TW201625815A - Liquid composition and etching process using the same - Google Patents
Liquid composition and etching process using the same Download PDFInfo
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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
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Abstract
Description
本發明關於一種液體組成物，該液體組成物用於在由銦、鎵、鋅及氧構成之氧化物(IGZO)上形成之銅或銅作為主成分之金屬化合物的蝕刻，抑制對於IGZO的損傷並蝕刻銅或銅作為主成分之金屬化合物；並係關於利用該液體組成物之蝕刻方法，及藉由該方法製造之基板。The present invention relates to a liquid composition for etching a metal compound containing copper or copper as a main component formed on an oxide (IGZO) composed of indium, gallium, zinc and oxygen to suppress damage to IGZO And etching a metal compound containing copper or copper as a main component; and an etching method using the liquid composition, and a substrate produced by the method.
近年，電子裝置的小型化、輕量化及低耗電化正發展中，特別是液晶顯示器、電致發光顯示器等顯示裝置的領域中，作為半導體層的材料，各種氧化物半導體材料的開發正進行中。In recent years, in the field of display devices such as liquid crystal displays and electroluminescence displays, development of various oxide semiconductor materials is underway in the field of display devices such as liquid crystal displays and electroluminescence displays. in.
氧化物半導體材料主要由銦、鎵、鋅及錫等構成，有人對銦・鎵・鋅氧化物(IGZO)、銦・鎵氧化物(IGO)、銦・錫・鋅氧化物(ITZO)、銦・鎵・鋅・錫氧化物(IGZTO)、鎵・鋅氧化物(GZO)、鋅・錫氧化物(ZTO)等各種組成進行了研究。其中特別是關於IGZO的研究正積極進行中。The oxide semiconductor material is mainly composed of indium, gallium, zinc, tin, etc., and is indium, gallium, zinc oxide (IGZO), indium, gallium oxide (IGO), indium, tin, zinc oxide (ITZO), indium. Various studies such as gallium, zinc, tin oxide (IGZTO), gallium, zinc oxide (GZO), and zinc/tin oxide (ZTO) have been studied. Among them, research on IGZO in particular is actively underway.
上述IGZO，例如作為薄膜電晶體(TFT; Thin Film Transistor)等電子元件使用時，可使用濺射法等成膜處理於玻璃等基板上形成。然後，使用抗蝕劑等形成掩膜進行蝕刻而形成電極圖案。進一步於其上使用濺射法等成膜處理形成銅(Cu)、鉬(Mo)等，然後，使用抗蝕劑等形成掩膜進行蝕刻而形成源極・汲極配線。該蝕刻方法有濕式(wet)法與乾式(dry)法，濕式法中使用蝕刻液。When the IGZO is used as an electronic component such as a thin film transistor (TFT), it can be formed on a substrate such as glass by a film formation process such as a sputtering method. Then, a mask is formed using a resist or the like to form an electrode pattern. Further, copper (Cu), molybdenum (Mo), or the like is formed by a film formation process such as a sputtering method, and then a mask is formed using a resist or the like to form a source/drain wiring. The etching method includes a wet method and a dry method, and an etching method is used in the wet method.
IGZO可藉由酸或鹼輕易地蝕刻為一般公知，使用該等蝕刻液形成源極・汲極配線時，作為基底的IGZO有容易腐蝕的傾向。由於該IGZO的腐蝕，有時會有TFT的電特性發生劣化的情況。故，通常於IGZO上形成保護層後，採用形成源極・汲極配線的蝕刻停止(etch stopper)型結構(參照圖1)，但製造變得繁雜，其結果為導致成本的增加。因此，為了採用保護層為非必要的背通道蝕刻(back-channel etch)型結構(參照圖2)，期望可有抑制對於IGZO的損傷並可蝕刻各種配線材料的蝕刻液。It is generally known that IGZO can be easily etched by an acid or a base. When the source/drain wiring is formed using these etching liquids, IGZO as a base tends to be easily corroded. Due to the corrosion of the IGZO, the electrical characteristics of the TFT may be deteriorated. Therefore, an etch stopper type structure (see FIG. 1) in which a source/drain wiring is formed is usually formed after forming a protective layer on IGZO, but the manufacturing is complicated, and as a result, an increase in cost is caused. Therefore, in order to use a back-channel etch type structure (see FIG. 2) which is unnecessary for the protective layer, it is desirable to have an etching liquid which can suppress damage to IGZO and can etch various wiring materials.
專利文獻1(國際公開第2011/021860號)中，揭示了使用由(A)過氧化氫5.0～25.0重量%、(B)氟化合物0.01～1.0重量%、(C)唑類化合物0.1～5.0重量%、(D)選自於由膦酸衍生物或其鹽構成之群組中之1種以上之化合物0.1～10.0重量%、及(E)水構成的蝕刻液而蝕刻銅作為主成分的金屬膜的方法。 但，專利文獻1中所揭示的蝕刻液，由過氧化氫、氟化合物、唑類化合物及膦酸衍生物或其鹽構成，但只揭示了1－羥基亞乙基－1,1－二膦酸或其鹽作為膦酸衍生物或其鹽，並沒有對摻合胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)、五亞乙基六胺八(亞甲基膦酸)加以記載。又，膦酸衍生物或其鹽係為過氧化氫的安定化而添加，並未提及對於IGZO的損傷。已確認摻合有過氧化氫、氟化合物、唑類化合物及1－羥基亞乙基－1,1－二膦酸的液體組成物對於IGZO的損傷(參照比較例2)，就抑制對於IGZO的損傷並蝕刻金屬化合物的液體組成物而言並非令人滿意。Patent Document 1 (International Publication No. 2011/021860) discloses the use of (A) 5.0 to 25.0% by weight of hydrogen peroxide, (B) 0.01 to 1.0% by weight of a fluorine compound, and (C) an azole compound of 0.1 to 5.0. The weight % and (D) are selected from 0.1 to 10.0% by weight of one or more compounds of the group consisting of a phosphonic acid derivative or a salt thereof, and (E) an etching liquid composed of water to etch copper as a main component. Method of metal film. However, the etching liquid disclosed in Patent Document 1 is composed of hydrogen peroxide, a fluorine compound, an azole compound, and a phosphonic acid derivative or a salt thereof, but only 1-hydroxyethylidene-1,1-diphosphine is disclosed. An acid or a salt thereof as a phosphonic acid derivative or a salt thereof, which is not doped with an amine tris(methylenephosphonic acid), N,N,N',N'-ethylenediamine oxime (methylene phosphonic acid) Diethylenetriamine penta (methylene phosphonic acid), bis(hexamethylene)triamine penta (methylene phosphonic acid), pentaethylene hexamine octa (methylene phosphonic acid) . Further, the phosphonic acid derivative or a salt thereof is added for the stabilization of hydrogen peroxide, and no damage to IGZO is mentioned. It has been confirmed that the liquid composition in which hydrogen peroxide, a fluorine compound, an azole compound, and 1-hydroxyethylidene-1,1-diphosphonic acid are blended is damaged by IGZO (refer to Comparative Example 2), and inhibition of IGZO is suppressed. It is not satisfactory to damage and etch the liquid composition of the metal compound.
專利文獻2(國際公開第2009/066750號)中，藉由使用由含有鹼的水溶液構成的鹼性蝕刻液組成物，於含有非晶系氧化物膜、與選自於由鋁(Al)、Al合金、銅(Cu)、Cu合金、銀(Ag)及Ag合金構成之群組中之至少1種所構成之金屬膜的疊層膜的蝕刻中，可選擇性地蝕刻該金屬膜。 但，專利文獻2中所揭示的蝕刻液組成物，為由含有鹼的水溶液構成的鹼性蝕刻液組成物，已確認摻合有過氧化氫及氨的液體組成物對於IGZO的損傷(參照比較例3)，就抑制對於IGZO的損傷並蝕刻金屬化合物的液體組成物而言並非令人滿意。 [專利文獻]In the patent document 2 (International Publication No. 2009/066750), an alkaline etching liquid composition comprising an aqueous solution containing an alkali is used, and an amorphous oxide film is contained and is selected from aluminum (Al). The metal film can be selectively etched in the etching of the laminated film of the metal film composed of at least one of the group consisting of an Al alloy, a copper (Cu), a Cu alloy, a silver (Ag), and an Ag alloy. However, the etching liquid composition disclosed in Patent Document 2 is an alkaline etching liquid composition composed of an aqueous solution containing a base, and it has been confirmed that the liquid composition in which hydrogen peroxide and ammonia are blended is damaged by IGZO (refer to comparison). Example 3) is not satisfactory in terms of suppressing damage to IGZO and etching a liquid composition of a metal compound. [Patent Literature]
[專利文獻1]國際公開第2011/021860號 [專利文獻2]國際公開第2009/066750號[Patent Document 1] International Publication No. 2011/021860 [Patent Document 2] International Publication No. 2009/066750
[發明所欲解決之課題][Problems to be solved by the invention]
本發明之課題為提供一種液體組成物，該液體組成物抑制對於IGZO的損傷並蝕刻在IGZO上形成之銅或銅作為主成分之金屬化合物；並提供一種蝕刻方法，其特徵為：利用該液體組成物使其接觸在IGZO上形成之銅或銅作為主成分之金屬化合物；並提供適用該蝕刻方法而製造之基板。 [解決課題之手段]An object of the present invention is to provide a liquid composition which suppresses damage to IGZO and etches a metal compound in which copper or copper is formed as a main component formed on IGZO, and provides an etching method characterized by using the liquid The composition is brought into contact with a metal compound in which copper or copper formed on IGZO is used as a main component; and a substrate manufactured by the etching method is provided. [Means for solving the problem]
本案發明人們為解決上述課題而進行研究的結果，發現特徵為：含有(A)過氧化氫、(B)酸、(C)氟離子供給源、(D)選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)、五亞乙基六胺八(亞甲基膦酸)構成之群組中之1種以上之化合物、(E)過氧化氫安定劑、及(F)水，且pH值為5以下之液體組成物，可解決上述課題。 本發明係基於此等發現而完成。亦即，本發明如下所述。As a result of research conducted by the inventors of the present invention to solve the above problems, it has been found to contain (A) hydrogen peroxide, (B) acid, (C) a fluoride ion supply source, and (D) selected from an amine group (Asian). Methylphosphonic acid), N,N,N',N'-ethylenediamine oxime (methylene phosphonic acid), diethylenetriamine penta (methylene phosphonic acid), bis(hexamethylene) One or more compounds of the group consisting of triamine penta (methylene phosphonic acid) and pentaethylene hexamine octa (methylene phosphonic acid), (E) hydrogen peroxide stabilizer, and (F) Water, and a liquid composition having a pH of 5 or less, can solve the above problems. The present invention has been completed based on these findings. That is, the present invention is as follows.
[1]一種液體組成物，係用以抑制對由銦、鎵、鋅及氧構成之氧化物的損傷，並蝕刻在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物，其特徵為：含有(A)過氧化氫、(B)酸、(C)氟離子供給源、(D)選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)、五亞乙基六胺八(亞甲基膦酸)構成之群組中之1種以上之化合物、(E)過氧化氫安定劑、及(F)水，且pH値為5以下。 [2]如第1項之液體組成物，其特徵為：用以蝕刻在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物，及選自於由鈦或鈦作為主成分之金屬化合物、鉬或鉬作為主成分之金屬化合物、鉬鈦合金、及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物。 [3]如第1項之液體組成物，其中，(B)酸係選自於由硝酸、硫酸、磷酸、鹽酸、氫氟酸、甲磺酸、醯胺硫酸、乙酸、甘醇酸、乳酸、丙二酸、馬來酸、琥珀酸、蘋果酸、酒石酸及檸檬酸構成之群組中之1種以上之化合物。 [4]如第1項之液體組成物，其中，(C)氟離子供給源係選自於由氫氟酸、氟化銨及酸性氟化銨構成之群組中之1種以上之化合物。 [5]如第1項之液體組成物，其特徵為：其中(E)過氧化氫安定劑係選自於由苯基脲、2－苯氧基乙醇(phenylglycol)、苯基乙二醇(phenylethyleneglycol)、苯酚磺酸、乙醯胺苯、乙醯氧乙苯胺、乙醯胺苯酚、羥基苯甲酸、對胺基苯甲酸、對胺基苯酚、3,5－二胺基苯甲酸、對胺基苯磺酸、苯胺、N－甲基苯胺、8－羥基喹啉、鄰乙醯替甲苯胺、間乙醯替甲苯胺、二苯胺、苯酚、及苯甲醚構成之群組中之1種以上之具有苯基之過氧化氫安定劑。 [6]如第5項之液體組成物，其中，具有苯基之過氧化氫安定劑係選自於由苯基脲、2－苯氧基乙醇、苯基乙二醇及苯酚磺酸構成之群組中之1種以上之化合物。 [7]一種蝕刻方法，係蝕刻銅或銅作為主成分之金屬化合物之方法，係使如第1至6項中任一項之液體組成物接觸在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物。 [8]一種蝕刻方法，係蝕刻銅或銅作為主成分之金屬化合物、及鈦或鈦作為主成分之金屬化合物之方法，係使如第1至6項中任一項之液體組成物接觸在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物、及鈦或鈦作為主成分之金屬化合物。 [9]一種蝕刻方法，係蝕刻銅或銅作為主成分之金屬化合物，及選自於由鉬或鉬作為主成分之金屬化合物、鉬鈦合金、及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物之方法，係使如第1至6項中任一項之液體組成物接觸在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物，及選自於由鈦或鈦作為主成分之金屬化合物、鉬鈦合金及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物。 [10]一種基板，係適用如第7項之蝕刻方法，藉由蝕刻在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物而製造。 [11]一種基板，係適用如第8項之蝕刻方法，藉由蝕刻在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物、及鈦或鈦作為主成分之金屬化合物而製造。 [12]一種基板，係適用如第9項之蝕刻方法，藉由蝕刻在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物，及選自於由鉬或鉬作為主成分之金屬化合物、鉬鈦合金、及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物而製造。 本發明之較佳態樣如下所示。 [1]一種液體組成物，係用以蝕刻在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物，其特徵為：含有(A)過氧化氫、(B)不含氟原子之酸(D成分除外)、(C)氟離子供給源、(D)選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)及五亞乙基六胺八(亞甲基膦酸)構成之群組中之1種以上之化合物、(E)過氧化氫安定劑、及(F)水，且pH値為5以下。 [2]如[1]之液體組成物，其中，(B)不含氟原子之酸係(B1)選自於由硝酸、硫酸、磷酸及鹽酸構成之群組中之1種以上之化合物。 [3]如[1]之液體組成物，其中，(B)不含氟原子之酸係(B1)與(B2)之組合，(B1)係選自於由硝酸、硫酸、磷酸及鹽酸構成之群組中之1種以上之化合物，(B2)係選自於由甲磺酸、醯胺硫酸、乙酸、甘醇酸、乳酸、丙二酸、馬來酸、琥珀酸、蘋果酸、酒石酸及檸檬酸構成之群組中之1種以上之化合物。 [4]如[1]至[3]中任一項之液體組成物，其中，(D)選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)及五亞乙基六胺八(亞甲基膦酸)構成之群組中之1種以上之化合物之含量為0.001質量%～0.1質量%之範圍內。 [5]如[1]至[4]中任一項之液體組成物，其中，(C)氟離子供給源係選自於由氫氟酸、氟化銨及酸性氟化銨構成之群組中之1種以上之化合物。 [6]如[1]至[5]中任一項之液體組成物，其中，(E)過氧化氫安定劑係選自於由苯基脲、2－苯氧基乙醇、苯基乙二醇、苯酚磺酸、乙醯胺苯、乙醯氧乙苯胺、乙醯胺苯酚、羥基苯甲酸、對胺基苯甲酸、對胺基苯酚、3,5－二胺基苯甲酸、對胺基苯磺酸、苯胺、N－甲基苯胺、8－羥基喹啉、鄰乙醯替甲苯胺、間乙醯替甲苯胺、二苯胺、苯酚及苯甲醚構成之群組中之1種以上之具有苯基之過氧化氫安定劑。 [7]如[6]之液體組成物，其中，具有苯基之過氧化氫安定劑係選自於由苯基脲、2－苯氧基乙醇、苯基乙二醇及苯酚磺酸構成之群組中之1種以上之化合物。 [8]如[1]至[7]中任一項之液體組成物，其係用於蝕刻在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物，及選自於由鈦或鈦作為主成分之金屬化合物、鉬或鉬作為主成分之金屬化合物、鉬鈦合金及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物。 [9]一種蝕刻方法，係蝕刻在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物之方法； 係使含有(A)過氧化氫、(B)不含氟原子之酸(D成分除外)、(C)氟離子供給源、(D)選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)及五亞乙基六胺八(亞甲基膦酸)構成之群組中之1種以上之化合物、(E)過氧化氫安定劑、及(F)水，且pH値為5以下之液體組成物，接觸在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物，而蝕刻銅或銅作為主成分之金屬化合物之方法。 [10]如[9]之蝕刻方法，其係蝕刻在由銦、鎵、鋅及氧構成之氧化物上未介隔保護層而形成之銅或銅作為主成分之金屬化合物。 [11]一種蝕刻方法，係蝕刻在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物、及鈦或鈦作為主成分之金屬化合物之方法； 係使含有(A)過氧化氫、(B)不含氟原子之酸(D成分除外)、(C)氟離子供給源、(D)選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)及五亞乙基六胺八(亞甲基膦酸)構成之群組中之1種以上之化合物、(E)過氧化氫安定劑、及(F)水，且pH値為5以下之液體組成物，接觸在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物、及鈦或鈦作為主成分之金屬化合物，而蝕刻銅或銅作為主成分之金屬化合物、及鈦或鈦作為主成分之金屬化合物之方法。 [12]如[11]之蝕刻方法，其係蝕刻在由銦、鎵、鋅及氧構成之氧化物上未介隔保護層而形成之銅或銅作為主成分之金屬化合物、及鈦或鈦作為主成分之金屬化合物。 [13]一種蝕刻方法，係蝕刻在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物，及選自於由鉬或鉬作為主成分之金屬化合物、鉬鈦合金、及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物之方法； 係使含有(A)過氧化氫、(B)不含氟原子之酸(D成分除外)、(C)氟離子供給源、(D)選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)及五亞乙基六胺八(亞甲基膦酸)構成之群組中之1種以上之化合物、(E)過氧化氫安定劑、及(F)水，且pH値為5以下之液體組成物，接觸在由銦、鎵、鋅及氧構成之氧化物上形成之銅或銅作為主成分之金屬化合物，及選自於由鉬或鉬作為主成分之金屬化合物、鉬鈦合金及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物，而蝕刻銅或銅作為主成分之金屬化合物，及選自於由鉬或鉬作為主成分之金屬化合物、鉬鈦合金及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物之方法。 [14]如[13]之蝕刻方法，其係蝕刻在由銦、鎵、鋅及氧構成之氧化物上未介隔保護層而形成之銅或銅作為主成分之金屬化合物，及選自於由鉬或鉬作為主成分之金屬化合物、鉬鈦合金、及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物。 [15]如[9]至[14]中任一項之液體組成物，其中，(B)不含氟原子之酸係(B1)選自於由硝酸、硫酸、磷酸及鹽酸構成之群組中之1種以上之化合物。 [16]如[9]至[14]中任一項之液體組成物，其中，(B)不含氟原子之酸係(B1)與(B2)之組合，(B1)係選自於由硝酸、硫酸、磷酸及鹽酸構成之群組中之1種以上之化合物，(B2)係選自於由甲磺酸、醯胺硫酸、乙酸、甘醇酸、乳酸、丙二酸、馬來酸、琥珀酸、蘋果酸、酒石酸及檸檬酸構成之群組中之1種以上之化合物。 [17]如[9]至[16]中任一項之液體組成物，其中，(D)選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)及五亞乙基六胺八(亞甲基膦酸)構成之群組中之1種以上之化合物之含量為0.001質量%～0.1質量%之範圍內。 [18]如[9]至[17]中任一項之液體組成物，其中，(C)氟離子供給源係選自於由氫氟酸、氟化銨及酸性氟化銨構成之群組中之1種以上之化合物。 [19]如[9]至[18]中任一項之液體組成物，其中，(E)過氧化氫安定劑係選自於由苯基脲、2－苯氧基乙醇、苯基乙二醇、苯酚磺酸、乙醯胺苯、乙醯氧乙苯胺、乙醯胺苯酚、羥基苯甲酸、對胺基苯甲酸、對胺基苯酚、3,5－二胺基苯甲酸、對胺基苯磺酸、苯胺、N－甲基苯胺、8－羥基喹啉、鄰乙醯替甲苯胺、間乙醯替甲苯胺、二苯胺、苯酚及苯甲醚構成之群組中之1種以上之具有苯基之過氧化氫安定劑。 [20]如[19]之液體組成物，其中，具有苯基之過氧化氫安定劑係選自於由苯基脲、2－苯氧基乙醇、苯基乙二醇及苯酚磺酸構成之群組中之1種以上之化合物。 [發明之效果][1] A liquid composition for suppressing damage to an oxide composed of indium, gallium, zinc, and oxygen, and etching copper or copper formed on an oxide composed of indium, gallium, zinc, and oxygen a metal component of a main component, comprising: (A) hydrogen peroxide, (B) acid, (C) a fluoride ion supply source, and (D) selected from the group consisting of aminotris (methylenephosphonic acid), N , N, N', N'-ethylenediamine oxime (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), bis(hexamethylene) triamine penta (methylene a compound of the group consisting of phosphonic acid), pentaethylenehexamine octa (methylene phosphonic acid), (E) hydrogen peroxide stabilizer, and (F) water, and having a pH of 5 the following. [2] The liquid composition according to Item 1, which is characterized by: a metal compound for etching copper or copper formed on an oxide composed of indium, gallium, zinc, and oxygen as a main component, and is selected from the group consisting of One or more metal compounds of a group consisting of a metal compound containing titanium or titanium as a main component, a metal compound containing molybdenum or molybdenum as a main component, a molybdenum-titanium alloy, and a metal compound containing molybdenum and titanium as main components. [3] The liquid composition according to Item 1, wherein the (B) acid is selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, methanesulfonic acid, decylamine sulfuric acid, acetic acid, glycolic acid, and lactic acid. One or more compounds selected from the group consisting of malonic acid, maleic acid, succinic acid, malic acid, tartaric acid, and citric acid. [4] The liquid composition according to Item 1, wherein the (C) fluoride ion supply source is one or more compounds selected from the group consisting of hydrofluoric acid, ammonium fluoride, and acidic ammonium fluoride. [5] The liquid composition according to Item 1, wherein (E) the hydrogen peroxide stabilizer is selected from the group consisting of phenylurea, 2-phenyloxyl (phenylglycol), and phenylethylene glycol ( Phenylethyleneglycol), phenolsulfonic acid, acetaminophen, acetophenone, acetaminophen phenol, hydroxybenzoic acid, p-aminobenzoic acid, p-aminophenol, 3,5-diaminobenzoic acid, p-amine One of a group consisting of benzenesulfonic acid, aniline, N-methylaniline, 8-hydroxyquinoline, o-acetamididine, m-ethylformamide, diphenylamine, phenol, and anisole The above hydrogen peroxide stabilizer having a phenyl group. [6] The liquid composition of item 5, wherein the hydrogen peroxide stabilizer having a phenyl group is selected from the group consisting of phenylurea, 2-phenoxyethanol, phenylethylene glycol, and phenolsulfonic acid. One or more compounds in the group. [7] An etching method for etching a metal compound of copper or copper as a main component, wherein the liquid composition according to any one of items 1 to 6 is contacted with oxidation by indium, gallium, zinc and oxygen A metal compound in which copper or copper is formed as a main component. [8] An etching method in which a metal compound which etches copper or copper as a main component and a metal compound in which titanium or titanium is a main component is a method in which the liquid composition according to any one of items 1 to 6 is contacted A metal compound containing copper or copper as a main component formed on an oxide composed of indium, gallium, zinc, and oxygen, and a metal compound containing titanium or titanium as a main component. [9] An etching method comprising a metal compound which etches copper or copper as a main component, and a metal compound selected from a metal compound containing molybdenum or molybdenum as a main component, a molybdenum titanium alloy, and a metal compound containing molybdenum and titanium as main components. A method of contacting one or more metal compounds in the group with copper or copper formed on an oxide composed of indium, gallium, zinc, and oxygen by contacting the liquid composition according to any one of items 1 to 6. A metal compound having a main component and one or more metal compounds selected from the group consisting of a metal compound containing titanium or titanium as a main component, a molybdenum titanium alloy, and a metal compound containing molybdenum and titanium as main components. [10] A substrate produced by the etching method according to item 7, which is formed by etching a metal compound containing copper or copper as a main component formed on an oxide composed of indium, gallium, zinc and oxygen. [11] A substrate to which the etching method according to item 8 is applied, by etching a metal compound containing copper or copper as a main component formed on an oxide composed of indium, gallium, zinc, and oxygen, and titanium or titanium as Manufactured from a metal compound of the main component. [12] A substrate to which the etching method according to item 9 is applied, by etching a metal compound having copper or copper as a main component formed on an oxide composed of indium, gallium, zinc, and oxygen, and is selected from the group consisting of Molybdenum or molybdenum is produced as a metal compound of a main component, a molybdenum-titanium alloy, and a metal compound of a group consisting of a metal compound containing molybdenum and titanium as a main component. Preferred aspects of the invention are as follows. [1] A liquid composition for etching a metal compound containing copper or copper formed on an oxide composed of indium, gallium, zinc, and oxygen as a main component, characterized by containing (A) hydrogen peroxide, (B) an acid having no fluorine atom (except for component D), (C) a source of fluoride ion, and (D) selected from the group consisting of aminotris(methylenephosphonic acid), N,N,N',N' - ethylenediamine oxime (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), bis(hexamethylene)triamine penta (methylene phosphonic acid) and pentaethylene One or more compounds of the group consisting of hexaamine octa (methylene phosphonic acid), (E) hydrogen peroxide stabilizer, and (F) water, and having a pH of 5 or less. [2] The liquid composition according to [1], wherein the (B) acid group (B1) having no fluorine atom is selected from the group consisting of one or more compounds selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and hydrochloric acid. [3] The liquid composition according to [1], wherein (B) a combination of an acid system (B1) and (B2) having no fluorine atom, (B1) is selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and hydrochloric acid. One or more compounds in the group, (B2) is selected from the group consisting of methanesulfonic acid, decylamine sulfuric acid, acetic acid, glycolic acid, lactic acid, malonic acid, maleic acid, succinic acid, malic acid, tartaric acid. And one or more compounds in the group consisting of citric acid. [4] The liquid composition according to any one of [1] to [3] wherein (D) is selected from the group consisting of aminotris(methylenephosphonic acid), N,N,N',N'- Ethylenediamine oxime (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), bis(hexamethylene)triamine penta (methylene phosphonic acid) and pentaethylene The content of one or more compounds in the group consisting of amine octa (methylene phosphonic acid) is in the range of 0.001% by mass to 0.1% by mass. [5] The liquid composition according to any one of [1] to [4] wherein the (C) fluoride ion supply source is selected from the group consisting of hydrofluoric acid, ammonium fluoride, and acidic ammonium fluoride. One or more compounds. [6] The liquid composition according to any one of [1] to [5] wherein (E) the hydrogen peroxide stabilizer is selected from the group consisting of phenylurea, 2-phenoxyethanol, and phenylethylene Alcohol, phenolsulfonic acid, acetophene benzene, acetophenone, acetaminophen phenol, hydroxybenzoic acid, p-aminobenzoic acid, p-aminophenol, 3,5-diaminobenzoic acid, p-amino group One or more of the group consisting of benzenesulfonic acid, aniline, N-methylaniline, 8-hydroxyquinoline, o-acetamididine, m-ethylformamide, diphenylamine, phenol, and anisole A hydrogen peroxide stabilizer having a phenyl group. [7] The liquid composition according to [6], wherein the hydrogen peroxide stabilizer having a phenyl group is selected from the group consisting of phenylurea, 2-phenoxyethanol, phenylethylene glycol, and phenolsulfonic acid. One or more compounds in the group. [8] The liquid composition according to any one of [1] to [7] which is used for etching a metal compound containing copper or copper as a main component formed on an oxide composed of indium, gallium, zinc and oxygen. And one or more metals selected from the group consisting of a metal compound containing titanium or titanium as a main component, a metal compound containing molybdenum or molybdenum as a main component, a molybdenum-titanium alloy, and a metal compound containing molybdenum and titanium as main components Compound. [9] An etching method for etching a metal compound having copper or copper as a main component formed on an oxide composed of indium, gallium, zinc, and oxygen; containing (A) hydrogen peroxide, (B) An acid containing no fluorine atom (except for component D), (C) a source of fluoride ion, and (D) selected from the group consisting of aminotris (methylene phosphonic acid), N, N, N', N'-ethylene Amine (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), bis (hexamethylene) triamine penta (methylene phosphonic acid) and pentaethylene hexamine a liquid composition having at least one of a group consisting of (methylene phosphonic acid), (E) a hydrogen peroxide stabilizer, and (F) water, and having a pH of 5 or less, in contact with indium, A method of etching a metal compound having copper or copper as a main component by forming a metal compound of copper or copper as a main component formed on an oxide composed of gallium, zinc and oxygen. [10] The etching method according to [9], which is a metal compound in which copper or copper formed as a main component is formed by etching a layer composed of indium, gallium, zinc, and oxygen without interposing a protective layer. [11] An etching method for etching a metal compound containing copper or copper as a main component formed on an oxide composed of indium, gallium, zinc, and oxygen, and a metal compound containing titanium or titanium as a main component; An acid containing (A) hydrogen peroxide, (B) a fluorine-free atom (excluding the D component), (C) a fluoride ion supply source, and (D) selected from the group consisting of aminotris (methylenephosphonic acid), N , N, N', N'-ethylenediamine oxime (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), bis(hexamethylene) triamine penta (methylene One or more compounds of the group consisting of phosphonic acid) and pentaethylenehexamine octa (methylene phosphonic acid), (E) hydrogen peroxide stabilizer, and (F) water, and having a pH of 5 The following liquid composition is in contact with a metal compound containing copper or copper as a main component formed on an oxide composed of indium, gallium, zinc, and oxygen, and a metal compound containing titanium or titanium as a main component, and etching copper or copper as a A method of a metal compound of a main component and a metal compound of titanium or titanium as a main component. [12] The etching method according to [11], which is a metal compound in which copper or copper is formed as a main component, and titanium or titanium is formed by etching an oxide composed of indium, gallium, zinc, and oxygen without interposing a protective layer. A metal compound as a main component. [13] An etching method for etching a metal compound containing copper or copper as a main component formed on an oxide composed of indium, gallium, zinc, and oxygen, and a metal compound selected from molybdenum or molybdenum as a main component, A method of forming a metal compound of a group consisting of a molybdenum-titanium alloy and a metal compound containing molybdenum and titanium as a main component; (A) hydrogen peroxide containing (A) hydrogen peroxide and (B) an acid having no fluorine atom (D) Except for the component), (C) a fluoride ion supply source, (D) selected from the group consisting of aminotris(methylenephosphonic acid), N,N,N',N'-ethylenediamine oxime (methylene phosphonic acid) ), diethylene triamine penta (methylene phosphonic acid), bis (hexamethylene) triamine penta (methylene phosphonic acid) and pentaethylene hexamine octa (methylene phosphonic acid) One or more compounds in the group, (E) hydrogen peroxide stabilizer, and (F) water, and a liquid composition having a pH of 5 or less, in contact with oxidation consisting of indium, gallium, zinc, and oxygen a metal compound containing copper or copper as a main component formed on the object, and a metal compound selected from the group consisting of a metal compound containing molybdenum or molybdenum as a main component, a molybdenum-titanium alloy, and a metal compound containing molybdenum and titanium as main components a metal compound of the above, and a metal compound which etches copper or copper as a main component, and a metal compound selected from a metal compound containing molybdenum or molybdenum as a main component, a molybdenum-titanium alloy, and a metal compound containing molybdenum and titanium as main components. A method of one or more metal compounds. [14] The etching method according to [13], which is a metal compound in which copper or copper as a main component is formed by etching a layer composed of indium, gallium, zinc, and oxygen without interposing a protective layer, and is selected from the group consisting of One or more metal compounds of a group consisting of a metal compound containing molybdenum or molybdenum as a main component, a molybdenum-titanium alloy, and a metal compound containing molybdenum and titanium as main components. [15] The liquid composition according to any one of [9] to [14] wherein (B) the acid group (B1) having no fluorine atom is selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and hydrochloric acid. One or more compounds. [16] The liquid composition according to any one of [9] to [14] wherein (B) a combination of an acid system (B1) and (B2) which does not contain a fluorine atom, (B1) is selected from One or more compounds selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and hydrochloric acid, and (B2) is selected from the group consisting of methanesulfonic acid, decylamine sulfuric acid, acetic acid, glycolic acid, lactic acid, malonic acid, and maleic acid. One or more compounds selected from the group consisting of succinic acid, malic acid, tartaric acid, and citric acid. [17] The liquid composition according to any one of [9] to [16] wherein (D) is selected from the group consisting of aminotris (methylenephosphonic acid), N, N, N', N'- Ethylenediamine oxime (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), bis(hexamethylene)triamine penta (methylene phosphonic acid) and pentaethylene The content of one or more compounds in the group consisting of amine octa (methylene phosphonic acid) is in the range of 0.001% by mass to 0.1% by mass. [18] The liquid composition according to any one of [9] to [17] wherein the (C) fluoride ion supply source is selected from the group consisting of hydrofluoric acid, ammonium fluoride, and acidic ammonium fluoride. One or more compounds. [19] The liquid composition according to any one of [9] to [18] wherein (E) the hydrogen peroxide stabilizer is selected from the group consisting of phenylurea, 2-phenoxyethanol, and phenylethylene Alcohol, phenolsulfonic acid, acetophene benzene, acetophenone, acetaminophen phenol, hydroxybenzoic acid, p-aminobenzoic acid, p-aminophenol, 3,5-diaminobenzoic acid, p-amino group One or more of the group consisting of benzenesulfonic acid, aniline, N-methylaniline, 8-hydroxyquinoline, o-acetamididine, m-ethylformamide, diphenylamine, phenol, and anisole A hydrogen peroxide stabilizer having a phenyl group. [20] The liquid composition according to [19], wherein the hydrogen peroxide stabilizer having a phenyl group is selected from the group consisting of phenylurea, 2-phenoxyethanol, phenylethylene glycol, and phenolsulfonic acid. One or more compounds in the group. [Effects of the Invention]
根據本發明，可提供一種液體組成物，該液體組成物抑制對於IGZO的損傷並蝕刻在IGZO上形成之銅或銅作為主成分之金屬化合物；並提供一種蝕刻方法，其特徵為：使該液體組成物接觸在IGZO上形成之銅或銅作為主成分之金屬化合物；並提供適用該蝕刻方法而製造之基板。又，由於該蝕刻方法可抑制對於IGZO的損傷，不須在IGZO上形成保護層，因此可大幅地降低製造成本，並達成高生產性。According to the present invention, there can be provided a liquid composition which suppresses damage to IGZO and etches a metal compound in which copper or copper is formed as a main component formed on IGZO; and provides an etching method characterized by: The composition is in contact with a metal compound in which copper or copper formed on IGZO is used as a main component; and a substrate manufactured by the etching method is provided. Moreover, since this etching method can suppress damage to IGZO, it is not necessary to form a protective layer on IGZO, so that the manufacturing cost can be greatly reduced and high productivity can be achieved.
＜液體組成物＞ 本發明之液體組成物，其特徵為：含有(A)過氧化氫、(B)不含氟原子之酸(D成分除外)、(C)氟離子供給源、(D)選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)、五亞乙基六胺八(亞甲基膦酸)構成之群組中之1種以上之化合物、(E)過氧化氫安定劑、及(F)水，且pH値為5以下；抑制對於IGZO的損傷，並蝕刻在IGZO上形成之銅或銅作為主成分之金屬化合物。<Liquid Composition> The liquid composition of the present invention is characterized by containing (A) hydrogen peroxide, (B) an acid having no fluorine atom (except for D component), (C) a fluoride ion supply source, and (D) Selected from aminotris (methylene phosphonic acid), N, N, N', N'-ethylenediamine oxime (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid) , one or more compounds of the group consisting of bis(hexamethylene)triamine penta (methylene phosphonic acid) and pentaethylenehexamine octa (methylene phosphonic acid), (E) A hydrogen peroxide stabilizer, and (F) water, and having a pH of 5 or less; suppressing damage to IGZO, and etching a metal compound containing copper or copper as a main component formed on IGZO.
(A)過氧化氫 本發明之液體組成物中，過氧化氫(以下有時稱為A成分)作為氧化劑具有將銅氧化的功能，且對於鉬具有氧化溶解的功能。該液體組成物中之過氧化氫之含量為1質量%以上較佳，2質量%以上更佳，3質量%以上尤佳，30質量%以下較佳，20質量%以下更佳，10質量%以下尤佳，8質量%以下特佳。例如，該液體組成物中之A成分之含量為1～30質量%較佳，2～20質量%更佳，2～10質量%尤佳，3～8質量%特佳。過氧化氫之含量為上述範圍內時，可確保對於含有銅及鉬等之金屬化合物的良好的蝕刻速率，且金屬化合物的蝕刻量的控制變得容易故較佳。(A) Hydrogen peroxide In the liquid composition of the present invention, hydrogen peroxide (hereinafter sometimes referred to as component A) has a function of oxidizing copper as an oxidizing agent, and has a function of oxidative dissolution of molybdenum. The content of hydrogen peroxide in the liquid composition is preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 3% by mass or more, more preferably 30% by mass or less, still more preferably 20% by mass or less, and 10% by mass. The following is particularly preferable, and 8% by mass or less is particularly preferable. For example, the content of the component A in the liquid composition is preferably from 1 to 30% by mass, more preferably from 2 to 20% by mass, still more preferably from 2 to 10% by mass, particularly preferably from 3 to 8% by mass. When the content of the hydrogen peroxide is within the above range, it is possible to ensure a good etching rate for a metal compound containing copper or molybdenum, and it is easy to control the amount of etching of the metal compound.
(B)不含氟原子之酸 本發明之液體組成物中，不含氟原子之酸(以下有時稱為B成分)為使因(A)過氧化氫而氧化的銅溶解者。 B成分可為無機酸亦可為有機酸，例如，可列舉硝酸、硫酸、磷酸、鹽酸、甲磺酸、醯胺硫酸、乙酸、甘醇酸、乳酸、丙二酸、馬來酸、琥珀酸、蘋果酸、酒石酸、檸檬酸等為較佳，硝酸、硫酸、甲磺酸、醯胺硫酸、乙酸更佳，其中硝酸、硫酸特佳。 該等酸可單獨或將多種混合使用。 其中，本發明中(B)不含氟原子之酸，宜含有(B1)選自於由硝酸、硫酸、磷酸及鹽酸構成之群組中之1種以上之化合物為較佳。又，(B)不含氟原子之酸係(B1)與(B2)之組合為較佳，(B1)係選自於由硝酸、硫酸、磷酸及鹽酸構成之群組中之1種以上之化合物，(B2)係選自於由甲磺酸、醯胺硫酸、乙酸、甘醇酸、乳酸、丙二酸、馬來酸、琥珀酸、蘋果酸、酒石酸及檸檬酸構成之群組中之1種以上之化合物。(B) Acid having no fluorine atom In the liquid composition of the present invention, an acid having no fluorine atom (hereinafter sometimes referred to as a component B) is one in which copper oxidized by (A) hydrogen peroxide is dissolved. The component B may be an inorganic acid or an organic acid, and examples thereof include nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, methanesulfonic acid, decylamine sulfuric acid, acetic acid, glycolic acid, lactic acid, malonic acid, maleic acid, and succinic acid. , malic acid, tartaric acid, citric acid, etc. are preferred, and nitric acid, sulfuric acid, methanesulfonic acid, guanamine sulfuric acid, and acetic acid are more preferable, and nitric acid and sulfuric acid are particularly preferred. These acids may be used singly or in combination of plural kinds. In the present invention, (B) the acid having no fluorine atom preferably contains (B1) one or more compounds selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid. Further, (B) a combination of an acid group (B1) and (B2) having no fluorine atom is preferred, and (B1) is selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid. The compound (B2) is selected from the group consisting of methanesulfonic acid, decylamine sulfuric acid, acetic acid, glycolic acid, lactic acid, malonic acid, maleic acid, succinic acid, malic acid, tartaric acid, and citric acid. One or more compounds.
該液體組成物中之B成分之含量為0.01質量%以上較佳，0.1質量%以上更佳，0.5質量%以上尤佳，1質量%以上特佳，30質量%以下較佳，20質量%以下更佳，15質量%以下尤佳，10質量%以下特佳。例如，該液體組成物中之B成分之含量為0.01～30質量%較佳，0.1～20質量%更佳，0.5～15質量%尤佳，1～10質量%特佳。B成分之含量為上述範圍時，可得到對於金屬化合物的良好的蝕刻速率及良好的銅的溶解性。The content of the component B in the liquid composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, more preferably 30% by mass or less, and most preferably 20% by mass or less. More preferably, it is particularly preferably 15% by mass or less, and particularly preferably 10% by mass or less. For example, the content of the component B in the liquid composition is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, particularly preferably 0.5 to 15% by mass, particularly preferably 1 to 10% by mass. When the content of the component B is in the above range, a good etching rate for a metal compound and good solubility of copper can be obtained.
(C)氟離子供給源 本發明之液體組成物中，氟離子供給源(以下有時稱為C成分)係蝕刻鈦的物質。 C成分只要為在液體組成物中產生負氟離子者即可，並無特別限制，可列舉氫氟酸、氟化銨、酸性氟化銨等為較佳，該等物質可單獨或將多種混合使用。其中，以低毒性的觀點觀之，氟化銨、酸性氟化銨更佳。(C) Fluoride ion supply source In the liquid composition of the present invention, a fluoride ion supply source (hereinafter sometimes referred to as a C component) is a material which etches titanium. The component C is not particularly limited as long as it generates negative fluoride ions in the liquid composition, and examples thereof include hydrofluoric acid, ammonium fluoride, and acidic ammonium fluoride. These may be used alone or in combination of plural kinds. use. Among them, ammonium fluoride and acidic ammonium fluoride are more preferable from the viewpoint of low toxicity.
該液體組成物中之C成分之含量為0.01質量%以上較佳，0.05質量%以上更佳，0.1質量%以上尤佳，0.2質量%以上特佳，10質量%以下較佳，1質量%以下更佳，0.5質量%以下尤佳。例如，該液體組成物中之C成分之含量為0.01～10質量%較佳，0.05～1質量%更佳，0.1～0.5質量%尤佳，0.2～0.5質量%特佳。C成分之含量為上述範圍內時，可得到對於金屬的良好的蝕刻速率。又，C成分之含量為10質量%以上時，裝置材料、玻璃等基板的腐蝕變得顯著故為不佳。The content of the component C in the liquid composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, more preferably 10% by mass or less, and 1% by mass or less. More preferably, it is preferably 0.5% by mass or less. For example, the content of the component C in the liquid composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 1% by mass, particularly preferably 0.1 to 0.5% by mass, particularly preferably 0.2 to 0.5% by mass. When the content of the component C is within the above range, a good etching rate for the metal can be obtained. In addition, when the content of the component C is 10% by mass or more, the corrosion of the substrate such as the device material or the glass becomes remarkable, which is not preferable.
(D)選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)及五亞乙基六胺八(亞甲基膦酸)構成之群組中之化合物 本發明之液體組成物中所使用之選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)及五亞乙基六胺八(亞甲基膦酸)構成之群組中之化合物(以下有時稱為D成分)，具有抑制IGZO的蝕刻速率的效果。因此，使用該液體組成物蝕刻在IGZO上形成之銅或銅作為主成分之金屬化合物時，可抑制對於IGZO的損傷。 D成分可分別單獨或多種混合使用，其中胺基三(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)更佳，胺基三(亞甲基膦酸)特佳。(D) is selected from the group consisting of aminotris (methylene phosphonic acid), N, N, N', N'-ethylenediamine oxime (methylene phosphonic acid), diethylene triamine five (methylene Compounds of the group consisting of phosphinic acid, bis(hexamethylene)triamine penta(methylenephosphonic acid) and pentaethylenehexamine octa(methylenephosphonic acid) Used in the group consisting of amine tris (methylene phosphonic acid), N, N, N', N'-ethylene diamine oxime (methylene phosphonic acid), diethylene triamine five (Asia a compound of the group consisting of methylphosphonic acid, bis(hexamethylene)triamine penta (methylene phosphonic acid) and pentaethylenehexamine octa (methylene phosphonic acid) (hereinafter sometimes referred to as It is the D component) and has an effect of suppressing the etching rate of IGZO. Therefore, when the liquid composition is used to etch a metal compound containing copper or copper as a main component formed on IGZO, damage to IGZO can be suppressed. The D component may be used alone or in combination of two or more, wherein the amine tris(methylenephosphonic acid), the bis(hexamethylene)triamine penta (methylene phosphonic acid) are more preferable, and the amine tris(methylenephosphine) Acid) is especially good.
該液體組成物中之D成分之含量為0.001質量%以上較佳，0.01質量%以上更佳，0.02質量%以上尤佳，0.05質量%以上特佳。D成分之含量為上述範圍內時，可抑制對由銦、鎵、鋅及氧構成之氧化物的損傷。又另一方面，D成分之含量，以經濟上的觀點觀之，為5質量%以下較佳，1質量%以下更佳，0.5質量%以下尤佳，0.1質量%以下特佳。The content of the component D in the liquid composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, particularly preferably 0.02% by mass or more, and particularly preferably 0.05% by mass or more. When the content of the component D is within the above range, damage to an oxide composed of indium, gallium, zinc, and oxygen can be suppressed. On the other hand, the content of the component D is preferably 5% by mass or less, more preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less.
(E)過氧化氫安定劑 本發明之液體組成物中，過氧化氫安定劑(以下有時稱為E成分)具有抑制過氧化氫分解的效果。因此，可在銅或銅作為主成分之金屬化合物、鉬或鉬作為主成分之金屬化合物、鈦或鈦作為主成分之金屬化合物溶解於該液體組成物中時抑制過氧化氫的分解。 E成分，通常只要為可作為過氧化氫的安定劑而使用者即可，並無限制，具有苯基之過氧化氫安定劑為較佳。 具有苯基之過氧化氫安定劑，可列舉苯基脲、2－苯氧基乙醇、苯基乙二醇、苯酚磺酸、乙醯胺苯、乙醯氧乙苯胺、乙醯胺苯酚、羥基苯甲酸、對胺基苯甲酸、對胺基苯酚、3,5－二胺基苯甲酸、對胺基苯磺酸、苯胺、N－甲基苯胺、8－羥基喹啉、鄰乙醯替甲苯胺、間乙醯替甲苯胺、二苯胺、苯酚及苯甲醚為較佳，苯基脲、2－苯氧基乙醇、苯基乙二醇及苯酚磺酸更佳，其中苯基脲及2－苯氧基乙醇特佳。該等物質可單獨或將多種混合使用。本發明之液體組成物中，過氧化氫安定劑為具有苯基之過氧化氫安定劑時，可特別地提高過氧化氫的安定性。(E) Hydrogen peroxide stabilizer The hydrogen peroxide stabilizer (hereinafter sometimes referred to as component E) of the liquid composition of the present invention has an effect of suppressing decomposition of hydrogen peroxide. Therefore, decomposition of hydrogen peroxide can be suppressed when a metal compound containing copper or copper as a main component, a metal compound containing molybdenum or molybdenum as a main component, or a metal compound containing titanium or titanium as a main component is dissolved in the liquid composition. The component E is usually a user which can be used as a stabilizer for hydrogen peroxide, and is not limited, and a hydrogen peroxide stabilizer having a phenyl group is preferred. Examples of the hydrogen peroxide stabilizer having a phenyl group include phenylurea, 2-phenoxyethanol, phenylethylene glycol, phenolsulfonic acid, acetaminophen, acetophenone, acetaminophen phenol, and hydroxyl group. Benzoic acid, p-aminobenzoic acid, p-aminophenol, 3,5-diaminobenzoic acid, p-aminobenzenesulfonic acid, aniline, N-methylaniline, 8-hydroxyquinoline, o-ethene Aniline, m-ethylformamide, diphenylamine, phenol and anisole are preferred, and phenylurea, 2-phenoxyethanol, phenylethylene glycol and phenolsulfonic acid are preferred, of which phenylurea and 2 - Phenoxyethanol is particularly preferred. These materials may be used singly or in combination of plural kinds. In the liquid composition of the present invention, when the hydrogen peroxide stabilizer is a hydrogen peroxide stabilizer having a phenyl group, the stability of hydrogen peroxide can be particularly improved.
該液體組成物中之E成分之含量，只要可充分獲得其添加效果即可，並無特別限制，為0.01質量%以上較佳，0.02質量%以上更佳，0.03質量%以上尤佳， 0.5質量%以下較佳，0.3質量%以下更佳，0.1質量%以下尤佳。例如，該液體組成物中之E成分之含量為0.01～0.5質量%較佳，0.02～0.3質量%更佳，0.03～0.1質量%尤佳。The content of the component E in the liquid composition is not particularly limited as long as the effect of the addition is sufficiently obtained, and is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and particularly preferably 0.03% by mass or more, and 0.5 mass%. % or less is preferable, and 0.3% by mass or less is more preferable, and 0.1% by mass or less is particularly preferable. For example, the content of the component E in the liquid composition is preferably 0.01 to 0.5% by mass, more preferably 0.02 to 0.3% by mass, still more preferably 0.03 to 0.1% by mass.
(F)水 本發明之液體組成物中所使用的水，並無特別限制，為已藉由蒸餾、離子交換處理、過濾處理、各種吸附處理等除去金屬離子、有機雜質、顆粒粒子等的水較佳，特別是純水或超純水較佳。(F) Water The water used in the liquid composition of the present invention is not particularly limited, and is water which has been removed by distillation, ion exchange treatment, filtration treatment, various adsorption treatments, and the like to remove metal ions, organic impurities, particles, and the like. Preferably, especially pure water or ultrapure water is preferred.
本發明之液體組成物，為得到期望的pH值，必要時可含有pH調節劑。pH調節劑可列舉氨水、氫氧化鈉、氫氧化鉀、四甲基氫氧化銨等為較佳，該等物質可單獨或將多種混合使用。 本發明之液體組成物之pH值之上限為5以下。pH值大於5時，過氧化氫的安定性降低，又銅或銅作為主成分之金屬化合物、鈦或鈦作為主成分之金屬化合物的蝕刻速率降低故為不佳。又本發明之液體組成物之pH值之下限並無限制，以抑制對裝置材料、周邊部件的損傷的觀點觀之，pH值為0以上較佳，1以上更佳。pH值為上述範圍時，可得到對於銅或銅作為主成分之金屬化合物、鉬或鉬作為主成分之金屬化合物、鈦或鈦作為主成分之金屬化合物的良好的蝕刻速率。The liquid composition of the present invention may contain a pH adjuster if necessary in order to obtain a desired pH. The pH adjusting agent may preferably be ammonia water, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide or the like, and these may be used singly or in combination of plural kinds. The upper limit of the pH of the liquid composition of the present invention is 5 or less. When the pH is more than 5, the stability of hydrogen peroxide is lowered, and the etching rate of the metal compound containing copper or copper as a main component and titanium or titanium as a main component is lowered, which is not preferable. Further, the lower limit of the pH of the liquid composition of the present invention is not limited, and from the viewpoint of suppressing damage to the device material and peripheral members, the pH is preferably 0 or more, more preferably 1 or more. When the pH is in the above range, a good etching rate can be obtained for a metal compound containing copper or copper as a main component, a metal compound containing molybdenum or molybdenum as a main component, and a metal compound containing titanium or titanium as a main component.
本發明之蝕刻液，除上述成分外，在不損害蝕刻液的效果的範圍內，可含有蝕刻液中通常所使用的各種添加劑。例如，可使用唑類化合物、pH緩衝劑等。The etching liquid of the present invention may contain various additives which are generally used in an etching liquid, in addition to the above components, within a range not impairing the effect of the etching liquid. For example, an azole compound, a pH buffer, or the like can be used.
＜蝕刻方法＞ 本發明之蝕刻方法中之蝕刻對象物，為在IGZO上形成之銅或銅作為主成分之金屬化合物。根據本發明之蝕刻方法，可抑制對於IGZO的損傷，並以良好的蝕刻速率蝕刻銅或銅作為主成分之金屬化合物。 又，本發明之蝕刻方法中之蝕刻對象物，為在IGZO上形成之選自於由鈦或鈦作為主成分之金屬化合物、鉬或鉬作為主成分之金屬化合物、鉬鈦合金、鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物。根據本發明之蝕刻方法，可抑制對於IGZO的損傷，並以良好的蝕刻速率蝕刻選自於由鈦或鈦作為主成分之金屬化合物、鉬或鉬作為主成分之金屬化合物、鉬鈦合金、鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物。 此外，本說明書中，「銅作為主成分之金屬化合物」，意即於金屬化合物中含有銅50質量%以上，較佳為60質量%以上，更佳為70質量%以上之金屬化合物。又，「鈦作為主成分之金屬化合物」，意即於金屬化合物中含有鈦50質量%以上，較佳為60質量%以上，更佳為70質量%以上之金屬化合物。「鉬作為主成分之金屬化合物」，意即於金屬化合物中含有鉬50質量%以上，較佳為60質量%以上，更佳為70質量%以上之金屬化合物。又，「鉬與鈦作為主成分之金屬化合物」，意即於金屬化合物中含有鉬與鈦之合計50質量%以上，較佳為60質量%以上，更佳為70質量%以上之金屬化合物。<Etching Method> The object to be etched in the etching method of the present invention is a metal compound containing copper or copper as a main component formed on IGZO. According to the etching method of the present invention, damage to IGZO can be suppressed, and a metal compound having copper or copper as a main component can be etched at a good etching rate. Further, the object to be etched in the etching method of the present invention is a metal compound formed on IGZO selected from a metal compound containing titanium or titanium as a main component, molybdenum or molybdenum as a main component, molybdenum titanium alloy, molybdenum and titanium. One or more metal compounds in the group consisting of metal compounds as a main component. According to the etching method of the present invention, damage to IGZO can be suppressed, and a metal compound selected from a metal compound containing titanium or titanium as a main component, molybdenum or molybdenum as a main component, molybdenum titanium alloy, molybdenum can be etched at a good etching rate. One or more metal compounds in the group consisting of a metal compound containing titanium as a main component. In the present specification, the term “metal compound containing copper as a main component” means a metal compound containing 50% by mass or more of copper, preferably 60% by mass or more, and more preferably 70% by mass or more. In addition, the metal compound containing titanium as a main component means that the metal compound contains 50% by mass or more of titanium, preferably 60% by mass or more, and more preferably 70% by mass or more. The metal compound containing molybdenum as a main component means that the metal compound contains 50% by mass or more of molybdenum, preferably 60% by mass or more, and more preferably 70% by mass or more. In addition, the metal compound containing a total of 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more, of the total amount of molybdenum and titanium is contained in the metal compound.
本發明之蝕刻方法具有使本發明之液體組成物接觸蝕刻對象物之步驟，本發明之液體組成物係特徵為：含有(A)過氧化氫、(B)不含氟原子之酸(D成分除外)、(C)氟離子供給源、(D)選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)及五亞乙基六胺八(亞甲基膦酸)構成之群組中之1種以上之金屬化合物、(E)過氧化氫安定劑、及(F)水，且pH值為5以下之液體組成物。本發明之液體組成物，如＜液體組成物＞中所述。此外，以鈦或鈦作為主成分之金屬化合物為蝕刻對象物時，本發明之液體組成物中之(C)氟離子供給源之含量為0.2質量%～0.5質量%較佳。 銅或銅作為主成分之金屬化合物，可列舉銅(金屬)、銅合金、或氧化銅、氮化銅等。鉬或鉬作為主成分之金屬化合物，可列舉鉬(金屬)、鉬合金、或氧化鉬、氮化鉬等。鈦或鈦作為主成分之金屬化合物，可列舉鈦(金屬)、鈦合金、或氧化鈦、氮化鈦等。The etching method of the present invention has a step of bringing the liquid composition of the present invention into contact with an object to be etched, and the liquid composition of the present invention is characterized by containing (A) hydrogen peroxide and (B) an acid having no fluorine atom (component D) Except), (C) a fluoride ion supply source, (D) selected from the group consisting of aminotris (methylene phosphonic acid), N, N, N', N'-ethylenediamine oxime (methylene phosphonic acid) , diethylene triamine penta (methylene phosphonic acid), bis (hexamethylene) triamine penta (methylene phosphonic acid) and pentaethylene hexamine octa (methylene phosphonic acid) One or more metal compounds in the group, (E) hydrogen peroxide stabilizer, and (F) water, and a liquid composition having a pH of 5 or less. The liquid composition of the present invention is as described in <Liquid Composition>. Further, when the metal compound containing titanium or titanium as a main component is an object to be etched, the content of the (C) fluoride ion supply source in the liquid composition of the present invention is preferably 0.2% by mass to 0.5% by mass. Examples of the metal compound containing copper or copper as a main component include copper (metal), copper alloy, copper oxide, copper nitride, and the like. Examples of the metal compound containing molybdenum or molybdenum as a main component include molybdenum (metal), molybdenum alloy, molybdenum oxide, molybdenum nitride, and the like. Examples of the metal compound containing titanium or titanium as a main component include titanium (metal), titanium alloy, titanium oxide, titanium nitride, and the like.
本發明之蝕刻方法中，就蝕刻對象物而言，可單獨蝕刻銅或銅作為主成分之金屬化合物，亦可單獨蝕刻選自於由鈦、鈦作為主成分之化合物、鉬、鉬作為主成分之金屬化合物、鉬鈦合金、及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之化合物。 又，亦可一次同時蝕刻(i)銅或銅作為主成分之金屬化合物，與(ii)選自於由鈦或鈦作為主成分之金屬化合物、鉬或鉬作為主成分之金屬化合物、鉬鈦合金及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之化合物。 根據本發明之蝕刻方法，可抑制對於IGZO的損傷，並以良好的蝕刻速率一次蝕刻(i)銅或銅作為主成分之金屬化合物，與(ii)選自於由鈦或鈦作為主成分之金屬化合物、鉬或鉬作為主成分之金屬化合物、鉬鈦合金及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之化合物。In the etching method of the present invention, in the etching object, a metal compound containing copper or copper as a main component may be separately etched, or a compound selected from titanium, titanium as a main component, molybdenum or molybdenum may be separately etched as a main component. One or more compounds selected from the group consisting of metal compounds, molybdenum-titanium alloys, and metal compounds containing molybdenum and titanium as main components. Further, it is also possible to simultaneously etch (i) a metal compound containing copper or copper as a main component, and (ii) a metal compound selected from a metal compound containing titanium or titanium as a main component, molybdenum or molybdenum as a main component, molybdenum and titanium. One or more compounds selected from the group consisting of alloys and metal compounds containing molybdenum and titanium as main components. According to the etching method of the present invention, damage to IGZO can be suppressed, and (i) a metal compound in which copper or copper is a main component is etched at a good etching rate, and (ii) is selected from titanium or titanium as a main component. One or more compounds selected from the group consisting of a metal compound, a metal compound containing molybdenum or molybdenum as a main component, a molybdenum-titanium alloy, and a metal compound containing molybdenum and titanium as main components.
本發明之蝕刻方法中係蝕刻對象物之銅或銅作為主成分之金屬化合物、選自於由鈦、鈦作為主成分金屬化合物、鉬、鉬作為主成分金屬化合物、鉬鈦合金、及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物，其形狀並無限制，使用選自於由該等金屬化合物構成之群組中之1種以上之金屬化合物作為平板顯示器的TFT陣列面板上的配線材料時，為薄膜形狀較佳。例如，在氧化矽等絕緣膜上將IGZO圖案化後，形成銅或銅作為主成分之金屬化合物的薄膜，於其上塗布抗蝕劑，將期望的圖案掩模進行曝光轉印、顯影而形成期望的抗蝕劑圖案者作為蝕刻對象物。又，蝕刻對象物亦可為由(i)銅或銅作為主成分之金屬化合物的薄膜，與(ii)選自於由鈦、鈦作為主成分之金屬化合物、鉬、鉬作為主成分之金屬化合物、鉬鈦合金及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之化合物的薄膜所構成的疊層結構。此時，可一次蝕刻由(i)銅或銅作為主成分之金屬化合物的薄膜，與(ii)選自於由鈦、鈦作為主成分之金屬化合物、鉬、鉬作為主成分之金屬化合物、鉬鈦合金及鉬與鈦作為主成分之金屬化合物構成之群組中之1種以上之金屬化合物的薄膜所構成的疊層結構。In the etching method of the present invention, a metal compound containing copper or copper as a main component of an object to be etched, a metal compound containing titanium, titanium as a main component, molybdenum, molybdenum as a main component metal compound, molybdenum titanium alloy, and molybdenum and The metal compound of one or more of the group consisting of a metal compound containing titanium as a main component is not limited in shape, and one or more metal compounds selected from the group consisting of such metal compounds are used as a flat panel display. The wiring material on the TFT array panel is preferably a film shape. For example, after patterning IGZO on an insulating film such as ruthenium oxide, a film of a metal compound containing copper or copper as a main component is formed, a resist is applied thereon, and a desired pattern mask is subjected to exposure transfer and development to form a film. A desired resist pattern is used as an object to be etched. Further, the object to be etched may be a film of a metal compound containing (i) copper or copper as a main component, and (ii) a metal selected from a metal compound containing titanium and titanium as a main component, molybdenum and molybdenum as main components. A laminated structure of a film of a compound, a molybdenum-titanium alloy, and a compound of one or more compounds selected from the group consisting of a metal compound containing molybdenum and titanium as a main component. In this case, a film of a metal compound containing (i) copper or copper as a main component and (ii) a metal compound selected from a metal compound containing titanium and titanium as a main component, molybdenum, and molybdenum as main components may be etched at a time. A laminated structure of a film of one or more metal compounds of a group consisting of a molybdenum-titanium alloy and a metal compound containing molybdenum and titanium as a main component.
本發明中的IGZO，只要本質上為由銦、鎵、鋅及氧構成之氧化物即可，並無特別限制。銦、鎵、鋅的原子比並無特別限制，通常為In/(In+Ga+Zn)＝0.2～0.8、Ga/(In+Ga+Zn)＝0.05～0.6、Zn/(In+Ga+Zn)＝0.05～0.6之範圍。又，亦可含有銦、鎵、鋅及氧以外的微量元素(表示為M)，微量元素的原子比為M/(In+Ga+Zn+M)＜0.05較佳。又，氧化物可為非晶系結構亦可具有結晶性。The IGZO in the present invention is not particularly limited as long as it is essentially an oxide composed of indium, gallium, zinc, and oxygen. The atomic ratio of indium, gallium, and zinc is not particularly limited, and is usually In/(In+Ga+Zn)=0.2 to 0.8, Ga/(In+Ga+Zn)=0.05 to 0.6, and Zn/(In+Ga+ Zn) = a range of 0.05 to 0.6. Further, a trace element other than indium, gallium, zinc, and oxygen (denoted as M) may be contained, and an atomic ratio of the trace element is preferably M/(In+Ga+Zn+M)<0.05. Further, the oxide may have an amorphous structure or may have crystallinity.
蝕刻對象物與液體組成物的接觸溫度為10～70℃的溫度較佳，20～60℃更佳，20～50℃特佳。為10～70℃的溫度範圍時，可得到良好的蝕刻速率。進一步於上述溫度範圍的蝕刻操作可抑制裝置的腐蝕。藉由升高液體組成物的溫度，可提高蝕刻速率，但只要考慮因水的蒸發等而液體組成物的組成變化變大等方面，適當決定最適處理溫度即可。The contact temperature of the object to be etched with the liquid composition is preferably 10 to 70 ° C, more preferably 20 to 60 ° C, and particularly preferably 20 to 50 ° C. When the temperature is in the range of 10 to 70 ° C, a good etching rate can be obtained. Further etching operations in the above temperature range can suppress corrosion of the device. The etching rate can be increased by increasing the temperature of the liquid composition. However, it is only necessary to appropriately determine the optimum processing temperature in consideration of the change in the composition of the liquid composition due to evaporation of water or the like.
使液體組成物接觸蝕刻對象物的方法並無特別限制，例如可採用藉由滴加液體組成物 (單晶圓旋轉處理)、噴霧等形式使其接觸對象物的方法、使對象物浸漬於液體組成物的方法等通常的濕蝕刻法。 【實施例】The method of bringing the liquid composition into contact with the object to be etched is not particularly limited. For example, a method of contacting the object by dropping a liquid composition (single wafer rotation treatment), spraying, or the like may be employed, and the object may be immersed in the liquid. A usual wet etching method such as a method of a composition. [Examples]
以下藉由本發明之實施例與比較例對其實施方式與效果進行具體說明，但本發明並不限定於該等實施例。Hereinafter, embodiments and effects of the present invention will be specifically described by way of examples and comparative examples of the present invention, but the present invention is not limited to the embodiments.
1.各種金屬(配線材料)的蝕刻速率的測定 使用在玻璃基板上藉由濺射法而成膜之銅(Cu)/鉬(Mo)疊層膜、Mo單層整面膜及鈦(Ti)單層整面膜，測定表1及表2所示之液體組成物對於Cu、Mo及Ti的蝕刻速率。蝕刻係利用將上述基板靜置浸漬於保持在35℃的液體組成物中的方法而進行。蝕刻前後的膜厚係使用螢光X射線分析儀SEA1200VX(Seiko Instruments Inc.製)進行測定，藉由將其膜厚差除以蝕刻時間而算出蝕刻速率。評價結果用以下的基準表示。 E：蝕刻速率100～未達1000nm/min G：蝕刻速率30～未達100nm/min或1000～未達5000nm/min F：蝕刻速率5～未達30nm/min或5000～未達10000nm/min P：蝕刻速率未達5nm/min或10000nm/min以上 此外，此處E、G及F為合格。1. Measurement of etching rate of various metals (wiring materials) A copper (Cu)/molybdenum (Mo) laminated film formed by a sputtering method on a glass substrate, a Mo single-layer full-surface film, and titanium (Ti) were used. The etching rate of Cu, Mo, and Ti of the liquid compositions shown in Tables 1 and 2 was measured for a single-layer full-face film. The etching was carried out by a method of allowing the substrate to be immersed in a liquid composition held at 35 ° C. The film thickness before and after the etching was measured using a fluorescent X-ray analyzer SEA1200VX (manufactured by Seiko Instruments Inc.), and the etching rate was calculated by dividing the film thickness difference by the etching time. The evaluation results are indicated by the following criteria. E: etching rate 100 to less than 1000 nm/min G: etching rate 30 to less than 100 nm/min or 1000 to less than 5000 nm/min F: etching rate 5 to less than 30 nm/min or 5000 to less than 10000 nm/min P : The etching rate is less than 5 nm/min or 10000 nm/min or more. Further, E, G, and F are acceptable here.
2.IGZO的蝕刻速率的測定 在玻璃基板上藉由濺射法而形成膜厚為500埃(50nm)的銦(In)、鎵(Ga)、鋅(Zn)及氧(O)的元素比為 1：1：1：4的IGZO膜，然後，使用表1及表2所示之液體組成物測定蝕刻速率。蝕刻係利用將上述基板靜置浸漬於保持在35℃的液體組成物中的方法而進行。蝕刻前後的膜厚係使用光學薄膜特性測定儀n&k Analyzer 1280(n&k Technology Inc.製)進行測定，藉由將其膜厚差除以蝕刻時間而算出蝕刻速率。進一步，算出添加作為D成分之選自於由胺基三(亞甲基膦酸)、N,N,N',N'－乙二胺肆(亞甲基膦酸)、二亞乙基三胺五(亞甲基膦酸)、雙(六亞甲基)三胺五(亞甲基膦酸)及五亞乙基六胺八(亞甲基膦酸)構成之群組中之1種以上之化合物後的蝕刻速率，與未添加D成分時的蝕刻速率的比率。評價結果用以下的基準表示。 E：蝕刻速率比(有D成分/無D成分)= 未達0.1 G：蝕刻速率比(有D成分/無D成分)=0.1～未達0.2 F：蝕刻速率比(有D成分/無D成分)=0.2～未達0.5 P：蝕刻速率比(有D成分/無D成分)=0.5以上 此外，此處E、G及F為合格。2. Measurement of etching rate of IGZO The element ratio of indium (In), gallium (Ga), zinc (Zn), and oxygen (O) having a film thickness of 500 Å (50 nm) was formed by sputtering on a glass substrate. The IGZO film was 1:1:1:4, and then the etching rate was measured using the liquid compositions shown in Tables 1 and 2. The etching was carried out by a method of allowing the substrate to be immersed in a liquid composition held at 35 ° C. The film thickness before and after the etching was measured using an optical film property measuring instrument n&k Analyzer 1280 (manufactured by N&K Technology Inc.), and the etching rate was calculated by dividing the film thickness difference by the etching time. Further, the addition as the component D is selected from the group consisting of aminotris(methylenephosphonic acid), N,N,N',N'-ethylenediamine oxime (methylene phosphonic acid), diethylene three One of a group consisting of amine penta (methylene phosphonic acid), bis(hexamethylene)triamine penta (methylene phosphonic acid), and pentaethylenehexamine octa (methylene phosphonic acid) The ratio of the etching rate after the above compound to the etching rate when the D component is not added. The evaluation results are indicated by the following criteria. E: etching rate ratio (with D component / no D component) = less than 0.1 G: etching rate ratio (with D component / no D component) = 0.1 ~ less than 0.2 F: etching rate ratio (with D component / no D Component) = 0.2 to less than 0.5 P: etching rate ratio (with D component / no D component) = 0.5 or more, where E, G, and F are acceptable.
3.銅(Cu)溶解時的過氧化氫安定性評價 將Cu粉末1000ppm溶解於表3所示之液體組成物中後，於35℃保存，算出過氧化氫的分解速度。評價結果用以下的基準表示。 E：過氧化氫分解速度未達0.1%/day G：過氧化氫分解速度0.1%/day～未達0.2%/day F：過氧化氫分解速度0.2%/day～未達0.3%/day P：過氧化氫分解速度0.3%/day以上 此外，此處E、G及F為合格。3. Evaluation of Hydrogen Peroxide Stability When Copper (Cu) Is Dissolved After dissolving 1000 ppm of Cu powder in the liquid composition shown in Table 3, the Cu powder was stored at 35 ° C to calculate the decomposition rate of hydrogen peroxide. The evaluation results are indicated by the following criteria. E: Hydrogen peroxide decomposition rate is less than 0.1%/day G: Hydrogen peroxide decomposition rate is 0.1%/day to less than 0.2%/day F: Hydrogen peroxide decomposition rate is 0.2%/day to less than 0.3%/day P : Hydrogen peroxide decomposition rate is 0.3%/day or more. Further, E, G, and F are acceptable here.
實施例1 於容量為100ml的聚丙烯容器中，加入純水81.75g及70%硝酸(和光純藥工業(股)公司製)2.86g。進一步加入31%酸性氟化銨(Stella Chemifa Co.製)0.81g及50%胺基三(亞甲基膦酸)水溶液(東京化成工業(股)公司製)0.20g後，溶解苯基脲(和光純藥工業(股)公司製)0.10g。最後加入35%過氧化氫(三菱瓦斯化學(股)公司製)14.29g，將其攪拌並充分混合各成分，以製備液體組成物。得到的液體組成物的過氧化氫的摻合量為5質量%，硝酸的摻合量為2質量%，酸性氟化銨的摻合量為0.25質量%，胺基三(亞甲基膦酸)的摻合量為0.10質量%，苯基脲的摻合量為0.10質量%。又，pH值為1.4。 使用所得到的液體組成物實施上述評價1及2，得到的結果如表1所示。Example 1 In a polypropylene container having a capacity of 100 ml, 81.75 g of pure water and 2.76 g of 70% nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added. After further adding 0.21 g of an acidic ammonium fluoride (manufactured by Stella Chemifa Co.) and 0.20 g of an aqueous solution of 50% of an aminotris(methylenephosphonic acid) (manufactured by Tokyo Chemical Industry Co., Ltd.), the phenylurea was dissolved. Wako Pure Chemical Industries Co., Ltd.) 0.10g. Finally, 14.29 g of 35% hydrogen peroxide (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added, and the ingredients were stirred and thoroughly mixed to prepare a liquid composition. The obtained liquid composition has a hydrogen peroxide blending amount of 5% by mass, a nitric acid blending amount of 2% by mass, an acidic ammonium fluoride blending amount of 0.25% by mass, and an amine tris(methylenephosphonic acid). The blending amount was 0.10% by mass, and the blending amount of phenylurea was 0.10% by mass. Also, the pH was 1.4. The above evaluations 1 and 2 were carried out using the obtained liquid composition, and the results obtained are shown in Table 1.
實施例2～4 除實施例1中之E成分如表1中所示以外，利用與實施例1同樣的方法製備液體組成物，並使用該液體組成物實施上述評價1及2。得到的結果如表1所示。Examples 2 to 4 A liquid composition was prepared in the same manner as in Example 1 except that the component E in Example 1 was as shown in Table 1, and the above evaluations 1 and 2 were carried out using the liquid composition. The results obtained are shown in Table 1.
實施例5、6 除實施例1中之C成分的濃度、E成分及pH值如表1中所示以外，利用與實施例1同樣的方法製備液體組成物，並使用該液體組成物實施上述評價1及2。得到的結果如表1所示。Examples 5 and 6 A liquid composition was prepared in the same manner as in Example 1 except that the concentration, the E component, and the pH of the component C in Example 1 were as shown in Table 1, and the liquid composition was used to carry out the above. Evaluation 1 and 2. The results obtained are shown in Table 1.
實施例7～9 除實施例1中之D成分的種類與濃度、及E成分如表1中所示以外，利用與實施例1同樣的方法製備液體組成物，並使用該液體組成物實施上述評價1及2。得到的結果如表1所示。Examples 7 to 9 The liquid composition was prepared in the same manner as in Example 1 except that the type and concentration of the component D in Example 1 and the component E were as shown in Table 1, and the liquid composition was used. Evaluation 1 and 2. The results obtained are shown in Table 1.
實施例10、11 除進一步添加乳酸作為實施例1中之B成分，且E成分及pH值如表1中所示以外，利用與實施例1同樣的方法製備液體組成物，並使用該液體組成物實施上述評價1及2。得到的結果如表1所示。Examples 10 and 11 A liquid composition was prepared and used in the same manner as in Example 1 except that lactic acid was further added as the component B in Example 1, and the components E and pH were as shown in Table 1. The above evaluations 1 and 2 were carried out. The results obtained are shown in Table 1.
實施例12 除以硫酸作為實施例1中之B成分，且E成分如表1中所示以外，利用與實施例1同樣的方法製備液體組成物，並使用該液體組成物實施上述評價1及2。得到的結果如表1所示。Example 12 A liquid composition was prepared in the same manner as in Example 1 except that sulfuric acid was used as the component B in Example 1, and the component E was as shown in Table 1, and the above evaluation 1 was carried out using the liquid composition. 2. The results obtained are shown in Table 1.
實施例13～17 除實施例1中之液體組成物的組成及pH值如表3中所示以外，利用與實施例1同樣的方法製備液體組成物，並使用該液體組成物實施上述評價3。得到的結果如表3所示。Examples 13 to 17 The liquid composition was prepared in the same manner as in Example 1 except that the composition and pH of the liquid composition in Example 1 were as shown in Table 3, and the above evaluation was carried out using the liquid composition. . The results obtained are shown in Table 3.
比較例1 除未含有實施例1中之D成分，且E成分如表2中所示以外，利用與實施例1同樣的方法製備液體組成物，並使用該液體組成物實施上述評價1及2。得到的結果如表2所示。Comparative Example 1 A liquid composition was prepared in the same manner as in Example 1 except that the component D in Example 1 was not contained, and the E component was as shown in Table 2, and the above evaluations 1 and 2 were carried out using the liquid composition. . The results obtained are shown in Table 2.
比較例2 除實施例1中之過氧化氫濃度、C成分及pH值如表2中所示，且未含有B成分、D成分及E成分，並添加1－羥基亞乙基－1,1－二膦酸及5－胺基－1H－四唑以外，利用與實施例1同樣的方法製備液體組成物，並使用該液體組成物實施上述評價1及2。得到的結果如表2所示。Comparative Example 2 The hydrogen peroxide concentration, the C component, and the pH value in Example 1 are as shown in Table 2, and the B component, the D component, and the E component were not contained, and 1-hydroxyethylidene-1,1 was added. A liquid composition was prepared in the same manner as in Example 1 except for the diphosphonic acid and 5-amino-1H-tetrazole, and the above evaluations 1 and 2 were carried out using the liquid composition. The results obtained are shown in Table 2.
比較例3 除實施例1中之過氧化氫濃度及pH值如表2中所示，且未含有B成分、C成分、D成分及E成分，並添加氨水以外，利用與實施例1同樣的方法製備液體組成物，並使用該液體組成物實施上述評價1及2。得到的結果如表2所示。Comparative Example 3 The same procedure as in Example 1 was carried out except that the hydrogen peroxide concentration and the pH value in Example 1 were as shown in Table 2, and the components B, C, D, and E were not contained, and ammonia water was added. Method A liquid composition was prepared, and the above evaluations 1 and 2 were carried out using the liquid composition. The results obtained are shown in Table 2.
比較例4～6 除實施例1中之液體組成物的組成及pH值如表3中所示以外，利用與實施例1同樣的方法製備液體組成物，並使用該液體組成物實施上述評價3。得到的結果如表3所示。Comparative Examples 4 to 6 The liquid composition was prepared in the same manner as in Example 1 except that the composition and pH of the liquid composition in Example 1 were as shown in Table 3, and the above evaluation was carried out using the liquid composition. . The results obtained are shown in Table 3.
從上述實施例1～17得知，本發明之液體組成物，可抑制對於IGZO的損傷，並以良好的蝕刻速率蝕刻在IGZO上形成之銅或銅作為主成分之金屬化合物，進一步，即使銅或銅作為主成分之金屬化合物發生溶解，亦可抑制過氧化氫的分解。 另一方面，從上述比較例1得知，液體組成物不含有D成分時不能充分地抑制對於IGZO的損傷。又，從上述比較例2及5得知，液體組成物不含有D成分時，即使含有1－羥基亞乙基－1,1－二膦酸亦不能充分地抑制對於IGZO的損傷，進一步，銅或銅作為主成分之金屬化合物溶解於液體組成物時，過氧化氫的分解速度變快。又，從上述比較例3及6得知，液體組成物不含有D成分，含有氨水，pH值高時不能充分地抑制對於IGZO的損傷，進一步，銅或銅作為主成分之金屬化合物的溶解性變低，過氧化氫的安定性亦變低。又，從上述比較例4得知，液體組成物不含有E成分時，銅或銅作為主成分之金屬化合物溶解時，過氧化氫的分解速度變快。It is understood from the above Examples 1 to 17 that the liquid composition of the present invention can suppress damage to IGZO, and etch a metal compound having copper or copper as a main component formed on IGZO at a good etching rate, and further, even copper Or the metal compound in which copper is a main component is dissolved, and decomposition of hydrogen peroxide can also be suppressed. On the other hand, it was found from the above Comparative Example 1 that the damage to IGZO could not be sufficiently suppressed when the liquid composition did not contain the D component. Further, from the above Comparative Examples 2 and 5, when the liquid composition does not contain the D component, even if 1-hydroxyethylidene-1,1-diphosphonic acid is contained, damage to IGZO cannot be sufficiently suppressed, and further, copper When the metal compound containing copper as a main component is dissolved in the liquid composition, the decomposition rate of hydrogen peroxide becomes faster. Moreover, it is understood from the above Comparative Examples 3 and 6 that the liquid composition does not contain the D component and contains ammonia water. When the pH is high, the damage to the IGZO cannot be sufficiently suppressed, and further, the solubility of the metal compound containing copper or copper as a main component is not satisfied. When it becomes lower, the stability of hydrogen peroxide also becomes lower. Further, from the above Comparative Example 4, when the liquid composition does not contain the E component, when the metal compound containing copper or copper as a main component is dissolved, the decomposition rate of hydrogen peroxide is increased.
[表1]
[表2]
[表3]
本發明之液體組成物，可於抑制對於IGZO的損傷的同時，以良好的蝕刻速率蝕刻銅或銅作為主成分之金屬化合物，因此在TFT製造步驟中，可將在IGZO上設置保護膜的先前的蝕刻停止型結構変更為保護層為非必要的背通道蝕刻型結構，因而可簡化製造步驟且大幅地降低製造成本。進一步，本發明之液體組成物，即使銅或銅作為主成分之金屬化合物發生溶解，過氧化氫的安定性亦高，因此可安全且安定地實施蝕刻操作。The liquid composition of the present invention can etch copper or copper as a main component metal compound at a good etching rate while suppressing damage to IGZO, and thus, in the TFT manufacturing step, a protective film can be provided on the IGZO. The etch stop structure 変 more protective layer is an unnecessary back channel etch type structure, thereby simplifying the manufacturing steps and greatly reducing the manufacturing cost. Further, in the liquid composition of the present invention, even if the metal compound containing copper or copper as a main component is dissolved, the stability of hydrogen peroxide is high, and therefore the etching operation can be carried out safely and stably.
1‧‧‧玻璃
2‧‧‧閘極電極
3‧‧‧閘極絕緣膜
6a‧‧‧源極電極
6b‧‧‧汲極電極
7‧‧‧保護層
8‧‧‧透明電極
9‧‧‧IGZO半導體層
10‧‧‧蝕刻停止層1‧‧‧glass
2‧‧‧gate electrode
3‧‧‧gate insulating film
6a‧‧‧Source electrode
6b‧‧‧汲electrode
7‧‧‧Protective layer
8‧‧‧Transparent electrode
9‧‧‧IGZO semiconductor layer
10‧‧‧etch stop layer
[圖1]係蝕刻停止型TFT剖面結構的示意圖。圖1中，於玻璃基板1上，形成閘極電極2及閘極絕緣膜3，於其上形成IGZO半導體層9、蝕刻停止層10、源極電極6a及汲極電極6b，進一步於其上形成保護層7及透明電極8。 [圖2]係背通道蝕刻型TFT剖面結構的示意圖。圖2中，於玻璃基板1上，形成閘極電極2及閘極絕緣膜3，於其上形成IGZO半導體層9、源極電極6a及汲極電極6b，進一步於其上形成保護層7及透明電極8。此處，在IGZO半導體層9上未介隔蝕刻停止層等保護層而形成配線材料，並藉由蝕刻處理形成源極電極6a及汲極電極6b。Fig. 1 is a schematic view showing a cross-sectional structure of an etch stop type TFT. In FIG. 1, a gate electrode 2 and a gate insulating film 3 are formed on a glass substrate 1, and an IGZO semiconductor layer 9, an etch stop layer 10, a source electrode 6a, and a drain electrode 6b are formed thereon, further thereon. The protective layer 7 and the transparent electrode 8 are formed. 2 is a schematic view showing a cross-sectional structure of a back channel etching type TFT. In FIG. 2, a gate electrode 2 and a gate insulating film 3 are formed on a glass substrate 1, and an IGZO semiconductor layer 9, a source electrode 6a, and a drain electrode 6b are formed thereon, and a protective layer 7 is further formed thereon. Transparent electrode 8. Here, a protective material such as an etch stop layer is not interposed on the IGZO semiconductor layer 9 to form a wiring material, and the source electrode 6a and the drain electrode 6b are formed by etching.
無no
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| TWI731229B (en) * | 2017-03-10 | 2021-06-21 | 日商Ａｄｅｋａ股份有限公司 | Etching solution composition and etching method |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018181896A1 (en) | 2017-03-31 | 2018-10-04 | 関東化學株式会社 | Etchant composition for etching titanium layer or titanium-containing layer, and etching method |
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Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3481379B2 (en) * | 1995-08-23 | 2003-12-22 | メック株式会社 | Electroplating method |
| CN101952485A (en) * | 2007-11-22 | 2011-01-19 | 出光兴产株式会社 | Etching liquid composition |
| KR20100040010A (en) * | 2008-10-09 | 2010-04-19 | (주)이그잭스 | Echant with low concentration of hydrogen peroxide for layers of copper or copper alloy |
| CN102227761A (en) * | 2008-12-26 | 2011-10-26 | 夏普株式会社 | Substrate for display panel, and display panel comprising same |
| WO2011021860A2 (en) | 2009-08-20 | 2011-02-24 | Dongwoo Fine-Chem Co., Ltd. | Method of fabricating array substrate for liquid crystal display |
| TWI530589B (en) * | 2009-12-25 | 2016-04-21 | Mitsubishi Gas Chemical Co | Etching liquid and method of manufacturing semiconductor device using the same |
| KR101709925B1 (en) * | 2010-01-28 | 2017-02-27 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Etching liquid for a copper/titanium multilayer thin film |
| KR101270560B1 (en) * | 2010-11-12 | 2013-06-03 | 오씨아이 주식회사 | Composition for etching metal layer |
| KR101901721B1 (en) * | 2011-07-26 | 2018-09-28 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Etchant for copper/molybdenum-based multilayer thin film |
| KR20140118492A (en) * | 2013-03-29 | 2014-10-08 | 동우 화인켐 주식회사 | Etching composition for copper-based metal layer and method of preparing metal line |
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| TWI759450B (en) * | 2018-03-27 | 2022-04-01 | 日商三菱瓦斯化學股份有限公司 | Etching solution, etching method, and manufacturing method of display device |
| TWI829876B (en) * | 2019-02-28 | 2024-01-21 | 南韓商易安愛富科技有限公司 | Metal layer etchant composition and metal layer etching method |
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