JP5706434B2 - Etching solution composition - Google Patents
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- JP5706434B2 JP5706434B2 JP2012536649A JP2012536649A JP5706434B2 JP 5706434 B2 JP5706434 B2 JP 5706434B2 JP 2012536649 A JP2012536649 A JP 2012536649A JP 2012536649 A JP2012536649 A JP 2012536649A JP 5706434 B2 JP5706434 B2 JP 5706434B2
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- 238000005530 etching Methods 0.000 title claims description 54
- 239000000203 mixture Substances 0.000 title claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- 239000010936 titanium Substances 0.000 claims description 22
- ZWOQODLNWUDJFT-UHFFFAOYSA-N aluminum lanthanum Chemical compound [Al].[La] ZWOQODLNWUDJFT-UHFFFAOYSA-N 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 229910052738 indium Inorganic materials 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
- 229910000858 La alloy Inorganic materials 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 65
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 7
- 229910020794 La-Ni Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000002313 adhesive film Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- -1 fluorine ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
Description
本発明は、インジウム系金属膜、アルミニウム−ランタニウム系合金膜及びチタニウム系金属膜からなる三重膜用エッチング液組成物に関する。 The present invention relates to a triple film etching solution composition comprising an indium metal film, an aluminum-lanthanum alloy film, and a titanium metal film.
フラットパネル表示装置において、基板上に金属配線を形成する過程は、通常、スパッタリングによって金属膜を形成する工程、金属膜上にフォトレジストを塗布し、露光及び現像して選択的な領域にフォトレジストを形成する工程、及び金属膜をエッチングする工程から構成される。また、個別的な単位工程前後の洗浄工程などを含む。このようなエッチング工程は、フォトレジストをマスクとして用いて選択的な領域に金属膜を残す工程を意味する。エッチング工程としては、通常、プラズマなどを用いたドライエッチング、又はエッチング液を用いるウェットエッチングが使用される。 In a flat panel display device, a process of forming a metal wiring on a substrate is usually a process of forming a metal film by sputtering, applying a photoresist on the metal film, exposing and developing the photoresist in a selective region. And a step of etching the metal film. In addition, it includes cleaning steps before and after individual unit steps. Such an etching process means a process of leaving a metal film in a selective region using a photoresist as a mask. As the etching step, dry etching using plasma or wet etching using an etching solution is usually used.
一方、フラットパネル表示装置において、画素電極として、インジウム系金属膜からなる透明伝導膜が主に使用される。また、ソース／ドレイン電極としては、アルミニウムランタン系合金膜、すなわちＡｌ−Ｌａ−Ｘ（Ｘ＝Ｍｇ、Ｚｎ、Ｉｎ、Ｃａ、Ｔｅ、Ｓｒ、Ｃｒ、Ｃｏ、Ｍｏ、Ｎｂ、Ｔａ、Ｗ、Ｎｉ、Ｎｄ、Ｓｎ、Ｆｅ、Ｓｉ、Ｍｏ、Ｐｔ及びＣから選択される金属）形態のアルミニウム合金膜が主に使用される。また、ソース／ドレイン電極の下部には、ソース／ドレイン電極と絶縁膜との接着のために、接着膜として、チタニウムを含む金属膜が主に使用される。 On the other hand, in a flat panel display device, a transparent conductive film made of an indium metal film is mainly used as a pixel electrode. As the source / drain electrodes, an aluminum lanthanum alloy film, that is, Al—La—X (X = Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, An aluminum alloy film in the form of a metal selected from Nd, Sn, Fe, Si, Mo, Pt and C is mainly used. In addition, a metal film containing titanium is mainly used as an adhesive film below the source / drain electrode for bonding the source / drain electrode and the insulating film.
従来では、フラットパネル表示装置の画素電極、ソース／ドレイン電極及び接着膜をエッチングするために、各電極毎に異なるエッチング液組成物を使用しなければならなかった。これにより、エッチング工程が複雑になり、非経済的であった。 Conventionally, in order to etch a pixel electrode, a source / drain electrode and an adhesive film of a flat panel display device, it is necessary to use a different etching solution composition for each electrode. This complicates the etching process and is uneconomical.
本発明の目的は、インジウム系金属膜、アルミニウム−ランタニウム系合金膜及びチタニウム系金属膜からなる三重膜を効率よく一括エッチングすることが可能なエッチング液組成物を提供することにある。 An object of the present invention is to provide an etching solution composition capable of efficiently collectively etching a triple film composed of an indium metal film, an aluminum-lanthanum alloy film, and a titanium metal film.
上記目的を達成するために、本発明は、組成物の総重量に対して、過酸化水素１重量％〜１５重量％、無機酸０．１重量％〜１０重量％、含フッ素化合物０．０１重量％〜５重量％、及び水残部を含むことを特徴とする、インジウム系金属膜、アルミニウム−ランタニウム系合金膜及びチタニウム系金属膜からなる三重膜用エッチング液組成物を提供する。 In order to achieve the above object, the present invention provides hydrogen peroxide of 1 to 15% by weight, inorganic acid of 0.1 to 10% by weight, fluorine-containing compound of 0.01% by weight based on the total weight of the composition. There is provided an etching solution composition for a triple film comprising an indium-based metal film, an aluminum-lanthanum-based alloy film, and a titanium-based metal film, characterized by comprising 5% by weight to 5% by weight and a water residue.
好ましくは、本発明は、組成物の総重量に対して、過酸化水素２重量％〜１２重量％、無機酸１重量％〜７重量％、含フッ素化合物０．１重量％〜２重量％、及び水残部を含むことを特徴とする、インジウム系金属膜、アルミニウム−ランタニウム系合金膜及びチタニウム系金属膜からなる三重膜用エッチング液組成物を提供する。 Preferably, the present invention relates to 2 to 12% by weight of hydrogen peroxide, 1 to 7% by weight of an inorganic acid, 0.1 to 2% by weight of a fluorine-containing compound, based on the total weight of the composition. And an etching solution composition for a triple film comprising an indium-based metal film, an aluminum-lanthanum alloy film, and a titanium-based metal film.
本発明のエッチング液組成物は、インジウム系金属膜、アルミニウム−ランタニウム系合金膜、及びチタニウム系金属膜それぞれに対するエッチング特性に優れる。また、本発明のエッチング液組成物は、アルミニウム−ランタニウム系合金膜のエッチング特性に優れてＡｌ−Ｌａ系合金膜の上部のメクレ現象などが発生しないので、インジウム系透明伝導膜、アルミニウム−ランタニウム系合金膜及びチタニウム系金属膜からなる三重膜を効率よく一括エッチングすることができる。また、本発明のエッチング液組成物を用いると、エッチング工程が相当単純化されるので、生産量を大幅増加させることができる。 The etching solution composition of the present invention is excellent in etching characteristics for indium metal films, aluminum-lanthanum alloy films, and titanium metal films. In addition, since the etching solution composition of the present invention is excellent in the etching characteristics of an aluminum-lanthanum alloy film and does not cause the meklet phenomenon on the upper part of the Al-La alloy film, the indium transparent conductive film, the aluminum-lanthanum system A triple film composed of an alloy film and a titanium metal film can be efficiently collectively etched. In addition, when the etching solution composition of the present invention is used, the etching process is considerably simplified, so that the production amount can be greatly increased.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のエッチング液組成物は、過酸化水素、無機酸、含フッ素化合物及び水を含む。 The etching solution composition of the present invention contains hydrogen peroxide, an inorganic acid, a fluorine-containing compound, and water.
本発明において、過酸化水素は主酸化剤の役目をする。前記過酸化水素は、組成物の総重量に対して、１重量％〜１５重量％で含まれることが好ましく、２重量％〜１２重量％で含まれることがさらに好ましい。上述した範囲を満足すると、インジウム系金属膜、アルミニウム−ランタニウム系合金膜及びチタニウム系金属膜の表面を容易に酸化させることができる。 In the present invention, hydrogen peroxide serves as the main oxidant. The hydrogen peroxide is preferably contained at 1 to 15% by weight, more preferably 2 to 12% by weight, based on the total weight of the composition. When the above range is satisfied, the surfaces of the indium metal film, the aluminum-lanthanum alloy film, and the titanium metal film can be easily oxidized.
また、本発明において、無機酸は補助酸化剤の役目をする。前記無機酸は、組成物の総重量に対して、０．１重量％〜１０重量％で含まれることが好ましく、１重量％〜７重量％で含まれることがさらに好ましい。上述した範囲を満足すると、前記過酸化水と共に、インジウム系金属膜、アルミニウム−ランタニウム系合金膜及びチタニウム系金属膜の表面をより容易に酸化させることができる。また、エッチング速度、サイドエッチング及びテーパー角を調節することが容易となる。 In the present invention, the inorganic acid serves as an auxiliary oxidizing agent. The inorganic acid is preferably contained in an amount of 0.1 to 10% by weight, more preferably 1 to 7% by weight, based on the total weight of the composition. When the above range is satisfied, the surfaces of the indium metal film, the aluminum-lanthanum alloy film, and the titanium metal film can be more easily oxidized together with the peroxide water. Further, it becomes easy to adjust the etching rate, side etching, and taper angle.
前記無機酸は、これに限定されず、硝酸、硫酸、及びこれらの組み合わせから選ばれる１種であることが好ましい。 The inorganic acid is not limited to this, and is preferably one selected from nitric acid, sulfuric acid, and combinations thereof.
本発明において、含フッ素化合物はインジウム系金属膜、アルミニウム−ランタニウム系合金膜、及びチタニウム系金属膜の表面をエッチングする役目をする。 In the present invention, the fluorine-containing compound serves to etch the surfaces of the indium metal film, the aluminum-lanthanum alloy film, and the titanium metal film.
前記含フッ素化合物は、組成物の総重量に対して０．０１重量％〜５重量％で含まれることが好ましく、０．１重量％〜２重量％で含まれることがさらに好ましい。上述した範囲で含まれると、酸化したインジウム系金属膜、アルミニウム−ランタニウム系合金膜及びチタニウム系金属膜の表面を容易にかつ適正量エッチングすることができる。 The fluorine-containing compound is preferably contained at 0.01 to 5% by weight, more preferably 0.1 to 2% by weight, based on the total weight of the composition. When included in the above-described range, the oxidized indium-based metal film, aluminum-lanthanum-based alloy film, and titanium-based metal film can be easily and appropriately etched.
この際、前記含フッ素化合物は、好ましくは溶解状態でフッ素イオン又は多原子フッ素イオンに解離できる化合物である。例えば、前記含フッ素化合物はフッ化アンモニウム、フッ化ナトリウム、フッ化カリウム、重フッ化アンモニウム、重フッ化ナトリウム及び重フッ化カリウムよりなる群から選ばれる１種又は２種以上でありうる。 In this case, the fluorine-containing compound is preferably a compound that can be dissociated into fluorine ions or polyatomic fluorine ions in a dissolved state. For example, the fluorine-containing compound may be one or more selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, and potassium bifluoride.
本発明のエッチング液組成物に含まれる水は脱イオン水を意味する。前記水は半導体工程用を使用し、好ましくは１８ＭΩ／ｃｍ以上の水を使用する。前記水は、組成物の総重量に対して、本発明のエッチング液組成物の総重量が１００重量％となるように残部含まれる。 The water contained in the etching solution composition of the present invention means deionized water. The water is used for a semiconductor process, and preferably water of 18 MΩ / cm or more is used. The water is contained in a balance such that the total weight of the etching solution composition of the present invention is 100% by weight with respect to the total weight of the composition.
本発明のエッチング液組成物は、前述した成分の他に公知の添加剤、例えばエッチング調節剤、界面活性剤及びｐＨ調節剤よりなる群から選ばれる１種又は２種以上をさらに含むことができる。 The etching solution composition of the present invention can further contain one or more selected from the group consisting of known additives, for example, an etching regulator, a surfactant and a pH regulator, in addition to the components described above. .
一方、本発明において、インジウム系金属膜は、透明導電膜であって、インジウム亜鉛酸化膜（ＩＺＯ）又はインジウム錫酸化膜（ＩＴＯ）であることを意味する。また、前記アルミニウム−ランタニウム系合金膜は、アルミニウムを主成分とするアルミニウム−ランタニウム合金膜であることを意味する。より詳しくは、前記アルミニウム−ランタニウム系合金膜は、アルミニウム９０原子％以上、Ｌａ１０原子％以下、及び他の金属（Ｘ）残部を含むＡｌ−Ｌａ又はＡｌ−Ｌａ−Ｘを意味する。ここで、前記他の金属（Ｘ）は、Ｍｇ、Ｚｎ、Ｉｎ、Ｃａ、Ｔｅ、Ｓｒ、Ｃｒ、Ｃｏ、Ｍｏ、Ｎｂ、Ｔａ、Ｗ、Ｎｉ、Ｎｄ、Ｓｎ、Ｆｅ、Ｓｉ、Ｔｉ、Ｐｔ及びＣよりなる群から選ばれる１種又は２種以上であることが好ましい。また、前記チタニウム系金属膜は、チタニウムを主成分とするチタニウム膜又はチタニウム合金膜であることを意味する。 On the other hand, in the present invention, the indium metal film is a transparent conductive film and means an indium zinc oxide film (IZO) or an indium tin oxide film (ITO). The aluminum-lanthanum-based alloy film means an aluminum-lanthanum alloy film containing aluminum as a main component. More specifically, the aluminum-lanthanum-based alloy film means Al-La or Al-La-X containing 90 atomic% or more of aluminum, 10 atomic% or less of La, and other metal (X) balance. Here, the other metal (X) includes Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd, Sn, Fe, Si, Ti, Pt, and the like. It is preferable that it is 1 type, or 2 or more types selected from the group consisting of C. The titanium metal film means a titanium film or a titanium alloy film containing titanium as a main component.
以下、実施例及び試験例によって本発明をさらに詳細に説明する。しかし、本発明の範囲はこれらの実施例及び試験例によって限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples. However, the scope of the present invention is not limited by these examples and test examples.
（実施例１〜実施例７及び比較例１〜比較例６）：エッチング液組成物の製造
下記表１に記載された成分及び組成比によって、エッチング液組成物が１８０ｋｇとなるように製造した。
(Examples 1 to 7 and Comparative Examples 1 to 6): Manufacture of Etching Solution Composition According to the components and composition ratios shown in Table 1 below, the etching solution composition was manufactured to 180 kg.
（試験例）：エッチング液組成物の特性評価
＜エッチング特性評価＞
試験用基板としては、ＳｉＮｘ層上にａ−ＩＴＯ／Ａｌ−Ｌａ−Ｎｉ／Ｔｉ三重膜が蒸着されており、一定形態の模様にフォトレジストがパターニングされたものを使用した。
(Test example): Characteristic evaluation of etching solution composition <Etching characteristic evaluation>
As a test substrate, an a-ITO / Al-La-Ni / Ti triple film was deposited on a SiNx layer, and a photoresist was patterned in a certain pattern.
噴射式エッチング方式の実験装備（ＳＥＭＥＳ社製、モデル名：ＥＴＣＨＥＲ（ＴＦＴ））内に前記実施例１〜７及び比較例１〜６のエッチング液組成物を仕込み、温度を３０℃にセットして加温した。その後、温度が３０±０．１℃に到達した後、エッチング工程を行った。総エッチング時間をＥＰＤを基準として３０％にした。試片を入れて噴射を開始し、エッチングが完了すると、取り出して脱イオン水で洗浄した後、熱風乾燥装置を用いて乾燥させ、フォトレジスト（ＰＲ）剥離機(stripper)を用いてフォトレジストを除去した。洗浄及び乾燥の後、電子走査顕微鏡（ＳＥＭ：ＨＩＴＡＣＨＩ社製、モデル名：Ｓ−４７００）を用いてエッチングプロファイルの傾斜角、サイドエッチ（ＣＤ：critical dimension）損失、エッチング残留物及び下部膜の損傷を評価した。その結果を下記表２に示す。 The etching solution compositions of Examples 1 to 7 and Comparative Examples 1 to 6 were charged into the experimental equipment (model name: ETCHER (TFT) manufactured by SEMES) of the jet etching method, and the temperature was set to 30 ° C. Warmed up. Thereafter, after the temperature reached 30 ± 0.1 ° C., an etching process was performed. The total etching time was 30% based on EPD. Put the specimen and start spraying. When the etching is completed, remove it, wash it with deionized water, dry it using a hot air dryer, and remove the photoresist using a photoresist (PR) stripper. Removed. After cleaning and drying, using an electron scanning microscope (SEM: manufactured by HITACHI, model name: S-4700), inclination angle of etching profile, loss of side etch (CD: critical dimension), etching residue and damage to lower film Evaluated. The results are shown in Table 2 below.
［エッチングプロファイルの評価基準］
◎：極めて優秀（ＣＤ Ｓｋｅｗ：≦１μｍ、テーパー角：４０°〜８０°）
○：優秀（ＣＤ Ｓｋｅｗ：≦１．５μｍ、テーパー角：４０°〜８０°）
△：良好（ＣＤ Ｓｋｅｗ：≦２μｍ、テーパー角：４０°〜８０°）
×：不良（金属膜の消失及び残渣発生）
[Evaluation criteria for etching profiles]
A: Extremely excellent (CD Skew: ≦ 1 μm, taper angle: 40 ° to 80 °)
○: Excellent (CD Skew: ≦ 1.5 μm, taper angle: 40 ° -80 °)
Δ: Good (CD Skew: ≦ 2 μm, taper angle: 40 ° to 80 °)
X: Defect (disappearance of metal film and generation of residue)
表２を参照すると、実施例１〜７のエッチング液組成物は、エッチングプロファイルに優れるうえ、下部膜の損傷及び残渣が発生しないため、ａ−ＩＴＯ／Ａｌ−Ｌａ−Ｎｉ／Ｔｉ三重膜に対する優れたエッチング特性を有することを確認することができた。 Referring to Table 2, the etching solution compositions of Examples 1 to 7 are excellent in etching profile and are excellent in a-ITO / Al-La-Ni / Ti triple films because damage and residue of the lower film are not generated. It was confirmed that the film had etching characteristics.
ところが、過酸化水素が過量入っている比較例１のエッチング液組成物の場合は、Ａｌ−Ｌａ−Ｎｉ薄膜の過エッチングによってエッチングプロファイルが非常に不良であった。また、硝酸が過量含有された比較例２のエッチング液組成物の場合は、過エッチングによるエッチングプロファイルの不良と下部膜の損傷が観察された。含フッ素化合物が入っていない比較例３のエッチング液組成物の場合は、上部ａ−ＩＴＯの未エッチングが発生した。 However, in the case of the etching solution composition of Comparative Example 1 containing an excessive amount of hydrogen peroxide, the etching profile was very poor due to over-etching of the Al—La—Ni thin film. Further, in the case of the etching solution composition of Comparative Example 2 containing an excessive amount of nitric acid, an etching profile defect due to overetching and damage to the lower film were observed. In the case of the etching solution composition of Comparative Example 3 containing no fluorine-containing compound, the upper a-ITO was not etched.
比較例４のエッチング液組成物の場合は、過量の含フッ素化合物によって下部膜の損傷が非常に大きく現れた。また、過酸化水素又は硝酸が入っていない比較例５及び比較例６のエッチング液組成物の場合は、エッチング速度が非常に遅く、残渣と不良エッチングプロファイルが観察された。 In the case of the etching solution composition of Comparative Example 4, the damage to the lower film was very large due to an excessive amount of the fluorine-containing compound. Moreover, in the case of the etching liquid compositions of Comparative Example 5 and Comparative Example 6 that did not contain hydrogen peroxide or nitric acid, the etching rate was very slow, and a residue and a defective etching profile were observed.
Claims (4)
過酸化水素１重量％〜１５重量％、
硝酸、硫酸、及びこれらの組み合わせよりなる群から選ばれる１種である無機酸０．１重量％〜１０重量％、
含フッ素化合物０．０１重量％〜５重量％、
及び水残部を含むことを特徴とする、インジウム亜鉛酸化膜（ＩＺＯ）及びインジウム錫酸化膜（ＩＴＯ）から選択されるインジウム系金属膜、アルミニウム−ランタニウム系合金膜及びチタニウム系金属膜からなる三重膜用一括エッチング液組成物。 With respect to the total weight of the composition,
1% to 15% by weight of hydrogen peroxide,
0.1% by weight to 10% by weight of an inorganic acid which is one selected from the group consisting of nitric acid, sulfuric acid, and combinations thereof ,
0.01 to 5% by weight of a fluorine-containing compound,
A triple film comprising an indium metal film selected from an indium zinc oxide film (IZO) and an indium tin oxide film (ITO) , an aluminum-lanthanum alloy film, and a titanium metal film, Etching composition for batch .
過酸化水素２重量％〜１２重量％、
無機酸１重量％〜７重量％、
含フッ素化合物０．１重量％〜２重量％、
及び水残部を含むことを特徴とする、請求項１に記載のインジウム系金属膜、アルミニウム−ランタニウム系合金膜及びチタニウム系金属膜からなる三重膜用一括エッチング液組成物。 With respect to the total weight of the composition,
2% to 12% by weight of hydrogen peroxide,
1% to 7% by weight of inorganic acid,
0.1 to 2% by weight of a fluorine-containing compound,
The batch etching solution composition for triple films comprising an indium-based metal film, an aluminum-lanthanum-based alloy film, and a titanium-based metal film according to claim 1, further comprising a water residue.
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