino di group as a chelate compound. Acetic acid (IDA) compounds. When the copper-molybdenum film is etched with this etching solution, the strip profile has excellent linearity, and there is no residue of molybdenum alloy after etching, but the problem is that the copper-molybdenum film thus etched after the etching solution is stored for 30 days The number of sheets is significantly reduced, so its exothermic stability and its storage stability are extremely deteriorated, and its etching performance on a three-layer copper-based metal film such as a MoTi / Cu / MoTi film is extremely deteriorated.
(專利文獻1)韓國專利申請公開10-2006-0064881 (Patent Document 1) Korean Patent Application Publication 10-2006-0064881
因此，為了解決上述問題，作出了本發明，本發明的一個目的是提供一種製造液晶顯示器用陣列基板的方法，所述陣列基板是由銅基金屬膜製成。 Therefore, 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 manufacturing an array substrate for a liquid crystal display, the array substrate being made of a copper-based metal film.
本發明的另一目的是提供一種用於銅基金屬膜的蝕刻劑組合物，所述蝕刻劑組合物提供優異的蝕刻輪廓並且提高貯存穩定性，而且所述蝕刻劑組合物能夠適用於包括鉬基金屬膜和銅基金屬膜的三層金屬膜。 Another object of the present invention is to provide an etchant composition for a copper-based metal film, the etchant composition provides an excellent etching profile and improves storage stability, and the etchant composition can be suitably used to include molybdenum Three-layer metal film of a base metal film and a copper-based metal film.
為了達到上述目的，本發明的一個方面提供一種製造液晶顯示器用陣列基板的方法，所述方法包括以下步驟：a)在基板上形成閘電極；b)在包括所述閘電極的基板上形成閘絕緣層；c)在所述閘絕緣層上形成半導體層(n+a-Si：H和a-Si：H)；d)在所述半導體層上形成源電極/汲電極；以及e)形成與所述汲電極連接的畫素電極，其中，所述步驟a)或d)包括通過蝕刻銅基金屬膜來形成各個電極的步驟，而且，在蝕刻所述銅基金屬膜中使用的蝕刻劑組合物包括作為用於增加被加工片材的數量的改進劑的檸檬酸。 In order to achieve the above object, one aspect of the present invention provides a method for manufacturing an array substrate for a liquid crystal display, the method including the following steps: a) forming a gate electrode on a substrate; b) forming a gate on a substrate including the gate electrode An insulating layer; c) forming a semiconductor layer (n + a-Si: H and a-Si: H) on the gate insulating layer; d) forming a source electrode / drain electrode on the semiconductor layer; and e) forming The pixel electrode connected to the drain electrode, wherein the step a) or d) includes a step of forming each electrode by etching a copper-based metal film, and an etchant used in etching the copper-based metal film The composition includes citric acid as an improver for increasing the number of processed sheets.
本發明的另一方面提供一種用於銅基金屬膜的蝕刻劑組合物，所述蝕刻劑組合物包括作為用於增加被加工片材的數量的改進劑的檸檬酸。 Another aspect of the present invention provides an etchant composition for a copper-based metal film, the etchant composition including citric acid as an improver for increasing the number of processed sheets.
本發明涉及一種用於銅基金屬膜的蝕刻劑組合物，所述蝕刻劑組合物包括作為用於增加被加工片材的數量的改進劑的檸檬酸。 The present invention relates to an etchant composition for a copper-based metal film, the etchant composition including citric acid as an improver for increasing the number of sheets to be processed.
在本發明中，銅基金屬膜(它是一種含銅的膜)包括：銅或 銅合金的單層膜；以及包括選自銅膜和銅合金膜中的至少一種以及選自鉬膜、鉬合金膜、鈦膜和鈦合金膜中的至少一種的多層膜。 In the present invention, the copper-based metal film (which is a copper-containing film) includes: copper or A single-layer film of a copper alloy; and a multilayer film including at least one selected from a copper film and a copper alloy film and at least one selected from a molybdenum film, a molybdenum alloy film, a titanium film, and a titanium alloy film.
這裡，合金膜可包括氮化物膜或氧化物膜。 Here, the alloy film may include a nitride film or an oxide film.
多層膜的實例可包括雙層膜和三層膜，諸如銅/鉬膜、銅/鉬合金膜、銅合金/鉬合金膜、銅/鈦膜等。這裡，銅/鉬膜包括鉬層和形成在該鉬層上的銅層；銅/鉬合金膜包括鉬合金層和形成在該鉬合金層上的銅層；銅合金/鉬合金膜包括鉬合金層和形成在該鉬合金層上的銅合金層；以及銅/鈦膜包括鈦層和形成在該鈦層上的銅層。 Examples of the multilayer film may include a double-layer film and a triple-layer film such as a copper / molybdenum film, a copper / molybdenum alloy film, a copper alloy / molybdenum alloy film, a copper / titanium film, and the like. Here, the copper / molybdenum film includes a molybdenum layer and a copper layer formed on the molybdenum layer; the copper / molybdenum alloy film includes a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer; the copper alloy / molybdenum alloy film includes a molybdenum alloy A layer and a copper alloy layer formed on the molybdenum alloy layer; and a copper / titanium film including a titanium layer and a copper layer formed on the titanium layer.
此外，鉬合金層是由鉬和選自由鈦(Ti)、鉭(Ta)、鉻(Cr)、鎳(Ni)、釹(Nd)和銦(In)組成的組中的至少一種金屬的合金製成的層。 In addition, the molybdenum alloy layer is an alloy of molybdenum and at least one metal selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In) Made of layers.
此外，本發明的蝕刻劑組合物可被優選地應用於包括銅或銅合金膜和鉬或鉬合金膜的多層膜。 In addition, the etchant composition of the present invention can be preferably applied to a multilayer film including a copper or copper alloy film and a molybdenum or molybdenum alloy film.
具體地，銅基金屬膜可以是包括鉬合金層、形成在該鉬合金層上的銅層和形成在該銅層上的鉬合金層的三層膜。優選地，銅基金屬膜可以是包括鉬基金屬膜和銅基金屬膜的三層膜。三層膜的具體實例可包括鉬/銅/鉬膜、鉬合金/銅/鉬合金膜、鉬/銅合金/鉬膜、鉬合金/銅合金/鉬合金膜等。 Specifically, the copper-based metal film may be a three-layer film including a molybdenum alloy layer, a copper layer formed on the molybdenum alloy layer, and a molybdenum alloy layer formed on the copper layer. Preferably, the copper-based metal film may be a three-layer film including a molybdenum-based metal film and a copper-based metal film. Specific examples of the three-layer film may include molybdenum / copper / molybdenum film, molybdenum alloy / copper / molybdenum alloy film, molybdenum / copper alloy / molybdenum film, molybdenum alloy / copper alloy / molybdenum alloy film, and the like.
1、蝕刻劑組合物 1.Etchant composition
本發明的蝕刻劑組合物中包含的檸檬酸是一種用於增加被加工片材的數量的改進劑，並用於增加銅基金屬膜的被加工片材的數量。作為用於增加被加工片材的數量的常規改進劑，亞氨基二乙酸(IDA)類化合物是在蝕刻工藝期間用於增加銅基金屬膜的被加工片材的數量的必需成分；但是，因為它具有自分解性質，其被加工片材的數量隨著時間的推移而減少。進一步地，有很多用於蝕刻銅基金屬膜的有機酸的實例，但不是所有的有機酸都有助於增加被加工片材的數量，而僅檸檬酸在蝕刻工藝期間起到增加 銅基金屬膜的被加工片材的數量的作用。基於蝕刻劑組合物的總重量，所含有的檸檬酸的量是1.0~10.0wt%，優選3.0~7.0wt%。當檸檬酸的量小於1.0wt%時，銅基金屬膜的蝕刻速率降低，因此可能存在蝕刻殘渣。當其量大於10.0wt%時，銅基金屬膜可能被過度蝕刻。 The citric acid contained in the etchant composition of the present invention is an improver for increasing the number of processed sheets, and is used for increasing the number of processed sheets of copper-based metal films. As a conventional improver for increasing the number of processed sheets, an iminodiacetic acid (IDA) -based compound is an essential component for increasing the number of processed sheets of a copper-based metal film during an etching process; however, because It has a self-decomposing property, and the number of sheets to be processed decreases over time. Further, there are many examples of organic acids used to etch copper-based metal films, but not all organic acids help increase the number of processed sheets, and only citric acid plays an increase during the etching process Effect of the number of processed sheets of copper-based metal film. Based on the total weight of the etchant composition, the amount of citric acid contained is 1.0 to 10.0 wt%, preferably 3.0 to 7.0 wt%. When the amount of citric acid is less than 1.0 wt%, the etching rate of the copper-based metal film is reduced, and thus etching residues may be present. When the amount is more than 10.0 wt%, the copper-based metal film may be excessively etched.
蝕刻劑組合物還包括選自由含氟化合物、唑類化合物和多元醇型表面活性劑組成的組中的一種或多種。蝕刻劑組合物還可以包括餘量的水。 The etchant composition further includes one or more selected from the group consisting of a fluorine-containing compound, an azole-based compound, and a polyol-type surfactant. The etchant composition may also include a balance of water.
蝕刻劑組合物中包括的過氧化氫(H2O2)是用於蝕刻銅基金屬膜的主要組分，起到增加含氟化合物的活性的作用。 Hydrogen peroxide (H 2 O 2 ) included in the etchant composition is a main component for etching a copper-based metal film, and plays a role of increasing the activity of a fluorine-containing compound.
基於蝕刻劑組合物的總重量，包含的過氧化氫(H2O2)的量是15.0~25.0wt%，優選18.0~23.0wt%。當過氧化氫的量小於15.0wt%時，銅基金屬膜不被蝕刻，或銅基金屬膜的蝕刻速率下降。當其量大於25.0wt%時，銅基金屬膜的蝕刻速率完全增加，因此難以控制該工藝。 Based on the total weight of the etchant composition, the amount of hydrogen peroxide (H 2 O 2 ) contained is 15.0 to 25.0 wt%, preferably 18.0 to 23.0 wt%. When the amount of hydrogen peroxide is less than 15.0 wt%, the copper-based metal film is not etched, or the etching rate of the copper-based metal film decreases. When the amount is more than 25.0 wt%, the etching rate of the copper-based metal film is completely increased, so it is difficult to control the process.
本發明的蝕刻劑組合物中包含的含氟化合物是在水中解離以產生氟離子的化合物。含氟化合物是用於蝕刻銅基金屬膜的主要組分，起到去除由鉬膜或鉬合金膜必然產生的殘餘渣滓的作用。 The fluorine-containing compound contained in the etchant composition of the present invention is a compound that dissociates in water to generate fluoride ions. The fluorine-containing compound is a main component for etching a copper-based metal film, and plays a role of removing residual scum necessarily generated by a molybdenum film or a molybdenum alloy film.
基於蝕刻劑組合物的總重量，包含的含氟化合物的量是0.01~1.0wt%，優選0.05~0.20wt%。當含氟化合物的量小於0.01wt%時，鉬膜或鉬合金膜的蝕刻速率下降，因此可能存在蝕刻殘渣。當其量大於1.0wt%時，存在玻璃基板的蝕刻速率增加的問題。 Based on the total weight of the etchant composition, the amount of the fluorine-containing compound contained is 0.01 to 1.0 wt%, preferably 0.05 to 0.20 wt%. When the amount of the fluorine-containing compound is less than 0.01% by weight, the etching rate of the molybdenum film or the molybdenum alloy film decreases, and thus etching residues may exist. When the amount is more than 1.0 wt%, there is a problem that the etching rate of the glass substrate increases.
只要含氟化合物能夠解離成氟離子或者多元氟離子，它就可以被用於相關領域中而沒有限制。然而，優選的是，含氟化合物是選自由氟化銨(NH4F)、氟化鈉(NaF)、氟化鉀(KF)、氟化氫銨(NH4F．HF)、氟氫化鈉(NaF．HF)和氟化氫鉀(KF．HF)組成的組中的至少一種。 As long as the fluorine-containing compound can dissociate into fluoride ion or polyfluoride ion, it can be used in related fields without limitation. However, it is preferable that the fluorine-containing compound is selected from the group consisting of ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium hydrogen fluoride (NH 4 F.HF), sodium fluorohydride (NaF HF) and potassium hydrogen fluoride (KF.HF).
本發明的蝕刻劑組合物中包含的唑類化合物起到控制銅基金 屬膜的蝕刻速率和減少圖案的CD損失的作用，因此增加了過程中的裕度(margin)。 The azole compound contained in the etchant composition of the present invention serves as a copper control fund The effect of the etch rate of the metal film and the reduction of the CD loss of the pattern, thus increasing the margin in the process.
基於蝕刻劑組合物的總重量，包含的唑類化合物的量是0.1~5.0wt%，優選0.3~1.0wt%。當唑類化合物的量小於0.1wt%時，銅基金屬膜的蝕刻速率快速增加，因此CD損失可能過度增大。當其量大於5.0wt%時，銅基金屬膜的蝕刻速率過度下降，因此可能存在蝕刻殘渣。優選的是，唑類化合物是選自由5-氨基***、3-氨基-1,2,4-***、4-氨基-4H-1,2,4-***、氨基四唑、苯並***、甲苯基***、吡唑、吡咯、咪唑、2-甲基咪唑、2-乙基咪唑、2-丙基咪唑、2-氨基咪唑、4-甲基咪唑、4-乙基咪唑和4-丙基咪唑組成的組中的至少一種。 Based on the total weight of the etchant composition, the amount of the contained azole compound is 0.1 to 5.0 wt%, preferably 0.3 to 1.0 wt%. When the amount of the azole-based compound is less than 0.1 wt%, the etching rate of the copper-based metal film rapidly increases, and thus the CD loss may increase excessively. When the amount thereof is more than 5.0 wt%, the etching rate of the copper-based metal film is excessively reduced, and thus etching residue may exist. Preferably, the azole compound is selected from the group consisting of 5-aminotriazole, 3-amino-1,2,4-triazole, 4-amino-4H-1,2,4-triazole, aminotetrazole, and benzo Triazole, tolyltriazole, pyrazole, pyrrole, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole, and At least one of the group consisting of 4-propylimidazole.
本發明的蝕刻劑組合物中包含的水並不特別限制，但是優選地，可以是去離子水。更優選地，水可以是電阻率(水中去除離子的程度)為18MΩ˙cm以上的去離子水。包含餘量的水，使得蝕刻劑組合物的總重量是100wt%。 The water contained in the etchant composition of the present invention is not particularly limited, but preferably, it may be deionized water. More preferably, the water may be deionized water having a resistivity (degree of removal of ions in water) of 18 MΩ˙cm or more. The balance of water was included so that the total weight of the etchant composition was 100% by weight.
同時，本發明的蝕刻劑組合物中包含的多元醇型表面活性劑通過降低表面張力起到提高蝕刻均勻性的作用。此外，通過包圍蝕刻銅膜之後的蝕刻劑中包含的銅離子以抑制銅離子的活性，多元醇型表面活性劑起到抑制過氧化氫的分解反應的作用。同樣地，當銅離子的活性降低時，在使用蝕刻劑期間可以使工藝穩定地前進。基於蝕刻劑組合物的總重量，包含的多元醇型表面活性劑的量是0.001~5.0wt%，優選0.1至3.0wt%。當多元醇型表面活性劑的量小於0.001wt%時，存在以下問題：蝕刻均勻性變差，而且過氧化氫的分解加速，因此當以預定量以上的量處理銅時發生放熱現象。當其量大於5.0wt%時，存在產生大量氣泡的問題。 At the same time, the polyol-type surfactant contained in the etchant composition of the present invention can improve the uniformity of etching by reducing the surface tension. In addition, by surrounding the copper ions contained in the etchant after the copper film is etched to suppress the activity of the copper ions, the polyol-type surfactant plays a role of suppressing the decomposition reaction of hydrogen peroxide. Likewise, when the activity of copper ions is reduced, the process can be stably advanced during the use of the etchant. The polyol surfactant is included in an amount of 0.001 to 5.0 wt%, preferably 0.1 to 3.0 wt%, based on the total weight of the etchant composition. When the amount of the polyol-type surfactant is less than 0.001 wt%, there are problems in that the etching uniformity is deteriorated, and the decomposition of hydrogen peroxide is accelerated, so an exothermic phenomenon occurs when copper is processed in an amount of more than a predetermined amount. When the amount is more than 5.0 wt%, there is a problem that a large number of bubbles are generated.
多元醇型表面活性劑可以選自由甘油、三乙二醇和聚乙二醇組成的組。優選地，多元醇型表面活性劑可以是三乙二醇。 The polyol-type surfactant may be selected from the group consisting of glycerin, triethylene glycol, and polyethylene glycol. Preferably, the polyol-type surfactant may be triethylene glycol.
本發明中使用的各組分可以通過習知方法來製備。優選的 是，本發明的蝕刻劑組合物具有足以用於半導體工藝的純度。 Each component used in the present invention can be prepared by a conventional method. Preferred Yes, the etchant composition of the present invention has a purity sufficient for a semiconductor process.
2、製造液晶顯示器用陣列基板的方法 2. Method for manufacturing array substrate for liquid crystal display
根據本發明的製造液晶顯示器用陣列基板的方法包括以下步驟：a)在基板上形成閘電極；b)在包括所述閘電極的基板上形成閘絕緣層；c)在所述閘絕緣層上形成半導體層(n+a-Si：H和a-Si：H)；d)在所述半導體層上形成源電極/汲電極；以及e)形成與所述汲電極連接的畫素電極，其中，步驟a)或d)包括步驟：在基板上形成銅基金屬膜，然後使用蝕刻劑組合物來蝕刻銅基金屬膜以形成閘電極線或源電極和汲電極。液晶顯示器用陣列基板可以是TFT陣列基板。 The method for manufacturing an array substrate for a liquid crystal display according to the present invention includes the following steps: a) forming a gate electrode on a substrate; b) forming a gate insulating layer on a substrate including the gate electrode; c) on the gate insulating layer Forming a semiconductor layer (n + a-Si: H and a-Si: H); d) forming a source electrode / drain electrode on the semiconductor layer; and e) forming a pixel electrode connected to the drain electrode, wherein Step a) or step d) includes the steps of: forming a copper-based metal film on the substrate, and then using an etchant composition to etch the copper-based metal film to form a gate electrode line or a source electrode and a drain electrode. The array substrate for a liquid crystal display may be a TFT array substrate.
在下文中，參照下面的實施例和比較例對本發明進行更詳細的描述。然而，這些實施例和比較例被提出以闡述本發明，而且本發明的範圍並不局限於此。 Hereinafter, the present invention is described in more detail with reference to the following examples and comparative examples. However, these examples and comparative examples are proposed to illustrate the present invention, and the scope of the present invention is not limited thereto.
(蝕刻劑組合物的製備及其性能評估1) (Preparation of Etchant Composition and Performance Evaluation 1)
實施例1-1至1-4和比較例1-1至1-4：蝕刻劑組合物的製備 Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4: Preparation of Etchant Composition
如下面的表1中所給出的，製備180kg的實施例1-1至1-4和比較例1-1至1-4的蝕刻劑組合物。 As given in Table 1 below, 180 kg of the etchant compositions of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4 were prepared.
※含氟化合物：氟化氫銨(NH4F．HF) ※ Fluorine compound: Ammonium hydrogen fluoride (NH 4 F.HF)
※唑類化合物：3-氨基-1,2,4-*** ※ azole compounds: 3-amino-1,2,4-triazole
※IDA：亞氨基二乙酸 ※ IDA: iminodiacetic acid
※NTA：次氮基三乙酸 ※ NTA: nitrilotriacetic acid
測試例：蝕刻劑組合物的性能評估 Test example: performance evaluation of the etchant composition
<Cu/MoTi蝕刻> <Cu / MoTi etching>
將MoTi沉積在玻璃基板(100mm×100mm)上，將銅膜沉積在MoTi上，然後通過光刻工藝使具有預定圖案的光致抗蝕劑形成在玻璃基板上。此後，使用實施例1-1至1-4和比較例1-1至1-4的各個蝕刻劑組合物來進行Cu/MoTi的蝕刻工藝。 MoTi was deposited on a glass substrate (100 mm × 100 mm), a copper film was deposited on MoTi, and a photoresist having a predetermined pattern was formed on the glass substrate by a photolithography process. Thereafter, each of the etchant compositions of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4 was used to perform a Cu / MoTi etching process.
使用注射型蝕刻裝置(型號名稱：ETCHER(TFT)(蝕刻機(TFT))，由SEMES公司製造)來進行蝕刻工藝。在蝕刻工藝中，蝕刻劑組合物的溫度被設置為約30℃，蝕刻時間被設置為100~300秒。使用SEM(型號名稱：S-4700，由日立公司製造)來檢查在蝕刻工藝期間所蝕刻的銅基金屬膜的輪廓，並在下面的表2中示出了其結果。 The etching process was performed using an injection-type etching apparatus (model name: ETCHER (TFT) (etching machine (TFT)), manufactured by SEMES). In the etching process, the temperature of the etchant composition is set to about 30 ° C, and the etching time is set to 100 to 300 seconds. The SEM (model name: S-4700, manufactured by Hitachi) was used to check the outline of the copper-based metal film etched during the etching process, and the results are shown in Table 2 below.
<被加工片材的數量的評估> <Evaluation of the number of processed sheets>
由實施例1-1至1-4和比較例1-1至1-4的各個蝕刻劑組合物製備了10升的十五等份試樣。然後，從10g到80g(以5g為增量)將銅粉添加到各個蝕刻劑組合物中，然後在預定時間內觀察各個蝕刻劑組合物的溫度變化。即使在預定時間已過去之後放熱反應也沒發生時所測得的蝕刻劑組合物的最大濃度被定義為蝕刻劑組合物的被加工片材的數量。 Fifteen aliquots of 10 liters were prepared from each of the etchant compositions of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4. Then, copper powder was added to each etchant composition from 10 g to 80 g (in 5 g increments), and then the temperature change of each etchant composition was observed for a predetermined time. The maximum concentration of the etchant composition measured when an exothermic reaction does not occur even after a predetermined time has elapsed is defined as the number of processed sheets of the etchant composition.
在下面的表2中示出了其評估結果。 The evaluation results are shown in Table 2 below.
<貯存30天後，被加工片材的數量的評估> <Evaluation of the number of processed sheets after 30 days of storage>
由實施例1-1至1-4和比較例1-1至1-4的各個蝕刻劑組合物製備了10升的十五等份試樣。隨後，將各個所提供的蝕刻劑組合物在室溫下貯存30天，從10g到80g(以5g為增量)將銅粉添加到其中，然後在預定時間內觀察各個蝕刻劑組合物的溫度變化。即使 在預定時間已過去之後放熱反應也沒發生時所測得的蝕刻劑組合物的最大濃度被定義為貯存30天後的蝕刻劑組合物的被加工片材的數量。在下面的表2中示出了評估結果。 Fifteen aliquots of 10 liters were prepared from each of the etchant compositions of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4. Subsequently, each provided etchant composition was stored at room temperature for 30 days, and copper powder was added thereto from 10 g to 80 g (in 5 g increments), and then the temperature of each etchant composition was observed for a predetermined time. Variety. even if The maximum concentration of the etchant composition measured when an exothermic reaction did not occur after a predetermined time has elapsed is defined as the number of processed sheets of the etchant composition after 30 days of storage. The evaluation results are shown in Table 2 below.
<蝕刻輪廓的評估標準> <Evaluation Criteria for Etching Profile>
○：錐角為35°以上至小於60° ○: Taper angle is 35 ° or more and less than 60 °
△：錐角為30°以上至小於35°或60°至65° △: Taper angle is 30 ° or more to less than 35 ° or 60 ° to 65 °
X：錐角為30°以下或大於65° X: Taper angle is below 30 ° or greater than 65 °
未蝕刻：未被蝕刻 Unetched: Not etched
<蝕刻線性的評估標準> <Evaluation Criteria for Etching Linearity>
○：以直線形成圖案 ○: Pattern is formed in a straight line
△：以比率為20%以下的曲線形成圖案 △: Pattern is formed by a curve with a ratio of 20% or less
X：以比率大於20%的曲線形成圖案 X: pattern is formed in a curve with a ratio greater than 20%
未蝕刻：未被蝕刻 Unetched: Not etched
參照上面的表2，能夠確定的是，實施例1-1至1-4的所有蝕刻劑組合物都表現出了良好的蝕刻性能。此外，能夠確定的是，在蝕刻銅基金屬膜時，實施例1-1至1-4的蝕刻劑組合物增加了銅基金屬膜的被加工片材的數量；而且，在它們被貯存30天之後，其隨時間推移的自分解沒有發生。 Referring to Table 2 above, it can be confirmed that all the etchant compositions of Examples 1-1 to 1-4 exhibit good etching performance. In addition, it can be confirmed that the etchant compositions of Examples 1-1 to 1-4 increase the number of processed sheets of the copper-based metal film when the copper-based metal film is etched; moreover, they are stored 30 After days, its self-decomposition did not occur over time.
相比之下，能夠確定的是，在銅基金屬膜的蝕刻中，雖然含有作為有機酸的乙醇酸的比較例1-1的蝕刻劑組合物表現出了良好的基本的蝕刻性能；但無助於增加銅基金屬膜的被加工片材的數量。 In contrast, it can be confirmed that, in the etching of a copper-based metal film, although the etchant composition of Comparative Example 1-1 containing glycolic acid as an organic acid exhibited good basic etching performance; Helps increase the number of processed sheets of copper-based metal films.
相比之下，能夠確定的是，在銅基金屬膜的蝕刻中，雖然含有作為有機酸的乙醇酸的比較例1-2的蝕刻劑組合物表現出了良好的基本的蝕刻性能；但在它被貯存30天之後，由於乙醇酸隨時間推移的自分解，銅基金屬膜的被加工片材的數量顯著下降。 In contrast, it can be confirmed that, in the etching of a copper-based metal film, although the etchant composition of Comparative Example 1-2 containing glycolic acid as an organic acid exhibited good basic etching performance; After it was stored for 30 days, the number of processed sheets of copper-based metal films decreased significantly due to the self-decomposition of glycolic acid over time.
此外，能夠確定的是，雖然在蝕刻銅基金屬膜的過程中，含有IDA作為用於增加被加工片材的數量的改進劑的比較例1-3和1-4的蝕刻劑組合物表現出了良好的基本的蝕刻性能並且增加了被加工片材的數量；但在它們被貯存30天之後，由於IDA隨時間推移的自分解，銅基金屬膜的被加工片材的數量顯著降低。 In addition, it can be confirmed that although the etchant compositions of Comparative Examples 1-3 and 1-4 containing IDA as an improver for increasing the number of sheets to be processed showed in the process of etching the copper-based metal film, Good basic etching properties were increased and the number of processed sheets was increased; but after they were stored for 30 days, the number of processed sheets of copper-based metal films was significantly reduced due to the self-decomposition of IDA over time.
(蝕刻劑組合物的製備及其性能評估2) (Preparation of Etchant Composition and Performance Evaluation 2)
實施例2-1至2-4和比較例2-1至2-3：蝕刻劑組合物的製備 Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3: Preparation of Etchant Composition
如下面的表3中所給出的，製備180kg的實施例2-1至2-4和比較例2-1至2-3的蝕刻劑組合物。 As given in Table 3 below, 180 kg of the etchant compositions of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3 were prepared.
※含氟化合物：氟化氫銨(NH4F．HF) ※ Fluorine compound: Ammonium hydrogen fluoride (NH 4 F.HF)
※唑類化合物：3-氨基-1,2,4-*** ※ azole compounds: 3-amino-1,2,4-triazole
※TEG：三乙二醇 ※ TEG: Triethylene glycol
※IDA：亞氨基二乙酸 ※ IDA: iminodiacetic acid
測試例：蝕刻劑組合物的性能評估 Test example: performance evaluation of the etchant composition
<Cu/MoTi蝕刻> <Cu / MoTi etching>
將MoTi沉積在玻璃基板(100mm×100mm)上，將銅膜沉積在MoTi上，然後通過光刻工藝使具有預定圖案的光致抗蝕劑形成在玻璃基板上。此後，使用實施例2-1至2-4和比較例2-1至2-3的各個蝕刻劑組合物來進行Cu/MoTi的蝕刻工藝。 MoTi was deposited on a glass substrate (100 mm × 100 mm), a copper film was deposited on MoTi, and then a photoresist having a predetermined pattern was formed on the glass substrate by a photolithography process. Thereafter, each of the etchant compositions of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3 was used to perform a Cu / MoTi etching process.
使用注射型蝕刻裝置(型號名稱：ETCHER(TFT)(蝕刻機(TFT))，由SEMES公司製造)來進行蝕刻工藝。在蝕刻工藝中，蝕刻劑組合物的溫度被設置為約30℃，蝕刻時間被設置為100~300秒。使用SEM(型號名稱：S-4700，由日立公司製造)來檢查在蝕刻工藝期間所蝕刻的銅基金屬膜的輪廓，並在下面的表4中示出了其結果。 The etching process was performed using an injection-type etching apparatus (model name: ETCHER (TFT) (etching machine (TFT)), manufactured by SEMES). In the etching process, the temperature of the etchant composition is set to about 30 ° C, and the etching time is set to 100 to 300 seconds. The SEM (model name: S-4700, manufactured by Hitachi) was used to check the outline of the copper-based metal film etched during the etching process, and the results are shown in Table 4 below.
<被加工片材的數量評估> <Assessment of the number of processed sheets>
由實施例2-1至2-4和比較例2-1至2-3的各個蝕刻劑組合物製備了10升的十五等份試樣。然後，從10g到80g(以5g為增量)將銅粉添加到各個蝕刻劑組合物中，然後在預定時間內觀察各個蝕刻劑組合物的溫度變化。即使在預定時間已過去之後放熱反應也沒發生時所測得的蝕刻劑組合物的最大濃度被定義為蝕刻劑組合物的被加工片材的數量。 Fifteen aliquots of 10 liters were prepared from each of the etchant compositions of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3. Then, copper powder was added to each etchant composition from 10 g to 80 g (in 5 g increments), and then the temperature change of each etchant composition was observed for a predetermined time. The maximum concentration of the etchant composition measured when an exothermic reaction does not occur even after a predetermined time has elapsed is defined as the number of processed sheets of the etchant composition.
在下面的表4中示出了其評估結果。 The evaluation results are shown in Table 4 below.
<貯存30天後，被加工片材的數量評估> <Assessment of the number of processed sheets after 30 days of storage>
由實施例2-1至2-4和比較例2-1至2-3的各個蝕刻劑組合物製備了10升的十五等份試樣。隨後，將各個所提供的蝕刻劑組合物在室溫下貯存30天，從10g到80g(以5g為增量)將銅粉添加到其中，然後在預定時間內觀察各個蝕刻劑組合物的溫度變化。即使在預定時間已過去之後放熱反應也沒發生時所測得的蝕刻劑組合 物的最大濃度被定義為貯存30天後的蝕刻劑組合物的被加工片材的數量。 Fifteen aliquots of 10 liters were prepared from each of the etchant compositions of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3. Subsequently, each provided etchant composition was stored at room temperature for 30 days, and copper powder was added thereto from 10 g to 80 g (in 5 g increments), and then the temperature of each etchant composition was observed for a predetermined time. Variety. Etchant combination measured when an exothermic reaction does not occur even after a predetermined time has elapsed The maximum concentration of an object is defined as the number of processed sheets of the etchant composition after 30 days of storage.
在下面的表4中示出了其評估結果。 The evaluation results are shown in Table 4 below.
<貯存穩定性的評估> <Evaluation of storage stability>
以10L的量製備了實施例2-1至2-4和比較例2-1至2-3的各個蝕刻劑組合物。隨後，將各個所製備的蝕刻劑組合物在室溫下貯存30天，將50g的銅粉添加到其中，然後觀察每個蝕刻劑組合物的溫度變化。 Each of the etchant compositions of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3 was prepared in an amount of 10 L. Subsequently, each of the prepared etchant compositions was stored at room temperature for 30 days, 50 g of copper powder was added thereto, and then the temperature change of each etchant composition was observed.
在下面的表4中示出了其評估結果。 The evaluation results are shown in Table 4 below.
<蝕刻輪廓的評估標準> <Evaluation Criteria for Etching Profile>
○：錐角為35°以上至小於60° ○: Taper angle is 35 ° or more and less than 60 °
△：錐角為30°以上至小於35°或60°至65° △: Taper angle is 30 ° or more to less than 35 ° or 60 ° to 65 °
X：錐角為30°以下或大於65° X: Taper angle is below 30 ° or greater than 65 °
未蝕刻：未被蝕刻 Unetched: Not etched
<蝕刻線性的評估標準> <Evaluation Criteria for Etching Linearity>
○：以直線形成圖案 ○: Pattern is formed in a straight line
△：以比率為20%以下的曲線形成圖案 △: Pattern is formed by a curve with a ratio of 20% or less
X：以比率大於20%的曲線形成圖案 X: pattern is formed in a curve with a ratio greater than 20%
未蝕刻：未被蝕刻 Unetched: Not etched
參照上面的表4，能夠確定的是，實施例2-1至2-4的所有蝕刻劑組合物都表現出了良好的蝕刻性能。此外，能夠確定的是，相互比較實施例2-1至2-4的蝕刻劑組合物，被加工片材的數量隨著多元醇型表面活性劑的量的增加而增加。具體地，能夠確定的是，在蝕刻銅基金屬膜時，含有多元醇型表面活性劑的實施例2-1至2-4的蝕刻劑組合物增加了銅基金屬膜的被加工片材的數量；而且，在它們被貯存30天之後，其隨時間推移的自分解沒有發生。 Referring to Table 4 above, it can be confirmed that all the etchant compositions of Examples 2-1 to 2-4 showed good etching performance. In addition, it can be confirmed that, when the etchant compositions of Examples 2-1 to 2-4 are compared with each other, the number of processed sheets increases as the amount of the polyol-type surfactant increases. Specifically, it can be determined that, when the copper-based metal film is etched, the etchant compositions of Examples 2-1 to 2-4 containing a polyol-based surfactant increase the Quantity; moreover, their self-decomposition did not occur over time after they were stored for 30 days.
相比之下，能夠確定的是，雖然在蝕刻銅基金屬膜的過程中，含有乙醇酸而不是檸檬酸的比較例1-1的蝕刻劑組合物表現出了良好的基本的蝕刻性能；但無助於增加銅基金屬膜的被加工片材的數量。 In contrast, it can be confirmed that although the etchant composition of Comparative Example 1-1 containing glycolic acid instead of citric acid exhibited good basic etching performance during the etching of the copper-based metal film; It does not help to increase the number of processed sheets of the copper-based metal film.
此外，能夠確定的是，雖然含有IDA作為用於增加被加工片材的數量的改進劑的比較例2-1的蝕刻劑組合物表現出了良好的基本的蝕刻性能，但在它被貯存30天之後，由於IDA隨時間推移的自分解，銅基金屬膜的被加工片材的數量顯著減少。 In addition, it can be confirmed that although the etchant composition of Comparative Example 2-1 containing IDA as an improver for increasing the number of processed sheets showed good basic etching performance, it was stored at 30 After several days, the number of processed sheets of the copper-based metal film was significantly reduced due to the self-decomposition of IDA over time.
此外，能夠確定的是，對比較例2-3的蝕刻劑組合物與實施例2-1的蝕刻劑組合物進行比較，因為比較例2-3的蝕刻劑組合物不含有多元醇型表面活性劑，所以它對於增加被加工片材的數量是無效的。因此，能夠確定的是，多元醇型表面活性劑有效地增加了銅(Cu)基金屬膜的被加工片材的數量。 In addition, it can be confirmed that the etchant composition of Comparative Example 2-3 is compared with the etchant composition of Example 2-1 because the etchant composition of Comparative Example 2-3 does not contain a polyol-type surface activity Agent, so it is not effective for increasing the number of processed sheets. Therefore, it can be confirmed that the polyol-type surfactant effectively increased the number of processed sheets of the copper (Cu) -based metal film.
此外，能夠確定的是，在實施例2-1至2-4的蝕刻劑組合物的情況中，即使當它們被貯存30天，然後將5000ppm的銅(Cu)添加到其中時，它們的溫度保持在初始溫度28~31℃，因此它們的放熱穩定性非常優異。 Further, it can be determined that, in the case of the etchant compositions of Examples 2-1 to 2-4, even when they were stored for 30 days, and then 5000 ppm of copper (Cu) was added thereto, their temperatures They are maintained at an initial temperature of 28 to 31 ° C, so their exothermic stability is excellent.
相比之下，能夠確定的是，因為貯存30天的比較例2-1的蝕刻劑組合物的銅蝕刻能力小於700ppm，所以當以5000ppm的量添加銅時，銅不能被融化。 In contrast, it can be confirmed that since the copper etching ability of the etchant composition of Comparative Example 2-1 stored for 30 days is less than 700 ppm, when copper is added in an amount of 5000 ppm, the copper cannot be melted.
在比較例2-2的蝕刻劑組合物的情況中，IDA存在於該蝕刻劑 組合物中，但在其中分解。因此，該蝕刻劑組合物不含有用於捕捉銅離子的額外組分，因此添加的銅離子與過氧化氫反應引起了放熱。 In the case of the etchant composition of Comparative Example 2-2, IDA is present in the etchant In the composition, but decomposed therein. Therefore, the etchant composition does not contain an additional component for capturing copper ions, and thus the added copper ions react with hydrogen peroxide to cause an exotherm.
能夠確定的是，雖然比較例2-3的蝕刻劑組合物含有檸檬酸，但它不含有多元醇型表面活性劑，因此其貯存穩定性變差。 It can be confirmed that, although the etchant composition of Comparative Example 2-3 contains citric acid, it does not contain a polyol-type surfactant, and therefore its storage stability is deteriorated.
(蝕刻劑組合物的製備及其性能評估3) (Preparation of Etchant Composition and Performance Evaluation 3)
實施例3-1至3-5和比較例3-1至3-3：蝕刻劑組合物的製備 Examples 3-1 to 3-5 and Comparative Examples 3-1 to 3-3: Preparation of Etchant Composition
如下面的表5中所給出的，製備180kg的實施例3-1至3-5和比較例3-1至3-3的蝕刻劑組合物。 As given in Table 5 below, 180 kg of the etchant compositions of Examples 3-1 to 3-5 and Comparative Examples 3-1 to 3-3 were prepared.
※含氟化合物：氟化氫銨(NH4F．HF) ※ Fluorine compound: Ammonium hydrogen fluoride (NH 4 F.HF)
※唑類化合物：3-氨基-1,2,4-*** ※ azole compounds: 3-amino-1,2,4-triazole
※多元醇型表面活性劑：三乙二醇 ※ Polyol type surfactant: Triethylene glycol
※IDA：亞氨基二乙酸 ※ IDA: iminodiacetic acid
※磷酸鹽：磷酸二氫鈉 ※ Phosphate: Sodium dihydrogen phosphate
測試例：評估蝕刻劑組合物的性能 Test example: Evaluation of the performance of the etchant composition
<MoTi/Cu/MoTi蝕刻> <MoTi / Cu / MoTi etching>
將MoTi沉積在玻璃基板(100mm×100mm)上，將銅膜沉積在MoTi上，然後通過光刻工藝使具有預定圖案的光致抗蝕劑形成在 玻璃基板上。此後，使用實施例3-1至3-5和比較例3-1至3-3的各個蝕刻劑組合物來進行三層膜(MoTi/Cu/MoTi)的蝕刻工藝。 MoTi is deposited on a glass substrate (100mm × 100mm), a copper film is deposited on MoTi, and a photoresist having a predetermined pattern is formed on the substrate by a photolithography process. On a glass substrate. Thereafter, each of the etchant compositions of Examples 3-1 to 3-5 and Comparative Examples 3-1 to 3-3 was used to perform an etching process of a three-layer film (MoTi / Cu / MoTi).
使用注射型蝕刻裝置(型號名稱：ETCHER(TFT)(蝕刻機(TFT))，由SEMES公司製造)來進行蝕刻工藝。在蝕刻工藝中，蝕刻劑組合物的溫度被設置為約30℃，蝕刻時間被設置為100~300秒。使用SEM(型號名稱：S-4700，由日立公司製造)來檢查在蝕刻工藝期間所蝕刻銅基金屬膜的輪廓，並在下面的表6中示出了其結果。 The etching process was performed using an injection-type etching apparatus (model name: ETCHER (TFT) (etching machine (TFT)), manufactured by SEMES). In the etching process, the temperature of the etchant composition is set to about 30 ° C, and the etching time is set to 100 to 300 seconds. The SEM (model name: S-4700, manufactured by Hitachi) was used to check the outline of the copper-based metal film etched during the etching process, and the results are shown in Table 6 below.
<被加工片材的數量的評估> <Evaluation of the number of processed sheets>
由實施例3-1至3-5和比較例3-1至3-3的各個蝕刻劑組合物製備了10升的十五等份試樣。然後，從10g到80g(以5g為增量)將銅粉添加到各個蝕刻劑組合物中，然後在預定時間內觀察各個蝕刻劑組合物的溫度變化。即使在預定時間已過去之後放熱反應也沒發生時所測得的蝕刻劑組合物的最大濃度被定義為蝕刻劑組合物的被加工片材的數量。 Fifteen aliquots of 10 liters were prepared from each of the etchant compositions of Examples 3-1 to 3-5 and Comparative Examples 3-1 to 3-3. Then, copper powder was added to each etchant composition from 10 g to 80 g (in 5 g increments), and then the temperature change of each etchant composition was observed for a predetermined time. The maximum concentration of the etchant composition measured when an exothermic reaction does not occur even after a predetermined time has elapsed is defined as the number of processed sheets of the etchant composition.
在下面的表6中示出了其評估結果。 The evaluation results are shown in Table 6 below.
<貯存30天後，被加工片材的數量的評估> <Evaluation of the number of processed sheets after 30 days of storage>
由實施例3-1至3-5和比較例3-1至3-3的各個蝕刻劑組合物製備了10升的十五等份試樣。隨後，將各個所提供的蝕刻劑組合物在室溫下貯存30天，從10g到80g(以5g為增量)將銅粉添加到其中，然後在預定時間內觀察各個蝕刻劑組合物的溫度變化。即使在預定時間已過去之後放熱反應也沒發生時所測得的蝕刻劑組合物的最大濃度被定義為貯存30天後的蝕刻劑組合物的被加工片材的數量。 Fifteen aliquots of 10 liters were prepared from each of the etchant compositions of Examples 3-1 to 3-5 and Comparative Examples 3-1 to 3-3. Subsequently, each provided etchant composition was stored at room temperature for 30 days, and copper powder was added thereto from 10 g to 80 g (in 5 g increments), and then the temperature of each etchant composition was observed for a predetermined time. Variety. The maximum concentration of the etchant composition measured when an exothermic reaction did not occur even after a predetermined time has elapsed is defined as the number of processed sheets of the etchant composition after 30 days of storage.
在下面的表6中示出了其評估結果。 The evaluation results are shown in Table 6 below.
<蝕刻輪廓的評估標準> <Evaluation Criteria for Etching Profile>
Cu/MoTi層 Cu / MoTi layer
○：錐角為35°以上至小於60° ○: Taper angle is 35 ° or more and less than 60 °
△：錐角為30°以上至小於35°或60°至65° △: Taper angle is 30 ° or more to less than 35 ° or 60 ° to 65 °
X：錐角為30°以下或大於65° X: Taper angle is below 30 ° or greater than 65 °
未蝕刻：未被蝕刻 Unetched: Not etched
MoTi/Cu/MoTi層 MoTi / Cu / MoTi layer
○：錐角為30°以上至小於45° ○: Taper angle is 30 ° or more and less than 45 °
△：錐角為20°以上至小於30°或45°至65° △: Cone angle is 20 ° or more to less than 30 ° or 45 ° to 65 °
X：錐角為20°以下或大於65° X: Taper angle is 20 ° or less or more than 65 °
未蝕刻：未被蝕刻 Unetched: Not etched
<蝕刻線性的評估標準> <Evaluation Criteria for Etching Linearity>
○：以直線形成圖案 ○: Pattern is formed in a straight line
△：以比率為20%以下的曲線形成圖案 △: Pattern is formed by a curve with a ratio of 20% or less
X：以比率大於20%的曲線形成圖案 X: pattern is formed in a curve with a ratio greater than 20%
未蝕刻：未被蝕刻 Unetched: Not etched
<上部MoTi尖端的評估標準> <Evaluation criteria for the upper MoTi tip>
○：MoTi尖端為0.00(μm)以上~小於0.03(μm) ○: MoTi tip is 0.00 (μm) or more to less than 0.03 (μm)
△：MoTi尖端為0.03(μm)以上~小於0.10(μm) △: MoTi tip is 0.03 (μm) or more to less than 0.10 (μm)
X：MoTi尖端為0.10(μm)以上 X: MoTi tip is 0.10 (μm) or more
未蝕刻：未被蝕刻 Unetched: Not etched
參照上面的表6，能夠確定的是，實施例3-1至3-5的所有蝕刻劑組合物都表現出了良好的蝕刻性能。此外，能夠確定的是，相互比較實施例3-1至3-5的蝕刻劑組合物，被加工片材的數量隨著檸檬酸的量的增加而增加。此外，能夠確定的是，比較實施例3-4的蝕刻劑組合物與實施例3-5的蝕刻劑組合物，當添加多元醇型表面活性劑時，被加工片材的數量增加。具體地，能夠確定的是，在蝕刻銅基金屬膜時，含有多元醇型表面活性劑的實施例3-1至3-5的蝕刻劑組合物增加了銅基金屬膜的加工片的數目；而且，在它們被貯存30天之後，其隨時間推移的自分解沒有發生。此外，由實施例3-1至3-5能夠確定的是，在三層膜(MoTi/Cu/MoTi)的蝕刻中，檸檬酸是用於控制MoTi尖端和保持45°以下的蝕刻輪廓所需的必需成分。 Referring to Table 6 above, it can be confirmed that all the etchant compositions of Examples 3-1 to 3-5 showed good etching performance. In addition, it can be confirmed that, when the etchant compositions of Examples 3-1 to 3-5 are compared with each other, the number of processed sheets increases as the amount of citric acid increases. In addition, it can be confirmed that when the etchant composition of Example 3-4 is compared with the etchant composition of Example 3-5, when a polyol-type surfactant is added, the number of sheets to be processed increases. Specifically, it can be determined that, when the copper-based metal film is etched, the etchant composition of Examples 3-1 to 3-5 containing a polyol-type surfactant increases the number of processed pieces of the copper-based metal film; Moreover, after they were stored for 30 days, their self-decomposition did not occur over time. In addition, it can be determined from Examples 3-1 to 3-5 that, in the etching of a three-layer film (MoTi / Cu / MoTi), citric acid is required to control the MoTi tip and maintain the etching profile below 45 ° Essential ingredients.
相比之下，能夠確定的是，雖然在銅基金屬膜的蝕刻中，含有作為有機酸的乙醇酸(GA)的比較例3-1的蝕刻劑組合物表現出了良好的基本的蝕刻性能；但無助於增加銅基金屬膜的被加工片材的數量；而且，在三層膜(MoTi/Cu/MoTi)的蝕刻中，其蝕刻輪廓和蝕刻線性不好。 In contrast, it can be confirmed that although in the etching of a copper-based metal film, the etchant composition of Comparative Example 3-1 containing glycolic acid (GA) as an organic acid exhibited good basic etching performance However, it does not help to increase the number of processed sheets of the copper-based metal film; moreover, in the etching of a three-layer film (MoTi / Cu / MoTi), its etching contour and etching linearity are not good.
此外，能夠確定的是，雖然在蝕刻銅基金屬膜的過程中，含 有作為有機酸的乙醇酸的比較例3-2的蝕刻劑組合物表現出了良好的基本的蝕刻性能；但在它被貯存30天之後，由於其隨時間推移的自分解，銅基金屬膜的被加工片材的數量顯著減少。 In addition, it can be confirmed that although the process of etching the copper-based metal film contains The etchant composition of Comparative Example 3-2 with glycolic acid as an organic acid exhibited good basic etching properties; but after it was stored for 30 days, the copper-based metal film due to its self-decomposition over time The number of processed sheets is significantly reduced.
此外，能夠確定的是，雖然含有IDA作為用於增加被加工片材的數量的改進劑的比較例3-3的蝕刻劑組合物表現出了良好的基本的蝕刻性能；但在它們被貯存30天之後，由於其隨時間推移的自分解，銅基金屬膜的被加工片材的數量顯著減少；而且，在三層膜(MoTi/Cu/MoTi)的蝕刻中，其蝕刻輪廓和蝕刻線性不好。 In addition, it can be confirmed that although the etchant composition of Comparative Example 3-3 containing IDA as an improver for increasing the number of processed sheets showed good basic etching performance; After several days, due to its self-decomposition over time, the number of processed sheets of the copper-based metal film was significantly reduced; moreover, in the etching of a three-layer film (MoTi / Cu / MoTi), its etch profile and etch linearity were it is good.
如上所述，根據本發明的銅基金屬膜的蝕刻劑組合物的優點在於：這種蝕刻劑組合物含有作為用於增加被加工片材的數量的改進劑的檸檬酸，因此通過蝕刻被加工片材的數量顯著增加，並且，特別地，即使在它被貯存30天以上的長時間之後，它仍然表現出在通過蝕刻被加工片材的數量方面上的優異效果，從而顯著地提高貯存穩定性。此外，這種蝕刻劑組合物的優點在於：其放熱穩定性顯著提高，而且其對諸如MoTi/Cu/MoTi膜等的三層銅基金屬膜的蝕刻性能非常優異。 As described above, the etchant composition of the copper-based metal film according to the present invention is advantageous in that this etchant composition contains citric acid as an improver for increasing the number of sheets to be processed, and is therefore processed by etching. The number of sheets is significantly increased, and, in particular, even after it is stored for a long time of more than 30 days, it still shows an excellent effect in terms of the number of sheets processed by etching, thereby significantly improving storage stability. Sex. In addition, such an etchant composition is advantageous in that its exothermic stability is remarkably improved, and its etching performance on a three-layer copper-based metal film such as a MoTi / Cu / MoTi film is very excellent.
雖然已經公開了本發明的優選實施方式用於說明目的，但該發明所屬技術領域中具有通常知識者將理解的是，各種修改、添加和替換是可能的，而不背離如在所附申請專利範圍中所公開的本發明的範圍和精神。 Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those with ordinary knowledge in the technical field to which this invention belongs will understand that various modifications, additions and substitutions are possible without departing from the patents as attached The scope and spirit of the present invention disclosed in the scope.
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Also Published As
| Publication number | Publication date |
|---|---|
| CN110147008A (en) | 2019-08-20 |
| CN104280916A (en) | 2015-01-14 |
| TW201503331A (en) | 2015-01-16 |
| CN110147008B (en) | 2022-03-22 |
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