TW201441347A - Etching solution, replenishing solution and wiring forming method - Google Patents
Etching solution, replenishing solution and wiring forming method Download PDFInfo
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/067—Etchants
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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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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0338—Layered conductor, e.g. layered metal substrate, layered finish layer, layered thin film adhesion layer
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Abstract
Description
本發明係與蝕刻液、補充液及配線形成方法有關者。 The present invention relates to an etching solution, a replenishing liquid, and a wiring forming method.
於電子裝置中所使用的觸控面板式的顯示裝置，具有顯示的區域和該顯示區域周圍的邊框區域。前述邊框區域，為了連接檢出觸控位置的電路，形成從顯示區域引出的複數配線。 A touch panel type display device used in an electronic device has a display area and a frame area around the display area. In the frame region, a plurality of wires drawn from the display region are formed in order to connect the circuit for detecting the touch position.
形成前述邊框區域的配線之方法，例如下述專利文獻1所揭露的，在包含金屬氧化物的電極層之上面，塗布銀漿(Silver paste)來形成配線的方法。但是，近年來，為了因應智慧型手機以及平板終端(tablet terminator)等小型高性能所需求的終端顯示裝置，要求降低配線材料的電阻值。在此，檢討使用比銀漿電阻低的銅為配線材料。 A method of forming a wiring of the frame region is, for example, a method of forming a wiring by applying a silver paste on an electrode layer containing a metal oxide as disclosed in Patent Document 1 below. However, in recent years, in order to respond to small-sized high-performance terminal devices such as smart phones and tablet terminators, it is required to reduce the resistance value of wiring materials. Here, it is reviewed that copper having a lower resistance than the silver paste is used as the wiring material.
使用銅為配線材料來形成前述邊框區域的配線之方法，檢討在包含金屬氧化物的電極層上形成銅層，按順序執 行前述銅層的圖案化與前述電極層的圖案化的方法。此一方法，首先，使用將銅溶解的蝕刻液，對電極層上的銅層蝕刻形成銅配線圖案後，使用不溶解銅，而溶解金屬氧化物的蝕刻液，來蝕刻在銅配線圖案間透出的電極層(金屬氧化物層)，而形成包含圖案化的電極層以及銅配線圖案的積層配線圖案的方法。 A method of forming wiring of the aforementioned frame region using copper as a wiring material, and reviewing formation of a copper layer on an electrode layer containing a metal oxide, in order A method of patterning the copper layer and patterning the electrode layer. In this method, first, an etching solution for dissolving copper is used, and a copper wiring pattern is formed on the electrode layer to form a copper wiring pattern, and then an etching solution in which metal oxide is dissolved without dissolving copper is used to etch the copper wiring pattern. A method of forming an electrode layer (metal oxide layer) to form a laminated wiring pattern including a patterned electrode layer and a copper wiring pattern.
然而，前述之方法，在銅層之蝕刻上使用的蝕刻液，與在電極層的蝕刻上使用的蝕刻液的2種蝕刻液，除必須加以管理外，而且蝕刻步驟有分成2次的必要，故難以提升生產性。 However, in the above method, the etching liquid used for etching the copper layer and the etching liquid used for the etching of the electrode layer must be managed in addition to the etching liquid, and the etching step is divided into two. Therefore, it is difficult to improve productivity.
另外，在包含金屬氧化物的電極層上形成銅層，使用能夠蝕刻銅及金屬氧化物兩者的蝕刻液，但也檢討在銅配線圖案形成後，蝕刻，在同一蝕刻槽內對該銅配線圖案間所露出的金屬氧化物進行蝕刻的方法(以下稱為「一起蝕刻」)。採用前述一起蝕刻之情況，因銅配線圖案的形成與金屬氧化物的蝕刻係在同一蝕刻液中進行，在溶液管理上，因為是在同一蝕刻槽內進行，可提升生產性。 Further, a copper layer is formed on the electrode layer containing the metal oxide, and an etching liquid capable of etching both copper and metal oxide is used. However, after the formation of the copper wiring pattern, etching is performed, and the copper wiring is formed in the same etching groove. A method of etching a metal oxide exposed between patterns (hereinafter referred to as "etching together"). In the case of the above-described etching together, since the formation of the copper wiring pattern and the etching of the metal oxide are performed in the same etching liquid, in the solution management, since it is performed in the same etching bath, the productivity can be improved.
專利文獻1：日本特開2008-77332號公報。 Patent Document 1: Japanese Laid-Open Patent Publication No. 2008-77332.
但是，於採用前述一起蝕刻之情況，在蝕刻銅配線圖案間的金屬氧化物之際，銅配線圖案會被腐蝕，而會有產生銅配線圖案之側面的銅配線被除去之所謂「側蝕」(Side etching)的現象之情況。 However, in the case of etching together, when the metal oxide between the copper wiring patterns is etched, the copper wiring pattern is corroded, and the copper wiring which causes the side surface of the copper wiring pattern is removed, so-called "side etching" (Side etching) phenomenon.
本發明鑑於前述向來技術的問題點，提供抑制銅配線側蝕的銅之蝕刻液與其補充液，以及配線形成方法。 The present invention has been made in view of the problems of the prior art, and provides an etching liquid for copper and a replenishing liquid thereof for suppressing side etching of copper wiring, and a wiring forming method.
本發明的銅之蝕刻液係由包含銅離子、鹵化物離子和非離子性界面活性劑的酸性水溶液所構成。本發明的銅之蝕刻液的前述非離子性界面活性劑之濁點(cloud point)為15~55℃。 The copper etching solution of the present invention is composed of an acidic aqueous solution containing copper ions, halide ions, and a nonionic surfactant. The nonionic surfactant of the copper etching solution of the present invention has a cloud point of 15 to 55 °C.
本發明的補充液為於將前述本發明的蝕刻液連續或重複使用之際，添加到前述蝕刻液中的補充液，係由包含鹵化物離子和非離子表面活性劑的酸性水溶液所構成。本發明的補充液之前述非離子性界面活性劑之濁點為15~55℃。 The replenishing liquid of the present invention is composed of an acidic aqueous solution containing a halide ion and a nonionic surfactant when the etching liquid of the present invention is continuously or repeatedly used. The nonionic surfactant of the replenishing liquid of the present invention has a cloud point of 15 to 55 °C.
本發明的配線形成方法包含：藉由使前述本發明的蝕刻液接觸在基材上依序積層有金屬氧化物層及銅層的積層板之前述銅層的一部分而蝕刻前述銅層的一部分，以形成銅配線圖案的步驟，與藉由使本發明的蝕刻液接觸前述金屬氧化物層的未積層前述銅配線圖案的部分而蝕刻前述金 屬氧化物層的前述部分，以形成包含經圖案化的金屬氧化物層以及前述銅配線圖案的積層配線圖案的步驟。於本發明的配線形成方法中，前述金屬氧化物層包含從鋅、錫、鋁、銦和鎵所組成之群組中所選出的一種以上之金屬的氧化物。 The wiring forming method of the present invention comprises: etching a part of the copper layer by contacting the etching liquid of the present invention with a part of the copper layer in which a metal oxide layer and a copper layer laminated layer are sequentially laminated on a substrate, In order to form a copper wiring pattern, the gold is etched by contacting the etching liquid of the present invention with a portion of the metal oxide layer in which the copper wiring pattern is not laminated. The foregoing portion of the oxide layer forms a step of forming a layered wiring pattern including the patterned metal oxide layer and the aforementioned copper wiring pattern. In the wiring forming method of the present invention, the metal oxide layer contains an oxide of one or more metals selected from the group consisting of zinc, tin, aluminum, indium, and gallium.
又，本發明之「銅層」，可以為僅由銅所構成之層，也可以為包含銅與其他金屬的銅合金所構成之層。再者，於本發明中，「銅」意指銅或銅合金。 Further, the "copper layer" of the present invention may be a layer composed only of copper, or may be a layer composed of a copper alloy containing copper and another metal. Further, in the present invention, "copper" means copper or a copper alloy.
再者，於本發明中的「濁點」，係以JIS K 2269為標準，將測定對象的非離子性界面活性劑之1重量%水溶液作為試料使用所測定的物理性質。又，在濁點為49℃以上的非離子性界面活性劑之情況，以保持試料在比預期的濁點高2~3℃的溫度的狀態，依JIS K 2269的標準來測定。 In addition, the "cloud point" in the present invention is a physical property measured by using a 1% by weight aqueous solution of a nonionic surfactant to be measured as a sample in accordance with JIS K 2269. Further, in the case of a nonionic surfactant having a cloud point of 49 ° C or higher, the sample is measured in accordance with JIS K 2269 in a state in which the sample is kept at a temperature 2 to 3 ° C higher than the expected cloud point.
依據本發明，可以提供能夠抑制銅配線圖案側蝕的銅之蝕刻液、其補充液以及配線形成方法。 According to the present invention, it is possible to provide a copper etching liquid capable of suppressing side etching of a copper wiring pattern, a replenishing liquid thereof, and a wiring forming method.
1‧‧‧基材 1‧‧‧Substrate
2‧‧‧金屬氧化物層 2‧‧‧ metal oxide layer
3‧‧‧銅層 3‧‧‧ copper layer
4‧‧‧罩蓋金屬層 4‧‧‧ Cover metal layer
5‧‧‧光阻圖案 5‧‧‧resist pattern
6‧‧‧罩蓋金屬配線圖案 6‧‧‧Cover metal wiring pattern
7‧‧‧銅配線圖案 7‧‧‧Bronze wiring pattern
8‧‧‧露出部分 8‧‧‧Exposed part
9‧‧‧金屬氧化物配線圖案 9‧‧‧Metal oxide wiring pattern
10‧‧‧積層配線圖案 10‧‧‧Multilayer wiring pattern
100‧‧‧積層板 100‧‧‧ laminate
L,W1,W2‧‧‧線寬 L, W1, W2‧‧‧ line width
S‧‧‧線距 S‧‧‧ line spacing
圖1(a)~(c)為示意顯示本發明的配線形成方法的一個實施形態之各步驟的剖面圖。 1(a) to 1(c) are cross-sectional views schematically showing respective steps of an embodiment of a wiring forming method of the present invention.
以下說明有關本發明的銅之蝕刻液所包含的各成分。又，如後所述，本發明的蝕刻液，不僅是銅，對用於銅的防鏽等的罩蓋金屬(cap metal)與金屬氧化物亦可蝕刻。 Hereinafter, each component contained in the copper etching solution of the present invention will be described. Further, as will be described later, the etching liquid of the present invention is not only copper, but also a cap metal and a metal oxide which are used for rust prevention of copper.
(銅離子) (Copper ions)
於本發明的蝕刻液中使用的銅離子，係以作為氧化金屬銅的成分來調配。銅離子，藉調配銅離子源，能被包含在蝕刻液中。作為銅離子源，例如可從氯化銅、硫酸銅、溴化銅、有機酸的銅鹽以及氫氧化銅選出一種以上者。 The copper ions used in the etching solution of the present invention are formulated as a component of the oxidized metal copper. Copper ions, by means of a copper ion source, can be included in the etchant. As the copper ion source, for example, one or more selected from copper chloride, copper sulfate, copper bromide, a copper salt of an organic acid, and copper hydroxide.
前述銅離子濃度，較佳為0.01~5重量%，更佳為0.1~1重量%，又更佳為0.2~0.7重量%。前述濃度若在0.01重量%以上，則因為蝕刻速度快，能夠迅速蝕刻銅。再者，前述濃度若在5重量%以下，則能夠維持銅的溶解安定性。又，為了藉抑制銅配線圖案側面之剝落，而提升銅配線圖案的直線性，前述濃度較佳為0.2~0.7重量%。 The copper ion concentration is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight, still more preferably 0.2 to 0.7% by weight. When the concentration is 0.01% by weight or more, the etching speed is fast, and copper can be quickly etched. In addition, when the concentration is 5% by weight or less, the dissolution stability of copper can be maintained. Further, in order to suppress the peeling of the side surface of the copper wiring pattern and to improve the linearity of the copper wiring pattern, the concentration is preferably 0.2 to 0.7% by weight.
(鹵化物離子) (halide ion)
本發明的蝕刻液所使用的鹵化物離子，係作為促進銅蝕刻的成分而調配。再者，鹵化物離子，在對銅與金屬氧 化物並存的蝕刻對象物蝕刻之情況，也具有除去金屬氧化物成分的功能。鹵化物離子，例如可以由氟化物離子、氯化物離子、溴化物離子以及碘化物離子選出一種以上，從銅的蝕刻性，以及操作性的觀點，較佳為氯化物離子、溴化物離子，更佳為氯化物離子。鹵化物離子，例如，將鹽酸、氫溴酸等的酸、或氯化鈉、氯化銨、氯化鈣、氯化鉀、溴化鉀、氟化鈉、碘化鉀、氯化銅、溴化銅等的鹽等，作為鹵化物離子源來調配，能夠包含在蝕刻液中。又，例如氯化銅，溴化銅，可以當作具有與鹵化物離子源和銅離子源兩邊之作用者來使用。 The halide ions used in the etching solution of the present invention are formulated as a component for promoting copper etching. Furthermore, halide ions, in the presence of copper and metal oxygen In the case where the etching target is etched, the metal oxide component is removed. The halide ion may be, for example, selected from fluoride ion, chloride ion, bromide ion, and iodide ion, and is preferably chloride ion or bromide ion from the viewpoint of copper etching property and handleability. Good for chloride ions. a halide ion, for example, an acid such as hydrochloric acid or hydrobromic acid, or sodium chloride, ammonium chloride, calcium chloride, potassium chloride, potassium bromide, sodium fluoride, potassium iodide, copper chloride or copper bromide. A salt or the like is prepared as a halide ion source and can be contained in an etching solution. Further, for example, copper chloride or copper bromide can be used as a function of both the halide ion source and the copper ion source.
前述蝕刻液中的鹵化物離子之濃度，較佳為1~36重量%，再好為5~25重量%，更好為10~20重量%。前述濃度若在1重量%以上，則可提升銅的蝕刻性。再者，前述濃度若在36重量%以下，則可以防止於蝕刻液中的鹵化物的析出。又，為了藉抑制銅配線圖案的側面之剝落，而提升銅配線圖案的直線性，前述濃度較佳為10~20重量%。再者，於蝕刻銅與金屬氧化物並存的蝕刻對象物的情形，鹵化物離子濃度，若在上述範圍內，則除了銅的蝕刻性外，有提升金屬氧化物的蝕刻性之傾向。 The concentration of the halide ions in the etching liquid is preferably from 1 to 36% by weight, more preferably from 5 to 25% by weight, still more preferably from 10 to 20% by weight. When the concentration is at least 1% by weight, the etching property of copper can be improved. Further, when the concentration is 36% by weight or less, precipitation of a halide in the etching liquid can be prevented. Further, in order to suppress the linearity of the copper wiring pattern by suppressing the peeling of the side surface of the copper wiring pattern, the concentration is preferably 10 to 20% by weight. In the case of etching an object to be etched in which copper and a metal oxide are etched, if the halide ion concentration is within the above range, the etching property of the metal oxide tends to be improved in addition to the etching property of copper.
(非離子性界面活性劑) (nonionic surfactant)
本發明的蝕刻液，為了抑制銅配線圖案的側蝕，調配濁點為15~55℃的一種以上之非離子性界面活性劑。能夠 使用的非離子性界面活性劑，雖沒有特別限制濁點為15~55℃，但可以在聚烯烴二醇衍生物(polyalkylene glycol derivatiye)，聚氧化烯烷基醚(polyoxyalkylene alkyl ether)、聚氧化烯烷基苯基醚(polyoxyalkylene alkylphenyl ether)，聚氧乙烯聚氧丙烯嵌段共聚物(polyoxyethylene polyoxypropylene block copolymer)、聚氧乙烯聚氧丙烯甘油醚(polyoxyethylene polyoxypropylene glyceryl ether)，聚氧化烯脂肪酸單酯(polyoxyalkylene fatty acid monoester)、聚氧化烯脂肪酸二酯(polyoxyalkylene fatty acid diester)，山梨糖醇高級脂肪酸酯(sorbitol higher fatty acid ester)、甘油高級脂肪酸酯(glycerin higher fatty acid ester)，蔗糖高級脂肪酸酯(sucrose higher fatty acid ester)等的非離子性界面活性劑中，適當選擇濁點為15~55℃者。 In the etching liquid of the present invention, in order to suppress side etching of the copper wiring pattern, one or more nonionic surfactants having a cloud point of 15 to 55 ° C are prepared. Nonionic surfactant can be used, although not particularly limited cloud point of 15 ~ 55 ℃, but the polyolefin glycol derivatives (polyalkylene glycol derivatiye), polyoxyalkylene alkyl ethers (polyoxyalkylene alkyl ether), poly Polyoxyalkylene alkylphenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene glyceryl ether, polyoxyalkylene fatty acid Polyoxyalkylene fatty acid monoester, polyoxyalkylene fatty acid diester, sorbitol higher fatty acid ester, glycerin higher fatty acid ester, sucrose Among the nonionic surfactants such as sucrose higher fatty acid ester, a cloud point of 15 to 55 ° C is appropriately selected.
為有效抑制銅配線圖案的側蝕，較佳使用濁點為17~38℃的非離子性界面活性劑。特別是，為了藉抑制銅配線圖案的側面之剝落而提升銅配圖案之直線性，較佳使用濁點為17~30℃的非離子性界面活性劑。 In order to effectively suppress the side etching of the copper wiring pattern, a nonionic surfactant having a cloud point of 17 to 38 ° C is preferably used. In particular, in order to enhance the linearity of the copper pattern by suppressing the peeling of the side surface of the copper wiring pattern, it is preferred to use a nonionic surfactant having a cloud point of 17 to 30 °C.
前述蝕刻液中的非離子性界面活性劑之濃度，較佳為0.01~20重量%，更佳為0.05~10重量%，又更佳為0.1~5重量%。前述濃度若在0.01~20重量%範圍內，則能夠有效抑制銅配線圖案的側蝕。又，為了藉抑制銅配線圖案的側面之剝落，而提升銅配線圖案之直線性，前述濃度 較佳為0.1~5重量%。 The concentration of the nonionic surfactant in the etching solution is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, still more preferably 0.1 to 5% by weight. When the concentration is in the range of 0.01 to 20% by weight, the side etching of the copper wiring pattern can be effectively suppressed. Moreover, in order to suppress the peeling of the side surface of the copper wiring pattern, the linearity of the copper wiring pattern is raised, the aforementioned concentration It is preferably 0.1 to 5% by weight.
(酸) (acid)
本發明的蝕刻液為酸性水溶液。作為讓蝕刻液呈酸性而調配的酸，沒有特別限制，例如可為甲磺酸(methanesulfonic acid)、苯磺酸(benzenesulfonic acid)、對-甲苯磺酸(p-toluenesulfonic acid)、牛磺酸(taurine)等的磺酸化合物(sulfonic acid compound)、鹽酸、氫溴酸、硫酸、硝酸、氟硼酸(fluoroboric acid)、磷酸等的無機酸、甲酸，乙酸，丙酸，丁酸等的羧酸。本發明的蝕刻液可以調配此等酸的一種或一種以上。 The etching solution of the present invention is an acidic aqueous solution. The acid to be formulated so as to make the etching liquid acidic is not particularly limited, and examples thereof include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid , and taurine ( A sulfonic acid compound such as Taurine ), a mineral acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, fluoroboric acid or phosphoric acid, or a carboxylic acid such as formic acid, acetic acid, propionic acid or butyric acid. The etching solution of the present invention may be formulated with one or more of these acids.
酸的濃度以H+濃度而論，較佳為0.01~1重量%，更佳為0.1~0.7重量%，又更佳為0.15~0.55重量%。前述濃度在0.01重量%之情況，因為蝕刻速度迅速，能夠快速地蝕刻銅。再者，前述濃度在1重量%以下之情況，可維持銅的溶解安定性。又，對銅與金屬氧化物並存的蝕刻對象物蝕刻的情況，若酸濃度在上述範圍內，則可提升金屬氧化物之蝕刻速度。再者，從提升銅配線圖案的直線性的觀點而言，較佳也是濃度在上述範圍內。為了讓酸濃度在上述範圍內，前述酸較佳使用無機酸。其中，在使用鹽酸、氫溴酸之情況，於調整蝕刻液的酸性的同時，也希望鹽酸、氫溴酸能成為前述鹵化物離子源。 The concentration of the acid is preferably from 0.01 to 1% by weight, more preferably from 0.1 to 0.7% by weight, still more preferably from 0.15 to 0.55% by weight, based on the H+ concentration. In the case where the aforementioned concentration is 0.01% by weight, since the etching speed is fast, copper can be etched quickly. Further, when the concentration is 1% by weight or less, the dissolution stability of copper can be maintained. Further, in the case where the etching target in which copper and the metal oxide coexist is etched, if the acid concentration is within the above range, the etching rate of the metal oxide can be increased. Further, from the viewpoint of improving the linearity of the copper wiring pattern, the concentration is preferably within the above range. In order to make the acid concentration within the above range, the above acid is preferably a mineral acid. Among them, in the case of using hydrochloric acid or hydrobromic acid, it is also desirable to adjust the acidity of the etching solution, and it is also desired that hydrochloric acid or hydrobromic acid can be the source of the halide ion.
本發明的蝕刻液，藉著將前述各成分溶解於水，而輕 易調製。前述之水，較佳為除去離子性物質及雜質的水，例如離子交換水、純水、超純水等較理想。又，本發明的蝕刻液，根據必要性也可以添加安定劑等之添加劑。 The etching solution of the present invention is lightly dissolved by dissolving the aforementioned components in water. Easy to modulate. The water is preferably water which removes ionic substances and impurities, such as ion-exchanged water, pure water, ultrapure water, and the like. Further, the etching liquid of the present invention may be added with an additive such as a stabilizer as necessary.
本發明的蝕刻液之用途，並無特別限制，例如不僅適用於僅由銅配線圖案所構成的配線圖案，也適用於包含金屬氧化物圖案及銅配線圖案的積層配線圖案等形成之際的蝕刻液。尤其是，在上述一同進行的蝕刻中，適用於包含金屬氧化物配線圖案及銅配線圖案的積層配線圖案形成之際的蝕刻液之情況，可以有效地抑制金屬氧化物配線圖案形成之際的銅配線圖案的側蝕。 The use of the etching liquid of the present invention is not particularly limited. For example, it is applied not only to a wiring pattern composed of only a copper wiring pattern, but also to etching when a laminated wiring pattern including a metal oxide pattern and a copper wiring pattern is formed. liquid. In particular, in the etching performed in the above-described manner, when it is applied to an etching liquid in which a laminated wiring pattern including a metal oxide wiring pattern and a copper wiring pattern is formed, it is possible to effectively suppress copper formation during formation of a metal oxide wiring pattern. Side etching of the wiring pattern.
其次說明有關本發明之補充液。本發明之補充液係在連續或反覆使用上述本發明之蝕刻液之際，添加至前述蝕刻液中的補充液，係由包含鹵化物離子以及非離子性界面活性劑的酸性水溶液所構成。為了讓本發明之補充液中調配的鹵化物離子、非離子性界面活性劑以及蝕刻液呈酸性而調配的酸和上述本發明的蝕刻液中調配的物質相同。 Next, the replenishing liquid relating to the present invention will be explained. The replenishing liquid of the present invention is composed of an acidic aqueous solution containing a halide ion and a nonionic surfactant when the etching liquid of the present invention is continuously or repeatedly used. The acid to be prepared in order to make the halide ion, the nonionic surfactant, and the etching solution formulated in the replenishing liquid of the present invention acidic is the same as that of the above-described etching liquid of the present invention.
藉添加前述補充液，適當保持前述蝕刻液的各成分比，而能夠穩定維持本發明的蝕刻液的效果。又，本發明之補充液，也可以進一步包含在銅離子濃度不超過0.7重量%之範圍內之氯化銅等的銅離子源。再者，本發明之補 充液，也可以調配前述成分以外之在蝕刻液中添加的成分。 By adding the above-mentioned replenishing liquid, it is possible to stably maintain the effect of the etching liquid of the present invention by appropriately maintaining the respective component ratios of the etching liquid. Further, the replenishing liquid of the present invention may further contain a copper ion source such as copper chloride in a range in which the copper ion concentration is not more than 0.7% by weight. Furthermore, the supplement of the present invention The liquid is added to the liquid, and the components added to the etching liquid other than the above components may be blended.
前述補充液中各成分之濃度，雖根據蝕刻液中各成分的濃度適當設定，但從上述本發明的蝕刻液的效果安定維持的觀點而言，較佳為鹵化物離子之濃度為1~36重量%、非離子性界面活性劑之濃度為0.01~40重量%，酸的濃度以H+之濃度而論，為0.01~1重量%。 The concentration of each component in the replenishing liquid is appropriately set depending on the concentration of each component in the etching solution. From the viewpoint of maintaining the effect of the etching liquid of the present invention, the concentration of the halide ion is preferably from 1 to 36. The weight %, the concentration of the nonionic surfactant is 0.01 to 40% by weight, and the concentration of the acid is 0.01 to 1% by weight in terms of the concentration of H + .
接著參照圖1(a)~(c)來說明本發明的配線形成方法。圖1(a)~(c)為示意顯示本發明的配線形成方法一個實施形態步驟剖面圖。 Next, a wiring forming method of the present invention will be described with reference to Figs. 1(a) to 1(c). 1(a) to 1(c) are cross-sectional views schematically showing the steps of a method of forming a wiring of the present invention.
首先，如圖1(a)所示，準備包含基材1與在基材1上依序形成的金屬氧化物層2，銅層3以及罩蓋金屬層4的積層板100，在此一積層板100的罩蓋金屬層4上形成光阻圖案5。光阻圖案5，通常形成為線寬(L)/線距(S)=1μm/1μm~100μm/100μm程度之圖案。又積層板也可以是在銅層上沒有罩蓋金屬層者。於銅層上沒有形成罩蓋金屬層的情況，在銅層上形成光阻圖案。 First, as shown in FIG. 1(a), a laminate 100 including a substrate 1 and a metal oxide layer 2, a copper layer 3, and a cap metal layer 4 which are sequentially formed on the substrate 1 is prepared, and a laminate is formed thereon. A photoresist pattern 5 is formed on the cap metal layer 4 of the board 100. The photoresist pattern 5 is usually formed in a pattern having a line width (L) / line pitch (S) = 1 μm / 1 μm to 100 μm / 100 μm. The laminated board may also be one in which no metal layer is covered on the copper layer. In the case where a cap metal layer is not formed on the copper layer, a photoresist pattern is formed on the copper layer.
基材1可以使用聚對苯二甲酸乙二醇酯薄膜(PET薄膜)等之樹脂基材，或玻璃基材。金屬氧化物層2為包含由鋅、錫、鋁、銦和鎵所構成群組中選出的一種以上之金屬 的氧化物之層，在基材1上直接，或介入由SiO2等所構成的底塗層來設置。在基材上設置金屬氧化物層2之方法，例如可採用真空蒸著、噴濺等公知方法。金屬氧化物層2的厚度較佳為5~200nm的程度。 As the substrate 1, a resin substrate such as a polyethylene terephthalate film (PET film) or a glass substrate can be used. The metal oxide layer 2 is a layer containing an oxide of one or more metals selected from the group consisting of zinc, tin, aluminum, indium, and gallium, directly on the substrate 1, or interposed by SiO 2 or the like. The undercoat is set. A method of providing the metal oxide layer 2 on the substrate may be, for example, a known method such as vacuum evaporation or sputtering. The thickness of the metal oxide layer 2 is preferably about 5 to 200 nm.
構成金屬氧化物層2的金屬氧化物，可以為單一金屬氧化物，也可以為複合金屬氧化物。例如，ZnO、SnO2、Al2O3、氧化銦錫(ITO)、氧化銦鋅(IZO)，或者對於ZnO導入異種金屬的複合金屬氧化物等。作為前述ZnO導入異種金屬的複合金屬氧化物，例如為導入鋁的AZO，與導入鎵的GZO等。尤其，由鋅、錫及鋁所構成的群組中選出的一種以上的金屬之氧化物以圖案形成性之觀點而言為較佳，更佳為由ITO、IZO、AZO及GZO選出一種以上之金屬氧化物。 The metal oxide constituting the metal oxide layer 2 may be a single metal oxide or a composite metal oxide. For example, ZnO, SnO 2 , Al 2 O 3 , indium tin oxide (ITO), indium zinc oxide (IZO), or a composite metal oxide in which a dissimilar metal is introduced into ZnO. The composite metal oxide into which the dissimilar metal is introduced as the ZnO is, for example, AZO to which aluminum is introduced, GZO to which gallium is introduced, or the like. In particular, an oxide of one or more metals selected from the group consisting of zinc, tin, and aluminum is preferable from the viewpoint of pattern formability, and more preferably one or more selected from the group consisting of ITO, IZO, AZO, and GZO. Metal oxide.
前述金屬氧化物雖可以為非晶質或結晶質的任一種金屬氧化物，但在結晶質之情況，於導電性及耐久性的提升上較理想。在金屬氧化物為結晶質之情況，以往的蝕刻液，蝕刻銅比蝕刻金屬氧化物更容易，故蝕刻金屬氧化物之際，難以抑制銅配線圖案7(圖1(b)參照)的側蝕。如後面所述，依據本實施形態的配線方法，因為使用上述本發明的蝕刻液，金屬氧化物即使為結晶質也能夠抑制銅配線圖案7的側蝕。 The metal oxide may be any amorphous or crystalline metal oxide, but in the case of crystallinity, it is preferable in terms of improvement in conductivity and durability. In the case where the metal oxide is crystalline, it is easier to etch the copper than the conventional etching solution. Therefore, when the metal oxide is etched, it is difficult to suppress the side etching of the copper wiring pattern 7 (refer to FIG. 1(b)). . As described later, according to the wiring method of the present embodiment, the etching solution of the present invention described above can suppress the side etching of the copper wiring pattern 7 even if the metal oxide is crystalline.
又，金屬氧化物是否為結晶質，例如，藉場發射穿透式電子顯微鏡(FE-TEM)來觀察金屬氧化物之表面而能夠判別。在金屬氧化物為結晶質之情況，例如可以觀察到多角形或長圓形狀之結晶粒。於本發明中，結晶質之金屬氧化物藉前述場發射穿透式電子顯微鏡(FE-TEM)觀察金屬氧化物表面之場合，前述結晶粒所占的面積比例超過50%者為佳，較佳是前述結晶粒所占的面積比例為從70%至100%的金屬氧化物。 Further, whether or not the metal oxide is crystalline, for example, can be discriminated by observing the surface of the metal oxide by a field emission transmission electron microscope (FE-TEM). In the case where the metal oxide is crystalline, for example, a polygonal or oblong-shaped crystal grain can be observed. In the present invention, in the case where the crystalline metal oxide is observed by the field emission transmission electron microscope (FE-TEM), the area ratio of the crystal grains is preferably 50% or more. It is a metal oxide having an area ratio of the aforementioned crystal grains of from 70% to 100%.
銅層3可藉例如真空蒸著、噴濺等公知方法來形成在金屬氧化物層2上。銅層3之較佳厚度為20~1000nm的程度。 The copper layer 3 can be formed on the metal oxide layer 2 by a known method such as vacuum evaporation or sputtering. The copper layer 3 preferably has a thickness of 20 to 1000 nm.
為了銅層3的防鏽等，可根據必要性在銅層3上設置罩蓋金屬層4。作為罩蓋金屬層4的材質，例如為鋁、鈦、鉻、鈷、鎳、鋅、鉬、銀，以及此等金屬與銅的合金等。但是，銅層3在由銅合金所構成的情況，罩蓋金屬層4較佳為與銅層3之材質不同的銅合金，或銅以外的合金所構成者。尤其，從銅層3的防鏽之觀點，以及圖案形成性之觀點而言，鎳、鉬，以及此等金屬與銅的合金選出一種以上者為佳。特別是，鎳/銅之重量比率為30/70~70/30的鎳-銅合金為佳。 For the rust prevention or the like of the copper layer 3, the cap metal layer 4 may be provided on the copper layer 3 as necessary. The material of the cover metal layer 4 is, for example, aluminum, titanium, chromium, cobalt, nickel, zinc, molybdenum, silver, or an alloy of such a metal and copper. However, when the copper layer 3 is made of a copper alloy, the cover metal layer 4 is preferably made of a copper alloy different from the material of the copper layer 3 or an alloy other than copper. In particular, from the viewpoint of rust prevention of the copper layer 3 and the pattern formability, it is preferable to select one or more of nickel, molybdenum, and alloys of such metals and copper. In particular, a nickel-copper alloy having a nickel/copper weight ratio of 30/70 to 70/30 is preferred.
罩蓋金屬層4可以由單層來構成，也可以由複數層來 構成。罩蓋金屬層4之厚度較佳為5~200nm程度。罩蓋金屬層4之形成方法，例如為真空蒸著、噴濺等的公知方法。 The cover metal layer 4 may be composed of a single layer or may be composed of a plurality of layers. Composition. The thickness of the cap metal layer 4 is preferably about 5 to 200 nm. The method of forming the cover metal layer 4 is, for example, a known method such as vacuum evaporation or sputtering.
其次，讓前述本發明之蝕刻液接觸銅層3，形成如圖1所示的銅配線圖案7。再者，讓前述本發明之蝕刻液接觸金屬氧化物層2之未積層銅配線圖案7之處(圖1(b)之露出部分8)，藉由形成圖1(c)所示的金屬氧化物配線圖案9，而獲得包含金屬氧化物配線圖案9、及銅配線圖案7的積層配線圖案10。在銅層3上形成罩蓋金屬4之情況，在前述本發明之蝕刻液接觸銅層3之前，讓前述本發明之蝕刻液接觸罩蓋金屬層4，形成如圖1(b)所示的罩蓋金屬配線圖案6。此一情況，積層配線圖案10如圖1(c)所示，在銅配線圖案7上具有罩蓋金屬配線圖案6。本實施形態中，藉由使本發明的蝕刻液接觸積層板100表面之光阻圖案5未積層之領域，而獲得預定形狀的積層配線圖案10。 Next, the etching liquid of the present invention is brought into contact with the copper layer 3 to form a copper wiring pattern 7 as shown in FIG. Further, the etching liquid of the present invention is brought into contact with the unlaminated copper wiring pattern 7 of the metal oxide layer 2 (exposed portion 8 of FIG. 1(b)) by forming the metal oxide shown in FIG. 1(c). The wiring pattern 9 is obtained, and the multilayer wiring pattern 10 including the metal oxide wiring pattern 9 and the copper wiring pattern 7 is obtained. In the case where the cap metal 4 is formed on the copper layer 3, before the etching liquid of the present invention contacts the copper layer 3, the etching liquid of the present invention is brought into contact with the cap metal layer 4 to form a metal layer 4 as shown in FIG. 1(b). The metal wiring pattern 6 is covered. In this case, the multilayer wiring pattern 10 has the cover metal wiring pattern 6 on the copper wiring pattern 7 as shown in FIG. 1(c). In the present embodiment, the etching liquid of the present invention is brought into contact with the field in which the photoresist pattern 5 on the surface of the laminated board 100 is not laminated, whereby the laminated wiring pattern 10 having a predetermined shape is obtained.
本實施形態，藉由使用前述本發明之蝕刻液形成銅配線圖案7，而能夠抑制形成銅配線圖案7之際的罩蓋金屬配線圖案6的側蝕。再者，藉由使用前述本發明之蝕刻液形成金屬氧化物配線圖案9，而能夠抑制形成金屬氧化物配線圖案9之際的罩蓋金屬配線圖案6以及銅配線圖案7的側蝕。藉此，可以抑制罩蓋金屬配線圖案6的線寬W1及銅配線圖案7的線寬W2之變細。 In the present embodiment, by forming the copper wiring pattern 7 using the etching liquid of the present invention, it is possible to suppress the side etching of the cap metal wiring pattern 6 when the copper wiring pattern 7 is formed. In addition, by forming the metal oxide wiring pattern 9 using the etching liquid of the present invention, it is possible to suppress the side etching of the cap metal wiring pattern 6 and the copper wiring pattern 7 when the metal oxide wiring pattern 9 is formed. Thereby, the line width W1 of the cover metal wiring pattern 6 and the line width W2 of the copper wiring pattern 7 can be suppressed from being thinned.
又，在形成由與銅層3不同的材質所構成的罩蓋金屬層4之情況，若以以往的蝕刻液蝕刻銅層3與金屬氧化物層2，則因賈凡尼腐蝕(Galvanic Corrosion)，恐會進行銅配線層7的側蝕。但是使用本發明的蝕刻液的情況，銅層3上即使形成不同金屬的罩蓋金屬層4，也能夠抑制銅配線層7的側蝕。 Further, in the case where the cap metal layer 4 made of a material different from the copper layer 3 is formed, when the copper layer 3 and the metal oxide layer 2 are etched by a conventional etching solution, Galvanic Corrosion is etched. It is feared that the side wiring of the copper wiring layer 7 will be performed. However, in the case of using the etching liquid of the present invention, even if the cap metal layer 4 of a different metal is formed on the copper layer 3, the side etching of the copper wiring layer 7 can be suppressed.
本發明的蝕刻液之使用方法沒有特別限制，例如為，在積層板100表面之光阻圖案5未積層之區域，噴灑前述蝕刻液之方法、或將設有光阻圖案5的積層板100浸漬於前述蝕刻液中的方法等。 The method of using the etching liquid of the present invention is not particularly limited, and for example, a method of spraying the etching liquid or a layer of the laminated plate 100 provided with the photoresist pattern 5 in a region where the photoresist pattern 5 on the surface of the laminated board 100 is not laminated is used. The method in the etching solution described above.
在噴灑蝕刻液的情況，較佳以前述蝕刻液之溫度保持30~60℃，噴灑壓力0.03~0.3MPa來處理。在浸漬蝕刻液之情況，較佳以前述蝕刻液之溫度保持30~60℃來處理。 In the case of spraying the etching liquid, it is preferred to treat the temperature of the etching liquid at 30 to 60 ° C and a spraying pressure of 0.03 to 0.3 MPa. In the case of immersing the etching liquid, it is preferred to treat the temperature of the etching liquid at 30 to 60 ° C.
本發明之實施形態，藉由使前述蝕刻液接觸積層板100表面之光阻圖案5未積層之區域蝕刻罩蓋金屬層4而形成罩蓋金屬配線圖案6，使蝕刻液接觸因罩蓋金屬層4的蝕刻所形成銅層3之露出部分而蝕刻銅層3，以形成銅配線圖案7。再者，藉由蝕刻液接觸因銅層3之蝕刻所形成的金屬氧化物層2之露出部分8而蝕刻金屬氧化物層2並形成金屬氧化物配線圖案9。如前述，本發明之蝕刻液 對於銅及金屬氧化物兩者都有侵蝕性。因此，在銅層3被蝕刻形成銅配線圖案7後，也可以繼續蝕刻金屬氧化物層2。亦即，本實施形態中，前述本發明之蝕刻液接觸銅層3，與前述本發明之蝕刻液接觸金屬氧化物層2可作為連續步驟來實施。 In the embodiment of the present invention, the cover metal wiring pattern 6 is formed by etching the cover metal layer 4 in a region where the etching liquid contacts the photoresist pattern 5 on the surface of the laminated board 100, and the etching liquid contacts the metal layer of the cover. The exposed portion of the copper layer 3 is formed by etching 4 to etch the copper layer 3 to form the copper wiring pattern 7. Further, the metal oxide layer 2 is etched by the etching liquid in contact with the exposed portion 8 of the metal oxide layer 2 formed by the etching of the copper layer 3, and the metal oxide wiring pattern 9 is formed. As described above, the etching solution of the present invention It is erosive for both copper and metal oxides. Therefore, after the copper layer 3 is etched to form the copper wiring pattern 7, the metal oxide layer 2 can be continuously etched. That is, in the present embodiment, the etching liquid of the present invention is in contact with the copper layer 3, and the contact with the etching liquid of the present invention in the metal oxide layer 2 can be carried out as a continuous step.
又，於本發明的實施形態中，罩蓋金屬層4之蝕刻處理與銅層3的蝕刻處理與金屬氧化物層2的蝕刻處理，可以在同一蝕刻槽中進行，也可以在各別蝕刻槽中進行。罩蓋金屬層4、銅層3及金屬氧化物層2若在相同蝕刻槽中處理，則能夠減少蝕刻步驟，而且蝕刻液管理亦被簡化，所以較佳。 Further, in the embodiment of the present invention, the etching treatment of the cap metal layer 4, the etching treatment of the copper layer 3, and the etching treatment of the metal oxide layer 2 may be performed in the same etching bath, or may be performed in the respective etching grooves. In progress. When the cap metal layer 4, the copper layer 3, and the metal oxide layer 2 are treated in the same etching bath, the etching step can be reduced, and the etching liquid management is also simplified, which is preferable.
罩蓋金屬層4之蝕刻與銅層3的蝕刻與金屬氧化物層2的蝕刻於各別蝕刻槽中進行時，在各別蝕刻槽中使用的蝕刻液之調配，可以為同一組成，也可以為不同組成。再者，複數蝕刻槽並沒有分別對應罩蓋金屬層4、銅層3以及金屬氧化物層2的蝕刻處理之必要。例如，於第一蝕刻槽中，除罩蓋金屬層4以及銅層3外，進行金屬氧化物層2之深度方向的一部分蝕刻處理後，也可以於第二蝕刻槽再對金屬氧化物層2進行蝕刻處理，而形成金屬氧化物層配線圖案9。 When the etching of the cap metal layer 4 and the etching of the copper layer 3 and the etching of the metal oxide layer 2 are performed in the respective etching grooves, the etching liquid used in the respective etching grooves may be the same composition or may be the same composition. For different compositions. Furthermore, the plurality of etching grooves do not necessarily correspond to the etching treatment of the cap metal layer 4, the copper layer 3, and the metal oxide layer 2, respectively. For example, in the first etching trench, after a part of the etching process in the depth direction of the metal oxide layer 2 is performed in addition to the cap metal layer 4 and the copper layer 3, the metal oxide layer 2 may be further applied to the second etching trench. An etching process is performed to form a metal oxide layer wiring pattern 9.
以上，說明有關本發明的配線形成方法的一個實施形 態，但本發明不為前述實施形態所限制。例如，前述實施形態雖然將罩蓋金屬層以本發明的蝕刻液來蝕刻，但也能夠以和本發明的蝕刻液不同的蝕刻液來蝕刻。再者，前述實施形態，雖主要以設置罩蓋金屬層之案例來說明，但本發明的配線形成方法也可以使用於沒有設置罩蓋金屬層的積層板。 The above describes an embodiment of the wiring forming method of the present invention. However, the present invention is not limited by the foregoing embodiments. For example, in the above embodiment, the cap metal layer is etched by the etching liquid of the present invention, but it can be etched with an etching liquid different from the etching liquid of the present invention. Further, although the above embodiment has been mainly described by the case of providing a cover metal layer, the wiring forming method of the present invention can also be applied to a laminated board in which a cover metal layer is not provided.
接著，一併說明有關本發明的實施例與比較例。又，本發明不能解釋為被下述實施例所限定者。 Next, examples and comparative examples relating to the present invention will be described together. Further, the present invention is not to be construed as being limited by the following examples.
(積層配線圖案之形成) (Formation of laminated wiring pattern)
在厚度100μm之PET薄膜上，準備依照包含結晶質的ITO的ITO層(厚度20μm)、銅層(厚度150μm)、鎳/銅重量比=30/70之鎳-銅合金層(厚度20nm)之順序形成的樣品積層板。使用此一積層板按照以下之順序進行積層配線圖案之形成。 On a PET film having a thickness of 100 μm, a nickel-copper alloy layer (thickness: 20 nm) in accordance with an ITO layer (thickness: 20 μm) containing a crystalline ITO, a copper layer (thickness: 150 μm), and a nickel/copper weight ratio of 30/70 was prepared. A sample laminate formed in sequence. The laminated wiring pattern was formed in the following order using this laminated board.
將前述積層板浸漬於10重量%的硫酸水溶液(溫度25℃)裡1分鐘，除去鎳-銅合金層表面之氧化物後，在此一鎳-銅合金層表面，使用乾膜光阻(商品號AQ-209A、旭化成電子材料公司製造)形成線/間隔=20μm/20μm的光阻 圖案。其次，將前述積層板在表1及表2所記載的各蝕刻液(溫度45℃)中浸漬90秒後，水洗/乾燥。又，表1的各蝕刻液係使銅離子及鹵化物離子濃度固定，而變更非離子界面活性劑的種類者。表2的各蝕刻液係使用和表1的實施例5相同的非離子界面活性劑，而變更鹵化銅及酸的種類與濃度，還有非離子界面活性劑的種類以及濃度者。表2一併顯示表1所示的實施例5的蝕刻液之組成以及評價結果。 The laminate was immersed in a 10% by weight aqueous sulfuric acid solution (temperature: 25 ° C) for 1 minute to remove the oxide on the surface of the nickel-copper alloy layer, and a dry film photoresist was used on the surface of the nickel-copper alloy layer. No. AQ-209A, manufactured by Asahi Kasei Electronic Materials Co., Ltd.) formed a line/space = 20 μm / 20 μm photoresist pattern. Next, the laminate was immersed in each of the etching liquids (temperature: 45 ° C) described in Tables 1 and 2 for 90 seconds, and then washed with water/dried. Further, in each of the etching liquids in Table 1, the concentration of the copper ions and the halide ions was fixed, and the type of the nonionic surfactant was changed. In each of the etching liquids of Table 2, the same nonionic surfactant as in Example 5 of Table 1 was used, and the type and concentration of the copper halide and the acid were changed, and the type and concentration of the nonionic surfactant were also used. Table 2 also shows the composition of the etching liquid of Example 5 shown in Table 1 and the evaluation results.
將乾燥後的各積層板的一部分取為樣品，以掃描式電子顯微鏡(型號JSM-7000F、日本電子公司製造)觀察表面，每一片積層板皆被除去和圖1(c)的金屬氧化物配線圖案9相當的ITO配線圖案間的ITO層。 A part of each of the dried laminated sheets was taken as a sample, and the surface was observed with a scanning electron microscope (Model JSM-7000F, manufactured by JEOL Ltd.), and each laminated board was removed and the metal oxide wiring of FIG. 1(c) was removed. The pattern 9 has an ITO layer between the ITO wiring patterns.
(側蝕量之測定) (Measurement of side erosion amount)
接著，將蝕刻後的各積層板的一部分取出10mm x 10mm之樣品，嵌入包埋樹脂中，進行能夠看出銅配線圖案的剖面之研磨加工後，藉使用掃描式電子顯微鏡(型號JSM-7000F、日本電子公司製造)的影像量測來測定銅配線圖案之寬度(圖1(c)之W2)中最細之處的寬度(最小寬度)。接著，將光阻圖案的線寬(20μm)減去所測定的前述最小寬度所得到之值作為側蝕量，算出任意選擇5處的側蝕量之平均值。結果(平均值)如表1及表2所示。 Next, a sample of 10 mm x 10 mm of each of the laminated sheets after the etching was taken out, embedded in an embedding resin, and a cross-section of the copper wiring pattern was observed, and then a scanning electron microscope (model JSM-7000F, The image (measured by JEOL Ltd.) measures the width (minimum width) of the thinnest part of the width of the copper wiring pattern (W2 in Fig. 1(c)). Next, the value obtained by subtracting the measured minimum width from the line width (20 μm) of the resist pattern was used as the side etching amount, and the average value of the side etching amount at the arbitrary five points was calculated. The results (average values) are shown in Tables 1 and 2.
(直線性之測定) (measurement of linearity)
從蝕刻後的各積層板的PET薄膜側邊，藉光學顯微鏡攝影銅配線圖案的底部影像，進行底部寬度的影像量測。於進行此一底部寬度的影像量測之際，沿銅配線圖案的長邊方向，以間隔5μm測定10點，將所得到的測定值之標準偏差值作成直線性(μm)。結果如表1及表2所示。 The bottom width image was measured by photographing the bottom image of the copper wiring pattern from the side of the PET film of each laminated plate after etching. When the image measurement of the bottom width was performed, 10 points were measured at intervals of 5 μm along the longitudinal direction of the copper wiring pattern, and the standard deviation value of the obtained measurement value was made linear (μm). The results are shown in Tables 1 and 2.
(綜合評價) (Overview)
綜合評價分為A~D的4個等級來評價。亦即，評價A為側蝕量未達6μm，且直線性未達1μm之情況；評價B為側蝕量未達6μm，且直線性在1μm以上未達2μm之情況；評價C為側蝕量在6μm以上未達7μm，且直線性在1μm以上未達2μm之情況；評價D為側蝕量在8μm以上，且直線性在2μm以上之情況。 The comprehensive evaluation is divided into four levels of A to D to evaluate. That is, the evaluation A is that the side etching amount is less than 6 μm, and the linearity is less than 1 μm; the evaluation B is that the side etching amount is less than 6 μm, and the linearity is less than 2 μm above 1 μm; the evaluation C is the side etching amount. When the thickness is less than 7 μm and the linearity is less than 2 μm, the linearity is 1 μm or more; and the evaluation D is a case where the amount of side etching is 8 μm or more and the linearity is 2 μm or more.
如表1、2所示，各實施例的每一個之側蝕量及直線性均良好，綜合評價也為A、B或C。另一方面，各比較例的每一個之側蝕量及直線性均較實施例差，綜合評價為D。 As shown in Tables 1 and 2, the amount of side etching and the linearity of each of the examples were good, and the overall evaluation was also A, B or C. On the other hand, the amount of side etching and the linearity of each of the comparative examples were inferior to those of the examples, and the overall evaluation was D.
(積層配線圖案之形成) (Formation of laminated wiring pattern)
準備在厚度2mm的玻璃板上依照包含結晶質的IZO之層(厚度20nm)、銅層(厚度150nm)、鉬層(厚度20nm)之順序形成的積層板。使用此一積層板按下列順序進行積層配線圖案之形成。 A laminated plate formed in the order of a layer containing a crystalline IZO (thickness: 20 nm), a copper layer (thickness: 150 nm), and a molybdenum layer (thickness: 20 nm) was prepared on a glass plate having a thickness of 2 mm. The laminated wiring pattern was formed in the following order using this laminated board.
將前述積層板在10重量%的硫酸水溶液(溫度25℃)中浸漬1分鐘，除去鉬層表面的氧化物後，在此一鉬層表面使用液狀光阻劑(商品號OFPR-800、東京應化工業公司製造)，形成線寬/線距=20μm/20μm的光阻圖案。接著，以和上述[由PET薄膜/ITO層/銅層/鎳-銅合金層所構成積層板之評價]相同的程序，獲得包含積層配線圖案的積層板。就所得到的各積層板取樣一部分，以掃描式電子顯微鏡(型號JSM-7000F、日本電子公司製造)觀察表面時，每一積層板皆被除去和圖1(c)之金屬氧化物配線圖案9相當的IZO配線圖案間的IZO層。 The laminate was immersed in a 10% by weight aqueous sulfuric acid solution (temperature: 25 ° C) for 1 minute to remove the oxide on the surface of the molybdenum layer, and then a liquid photoresist was used on the surface of the molybdenum layer (product number OFPR-800, Tokyo). A photoresist pattern having a line width/line pitch = 20 μm / 20 μm was formed. Next, a laminate including a laminated wiring pattern was obtained in the same procedure as the above [Evaluation of a laminate formed of a PET film/ITO layer/copper layer/nickel-copper alloy layer]. A part of each of the obtained laminates was sampled, and when the surface was observed with a scanning electron microscope (Model JSM-7000F, manufactured by JEOL Ltd.), each of the laminates was removed and the metal oxide wiring pattern 9 of Fig. 1(c) was removed. A comparable IZO layer between IZO wiring patterns.
(評價) (Evaluation)
以和上述[由PET薄膜/ITO層/銅層/鎳-銅合金層所構成積層板之評價]同樣進行評價。結果如表3所示。 The evaluation was carried out in the same manner as in the above [Evaluation of a laminate composed of a PET film/ITO layer/copper layer/nickel-copper alloy layer]. The results are shown in Table 3.
表3和表1所示的結果相同，非離子系界面活性劑之濁點與銅配線圖案的蝕刻性之間，被認定有一定的相關關係。亦即，各實施例之每個側蝕量及直線性均良好，綜合評價也為A、B或C。反之，各比較例之每個側蝕量及直線性和實施例相比皆較差，綜合評價為D。就此等結果可知，藉由使用本發明的蝕刻液，不論金屬氧化物層與罩蓋金屬層的材質為何，皆能夠將銅與金屬氧化物並存的蝕刻對象物共同以低側蝕量進行蝕刻。 The results shown in Table 3 and Table 1 are the same, and there is a certain correlation between the cloud point of the nonionic surfactant and the etching property of the copper wiring pattern. That is, each of the side etching amount and the linearity of each of the examples was good, and the overall evaluation was also A, B or C. On the contrary, each of the side etching amount and the linearity of each comparative example was inferior to the examples, and the overall evaluation was D. As a result of the above, it is understood that the etching liquid of the present invention can be etched with a low side etching amount together with an etching target in which copper and a metal oxide coexist, regardless of the material of the metal oxide layer and the cap metal layer.
1‧‧‧基材 1‧‧‧Substrate
2‧‧‧金屬氧化物層 2‧‧‧ metal oxide layer
3‧‧‧銅層 3‧‧‧ copper layer
4‧‧‧罩蓋金屬層 4‧‧‧ Cover metal layer
5‧‧‧光阻圖案 5‧‧‧resist pattern
6‧‧‧罩蓋金屬配線圖案 6‧‧‧Cover metal wiring pattern
7‧‧‧銅配線圖案 7‧‧‧Bronze wiring pattern
8‧‧‧露出部分 8‧‧‧Exposed part
9‧‧‧金屬氧化物配線圖案 9‧‧‧Metal oxide wiring pattern
10‧‧‧積層配線圖案 10‧‧‧Multilayer wiring pattern
100‧‧‧積層板 100‧‧‧ laminate
L,W1,W2‧‧‧線寬 L, W1, W2‧‧‧ line width
S‧‧‧線距 S‧‧‧ line spacing
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| JP5018581B2 (en) * | 2008-03-21 | 2012-09-05 | 東亞合成株式会社 | Etching method of transparent conductive film using etching solution |
| JP2009235438A (en) * | 2008-03-26 | 2009-10-15 | Toagosei Co Ltd | Etching liquid, etching method using the same, and substrate to be etched |
| JP5443863B2 (en) * | 2009-07-09 | 2014-03-19 | 株式会社Ａｄｅｋａ | Etching composition for copper-containing material and method for etching copper-containing material |
-
2014
- 2014-02-19 JP JP2015512332A patent/JP6354084B2/en not_active Expired - Fee Related
- 2014-02-19 CN CN201480021975.0A patent/CN105143515B/en not_active Expired - Fee Related
- 2014-02-19 WO PCT/JP2014/053844 patent/WO2014171174A1/en active Application Filing
- 2014-02-19 KR KR1020157030028A patent/KR20150142695A/en active IP Right Grant
- 2014-03-03 TW TW103107018A patent/TWI634194B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CN105143515B (en) | 2019-03-08 |
| JPWO2014171174A1 (en) | 2017-02-16 |
| TWI634194B (en) | 2018-09-01 |
| JP6354084B2 (en) | 2018-07-11 |
| CN105143515A (en) | 2015-12-09 |
| WO2014171174A1 (en) | 2014-10-23 |
| KR20150142695A (en) | 2015-12-22 |
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