WO2015005053A1 - Liquid composition for cleaning/removing copper-containing adhering matter from surface of oxide comprising indium, gallium, zinc, and oxygen (igzo), method for cleaning igzo surface using said liquid composition, and substrate cleaned using said method for cleaning - Google Patents

Liquid composition for cleaning/removing copper-containing adhering matter from surface of oxide comprising indium, gallium, zinc, and oxygen (igzo), method for cleaning igzo surface using said liquid composition, and substrate cleaned using said method for cleaning Download PDF

Info

Publication number
WO2015005053A1
WO2015005053A1 PCT/JP2014/065548 JP2014065548W WO2015005053A1 WO 2015005053 A1 WO2015005053 A1 WO 2015005053A1 JP 2014065548 W JP2014065548 W JP 2014065548W WO 2015005053 A1 WO2015005053 A1 WO 2015005053A1
Authority
WO
WIPO (PCT)
Prior art keywords
igzo
liquid composition
copper
cleaning
molybdenum
Prior art date
Application number
PCT/JP2014/065548
Other languages
French (fr)
Japanese (ja)
Inventor
聡 玉井
邦夫 夕部
Original Assignee
三菱瓦斯化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to KR1020157023345A priority Critical patent/KR102000726B1/en
Priority to CN201480033266.4A priority patent/CN105359257B/en
Priority to JP2015526224A priority patent/JP6418156B2/en
Publication of WO2015005053A1 publication Critical patent/WO2015005053A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/66007—Multistep manufacturing processes
    • H01L29/66969—Multistep manufacturing processes of devices having semiconductor bodies not comprising group 14 or group 13/15 materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate

Definitions

  • Patent Document 4 does not describe the corrosiveness of the IGZO semiconductor layer. Moreover, it is described that the effect of removing metal contamination on the surface of the semiconductor substrate is improved by including a complexing agent, but IGZO may be corroded by the complexing agent (ammonium fluoride is exemplified). Yes (see Comparative Example 10).
  • the liquid composition disclosed in Patent Document 5 is intended to etch IGZO, and there is no disclosure about the cleaning / removability of deposits containing copper or molybdenum. In addition, the use of the liquid composition may corrode the IGZO semiconductor layer and corrode the wiring containing copper.
  • One or more concentrations selected from the group consisting of hydroxycarboxylic acid or a salt thereof (simply referred to as component (A)) or dicarboxylic acid or a salt thereof (simply referred to as component (B)) may be: It is preferably contained in the liquid composition in the range of 0.001 to 30% by mass, more preferably in the range of 0.01 to 25% by mass, particularly preferably in the range of 0.02 to 20% by mass. The range of 1 to 10% by mass is more preferable, and the range of 1 to 5% by mass is even more preferable.
  • an IGZO semiconductor layer is formed on a substrate, and a substrate having a wiring containing copper or copper and molybdenum thereon is used as an object to be cleaned.
  • a layer made of IGZO, a layer made of molybdenum and a layer made of copper are sequentially laminated on a substrate such as glass, and a resist is coated thereon, and a desired pattern mask is exposed and transferred, and developed. Thus, a desired resist pattern is formed. Thereafter, the multilayer wiring containing copper and molybdenum can be selectively etched with an etching solution.
  • IGZO film thickness: 500 mm A layer of IGZO (IGZO film thickness: 500 mm) formed by sputtering IGZO having an element ratio of indium, gallium, zinc and oxygen of 1: 1: 1: 4 on a glass substrate (size: 150 mm ⁇ 150 mm). ) To form an IGZO / glass substrate.
  • the substrate after immersion was rinsed with pure water and then dried with a blower.
  • XPS X-ray photoelectron spectroscopy
  • Comparative Examples 9 and 10 A liquid composition was prepared and various evaluations were performed in the same manner as in Example 1 except that the composition shown in Table 5 was used. The results are shown in Table 5.
  • the etching rate of copper and the etching rate of molybdenum are high, and the anticorrosion property of copper and the anticorrosion property of molybdenum may be reduced by containing hydrogen peroxide. I understood.
  • the etching rate of IGZO was high, and it was found that the liquid composition was not applicable to cleaning and removal of deposits containing copper on the IGZO surface. .

Abstract

　Provided is: a liquid composition for cleaning/removing copper-containing adhering matter from the surface of an oxide comprising indium, gallium, zinc, and oxygen (IGZO) without corroding an IGZO semiconductor layer or copper-containing wiring; a method for cleaning the IGZO surface using said liquid composition; and a substrate cleaned using said method for cleaning. In the present invention, a liquid composition having a pH of 1.5-10 is used, the composition containing hydroxycarboxylic acid and dicarboxylic acid, or at least one salt selected from the group consisting of salts thereof.

Description

インジウム、ガリウム、亜鉛、および酸素からなる酸化物（ＩＧＺＯ）の表面より銅を含む付着物を洗浄・除去する液体組成物、およびその液体組成物を用いたＩＧＺＯ表面の洗浄方法、並びにその洗浄方法により洗浄される基板Liquid composition for cleaning and removing deposits containing copper from the surface of oxide (IGZO) composed of indium, gallium, zinc, and oxygen, IGZO surface cleaning method using the liquid composition, and cleaning method therefor Substrate cleaned by
　本発明は液体組成物に関し、ＩＧＺＯの表面よりＩＧＺＯ半導体層や銅を含む配線を腐食することなく、銅を含む付着物を洗浄・除去する液体組成物、およびその液体組成物を用いたＩＧＺＯ表面の洗浄方法、並びにその洗浄方法により洗浄される基板に関する。 The present invention relates to a liquid composition, and a liquid composition for cleaning and removing deposits containing copper without corroding an IGZO semiconductor layer or wiring containing copper from the surface of IGZO, and an IGZO surface using the liquid composition And a substrate to be cleaned by the cleaning method.
　液晶表示装置では、画素を構成する表示領域に薄膜トランジスタ（ＴＦＴ：Ｔｈｉｎ　Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）を用いた方式がテレビを含めた多くの電子材料部品用途で採用されている。このＴＦＴ構造においては、一般に半導体層にアモルファスシリコンが使用され、配線材料にアルミニウムまたはアルミニウム合金が用いられている。しかし、ディスプレイの大型化および高解像度化に伴い、これらのような材料では、電界効果移動度や配線抵抗などの特性に起因した信号遅延の問題が発生し、均一な画面表示が困難になる傾向にある。 In a liquid crystal display device, a method using a thin film transistor (TFT) for a display region constituting a pixel is employed in many electronic material parts including a television. In this TFT structure, amorphous silicon is generally used for the semiconductor layer, and aluminum or an aluminum alloy is used for the wiring material. However, with the increase in size and resolution of displays, these materials tend to cause signal delay problems due to characteristics such as field-effect mobility and wiring resistance, making uniform screen display difficult. It is in.
　そのため最近では、半導体層として各種の酸化物半導体材料の開発がなされている。酸化物半導体材料は、主にインジウム、ガリウム、亜鉛、錫および酸素等から構成されるインジウム・ガリウム・亜鉛酸化物（ＩＧＺＯ）、インジウム・ガリウム酸化物（ＩＧＯ）、インジウム・錫・亜鉛酸化物（ＩＴＺＯ）、インジウム・ガリウム・亜鉛・錫酸化物（ＩＧＺＴＯ）、ガリウム・亜鉛酸化物（ＧＺＯ）、および亜鉛・錫酸化物（ＺＴＯ）等、種々の組成物の使用が検討されている。この中でも近年特にＩＧＺＯについての検討が盛んに行われている。 Therefore, recently, various oxide semiconductor materials have been developed as semiconductor layers. Oxide semiconductor materials include indium gallium zinc oxide (IGZO), indium gallium oxide (IGO), indium tin gallium oxide (IGO) mainly composed of indium, gallium, zinc, tin and oxygen ( The use of various compositions such as ITZO), indium / gallium / zinc / tin oxide (IGZTO), gallium / zinc oxide (GZO), and zinc / tin oxide (ZTO) has been studied. Of these, IGZO has been actively studied in recent years.
　また、配線材料としてはアルミニウムまたはアルミニウム合金から、より電気抵抗が低い材料である銅または銅合金を配線材料とした構造が検討されている。しかし、銅は抵抗が低いという利点を有する一方、ゲート配線で用いる場合はガラス等の基板との密着性が十分でないという課題に加え、ソース・ドレイン配線で用いる場合はその下地となる半導体層への銅金属の拡散が生じる場合があるといった問題点が指摘されている。これを防止するために、ガラス等の基板との密着性が高く、半導体層への拡散が生じ難く、バリア性をも兼ね備えた金属を配するバリア膜の積層の検討が行われており、当該金属としてモリブデンやモリブデン合金などが注目されている。 Also, a structure in which the wiring material is made of copper or a copper alloy, which is a material having a lower electrical resistance, from aluminum or an aluminum alloy is being studied. However, copper has the advantage of low resistance, but in addition to the problem of insufficient adhesion to a substrate such as glass when used in gate wiring, it is also used as a base semiconductor layer when used in source / drain wiring. It has been pointed out that some copper metals may diffuse. In order to prevent this, the adhesion of a substrate such as glass is high, diffusion to the semiconductor layer is difficult to occur, and a layering of a barrier film that disposes a metal that also has a barrier property has been studied. Molybdenum and molybdenum alloys are attracting attention as metals.
　これらの銅を含む多層膜配線は、スパッタ法などの公知の成膜技術を用いて基板上に形成し、次いでレジストなどをマスクにしてエッチングして電極パターンを形成することにより得られる。エッチングの方式には、エッチング液を用いる湿式法（ウェットエッチング）とプラズマ等のエッチングガスを用いる乾式法（ドライエッチング）とがある。銅を含む多層膜配線のウェットエッチングに関しては、例えば特許文献１に、中性塩と無機酸と有機酸の中から選択された少なくとも一つと過酸化水素とを含む銅／モリブデンをエッチングするエッチング液が紹介されている。
　また、ＩＧＺＯを腐食しない銅／モリブデンエッチング液として、特許文献２が紹介されている。 These multilayer wiring containing copper can be obtained by forming on a substrate using a known film forming technique such as sputtering, and then forming an electrode pattern by etching using a resist or the like as a mask. Etching methods include a wet method using an etchant (wet etching) and a dry method using an etching gas such as plasma (dry etching). Regarding wet etching of multilayer wiring containing copper, for example, Patent Document 1 discloses an etching solution for etching copper / molybdenum containing at least one selected from a neutral salt, an inorganic acid, and an organic acid and hydrogen peroxide. Has been introduced.
Patent Document 2 is introduced as a copper / molybdenum etching solution that does not corrode IGZO.
　図１に、ＩＧＺＯを半導体層とし、銅を含む配線を有するＴＦＴ構造を有する基板断面の模式図を示す。銅のエッチング液は、銅を含む膜や銅およびモリブデンを含む膜のエッチング時にＩＧＺＯ半導体層に接液するが、エッチング液には銅、モリブデンなどといった金属が溶解する。そのため、ＩＧＺＯ表面にエッチング液中の銅、モリブデンなどの遷移金属元素を含む付着物による汚染が生じる可能性がある。ここで「付着物」とは、ＩＧＺＯ表面に付着した、金属酸化物、金属水酸化物、金属塩、金属イオンなどの状態で存在している化学種を意味する。すなわち、金属の状態にある化学種はここでいう付着物には含まれない。また、ＩＧＺＯは表面の金属元素が欠損してしまう可能性が指摘されており、その欠損部位にエッチング液に溶解した遷移金属元素を含む化学種が取り込まれることによって汚染が生じる可能性もある。このようにしてＩＧＺＯ表面に取り込まれた化学種もここでいう「付着物」に包含される。一般的に、半導体表面に遷移金属元素を含む化学種が付着すると、電気抵抗や耐久性等の半導体特性に悪影響を及ぼすことが知られている。また一方で、本発明者らはＩＧＺＯ表面に銅イオンやモリブデンイオンなどの付着物が付着した場合、半導体特性が低下することを確認している。 FIG. 1 shows a schematic diagram of a cross section of a substrate having a TFT structure with IGZO as a semiconductor layer and wiring containing copper. The copper etchant is in contact with the IGZO semiconductor layer during etching of a film containing copper or a film containing copper and molybdenum, but a metal such as copper or molybdenum is dissolved in the etchant. Therefore, the surface of the IGZO may be contaminated with deposits containing transition metal elements such as copper and molybdenum in the etching solution. Here, the “attachment” means a chemical species that is attached to the IGZO surface and exists in a state such as a metal oxide, a metal hydroxide, a metal salt, or a metal ion. That is, chemical species in a metal state are not included in the deposits referred to here. Further, it has been pointed out that IGZO may lose a metal element on the surface, and contamination may occur when a chemical species containing a transition metal element dissolved in an etching solution is taken into the defect part. The chemical species thus taken into the surface of the IGZO are also included in the “adhesion” here. Generally, it is known that when a chemical species containing a transition metal element adheres to a semiconductor surface, it adversely affects semiconductor characteristics such as electric resistance and durability. On the other hand, the present inventors have confirmed that the semiconductor characteristics are deteriorated when deposits such as copper ions and molybdenum ions adhere to the IGZO surface.
　Ｓｉ半導体表面の銅を含む付着物を洗浄・除去する液体組成物として、特許文献３には、クエン酸と過酸化水素を含みｐＨ値を３～４に調節した液体組成物により、Ｓｉ半導体表面の銅などの重金属汚染を洗浄することができると開示されている。
　また、特許文献４には、カルボキシル基を少なくとも１個有する有機酸と錯化剤を含んでなる洗浄液で、金属配線を腐食することなく、Ｓｉ半導体基板表面の金属汚染（Ａｌ、Ｆｅ、Ｃｕ）を除去することができるとの報告がある。 As a liquid composition for cleaning and removing deposits containing copper on the surface of the Si semiconductor, Patent Document 3 discloses a liquid composition containing citric acid and hydrogen peroxide and having a pH value adjusted to 3-4, It is disclosed that heavy metal contamination such as copper can be cleaned.
Further, Patent Document 4 discloses a metal contamination (Al, Fe, Cu) on the surface of a Si semiconductor substrate without corroding a metal wiring with a cleaning liquid containing an organic acid having at least one carboxyl group and a complexing agent. There is a report that can be removed.
　また、特許文献５には、酢酸、クエン酸、塩酸または過塩素酸のいずれか一種を含む液体組成物により、ＩＧＺＯがエッチングされるとの報告がある。 Further, Patent Document 5 reports that IGZO is etched by a liquid composition containing any one of acetic acid, citric acid, hydrochloric acid and perchloric acid.
特開２００２－３０２７８０号公報JP 2002-302780 A 国際公開２０１３／０１５３２２号International Publication No. 2013/015322 特開２００７－１５０１９６号公報JP 2007-150196 A 特開１９９８－７２５９４号公報Japanese Patent Laid-Open No. 1998-72594 特開２００８－４１６９５号公報JP 2008-41695 A
　しかし、特許文献１には、ＩＧＺＯの腐食性については言及されていない。また、重金属汚染の洗浄性についての開示はない。
　特許文献２には、ＩＧＺＯを腐食しないことが記載されているが、エッチング液中に溶解した銅、モリブデンによるＩＧＺＯへの重金属汚染についての言及はない。
　特許文献３には、ＩＧＺＯ半導体層や銅を含む配線の腐食性（エッチングレート）についての記載はない。また、過酸化水素を含むことによって、銅などの金属汚染の洗浄効果が向上すると記載されているが、過酸化水素によって腐食が増大する金属を配線に用いる場合は、過酸化水素を使用することはできない（例えば、過酸化水素はモリブデンを腐食する。また過酸化水素と酸を含む液体組成物は銅を腐食する。このため、銅やモリブデンなどの金属を配線に用いる場合には、過酸化水素や過酸化水素と酸を含む液体組成物をＩＧＺＯ表面の洗浄に使用することはできない。比較例９参照）。さらに、エッチング液中の銅を含む化学種がＩＧＺＯ表面に付着する場合は、Ｓｉ半導体ウエハ表面に付着する銅などの重金属汚染とは化学状態が異なると考えられ、Ｓｉ半導体表面に付着した銅などの重金属汚染を除去することはできても、ＩＧＺＯ表面上に付着した銅を含む付着物を除去しきれない可能性がある。また、ＩＧＺＯ半導体表面に付着した銅を含む付着物を除去することはできても、Ｓｉ半導体表面に付着した銅などの重金属汚染を除去しきれない場合もある。
　特許文献４には、ＩＧＺＯ半導体層の腐食性についての記述はない。また、錯化剤を含むことによって、半導体基板表面の金属汚染の除去効果が向上すると記載されているが、錯化剤（フッ化アンモニウムが例示されている）によってＩＧＺＯが腐食してしまう場合がある（比較例１０参照）。
　特許文献５に開示されている液体組成物はＩＧＺＯのエッチングを目的としており、銅やモリブデンを含む付着物の洗浄・除去性についての開示はない。また、該液体組成物の使用は、ＩＧＺＯ半導体層を腐食するうえ、銅を含む配線を腐食する可能性も存在する。 However, Patent Document 1 does not mention the corrosiveness of IGZO. Moreover, there is no disclosure about detergency of heavy metal contamination.
Patent Document 2 describes that IGZO is not corroded, but there is no mention of heavy metal contamination of IGZO by copper and molybdenum dissolved in an etching solution.
Patent Document 3 does not describe the corrosiveness (etching rate) of wiring containing IGZO semiconductor layers and copper. In addition, it is stated that the cleaning effect of copper and other metal contamination is improved by containing hydrogen peroxide, but when using metal that increases corrosion due to hydrogen peroxide for wiring, use hydrogen peroxide. (For example, hydrogen peroxide corrodes molybdenum. Liquid compositions containing hydrogen peroxide and acids corrode copper. For this reason, when metals such as copper and molybdenum are used for wiring, A liquid composition containing hydrogen, hydrogen peroxide and an acid cannot be used for cleaning the surface of IGZO (see Comparative Example 9). Furthermore, when chemical species including copper in the etching solution adheres to the IGZO surface, it is considered that the chemical state is different from heavy metal contamination such as copper adhering to the Si semiconductor wafer surface, such as copper adhering to the Si semiconductor surface. Although it is possible to remove heavy metal contamination, there is a possibility that deposits including copper deposited on the IGZO surface cannot be completely removed. Moreover, even if the deposits containing copper adhering to the IGZO semiconductor surface can be removed, heavy metal contamination such as copper adhering to the Si semiconductor surface may not be completely removed.
Patent Document 4 does not describe the corrosiveness of the IGZO semiconductor layer. Moreover, it is described that the effect of removing metal contamination on the surface of the semiconductor substrate is improved by including a complexing agent, but IGZO may be corroded by the complexing agent (ammonium fluoride is exemplified). Yes (see Comparative Example 10).
The liquid composition disclosed in Patent Document 5 is intended to etch IGZO, and there is no disclosure about the cleaning / removability of deposits containing copper or molybdenum. In addition, the use of the liquid composition may corrode the IGZO semiconductor layer and corrode the wiring containing copper.
　このような状況下、ＩＧＺＯ半導体層および銅または銅およびモリブデンを含む配線を腐食することなく、ＩＧＺＯ表面より、銅または銅およびモリブデンを含む付着物を洗浄・除去できる、ＩＧＺＯ表面の洗浄液が望まれていた。
　従って本発明は、ＩＧＺＯの表面よりＩＧＺＯ半導体層や銅または銅およびモリブデンを含む配線を腐食することなく、銅または銅およびモリブデンを含む付着物を洗浄・除去する液体組成物、およびこれを用いた洗浄方法、並びに該洗浄方法により洗浄された基板を提供することを目的とするものである。 Under such circumstances, a cleaning liquid for the IGZO surface that can clean and remove deposits containing copper or copper and molybdenum from the IGZO surface without corroding the wiring containing IGZO semiconductor layer and copper or copper and molybdenum is desired. It was.
Therefore, the present invention uses a liquid composition for cleaning and removing deposits containing copper or copper and molybdenum without corroding the IGZO semiconductor layer and the wiring containing copper or copper and molybdenum from the surface of the IGZO, and the same. It is an object of the present invention to provide a cleaning method and a substrate cleaned by the cleaning method.
　本発明者らは上記問題点を解決するために鋭意検討した結果、特定のヒドロキシルカルボン酸およびジカルボン酸、またはそれらの塩からなる郡より選択されるいずれか一つを含み、ｐＨ値を１．５～１０に調節した液体組成物において上記した問題点、課題を解決できることを見出した。
　すなわち、本発明は以下のとおりである。
１．銅を含む配線を腐食することなく、インジウム、ガリウム、亜鉛、および酸素からなる酸化物（ＩＧＺＯ）の表面より銅を含む付着物を洗浄・除去する液体組成物であって、
ヒドロキシカルボン酸およびジカルボン酸、またはそれらの塩からなる群より選択される一種以上を含み、ｐＨ値が１.５～１０である液体組成物。
２．前記銅を含む付着物が銅およびモリブデンを含む付着物である第１項に記載の液体組成物。
３．前記ヒドロキシカルボン酸が、クエン酸、酒石酸、乳酸、およびグリコール酸からなる群より選ばれる少なくとも一種である第１項または第２項に記載の液体組成物。
４．前記ジカルボン酸が、マロン酸、マレイン酸、無水マレイン酸、およびコハク酸からなる群より選ばれる少なくとも一種である第１項～第３項のいずれか一項に記載の液体組成物。
５．前記ヒドロキシカルボン酸およびジカルボン酸、またはそれらの塩からなる群より選択される一種以上の濃度が、０．００１～３０質量％である、第１項～第４項のいずれか一項に記載の液体組成物。
６．ｐＨ調節剤として、水酸化ナトリウム、水酸化カリウム、アンモニア、テトラメチルアンモニウムヒドロキシド、２－アミノエタノール、および１－アミノ－２－プロパノールからなる群より選ばれる少なくとも一種を含む、第１項～第５項のいずれか一項に記載の液体組成物。
７．インジウム、ガリウム、亜鉛、および酸素からなる酸化物（ＩＧＺＯ）の表面より、ＩＧＺＯ半導体層を腐食することなく、かつ銅を含む配線を腐食することなく、銅を含む付着物を洗浄・除去する方法であって、ＩＧＺＯ半導体層と銅を含む配線を有した基板上のＩＧＺＯ表面に、第１項～第６項のいずれか一項に記載の液体組成物を接触させることを含む、ＩＧＺＯ表面の洗浄方法。
８．インジウム、ガリウム、亜鉛、および酸素からなる酸化物（ＩＧＺＯ）の表面より、ＩＧＺＯ半導体層を腐食することなく、かつ銅およびモリブデンを含む配線を腐食することなく、銅およびモリブデンを含む付着物を洗浄・除去する方法であって、ＩＧＺＯ半導体層と、銅およびモリブデンを含む配線とを有した基板上のＩＧＺＯ表面に、第１項～第６項のいずれか一項に記載の液体組成物を接触させることを含む、ＩＧＺＯ表面の洗浄方法。
９．第７項または第８項に記載の方法により洗浄された、インジウム、ガリウム、亜鉛、および酸素からなる酸化物（ＩＧＺＯ）半導体層と、銅または銅およびモリブデンを含む配線とを有した基板。 As a result of intensive studies to solve the above problems, the present inventors have included any one selected from the group consisting of a specific hydroxyl carboxylic acid and dicarboxylic acid, or a salt thereof, and a pH value of 1. It has been found that the above-mentioned problems and problems can be solved in a liquid composition adjusted to 5-10.
That is, the present invention is as follows.
1. A liquid composition for cleaning and removing deposits containing copper from the surface of an oxide (IGZO) made of indium, gallium, zinc, and oxygen without corroding wiring containing copper,
A liquid composition comprising at least one selected from the group consisting of hydroxycarboxylic acids and dicarboxylic acids, or salts thereof, and having a pH value of 1.5 to 10.
2. The liquid composition according to claim 1, wherein the deposit containing copper is a deposit containing copper and molybdenum.
3. Item 3. The liquid composition according to Item 1 or 2, wherein the hydroxycarboxylic acid is at least one selected from the group consisting of citric acid, tartaric acid, lactic acid, and glycolic acid.
4). 4. The liquid composition according to any one of items 1 to 3, wherein the dicarboxylic acid is at least one selected from the group consisting of malonic acid, maleic acid, maleic anhydride, and succinic acid.
5. The concentration of one or more selected from the group consisting of the hydroxycarboxylic acid and the dicarboxylic acid, or a salt thereof is 0.001 to 30% by mass, according to any one of Items 1 to 4. Liquid composition.
6). Items 1 to 4 comprising at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, tetramethylammonium hydroxide, 2-aminoethanol, and 1-amino-2-propanol as a pH regulator. 6. The liquid composition according to any one of items 5.
7). A method for cleaning and removing deposits containing copper from the surface of an oxide (IGZO) made of indium, gallium, zinc, and oxygen without corroding the IGZO semiconductor layer and without corroding the wiring containing copper. An IGZO surface comprising: contacting an IGZO surface on a substrate having a wiring containing IGZO semiconductor layer and copper with the liquid composition according to any one of Items 1 to 6. Cleaning method.
8). Cleaning the deposits containing copper and molybdenum from the surface of oxide (IGZO) consisting of indium, gallium, zinc, and oxygen without corroding the IGZO semiconductor layer and without corroding the wiring containing copper and molybdenum. A method for removing, wherein the liquid composition according to any one of Items 1 to 6 is brought into contact with an IGZO surface on a substrate having an IGZO semiconductor layer and a wiring including copper and molybdenum. A method for cleaning the surface of IGZO, comprising:
9. A substrate having an oxide (IGZO) semiconductor layer made of indium, gallium, zinc, and oxygen and a wiring containing copper, copper, and molybdenum cleaned by the method according to item 7 or 8.
　本発明の液体組成物を用いることにより、ＩＧＺＯ半導体層および銅を含む配線を腐食することなく、ＩＧＺＯ表面より銅を含む付着物を洗浄・除去することができる。したがって、ディスプレイの大型化、高解像度化および低消費電力化に対応したＩＧＺＯ半導体層の表面洗浄用液体組成物を提供できる。 By using the liquid composition of the present invention, it is possible to clean and remove deposits containing copper from the IGZO surface without corroding the wiring containing IGZO semiconductor layer and copper. Therefore, it is possible to provide a liquid composition for cleaning the surface of an IGZO semiconductor layer corresponding to an increase in display size, resolution, and power consumption.
ＩＧＺＯを半導体層とし、銅を含む膜を配線としたＴＦＴ構造を有する基板断面の模式図である。It is a schematic diagram of a substrate cross section having a TFT structure using IGZO as a semiconductor layer and a film containing copper as a wiring. 銅イオンを付着させた後のＩＧＺＯ表面のＸＰＳスペクトルである。It is an XPS spectrum of the IGZO surface after making copper ion adhere. 銅イオンを付着させた後、続いて実施例１の液体組成物でＩＧＺＯ表面を洗浄した後のＩＧＺＯ表面のＸＰＳスペクトルである。It is an XPS spectrum of the IGZO surface after making a copper ion adhere and then wash | cleaning the IGZO surface with the liquid composition of Example 1. FIG.
＜液体組成物＞
　本発明による液体組成物は、ＩＧＺＯ半導体層や銅を含む配線を腐食することなく、ＩＧＺＯ表面より銅を含む付着物を洗浄・除去する液体組成物であって、該液体組成物はヒドロキシカルボン酸およびジカルボン酸、またはそれらの塩からなる群より選択される一種以上を含み、ｐＨ値が１．５～１０である。
　本明細書において「銅を含む付着物」とは、ＩＧＺＯ表面に付着した、少なくとも銅を含む金属の酸化物、水酸化物または塩などの金属化合物、あるいは、少なくとも銅を含む金属のイオンなどをいい、金属単体を除く。なお、この「銅を含む付着物」には、ＩＧＺＯ表面の欠損部位に取り込まれた、エッチング液に溶解した遷移金属元素を含む化学種も包含される。
　また、本明細書において、「ＩＧＺＯ半導体層を腐食することがない」とは、ＩＧＺＯのエッチングレートが３０Å／ｍｉｎ未満であることを意味する。また、「銅を含む配線を腐食することがない」とは、銅のエッチングレートが３０Å／ｍｉｎ未満であることを意味する。また、「銅およびモリブデンを含む配線を腐食することがない」とは、銅のエッチングレートが３０Å／ｍｉｎ未満であり、かつモリブデンのエッチングレートが３０Å／ｍｉｎ未満であることを意味する。
　このような特定の成分を含有する液体組成物を用いることで、ＩＧＺＯ半導体層や銅を含む配線を腐食することなく、ＩＧＺＯ表面より銅を含む付着物を洗浄・除去することができる。また、本発明の好ましい態様によれば、モリブデンを含む付着物を洗浄・除去することもできる。また、銅を含む付着物およびモリブデンを含む付着物を同時に除去することもできる。 <Liquid composition>
The liquid composition according to the present invention is a liquid composition that cleans and removes deposits containing copper from the IGZO surface without corroding the IGZO semiconductor layer and the wiring containing copper, and the liquid composition is a hydroxycarboxylic acid. And one or more selected from the group consisting of dicarboxylic acids or salts thereof, and having a pH value of 1.5 to 10.
In the present specification, the “adhesion containing copper” refers to a metal compound such as an oxide, hydroxide or salt of a metal containing at least copper, or a metal ion containing at least copper or the like attached to the IGZO surface. Good, excluding single metal. The “adhesive material including copper” includes chemical species including a transition metal element dissolved in an etching solution and taken into a defect site on the surface of the IGZO.
Further, in this specification, “does not corrode the IGZO semiconductor layer” means that the etching rate of IGZO is less than 30 Å / min. Further, “does not corrode wiring containing copper” means that the etching rate of copper is less than 30 Å / min. Further, “does not corrode wiring containing copper and molybdenum” means that the etching rate of copper is less than 30 Å / min and the etching rate of molybdenum is less than 30 Å / min.
By using such a liquid composition containing a specific component, it is possible to wash and remove deposits containing copper from the IGZO surface without corroding the IGZO semiconductor layer and the wiring containing copper. Moreover, according to the preferable aspect of this invention, the deposit | attachment containing molybdenum can also be wash | cleaned and removed. Moreover, the deposit containing copper and the deposit containing molybdenum can be simultaneously removed.
　本発明による液体組成物は、ＩＧＺＯ表面を洗浄する際に使用されるものであり、ＩＧＺＯ表面よりＩＧＺＯ半導体層を腐食することなく、かつ銅を含む配線を腐食することなく、銅を含む付着物を洗浄・除去することができる。また、本発明の好ましい態様によれば、本発明による液体組成物は、ＩＧＺＯ半導体層を腐食することなく、かつモリブデンを含む配線を腐食することなく、ＩＧＺＯ表面から少なくとも銅を含む付着物を除去することができる。また、本発明の好ましい態様によれば、本発明による液体組成物は、ＩＧＺＯ半導体層を腐食することなく、かつ銅およびモリブデンを含む単層膜または多層膜配線を腐食することなく、ＩＧＺＯ表面から銅を含む付着物およびモリブデンを含む付着物を洗浄・除去することができる。
　本発明による液体組成物の、特に好ましい様態においては、ＩＧＺＯを半導体層とし、銅を含む単層膜または多層膜を配線としたＴＦＴ構造を有する基板において、ＩＧＺＯ半導体層を腐食することなく、また銅または銅およびモリブデンを含む配線を腐食することなく、ＩＧＺＯ表面より銅または銅およびモリブデンを含む付着物を洗浄・除去することができる。 The liquid composition according to the present invention is used when cleaning the IGZO surface, and does not corrode the IGZO semiconductor layer from the IGZO surface, and does not corrode the wiring containing copper, and the deposit containing copper. Can be cleaned and removed. According to a preferred aspect of the present invention, the liquid composition according to the present invention removes deposits containing at least copper from the surface of the IGZO without corroding the IGZO semiconductor layer and without corroding the wiring containing molybdenum. can do. Further, according to a preferred aspect of the present invention, the liquid composition according to the present invention can be applied from the surface of the IGZO without corroding the IGZO semiconductor layer and without corroding the monolayer film or the multilayer film wiring containing copper and molybdenum. Deposits containing copper and deposits containing molybdenum can be cleaned and removed.
In a particularly preferred embodiment of the liquid composition according to the present invention, in a substrate having a TFT structure in which IGZO is a semiconductor layer and a single-layer film or a multilayer film containing copper is used as a wiring, the IGZO semiconductor layer is not corroded. Deposits containing copper or copper and molybdenum can be cleaned and removed from the surface of the IGZO without corroding the wiring containing copper or copper and molybdenum.
　以下、本発明による液体組成物を構成する各成分について具体的に説明する。 Hereinafter, each component constituting the liquid composition according to the present invention will be described in detail.
（Ａ）ヒドロキシカルボン酸
　本発明による液体組成物に含まれるヒドロキシカルボン酸は金属イオンと錯体を形成し、ＩＧＺＯ表面より銅を含む付着物を洗浄・除去する機能を有するものである。ヒドロキシカルボン酸としては、ヒドロキシカルボン酸およびヒドロキシカルボン酸の塩からなる群より選択されるものである。ここで言うヒドロキシカルボン酸とは、ヒドロキシ基とカルボキシル基をそれぞれ１つ以上、分子内に含む化合物のことである。ヒドロキシカルボン酸としては、クエン酸、酒石酸、乳酸、グリコール酸、リンゴ酸、シトラマル酸、イソクエン酸、グルカル酸、ガラクタル酸などが好ましく挙げられる。これらの中でも、特にクエン酸、酒石酸、乳酸、グリコール酸が好ましい。これらヒドロキシカルボン酸は単独で使用してもよく、また、複数を組み合わせて使用してもよい。また、これらのヒドロキシカルボン酸の塩を使用してもよく、たとえば、ナトリウム塩、カリウム塩、アンモニウム塩、テトラメチルアンモニウム塩などが例示される。 (A) Hydroxycarboxylic acid The hydroxycarboxylic acid contained in the liquid composition according to the present invention forms a complex with a metal ion, and has a function of washing and removing deposits containing copper from the IGZO surface. The hydroxycarboxylic acid is selected from the group consisting of hydroxycarboxylic acids and hydroxycarboxylic acid salts. The term “hydroxycarboxylic acid” as used herein refers to a compound containing at least one hydroxy group and one carboxyl group in the molecule. Preferred examples of the hydroxycarboxylic acid include citric acid, tartaric acid, lactic acid, glycolic acid, malic acid, citramalic acid, isocitric acid, glucaric acid, and galactaric acid. Among these, citric acid, tartaric acid, lactic acid, and glycolic acid are particularly preferable. These hydroxycarboxylic acids may be used alone or in combination. These hydroxycarboxylic acid salts may be used, and examples thereof include sodium salts, potassium salts, ammonium salts, and tetramethylammonium salts.
（Ｂ）ジカルボン酸
　本発明による液体組成物に含まれるジカルボン酸は金属イオンと錯体を形成し、ＩＧＺＯ表面より銅を含む付着物を洗浄・除去する機能を有するものである。ジカルボン酸としては、ジカルボン酸、ジカルボン酸の塩、カルボン酸無水物からなる群より選択されるものである。ここで言うジカルボン酸とは分子内にカルボキシル基を２つ有し、ヒドロキシル基を有さない化合物のことである。ジカルボン酸としては、シュウ酸、マロン酸、マレイン酸、無水マレイン酸、グルタル酸、コハク酸、アジピン酸、１,２―シクロヘキサンジカルボン酸、フタル酸などが好ましく挙げられる。これらジカルボン酸化合物は、単独で使用してもよく、また、複数を組み合わせて使用してもよい。また、これらのジカルボン酸の塩を使用してもよく、たとえば、ナトリウム塩、カリウム塩、アンモニウム塩、テトラメチルアンモニウム塩などが例示される。 (B) Dicarboxylic acid The dicarboxylic acid contained in the liquid composition according to the present invention forms a complex with a metal ion and has a function of washing and removing deposits containing copper from the IGZO surface. The dicarboxylic acid is selected from the group consisting of dicarboxylic acids, dicarboxylic acid salts, and carboxylic anhydrides. The dicarboxylic acid referred to here is a compound having two carboxyl groups in the molecule and no hydroxyl group. Preferred examples of the dicarboxylic acid include oxalic acid, malonic acid, maleic acid, maleic anhydride, glutaric acid, succinic acid, adipic acid, 1,2-cyclohexanedicarboxylic acid, and phthalic acid. These dicarboxylic acid compounds may be used alone or in combination of two or more. Further, salts of these dicarboxylic acids may be used, and examples thereof include sodium salts, potassium salts, ammonium salts, and tetramethylammonium salts.
　ヒドロキシカルボン酸またはその塩（単に（Ａ）成分と言う場合がある）、ジカルボン酸またはその塩（単に（Ｂ）成分）と言う場合がある）からなる群より選択される一種以上の濃度は、液体組成物中に０．００１～３０質量％の範囲で含まれていることが好ましく、０．０１～２５質量％の範囲がより好ましく、特に０．０２～２０質量％の範囲が好ましく、０．１～１０質量%の範囲がさらに好ましく、１～５質量％の範囲がさらにより好ましい。 One or more concentrations selected from the group consisting of hydroxycarboxylic acid or a salt thereof (simply referred to as component (A)) or dicarboxylic acid or a salt thereof (simply referred to as component (B)) may be: It is preferably contained in the liquid composition in the range of 0.001 to 30% by mass, more preferably in the range of 0.01 to 25% by mass, particularly preferably in the range of 0.02 to 20% by mass. The range of 1 to 10% by mass is more preferable, and the range of 1 to 5% by mass is even more preferable.
（Ｃ）ｐＨ調節剤
　本発明による液体組成物は、必要に応じて、ｐＨ調節剤（単に（Ｃ）成分という場合がある）を含んでいてもよい。ｐＨ調節剤は液体組成物のｐＨ値を１．５～１０の範囲に調節する役割を持つ。 (C) pH adjuster The liquid composition according to the present invention may contain a pH adjuster (sometimes simply referred to as the component (C)), if necessary. The pH adjuster has a role of adjusting the pH value of the liquid composition in the range of 1.5 to 10.
　ｐＨ調節剤（（Ｃ）成分）としては、上記した液体組成物の効果を阻害しないものであれば特に制限はなく、例えば、アンモニア（ＮＨ３）；水酸化ナトリウム（ＮａＯＨ）や水酸化カリウム（ＫＯＨ）などの金属水酸化物；イソプロピルアミン、ターシャリーブチルアミン、２－アミノエタノール、１－アミノ－２－プロパノールなどのアミン類；ヒドロキシルアミンなどのヒドロキシルアミン類；テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシドなどのアルキルアンモニウムヒドロキシドなどが好ましく挙げられる。これらｐＨ調整剤は、単独で使用してもよく、又、複数を組み合わせて使用してもよい。これらのなかでも、アンモニア、水酸化カリウム、テトラメチルアンモニウムヒドロキシド、２－アミノエタノール、１－アミノ－２－プロパノールが好ましい。 The pH adjuster (component (C)) is not particularly limited as long as it does not inhibit the effect of the liquid composition described above. For example, ammonia (NH 3 ); sodium hydroxide (NaOH) or potassium hydroxide ( Metal hydroxides such as KOH); amines such as isopropylamine, tertiary butylamine, 2-aminoethanol, 1-amino-2-propanol; hydroxylamines such as hydroxylamine; tetramethylammonium hydroxide (TMAH), Preferable examples include alkylammonium hydroxides such as tetraethylammonium hydroxide and tetrapropylammonium hydroxide. These pH adjusters may be used alone or in combination. Of these, ammonia, potassium hydroxide, tetramethylammonium hydroxide, 2-aminoethanol, and 1-amino-2-propanol are preferable.
　上記した本発明による液体組成物は、（Ａ）ヒドロキシカルボン酸および（Ｂ）ジカルボン酸、またはそれらの塩からなる群より選択されるいずれか一種以上を含み、ｐＨ値が１．５～１０の範囲である。液体組成物のｐＨ値の範囲を上記の範囲とすることにより、ＩＧＺＯ半導体層および銅を含む配線を腐食することなく、ＩＧＺＯ表面より銅を含む付着物を洗浄・除去することができる。ｐＨ値が１．５未満であると、ＩＧＺＯ半導体層や配線へのダメージが増加する傾向にあるため、好ましくない。一方、ｐＨ値が１０を超えると、銅を含む付着物の洗浄・除去能力が低下する傾向にあるため好ましくない。液体組成物の好ましいｐＨ値の範囲は１．５～１０である。より好ましいｐＨ値の範囲は、１．６～９．５であり、１.７～９．２が特に好ましい。 The liquid composition according to the present invention includes at least one selected from the group consisting of (A) a hydroxycarboxylic acid and (B) a dicarboxylic acid, or a salt thereof, and has a pH value of 1.5 to 10. It is a range. By setting the range of the pH value of the liquid composition to the above range, deposits containing copper can be cleaned and removed from the surface of the IGZO without corroding the wiring containing the IGZO semiconductor layer and copper. A pH value of less than 1.5 is not preferable because damage to the IGZO semiconductor layer and wiring tends to increase. On the other hand, if the pH value exceeds 10, it is not preferable because the ability to clean and remove deposits containing copper tends to decrease. The preferred pH value range of the liquid composition is 1.5-10. A more preferable pH value range is 1.6 to 9.5, and 1.7 to 9.2 is particularly preferable.
　本発明による液体組成物中のｐＨ調整剤の含有量は、液体組成物のｐＨ値が所望の値となるように、他の成分の含有量によって適宜決定されるものである。 The content of the pH adjusting agent in the liquid composition according to the present invention is appropriately determined depending on the contents of other components so that the pH value of the liquid composition becomes a desired value.
　本発明による液体組成物は、上記した（Ａ）成分、または（Ｂ）成分、および必要に応じて添加する（Ｃ）成分のほか、水、その他、洗浄用の液体組成物に通常用いられる各種の水溶性有機溶剤や添加剤を、上記した液体組成物の効果を害しない範囲で含むことができる。例えば、水としては、蒸留、イオン交換処理、フイルター処理、各種吸着処理などによって金属イオンや有機不純物、パーテイクル粒子などがあらかじめ除去されたものが好ましく、純水がより好ましく、特に超純水が好ましい。 The liquid composition according to the present invention is not limited to the above-described component (A), component (B), and component (C) to be added as necessary, and various types of liquid compositions that are commonly used for water and other cleaning liquid compositions. These water-soluble organic solvents and additives can be included within a range that does not impair the effects of the liquid composition described above. For example, as water, those from which metal ions, organic impurities, particle particles, etc. have been removed in advance by distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc. are preferred, pure water is more preferred, and ultrapure water is particularly preferred. .
　水溶性有機溶剤としては、上記した液体組成物の効果を阻害しないものであれば特に制限はなく、例えば、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテルなどのエチレングリコール類；メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、ｔ－ブタノールなどのアルコール類；エチレングリコール、プロピレングリコール、グリセリン等が好適に使用できる。 The water-soluble organic solvent is not particularly limited as long as it does not inhibit the effect of the liquid composition described above. For example, ethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc. Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and t-butanol; ethylene glycol, propylene glycol, glycerin and the like can be preferably used.
　本発明による液体組成物は、銅の防食剤として公知の添加剤を含むことができる。たとえば、ベンゾトリアゾール、５－アミノ－１Ｈ－テトラゾール、イミダゾール、ピラゾールといったアゾール化合物、およびリン酸等を含むことができる。 The liquid composition according to the present invention may contain an additive known as a copper anticorrosive. For example, it may include azole compounds such as benzotriazole, 5-amino-1H-tetrazole, imidazole and pyrazole, and phosphoric acid.
＜ＩＧＺＯ表面の洗浄方法＞
　本発明によるＩＧＺＯ表面の洗浄方法は、ＩＧＺＯ表面よりＩＧＺＯ半導体層や銅を含む配線を腐食することなく、銅を含む付着物を洗浄・除去する洗浄方法であって、ＩＧＺＯ半導体層と銅を含む配線を有した基板上のＩＧＺＯ表面に、上記の液体組成物を接触させる工程を含むものである。本発明の方法によれば、ＩＧＺＯ表面よりＩＧＺＯ半導体層を腐食することなく、かつ銅を含む配線を腐食することなく、銅を含む付着物を洗浄・除去することができる。 <How to clean the IGZO surface>
The cleaning method for the IGZO surface according to the present invention is a cleaning method for cleaning and removing deposits containing copper without corroding the IGZO semiconductor layer and the wiring containing copper from the IGZO surface, and includes the IGZO semiconductor layer and copper. The method includes a step of bringing the liquid composition into contact with an IGZO surface on a substrate having wiring. According to the method of the present invention, it is possible to clean and remove deposits containing copper without corroding the IGZO semiconductor layer from the IGZO surface and without corroding the wiring containing copper.
　さらに、本発明による洗浄方法は、基板上にＩＧＺＯ半導体層を成膜し、その上に銅または銅およびモリブデンを含む配線を有した基板を洗浄対象物とする。 Further, in the cleaning method according to the present invention, an IGZO semiconductor layer is formed on a substrate, and a substrate having a wiring containing copper or copper and molybdenum thereon is used as an object to be cleaned.
　洗浄対象物は、例えばガラス等の基板上にＩＧＺＯからなる層とモリブデンからなる層と銅からなる層とを順次積層し、その上にレジストを塗布し、所望のパターンマスクを露光転写し、現像して所望のレジストパターンを形成する。その後、エッチング液により銅およびモリブデンを含む多層膜配線を選択的にエッチングすることにより得ることができる。 For the object to be cleaned, for example, a layer made of IGZO, a layer made of molybdenum and a layer made of copper are sequentially laminated on a substrate such as glass, and a resist is coated thereon, and a desired pattern mask is exposed and transferred, and developed. Thus, a desired resist pattern is formed. Thereafter, the multilayer wiring containing copper and molybdenum can be selectively etched with an etching solution.
　洗浄対象物に液体組成物を接触させる方法には特に制限はなく、例えば洗浄対象物を液体組成物に浸漬させる方法や、液体組成物の滴下（枚葉スピン処理）やスプレーなどの形式により対象物に接触させる方法などを採用することができる。本発明においてはいずれの方法でも洗浄が可能である。 There is no particular limitation on the method of bringing the liquid composition into contact with the object to be cleaned. For example, the object depends on the method of immersing the object to be cleaned in the liquid composition, the form of dripping the liquid composition (single wafer spin treatment), spraying, or the like. A method of contacting an object can be employed. In the present invention, any method can be used for cleaning.
　液体組成物の使用温度としては、１０～７０℃の温度が好ましく、特に２０～５０℃が好ましい。７０℃以上であれば、ＩＧＺＯ半導体層へのダメージが大きくなるため好ましくない。また、液体組成物の温度を高くすると水分の蒸発によって液体組成物の濃度変化が大きくなるため好ましくない。１０℃より低い温度では冷却装置が必要となり、コストが増加するため実用上好ましくない。適宜最適な処理温度を決定すればよい。 The working temperature of the liquid composition is preferably 10 to 70 ° C., more preferably 20 to 50 ° C. If it is 70 degreeC or more, since the damage to an IGZO semiconductor layer becomes large, it is unpreferable. Further, it is not preferable to raise the temperature of the liquid composition because the concentration change of the liquid composition increases due to evaporation of moisture. A temperature lower than 10 ° C. is not practically preferable because a cooling device is required and the cost increases. What is necessary is just to determine the optimal processing temperature suitably.
　次に、本発明を実施例によりさらに詳しく説明するが、本発明の範囲がこれらの例によってなんら限定されるものではない。 Next, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.
＜銅を含む付着物の洗浄・除去性能の評価＞
　銅イオン付着処理として、参考例１で得られたＩＧＺＯ／ガラス基板を、０．２５質量％－硫酸銅水溶液（硫酸銅５水和物、和光純薬工業株式会社製、試薬特級、分子量２４９．６９）（銅イオンとして１０００ｐｐｍ含有）に２５℃、１分間浸漬させた。基板上の余分な硫酸銅水溶液を純水で洗い流した（リンス処理）後、ブロワーで乾燥した。続いて上記基板を表１～４に記載の液体組成物に２５℃、１分間浸漬させ、液体組成物浸漬後の基板を純水でリンス処理した後、ブロワーで乾燥した。得られたＩＧＺＯ／ガラス基板について、サーモフィッシャーサイエンティフィック株式会社製Ｘ線光電子分光計Ｋ－ａｌｐｈａを用いて、ＩＧＺＯ表面の銅元素を分析した（Ｃ１ｓのピーク（２８５．２ｅＶ）を標準としてピーク位置を補正した）。銅元素（Ｃｕ２ｐのピーク）が検出されないものを合格品とした。 <Evaluation of cleaning and removal performance of deposits containing copper>
As the copper ion adhesion treatment, the IGZO / glass substrate obtained in Reference Example 1 was added to a 0.25% by mass-copper sulfate aqueous solution (copper sulfate pentahydrate, manufactured by Wako Pure Chemical Industries, Ltd., reagent grade, molecular weight 249. 69) It was immersed in (containing 1000 ppm as copper ions) at 25 ° C. for 1 minute. The excess copper sulfate aqueous solution on the substrate was washed away with pure water (rinse treatment), and then dried with a blower. Subsequently, the substrate was immersed in the liquid compositions described in Tables 1 to 4 at 25 ° C. for 1 minute. The substrate after immersion in the liquid composition was rinsed with pure water and then dried with a blower. The obtained IGZO / glass substrate was analyzed for copper element on the surface of IGZO using an X-ray photoelectron spectrometer K-alpha manufactured by Thermo Fisher Scientific Co., Ltd. (C1s peak (285.2 eV) as a standard) Corrected position). Those in which no copper element (Cu2p peak) was detected were regarded as acceptable products.
＜モリブデンを含む付着物の洗浄・除去性能の評価＞
　モリブデンイオン付着処理として、参考例１で得られたＩＧＺＯ／ガラス基板を０．１７質量％－７モリブデン酸６アンモニウム水溶液（７モリブデン酸６アンモニウム４水和物、和光純薬工業株式会社製、試薬特級、分子量１２３５．８６）（モリブデンイオンとして１０００ｐｐｍ含有）に２５℃、１分間浸漬させた。基板上の余分な７モリブデン酸６アンモニウム水溶液を純水で洗い流した（リンス処理）後、ブロワーで乾燥した。続いて上記基板を、表１に記載の液体組成物に２５℃、１分間浸漬させ、液体組成物浸漬後の基板を純水でリンス処理した後、ブロワーで乾燥した。得られたＩＧＺＯ／ガラス基板について、サーモフィッシャーサイエンティフィック株式会社製Ｘ線光電子分光計Ｋ－ａｌｐｈａを用いて、ＩＧＺＯ表面のモリブデン元素を分析した（Ｃ１ｓのピーク（２８５．２ｅＶ）を標準としてピーク位置を補正した）。モリブデン元素（Ｍｏ３ｄのピーク）が検出されないものを合格品とした。 <Evaluation of cleaning and removal performance of deposits containing molybdenum>
As the molybdenum ion adhesion treatment, the IGZO / glass substrate obtained in Reference Example 1 was treated with 0.17 mass% -7 ammonium molybdate aqueous solution (7 ammonium molybdate tetrahydrate, manufactured by Wako Pure Chemical Industries, Ltd., reagent. Special grade, molecular weight 1235.86) (containing 1000 ppm as molybdenum ions) at 25 ° C. for 1 minute. Excess 6 ammonium molybdate aqueous solution on the substrate was washed away with pure water (rinse treatment), and then dried with a blower. Subsequently, the substrate was immersed in the liquid composition described in Table 1 at 25 ° C. for 1 minute, and the substrate after immersion in the liquid composition was rinsed with pure water and then dried with a blower. The obtained IGZO / glass substrate was analyzed for molybdenum element on the surface of the IGZO using an X-ray photoelectron spectrometer K-alpha manufactured by Thermo Fisher Scientific Co., Ltd. (peak with C1s peak (285.2 eV) as a standard) Corrected position). Those in which no molybdenum element (Mo3d peak) was detected were regarded as acceptable products.
＜銅を含む付着物およびモリブデンを含む付着物の洗浄・除去性能の評価＞
　モリブデンイオンの付着処理として、参考例１で得られたＩＧＺＯ／ガラス基板を、０．１７質量％－７モリブデン酸６アンモニウム水溶液（７モリブデン酸６アンモニウム４水和物、和光純薬工業株式会社製、試薬特級、分子量１２３５．８６）（モリブデンイオンとして１０００ｐｐｍ含有）に２５℃で１分間浸漬させた。基板上の余分な７モリブデン酸６アンモニウム水溶液を純水で洗い流した後、銅イオン付着処理として、０．２５質量％－硫酸銅水溶液（硫酸銅５水和物、和光純薬工業株式会社製、試薬特級、分子量２４９．６９）（銅イオンとして１０００ｐｐｍ含有）に２５℃で１分間浸漬させた。基板上の余分な硫酸銅水溶液を純水で洗い流した後、ブロワーで乾燥した。続いて上記基板を表１に記載の液体組成物に２５℃で１分間浸漬させ、液体組成物浸漬後の基板を純水でリンス処理した後、ブロワーで乾燥した。得られたＩＧＺＯ／ガラス基板について、サーモフィッシャーサイエンティフィック株式会社製Ｘ線光電子分光計Ｋ－ａｌｐｈａを用いて、ＩＧＺＯ表面の銅元素およびモリブデン元素を分析した（Ｃ１ｓのピーク（２８５．２ｅＶ）を標準としてピーク位置を補正した）。銅元素（Ｃｕ２ｐのピーク）およびモリブデン元素（Ｍｏ３ｄのピーク）がいずれも検出されないものを合格品とした。 <Evaluation of cleaning and removal performance of deposits containing copper and deposits containing molybdenum>
As an adhesion treatment of molybdenum ions, the IGZO / glass substrate obtained in Reference Example 1 was treated with 0.17% by mass-7 ammonium molybdate aqueous solution (7 ammonium molybdate tetrahydrate, manufactured by Wako Pure Chemical Industries, Ltd.). , Reagent special grade, molecular weight 1235.86) (containing 1000 ppm as molybdenum ions) at 25 ° C. for 1 minute. After rinsing off the excess hexammonium molybdate aqueous solution on the substrate with pure water, as a copper ion adhesion treatment, 0.25% by mass-copper sulfate aqueous solution (copper sulfate pentahydrate, manufactured by Wako Pure Chemical Industries, Ltd., Reagent grade, molecular weight 249.69) (containing 1000 ppm as copper ion) was immersed at 25 ° C. for 1 minute. The excess copper sulfate aqueous solution on the substrate was washed away with pure water and then dried with a blower. Subsequently, the substrate was immersed in the liquid composition described in Table 1 for 1 minute at 25 ° C., and the substrate after immersion in the liquid composition was rinsed with pure water and then dried with a blower. The obtained IGZO / glass substrate was analyzed for the copper element and the molybdenum element on the IGZO surface (C1s peak (285.2 eV)) using an X-ray photoelectron spectrometer K-alpha manufactured by Thermo Fisher Scientific Co., Ltd. The peak position was corrected as a standard). A product in which neither copper element (Cu2p peak) nor molybdenum element (Mo3d peak) was detected was regarded as an acceptable product.
＜ＩＧＺＯのエッチングレート（防食性）の評価＞
　参考例１で得られたＩＧＺＯ／ガラス基板を表１～４に記載の液体組成物に２５℃で１分間浸漬させ、処理前後のＩＧＺＯ膜厚を、ｎ＆ｋ Ｔｅｃｈｎｏｌｏｇｙ Ｉｎｃ．製の光学式薄膜特性測定装置ｎ＆ｋ Ａｎａｌｙｚｅｒ １２８０により測定し、処理前後の膜厚差をエッチング時間で除することによりエッチングレートを算出した。ＩＧＺＯのエッチングレートが３０Å／ｍｉｎ未満であるものを合格品とした。 <Evaluation of etching rate (anticorrosion) of IGZO>
The IGZO / glass substrate obtained in Reference Example 1 was immersed in the liquid compositions described in Tables 1 to 4 at 25 ° C. for 1 minute, and the IGZO film thickness before and after the treatment was determined using n & k Technology Inc. An etching rate was calculated by measuring with an optical thin film property measuring apparatus n & k Analyzer 1280 manufactured by manufacturing, and dividing the film thickness difference before and after the treatment by the etching time. Those having an IGZO etching rate of less than 30 liters / min were regarded as acceptable products.
＜銅のエッチングレート（防食性）の評価＞
　参考例２で得られた銅／モリブデン／ガラス基板を表１～４に記載の液体組成物に２５℃で６０分間浸漬させた。浸漬処理前後の銅の膜厚をＳＩＩナノテクノロジー社製の蛍光Ｘ線分析装置ＳＥＡ１２００ＶＸにより測定し、処理前後の膜厚差をエッチング時間で除することによりエッチングレートを算出した。銅のエッチングレートが３０Å／ｍｉｎ未満であるものを合格品とした。 <Evaluation of copper etching rate (anticorrosion)>
The copper / molybdenum / glass substrate obtained in Reference Example 2 was immersed in the liquid compositions shown in Tables 1 to 4 at 25 ° C. for 60 minutes. The copper film thickness before and after the immersion treatment was measured by a fluorescent X-ray analyzer SEA1200VX manufactured by SII Nanotechnology, and the etching rate was calculated by dividing the film thickness difference before and after the treatment by the etching time. A copper etching rate of less than 30 kg / min was regarded as an acceptable product.
＜モリブデンのエッチングレート（防食性）の評価＞
　参考例３で得られたモリブデン／ガラス基板を表１～４に記載の液体組成物に２５℃で６０分間浸漬させた。浸漬処理前後のモリブデンの膜厚をＳＩＩナノテクノロジー社製の蛍光Ｘ線分析装置ＳＥＡ１２００ＶＸにより測定し、処理前後の膜厚差をエッチング時間で除することによりエッチングレートを算出した。モリブデンのエッチングレートが３０Å／ｍｉｎ未満であるものを合格品とした。 <Evaluation of etching rate (anticorrosion) of molybdenum>
The molybdenum / glass substrate obtained in Reference Example 3 was immersed in the liquid compositions described in Tables 1 to 4 at 25 ° C. for 60 minutes. The molybdenum film thickness before and after the immersion treatment was measured with a fluorescent X-ray analyzer SEA1200VX manufactured by SII Nanotechnology, and the etching rate was calculated by dividing the film thickness difference before and after the treatment by the etching time. A product with an molybdenum etching rate of less than 30 liters / min was regarded as an acceptable product.
＜参考例１：ＩＧＺＯ／ガラス基板の作製＞
　ガラス基板（寸法：１５０ｍｍ×１５０ｍｍ）上にインジウム、ガリウム、亜鉛および酸素の元素比が１：１：１：４であるＩＧＺＯをスパッタ法により成膜してＩＧＺＯからなる層（ＩＧＺＯ膜厚：５００Å）を形成し、ＩＧＺＯ／ガラス基板を作製した。 <Reference Example 1: Production of IGZO / Glass Substrate>
A layer of IGZO (IGZO film thickness: 500 mm) formed by sputtering IGZO having an element ratio of indium, gallium, zinc and oxygen of 1: 1: 1: 4 on a glass substrate (size: 150 mm × 150 mm). ) To form an IGZO / glass substrate.
＜参考例２：銅／モリブデン／ガラス基板の作製＞
　ガラス基板（寸法：１５０ｍｍ×１５０ｍｍ）上にモリブデンをスパッタ法により成膜してモリブデン（金属）からなる層（モリブデン膜厚：３００Å）を形成し、次いで銅をスパッタ法により成膜して銅（金属）からなる層（銅膜厚：３０００Å）を形成し、銅／モリブデン／ガラス基板を作製した。 <Reference Example 2: Production of copper / molybdenum / glass substrate>
A layer of molybdenum (metal) (molybdenum film thickness: 300 mm) is formed on a glass substrate (dimensions: 150 mm × 150 mm) by sputtering to form a layer of molybdenum (metal) (molybdenum film thickness: 300 mm). A layer made of (metal) (copper film thickness: 3000 mm) was formed to produce a copper / molybdenum / glass substrate.
＜参考例３：モリブデン／ガラス基板の作製＞
　ガラス基板（寸法：１５０ｍｍ×１５０ｍｍ）上にモリブデンをスパッタ法により成膜してモリブデン（金属）からなる層（モリブデン膜厚：２０００Å）を形成し、モリブデン／ガラス基板を作製した。 <Reference Example 3: Production of molybdenum / glass substrate>
Molybdenum was formed on a glass substrate (dimensions: 150 mm × 150 mm) by sputtering to form a layer (molybdenum film thickness: 2000 mm) made of molybdenum (metal), thereby producing a molybdenum / glass substrate.
実施例１
　液体組成物の調製
　容量１０Ｌのポリプロピレン容器に純水９．９０ｋｇと、（Ａ）カルボン酸化合物であるクエン酸（和光純薬工業株式会社製、食品添加物グレード、分子量２１０．１４）０．１ｋｇを投入した。攪拌してクエン酸の溶解を確認し、液体組成物（１質量％－クエン酸水溶液）を得た。得られた液体組成物のｐＨ値は２．２であった。 Example 1
Preparation of liquid composition In a 10 L polypropylene container, 9.90 kg of pure water and (A) citric acid as a carboxylic acid compound (made by Wako Pure Chemical Industries, Ltd., food additive grade, molecular weight 210.14) 0.1 kg Was introduced. Stirring was performed to confirm the dissolution of citric acid, and a liquid composition (1% by mass-citric acid aqueous solution) was obtained. The pH value of the obtained liquid composition was 2.2.
　銅を含む付着物を除去するための洗浄処理
　参考例１で得られたＩＧＺＯ／ガラス基板を０．２５質量％－硫酸銅水溶液（銅イオンとして１０００ｐｐｍ含有）に２５℃で１分間浸漬させ、銅イオンを付着させた。余分の硫酸銅水溶液を除去するために浸漬後の基板を純水でリンス処理した後、ブロワーで乾燥した。銅イオン付着処理後のＩＧＺＯ／ガラス基板をＸ線光電子分光法（ＸＰＳ）により分析したところ、９３３ｅＶと９５３ｅＶにＣｕ２ｐのピークが観察された。このピークよりＩＧＺＯ表面に銅を含む付着物が銅元素として０．７ａｔ％付着していることがわかった。得られたスペクトルを図２に示す。 Cleaning treatment for removing deposits containing copper The IGZO / glass substrate obtained in Reference Example 1 was dipped in an aqueous solution of 0.25% by mass-containing copper sulfate (containing 1000 ppm as copper ions) at 25 ° C. for 1 minute. Ions were deposited. In order to remove excess copper sulfate aqueous solution, the substrate after immersion was rinsed with pure water and then dried with a blower. When the IGZO / glass substrate after the copper ion adhesion treatment was analyzed by X-ray photoelectron spectroscopy (XPS), Cu2p peaks were observed at 933 eV and 953 eV. From this peak, it was found that 0.7 at% of the deposit containing copper was deposited on the IGZO surface as a copper element. The obtained spectrum is shown in FIG.
　続いて、銅イオン付着処理後のＩＧＺＯ／ガラス基板を、先に調製した液体組成物（１質量％－クエン酸水溶液）に２５℃で１分間浸漬させた。浸漬後の基板を純水でリンス処理した後、ブロワーで乾燥した。洗浄処理後のＩＧＺＯ／ガラス基板をＸＰＳ分析した。得られたスペクトルを図３に示す。ＩＧＺＯ表面に銅元素に基づく９３３ｅＶと９５３ｅＶのピークは検出されず、液体組成物（１質量％－クエン酸水溶液）を用いた洗浄処理によりＩＧＺＯ表面の銅を含む付着物が洗浄・除去されていることが確認された。 Subsequently, the IGZO / glass substrate after the copper ion adhesion treatment was immersed in the previously prepared liquid composition (1 mass% -citric acid aqueous solution) at 25 ° C. for 1 minute. The substrate after immersion was rinsed with pure water and then dried with a blower. The XPS analysis of the IGZO / glass substrate after the cleaning treatment was performed. The obtained spectrum is shown in FIG. The peaks of 933 eV and 953 eV based on the copper element were not detected on the IGZO surface, and deposits containing copper on the IGZO surface were cleaned and removed by the cleaning treatment using the liquid composition (1% by mass-citric acid aqueous solution). It was confirmed.
　モリブデンを含む付着物を除去するための洗浄処理
　参考例１で得られたＩＧＺＯ／ガラス基板を０．１７質量％－７モリブデン酸６アンモニウム水溶液（モリブデンイオンとして１０００ｐｐｍ含有）に２５℃で１分間浸漬させ、モリブデンイオンを付着処理をした。７モリブデン酸６アンモニウム水溶液浸漬後の基板を純水でリンス処理した後、ブロワーで乾燥した。モリブデンイオン付着処理後のＩＧＺＯ／ガラス基板をＸ線光電子分光法（ＸＰＳ）により分析したところ、２２８ｅＶと２３１ｅＶにＭｏ３ｄのピークが検出され、表面にモリブデンを含む付着物がモリブデン元素として０．３ａｔ％付着していることがわかった。 Cleaning treatment for removing deposits containing molybdenum The IGZO / glass substrate obtained in Reference Example 1 was immersed in a 0.17% by mass-7 aqueous solution of 6 ammonium molybdate (containing 1000 ppm as molybdenum ions) at 25 ° C. for 1 minute. Then, the molybdenum ions were attached. The substrate after immersion in the aqueous solution of 7 ammonium molybdate was rinsed with pure water and then dried with a blower. When the IGZO / glass substrate after the molybdenum ion deposition treatment was analyzed by X-ray photoelectron spectroscopy (XPS), Mo3d peaks were detected at 228 eV and 231 eV, and the deposit containing molybdenum on the surface was 0.3 at% as molybdenum element. It was found that it was attached.
　続いて、モリブデンイオン付着処理後のＩＧＺＯ／ガラス基板を、先に調製した液体組成物（１質量％－クエン酸水溶液）に２５℃で１分間浸漬させた。浸漬後の基板を純水でリンス処理した後、ブロワーで乾燥した。洗浄処理後のＩＧＺＯ／ガラス基板をＸＰＳ分析した。ＩＧＺＯ表面にモリブデン元素に基づく２２８ｅＶと２３１ｅＶのピークは検出されず、液体組成物（１質量％－クエン酸水溶液）を用いた洗浄処理により、ＩＧＺＯ表面のモリブデンを含む付着物が洗浄・除去されていることが確認された。 Subsequently, the IGZO / glass substrate after the molybdenum ion adhesion treatment was immersed in the previously prepared liquid composition (1 mass% -citric acid aqueous solution) at 25 ° C. for 1 minute. The substrate after immersion was rinsed with pure water and then dried with a blower. The XPS analysis of the IGZO / glass substrate after the cleaning treatment was performed. The peaks of 228 eV and 231 eV based on the molybdenum element were not detected on the IGZO surface, and the deposits containing molybdenum on the IGZO surface were cleaned and removed by the cleaning treatment using the liquid composition (1% by mass-citric acid aqueous solution). It was confirmed that
　銅を含む付着物およびモリブデンを含む付着物を除去するための洗浄処理
　参考例１で得られたＩＧＺＯ／ガラス基板を０．１７質量％－７モリブデン酸６アンモニウム水溶液（モリブデンイオンとして１０００ｐｐｍ含有）に２５℃で１分間浸漬させ、モリブデンイオンを付着処理させた。余分な７モリブデン酸６アンモニウム水溶液を純水で洗い流した後、０．２５質量％－硫酸銅水溶液（銅イオンとして１０００ｐｐｍ含有）に２５℃で１分間浸漬させ、銅イオンを付着させた。余分な硫酸銅水溶液を除去するために浸漬後の基板を純水でリンス処理した後、ブロワーで乾燥した。銅イオンおよびモリブデンイオンの付着処理後のＩＧＺＯ／ガラス基板をＸ線光電子分光法（ＸＰＳ）により分析したところ、９３３ｅＶと９５３ｅＶにＣｕ２ｐのピーク、および２２８ｅＶと２３１ｅＶにＭｏ３ｄのピークが観察された。これらのピークよりＩＧＺＯ表面に銅を含む付着物が銅元素として０．４ａｔ％、およびモリブデンを含む付着物がモリブデン元素として０．３ａｔ％付着していることがわかった。 Cleaning treatment for removing deposits containing copper and deposits containing molybdenum The IGZO / glass substrate obtained in Reference Example 1 was added to a 0.17 mass% -7 ammonium hexamolybdate aqueous solution (containing 1000 ppm as molybdenum ions). Immersion was performed at 25 ° C. for 1 minute to deposit molybdenum ions. Excess 6 ammonium molybdate aqueous solution was washed away with pure water, and then immersed in a 0.25% by mass-copper sulfate aqueous solution (containing 1000 ppm as copper ions) at 25 ° C. for 1 minute to attach copper ions. In order to remove excess copper sulfate aqueous solution, the substrate after immersion was rinsed with pure water and then dried with a blower. When the IGZO / glass substrate after the adhesion treatment of copper ions and molybdenum ions was analyzed by X-ray photoelectron spectroscopy (XPS), Cu2p peaks were observed at 933 eV and 953 eV, and Mo3d peaks were observed at 228 eV and 231 eV. From these peaks, it was found that the deposit containing copper adhered to the surface of IGZO as 0.4 at% as a copper element and the deposit containing molybdenum as 0.3 at% as a molybdenum element.
　続いて、銅イオンおよびモリブデンイオンを付着処理後のＩＧＺＯ／ガラス基板を、先に調製した液体組成物（１質量％－クエン酸水溶液）に２５℃で１分間浸漬させた。浸漬後の基板を純水でリンス処理した後、ブロワーで乾燥した。洗浄処理後のＩＧＺＯ／ガラス基板をＸＰＳ分析した。ＩＧＺＯ表面に銅元素に基づく９３３ｅＶと９５３ｅＶのピーク、およびモリブデン元素に基づく２２８ｅＶと２３１ｅＶのピークはいずれも検出されず、液体組成物（１質量％－クエン酸水溶液）を用いた洗浄処理によりＩＧＺＯ表面の銅を含む付着物およびモリブデンを含む付着物が除去されていることが確認された。 Subsequently, the IGZO / glass substrate after the adhesion treatment of copper ions and molybdenum ions was immersed in the previously prepared liquid composition (1% by mass-citric acid aqueous solution) at 25 ° C. for 1 minute. The substrate after immersion was rinsed with pure water and then dried with a blower. The XPS analysis of the IGZO / glass substrate after the cleaning treatment was performed. Neither the 933 eV and 953 eV peaks based on the copper element, nor the 228 eV and 231 eV peaks based on the molybdenum element were detected on the IGZO surface, and the IGZO surface was washed with a liquid composition (1% by mass-citric acid aqueous solution). It was confirmed that deposits containing copper and deposits containing molybdenum were removed.
　ＩＧＺＯのエッチングレートの評価
　参考例１で得られたＩＧＺＯ／ガラス基板を、先に調製した液体組成物（１質量％－クエン酸水溶液）に２５℃で１分間浸漬させた。処理後のＩＧＺＯ／ガラス基板を、ｎ＆ｋ Ｔｅｃｈｎｏｌｏｇｙ Ｉｎｃ．製の光学式薄膜特性測定装置ｎ＆ｋ Ａｎａｌｙｚｅｒ １２８０により測定し、処理前後のＩＧＺＯの膜厚差をエッチング時間で除することによりエッチングレートを算出した。結果を表１に示す。ＩＧＺＯのエッチングレートは３．０Å／ｍｉｎであり、合格であった。 Evaluation of IGZO Etching Rate The IGZO / glass substrate obtained in Reference Example 1 was immersed in the previously prepared liquid composition (1 mass% -citric acid aqueous solution) at 25 ° C. for 1 minute. The treated IGZO / glass substrate was then transferred to n & k Technology Inc. An etching rate was calculated by measuring with an optical thin film characteristic measuring apparatus n & k Analyzer 1280 manufactured by the manufacturer and dividing the film thickness difference of IGZO before and after the treatment by the etching time. The results are shown in Table 1. The etching rate of IGZO was 3.0 kg / min, which was acceptable.
　銅のエッチングレートの評価
　参考例２で得られた銅／モリブデン／ガラス基板を、先に調製した液体組成物（１質量％－クエン酸水溶液）に２５℃で６０分間浸漬させた。処理後の銅／モリブデン／ガラス基板を、ＳＩＩナノテクノロジー社製の蛍光Ｘ線分析装置ＳＥＡ１２００ＶＸにより測定し、処理前後の銅の膜厚差をエッチング時間で除することによりエッチングレートを算出した。結果を表１に示す。銅のエッチングレートは２．７Å／ｍｉｎであり、合格であった。 Evaluation of Copper Etching Rate The copper / molybdenum / glass substrate obtained in Reference Example 2 was immersed in the previously prepared liquid composition (1 mass% -citric acid aqueous solution) at 25 ° C. for 60 minutes. The copper / molybdenum / glass substrate after the treatment was measured by a fluorescent X-ray analyzer SEA1200VX manufactured by SII Nanotechnology, and the etching rate was calculated by dividing the difference in copper film thickness before and after the treatment by the etching time. The results are shown in Table 1. The etching rate of copper was 2.7 kg / min, which was acceptable.
モリブデンのエッチングレートの評価
　参考例３で得られたモリブデン／ガラス基板を、先に調製した液体組成物（１質量％－クエン酸水溶液）に２５℃で６０分間浸漬させた。処理後のモリブデン／ガラス基板をＳＩＩナノテクノロジー社製の蛍光Ｘ線分析装置ＳＥＡ１２００ＶＸにより測定し、処理前後のモリブデンの膜厚差をエッチング時間で除することによりエッチングレートを算出した。結果を表１に示す。モリブデンのエッチングレートは１Å／ｍｉｎ未満であり、合格であった。 Evaluation of Molybdenum Etching Rate The molybdenum / glass substrate obtained in Reference Example 3 was immersed in the previously prepared liquid composition (1 mass% -citric acid aqueous solution) at 25 ° C. for 60 minutes. The treated molybdenum / glass substrate was measured with a fluorescent X-ray analyzer SEA1200VX manufactured by SII Nanotechnology, and the etching rate was calculated by dividing the difference in molybdenum film thickness before and after the treatment by the etching time. The results are shown in Table 1. The etching rate of molybdenum was less than 1 kg / min, which was acceptable.
実施例２～３６
　表２および表３に示す組成とした以外は実施例１と同様にして、液体組成物を調製した。該液体組成物を用いて、銅を含む付着物の洗浄・除去性能、ＩＧＺＯ、銅、およびモリブデンのエッチングレート（防食性）の評価を行った。結果を表２および表３に示す。実施例２～３６のいずれの液体組成物に関しても、銅を含む付着物の洗浄・除去性は合格（銅元素に基づく９３３ｅＶと９５３ｅＶのＣｕ２ｐピークが検出されない）であり、またＩＧＺＯ、銅、およびモリブデンのエッチングレートはいずれも合格（３０Å／ｍｉｎ未満）であった。 Examples 2 to 36
A liquid composition was prepared in the same manner as in Example 1 except that the compositions shown in Table 2 and Table 3 were used. Using the liquid composition, the cleaning / removal performance of the deposits containing copper and the etching rate (anticorrosion) of IGZO, copper, and molybdenum were evaluated. The results are shown in Table 2 and Table 3. For any of the liquid compositions of Examples 2-36, the cleaning / removability of the deposit containing copper is acceptable (the 933 eV and 953 eV Cu2p peaks based on the copper element are not detected), and IGZO, copper, and The molybdenum etching rates were all acceptable (less than 30 kg / min).
比較例１
　容量１０Ｌのポリプロピレン容器に純水９．８５ｋｇと、１０％硫酸（和光純薬工業株式会社製、分子量９８．０８）０．０５ｋｇと、酢酸（和光純薬工業株式会社製、分子量６０．０５）０．１ｋｇを投入、攪拌し、液体組成物を調製した。得られた液体組成物のｐＨ値は２．０であった。該液体組成物を用いて各種評価を行った結果を表４に示す。ＩＧＺＯのエッチングレートが６８Å／ｍｉｎであり、不合格であった。 Comparative Example 1
In a 10 L polypropylene container, 9.85 kg of pure water, 0.05 kg of 10% sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 98.08) and acetic acid (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 60.05) 0.1 kg was added and stirred to prepare a liquid composition. The pH value of the obtained liquid composition was 2.0. Table 4 shows the results of various evaluations using the liquid composition. The etching rate of IGZO was 68 kg / min, which was not acceptable.
比較例２
　容量１０Ｌのポリプロピレン容器に純水９．２９ｋｇと、酢酸　０．１ｋｇと、２５％テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）０．６１ｋｇを投入、攪拌し、液体組成物を調製した。得られた液体組成物のｐＨ値は９．０であった。該液体組成物を用いて各種評価を行った結果を表４に示す。銅を含む付着物を洗浄・除去することができず、ＩＧＺＯ表面の洗浄性能に劣ることが分かった。 Comparative Example 2
A liquid composition was prepared by adding 9.29 kg of pure water, 0.1 kg of acetic acid, and 0.61 kg of 25% tetramethylammonium hydroxide (TMAH) to a polypropylene container having a capacity of 10 L and stirring. The pH value of the obtained liquid composition was 9.0. Table 4 shows the results of various evaluations using the liquid composition. It was found that deposits containing copper could not be cleaned and removed, and the cleaning performance of the IGZO surface was poor.
　比較例３～８
　表４に示す組成とした以外は、実施例１と同様にして、液体組成物を調製し、各種評価を行った。結果を表４に示す。比較例３～８のいずれの液体組成物もＩＧＺＯのエッチングレートが高い、もしくは銅を含む付着物を洗浄・除去できず、不合格であった。 Comparative Examples 3-8
A liquid composition was prepared and subjected to various evaluations in the same manner as in Example 1 except that the composition shown in Table 4 was used. The results are shown in Table 4. Any of the liquid compositions of Comparative Examples 3 to 8 failed because the etching rate of IGZO was high or the deposits containing copper could not be cleaned and removed.
　比較例９、１０
　表５に示す組成とした以外は、実施例１と同様にして、液体組成物を調製し、各種評価を行った。結果を表５に示す。液体組成物が過酸化水素を含む比較例９では、銅のエッチングレートおよびモリブデンのエッチングレートが高く、過酸化水素を含むことによって、銅の防食性およびモリブデンの防食性が低下してしまうことが分かった。また、液体組成物が錯化剤であるフッ化アンモニウムを含む比較例１０では、ＩＧＺＯのエッチングレートが高く、ＩＧＺＯ表面上の銅を含む付着物の洗浄・除去には適用出来ないことが分かった。 Comparative Examples 9 and 10
A liquid composition was prepared and various evaluations were performed in the same manner as in Example 1 except that the composition shown in Table 5 was used. The results are shown in Table 5. In Comparative Example 9 in which the liquid composition contains hydrogen peroxide, the etching rate of copper and the etching rate of molybdenum are high, and the anticorrosion property of copper and the anticorrosion property of molybdenum may be reduced by containing hydrogen peroxide. I understood. Further, in Comparative Example 10 in which the liquid composition contains ammonium fluoride as a complexing agent, the etching rate of IGZO was high, and it was found that the liquid composition was not applicable to cleaning and removal of deposits containing copper on the IGZO surface. .
　以上の評価結果からも明らかなように、本発明の液体組成物はいずれも、ＩＧＺＯ半導体層や銅または銅およびモリブデンを含む配線を腐食することなく、ＩＧＺＯ表面から銅または銅およびモリブデンを含む付着物を洗浄・除去することができた。 As is clear from the above evaluation results, any of the liquid compositions of the present invention does not corrode the IGZO semiconductor layer and the wiring containing copper or copper and molybdenum, and does not corrode the copper composition containing copper or copper and molybdenum from the IGZO surface. The kimono could be washed and removed.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　本発明による液体組成物は、ＩＧＺＯ表面に付着した銅または銅およびモリブデンを含む付着物の洗浄・除去に好適に用いることができる。本発明の液体組成物を用いることにより、ＩＧＺＯ半導体層や銅または銅およびモリブデンを含む配線を腐食することなく、ＩＧＺＯ表面から銅または銅およびモリブデンを含む付着物を洗浄・除去することができる。  The liquid composition according to the present invention can be suitably used for cleaning / removing deposits containing copper or copper and molybdenum adhering to the IGZO surface. By using the liquid composition of the present invention, it is possible to clean and remove deposits containing copper or copper and molybdenum from the IGZO surface without corroding the IGZO semiconductor layer and the wiring containing copper or copper and molybdenum.

Claims (9)

  1. 　銅を含む配線を腐食することなく、インジウム、ガリウム、亜鉛、および酸素からなる酸化物（ＩＧＺＯ）の表面より銅を含む付着物を洗浄・除去する液体組成物であって、
    ヒドロキシカルボン酸およびジカルボン酸、またはそれらの塩からなる群より選択される一種以上を含み、ｐＨ値が１.５～１０である液体組成物。     A liquid composition for cleaning and removing deposits containing copper from the surface of an oxide (IGZO) made of indium, gallium, zinc, and oxygen without corroding wiring containing copper,
    A liquid composition comprising at least one selected from the group consisting of hydroxycarboxylic acids and dicarboxylic acids, or salts thereof, and having a pH value of 1.5 to 10.
  2. 　前記銅を含む付着物が銅およびモリブデンを含む付着物である請求項１に記載の液体組成物。 2. The liquid composition according to claim 1, wherein the deposit containing copper is a deposit containing copper and molybdenum.
  3. 　前記ヒドロキシカルボン酸が、クエン酸、酒石酸、乳酸、およびグリコール酸からなる群より選ばれる少なくとも一種である請求項１または２に記載の液体組成物。 The liquid composition according to claim 1 or 2, wherein the hydroxycarboxylic acid is at least one selected from the group consisting of citric acid, tartaric acid, lactic acid, and glycolic acid.
  4. 　前記ジカルボン酸が、マロン酸、マレイン酸、無水マレイン酸、およびコハク酸からなる群より選ばれる少なくとも一種である請求項１～３のいずれか一項に記載の液体組成物。 The liquid composition according to any one of claims 1 to 3, wherein the dicarboxylic acid is at least one selected from the group consisting of malonic acid, maleic acid, maleic anhydride, and succinic acid.
  5. 　前記ヒドロキシカルボン酸およびジカルボン酸、またはそれらの塩からなる群より選択される一種以上の濃度が、０．００１～３０質量％である請求項１～４のいずれか一項に記載の液体組成物。 The liquid composition according to any one of claims 1 to 4, wherein the concentration of one or more selected from the group consisting of the hydroxycarboxylic acid and the dicarboxylic acid, or a salt thereof is 0.001 to 30% by mass. .
  6. 　ｐＨ調節剤として、水酸化ナトリウム、水酸化カリウム、アンモニア、テトラメチルアンモニウムヒドロキシド、２－アミノエタノール、および１－アミノ－２－プロパノールからなる群より選ばれる少なくとも一種を含む請求項１～５のいずれか一項に記載の液体組成物。 6. The pH regulator according to claim 1, comprising at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, tetramethylammonium hydroxide, 2-aminoethanol, and 1-amino-2-propanol. The liquid composition according to any one of the above.
  7. 　インジウム、ガリウム、亜鉛、および酸素からなる酸化物（ＩＧＺＯ）の表面より、ＩＧＺＯ半導体層を腐食することなく、かつ銅を含む配線を腐食することなく、銅を含む付着物を洗浄・除去する方法であって、ＩＧＺＯ半導体層と銅を含む配線を有した基板上のＩＧＺＯ表面に請求項１～６のいずれか一項に記載の液体組成物を接触させることを含む、ＩＧＺＯ表面の洗浄方法。 A method for cleaning and removing deposits containing copper from the surface of an oxide (IGZO) made of indium, gallium, zinc, and oxygen without corroding the IGZO semiconductor layer and without corroding the wiring containing copper. A method for cleaning an IGZO surface, comprising bringing the liquid composition according to any one of claims 1 to 6 into contact with an IGZO surface on a substrate having a wiring containing IGZO semiconductor layers and copper.
  8. 　インジウム、ガリウム、亜鉛、および酸素からなる酸化物（ＩＧＺＯ）の表面より、ＩＧＺＯ半導体層を腐食することなく、かつ銅およびモリブデンを含む配線を腐食することなく、銅およびモリブデンを含む付着物を洗浄・除去する方法であって、ＩＧＺＯ半導体層と、銅およびモリブデンを含む配線とを有した基板上のＩＧＺＯ表面に、請求項１～６のいずれか一項に記載の液体組成物を接触させることを含む、ＩＧＺＯ表面の洗浄方法。 Cleaning the deposits containing copper and molybdenum from the surface of oxide (IGZO) consisting of indium, gallium, zinc, and oxygen without corroding the IGZO semiconductor layer and without corroding the wiring containing copper and molybdenum. A method of removing, wherein the liquid composition according to any one of claims 1 to 6 is brought into contact with an IGZO surface on a substrate having an IGZO semiconductor layer and a wiring including copper and molybdenum. A method for cleaning an IGZO surface, comprising:
  9. 　請求項７または８に記載の方法により洗浄された、インジウム、ガリウム、亜鉛、および酸素からなる酸化物（ＩＧＺＯ）半導体層と、銅または銅およびモリブデンを含む配線とを有した基板。 A substrate having an oxide (IGZO) semiconductor layer made of indium, gallium, zinc, and oxygen and a wiring containing copper, copper, and molybdenum cleaned by the method according to claim 7 or 8.
PCT/JP2014/065548 2013-07-09 2014-06-12 Liquid composition for cleaning/removing copper-containing adhering matter from surface of oxide comprising indium, gallium, zinc, and oxygen (igzo), method for cleaning igzo surface using said liquid composition, and substrate cleaned using said method for cleaning WO2015005053A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020157023345A KR102000726B1 (en) 2013-07-09 2014-06-12 Liquid composition for cleaning/removing copper-containing adhering matter from surface of oxide comprising indium, gallium, zinc, and oxygen (igzo), method for cleaning igzo surface using said liquid composition, and substrate cleaned using said method for cleaning
CN201480033266.4A CN105359257B (en) 2013-07-09 2014-06-12 From the surface clean and the fluid composition for removing cupric attachment and the cleaning method on the IGZO surfaces for having used the fluid composition, and the substrate using cleaning method cleaning of the oxide (IGZO) being made up of indium, gallium, zinc and oxygen
JP2015526224A JP6418156B2 (en) 2013-07-09 2014-06-12 Liquid composition for cleaning and removing deposits containing copper from the surface of oxide (IGZO) composed of indium, gallium, zinc, and oxygen, IGZO surface cleaning method using the liquid composition, and cleaning method therefor Substrate cleaned by

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-143761 2013-07-09
JP2013143761 2013-07-09

Publications (1)

Publication Number Publication Date
WO2015005053A1 true WO2015005053A1 (en) 2015-01-15

Family

ID=52279742

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/065548 WO2015005053A1 (en) 2013-07-09 2014-06-12 Liquid composition for cleaning/removing copper-containing adhering matter from surface of oxide comprising indium, gallium, zinc, and oxygen (igzo), method for cleaning igzo surface using said liquid composition, and substrate cleaned using said method for cleaning

Country Status (5)

Country Link
JP (1) JP6418156B2 (en)
KR (1) KR102000726B1 (en)
CN (1) CN105359257B (en)
TW (1) TWI623607B (en)
WO (1) WO2015005053A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108598041A (en) * 2018-05-09 2018-09-28 深圳市华星光电技术有限公司 The production method of tft array substrate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001044161A (en) * 1999-08-03 2001-02-16 Kao Corp Liquid detergent composition
JP2002050607A (en) * 2000-08-03 2002-02-15 Kaijo Corp Substrate treatment method
WO2013015322A1 (en) * 2011-07-26 2013-01-31 三菱瓦斯化学株式会社 Etchant for copper/molybdenum-based multilayer thin film

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3219020B2 (en) 1996-06-05 2001-10-15 和光純薬工業株式会社 Cleaning agent
JP3165801B2 (en) * 1997-08-12 2001-05-14 関東化学株式会社 Cleaning solution
KR100379824B1 (en) 2000-12-20 2003-04-11 엘지.필립스 엘시디 주식회사 Etchant and array substrate for electric device with Cu lines patterend on the array substrate using the etchant
JP3843112B2 (en) * 2003-08-27 2006-11-08 松下電器産業株式会社 Manufacturing method of semiconductor device
JP4857738B2 (en) 2005-11-30 2012-01-18 信越半導体株式会社 Semiconductor wafer cleaning method and manufacturing method
JP5328083B2 (en) 2006-08-01 2013-10-30 キヤノン株式会社 Oxide etching method
JP5513196B2 (en) * 2010-03-25 2014-06-04 富士フイルム株式会社 Cleaning composition and method for manufacturing semiconductor device
KR101263890B1 (en) 2011-08-03 2013-05-13 박창희 System for disassembling a scrapped car
CN102593065B (en) * 2012-03-14 2013-11-27 复旦大学 Preparation method for backgate thin film transistor storage

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001044161A (en) * 1999-08-03 2001-02-16 Kao Corp Liquid detergent composition
JP2002050607A (en) * 2000-08-03 2002-02-15 Kaijo Corp Substrate treatment method
WO2013015322A1 (en) * 2011-07-26 2013-01-31 三菱瓦斯化学株式会社 Etchant for copper/molybdenum-based multilayer thin film

Also Published As

Publication number Publication date
KR102000726B1 (en) 2019-07-16
JP6418156B2 (en) 2018-11-07
CN105359257B (en) 2018-03-06
CN105359257A (en) 2016-02-24
TW201504398A (en) 2015-02-01
TWI623607B (en) 2018-05-11
JPWO2015005053A1 (en) 2017-03-02
KR20160028998A (en) 2016-03-14

Similar Documents

Publication Publication Date Title
TWI531639B (en) Etching solution for copper/molybdenum-based multilayer thin films
JP6711437B2 (en) Semiconductor device substrate cleaning liquid and method for cleaning semiconductor device substrate
JP4304988B2 (en) Semiconductor device substrate cleaning method
EP2119765B1 (en) Cleaning liquid composition for a semiconductor substrate
TWI678601B (en) Cleaning liquid for semiconductor element capable of suppressing damage of tungsten-containing material and method for cleaning semiconductor element using the cleaning liquid
WO2003065433A1 (en) Liquid detergent for semiconductor device substrate and method of cleaning
JP6488740B2 (en) Substrate cleaning liquid for semiconductor device and method for cleaning semiconductor device
WO2015119925A1 (en) Non-amine post-cmp compositions and method of use
JP2007526647A (en) Improved acidic chemicals for post-CMP cleaning
WO2005076332A1 (en) Substrate cleaning liquid for semiconductor device and cleaning method
JP5801594B2 (en) Cleaning composition, cleaning method using the same, and semiconductor device manufacturing method
TW201932588A (en) Treatment liquid for semiconductor wafers, which contains hypochlorite ions
JP2010093126A (en) Alkaline aqueous solution composition for substrate processing
JP5971246B2 (en) Etching solution of copper or copper-based compound
TW201622030A (en) Semiconductor element cleaning solution that suppresses damage to tantalum-containing materials, and cleaning method using same
JPH05259140A (en) Cleaning liquid for semiconductor substrate
US20120080053A1 (en) Method for cleaning of semiconductor substrate and acidic solution
JP5515588B2 (en) Wafer cleaning water and wafer cleaning method
JP6418156B2 (en) Liquid composition for cleaning and removing deposits containing copper from the surface of oxide (IGZO) composed of indium, gallium, zinc, and oxygen, IGZO surface cleaning method using the liquid composition, and cleaning method therefor Substrate cleaned by
KR20070107242A (en) Cleaner for copper molybdenum tft
KR101101378B1 (en) Rinse composition for tft-lcd
JP5206177B2 (en) Resist stripping composition and method for manufacturing semiconductor device using the same
JP2012058273A (en) Photoresist residue and polymer residue removing liquid composition
TWI788452B (en) Fluoride based cleaning composition
JP2003338484A (en) Cleaning solution for semiconductor substrate

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201480033266.4

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14822516

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015526224

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20157023345

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14822516

Country of ref document: EP

Kind code of ref document: A1