JP5788400B2 - Etching solution composition - Google Patents
Etching solution composition Download PDFInfo
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- JP5788400B2 JP5788400B2 JP2012536650A JP2012536650A JP5788400B2 JP 5788400 B2 JP5788400 B2 JP 5788400B2 JP 2012536650 A JP2012536650 A JP 2012536650A JP 2012536650 A JP2012536650 A JP 2012536650A JP 5788400 B2 JP5788400 B2 JP 5788400B2
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- 238000005530 etching Methods 0.000 title claims description 73
- 239000000203 mixture Substances 0.000 title claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 63
- 239000002184 metal Substances 0.000 claims description 63
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 30
- 239000010936 titanium Substances 0.000 claims description 26
- 229910052719 titanium Inorganic materials 0.000 claims description 25
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- 229910052750 molybdenum Inorganic materials 0.000 claims description 22
- 239000011733 molybdenum Substances 0.000 claims description 19
- 229910052738 indium Inorganic materials 0.000 claims description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000011737 fluorine Substances 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- -1 FeCl 3 Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 150000002506 iron compounds Chemical class 0.000 claims description 7
- ZWOQODLNWUDJFT-UHFFFAOYSA-N aluminum lanthanum Chemical compound [Al].[La] ZWOQODLNWUDJFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910000858 La alloy Inorganic materials 0.000 claims description 4
- 229910052759 nickel 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
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium 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
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-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
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-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
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 239000000758 substrate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910020794 La-Ni Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- SFASQLIGRADPEE-UHFFFAOYSA-N [AlH3].[Ni].[La] Chemical compound [AlH3].[Ni].[La] SFASQLIGRADPEE-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect 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
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Electrodes Of Semiconductors (AREA)
Description
本発明は、半導体装置及びフラットパネル表示装置、特に、ＴＦＴ又はＯＬＥＤなどのゲート、ソース／ドレインアレイ配線用として用いられるインジウム系金属膜、アルミニウム系金属膜、及びチタニウム系又はモリブデン系金属膜からなる三重膜をエッチングすることが可能なエッチング液組成物に関する。 The present invention comprises a semiconductor device and a flat panel display device, in particular, a gate such as a TFT or OLED, an indium metal film used for a source / drain array wiring, an aluminum metal film, and a titanium or molybdenum metal film. The present invention relates to an etchant composition capable of etching a triple 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、アルミニウム系金属膜、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ランタン系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、緩衝膜として、チタニウム又はモリブデン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-based metal film, that is, Al-La-X (X = Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd , A metal selected from Sn, Fe, Si, Mo, Pt and C) in the form of an aluminum lanthanum alloy film. In addition, a metal film containing titanium or molybdenum is mainly used as a buffer film under the source / drain electrode for bonding the source / drain electrode and the insulating film.
このようなフラットパネル表示装置の画素電極、ソース／ドレイン電極及び緩衝膜をエッチングするために、従来では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。例えば、特許文献１では、リン酸、硝酸、水溶性有機酸、エッチング活性剤、エッチング調節剤及び水を含むエッチング液組成物を開示している。ところが、前記組成物は、アルミニウム、ニッケル及び添加金属からなる単一膜には効果があるが、多重膜ではエッチング特性が発揮されない。 In order to etch the pixel electrode, the source / drain electrode and the buffer film of such a flat panel display device, it has been conventionally necessary to use a different etching solution composition for each electrode. For example, Patent Document 1 discloses an etching solution composition containing phosphoric acid, nitric acid, a water-soluble organic acid, an etching activator, an etching regulator, and water. However, the composition is effective for a single film made of aluminum, nickel and an additive metal, but the etching characteristics are not exhibited in a multi-layer film.
よって、フラットパネル表示装置の画素電極、ソース／ドレイン電極及び緩衝膜を一括エッチングすることが可能な新しいエッチング液組成物の開発が求められている。 Therefore, development of a new etchant composition that can collectively etch pixel electrodes, source / drain electrodes, and buffer films of flat panel display devices is required.
本発明の目的は、半導体装置及びフラットパネル表示装置で配線として用いられる、インジウムを含む金属膜、アルミニウムを含む金属膜、特にアルミニウムランタニウムニッケル合金膜、並びチタニウム又はモリブデンを含む金属膜からなる三重膜を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 a triple film composed of a metal film containing indium, a metal film containing aluminum, particularly an aluminum lanthanum nickel alloy film, and a metal film containing titanium or molybdenum, which are used as wirings in semiconductor devices and flat panel display devices. An object of the present invention is to provide an etchant composition capable of collectively etching a film.
また、本発明の他の目的は、エッチング工程を簡素化させ、生産性を向上させることができ且つエッチング特性に優れたエッチング液組成物を提供することにある。 Another object of the present invention is to provide an etching solution composition that can simplify the etching process, improve productivity, and is excellent in etching characteristics.
また、本発明の別の目的は、高価の装備構成を必要とせず、大面積化に有利であって非常に経済的なエッチング液組成物を提供することにある。 Another object of the present invention is to provide an etching solution composition that does not require an expensive equipment configuration and is advantageous for increasing the area and is very economical.
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、鉄化合物０．１重量％〜１０重量％、硝酸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、アルミニウム系金属膜、及びチタニウム系又はモリブデン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 an iron compound of 0.1 wt% to 10 wt%, nitric acid of 0.1 wt% to 10 wt%, and a fluorine-containing compound of 0.01 wt%, based on the total weight of the composition. There is provided an etching solution composition for triple films comprising an indium-based metal film, an aluminum-based metal film, and a titanium-based or molybdenum-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、鉄化合物１重量％〜７重量％、硝酸２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、アルミニウム系金属膜、及びチタニウム系又はモリブデン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 is based on 1% to 7% by weight of iron compound, 2% to 7% by weight of nitric acid, 0.1% to 2% by weight of fluorine-containing compound, and water based on the total weight of the composition. Provided is a triple-film etching solution composition comprising an indium-based metal film, an aluminum-based metal film, and a titanium-based or molybdenum-based metal film.
また、本発明は、前記組成物にリン酸塩化合物０．１重量％〜５重量％をさらに含む、三重膜用エッチング液組成物を提供する。 Moreover, this invention provides the etching liquid composition for triple membranes which further contains 0.1 weight%-5 weight% of phosphate compounds in the said composition.
本発明のエッチング液組成物は、インジウムを含む金属膜、アルミニウムを含む金属膜、及びチタニウム又はモリブデンを含む金属膜からなる三重膜を一括エッチングすることができるため、エッチング工程を簡素化させ且つ生産性を向上させる。また、本発明のエッチング液組成物は、エッチング速度が速く、下部膜及び装備に対する損傷がなく、均一なエッチングが可能であって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、高価の装備構成を必要とせず、大面積化に有利であって非常に経済的である。 The etching solution composition of the present invention simplifies the etching process and can produce a triple film consisting of a metal film containing indium, a metal film containing aluminum, and a metal film containing titanium or molybdenum. Improve sexiness. In addition, the etching solution composition of the present invention has a high etching rate, no damage to the lower film and equipment, uniform etching, and excellent etching characteristics. In addition, the etching solution composition of the present invention does not require an expensive equipment configuration, is advantageous for increasing the area, and is very economical.
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、鉄化合物、硝酸、含フッ素化合物及び水を含む。 The etching solution composition of the present invention contains an iron compound, nitric acid, a fluorine-containing compound, and water.
本発明において、鉄化合物は、アルミニウム系金属膜及びチタニウム系又はモリブデン系金属膜の表面を酸化させる役目をする。 In the present invention, the iron compound serves to oxidize the surfaces of the aluminum-based metal film and the titanium-based or molybdenum-based metal film.
前記鉄化合物は、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。上述した範囲未満で含まれると、アルミニウムを含む金属膜のエッチング速度が低下し、これにより残渣が発生する。また、不均一なエッチング特性により、基板内に斑が発生する。上述した範囲を超過すると、過度なエッチング速度によって、アルミニウムを含む金属膜とチタニウム又はモリブデンを含む金属膜が消失してしまうおそれがある。 The iron compound 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 content is less than the above-described range, the etching rate of the metal film containing aluminum is reduced, thereby generating a residue. Also, unevenness occurs in the substrate due to non-uniform etching characteristics. When the above range is exceeded, there is a possibility that the metal film containing aluminum and the metal film containing titanium or molybdenum may disappear due to an excessive etching rate.
前記鉄化合物は、特に限定されないが、例えば、ＦｅＣｌ３、Ｆｅ（ＮＯ３）３、Ｆｅ２（ＳＯ４）３、ＮＨ４Ｆｅ（ＳＯ４）２、Ｆｅ（ＣｌＯ４）３、ＦｅＰＯ４、Ｆｅ（ＮＨ４）-３（Ｃ２Ｏ４）３などを挙げることができ、これらをそれぞれ単独で或いは２以上組み合わせて使用することができる。 The iron compound is not particularly limited. For example, FeCl 3 , Fe (NO 3 ) 3 , Fe 2 (SO 4 ) 3 , NH 4 Fe (SO 4 ) 2 , Fe (ClO 4 ) 3 , FePO 4 , Fe (NH 4 ) -3 (C 2 O 4 ) 3 and the like can be mentioned, and these can be used alone or in combination of two or more.
本発明において、硝酸は、アルミニウム系金属膜とチタニウム系又はモリブデン系金属膜の表面を酸化させる役目をする。 In the present invention, nitric acid serves to oxidize the surfaces of the aluminum-based metal film and the titanium-based or molybdenum-based metal film.
前記硝酸は、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、２重量％〜７重量％で含まれることがさらに好ましい。上述した範囲未満で含まれると、アルミニウム系金属膜とチタニウム系又はモリブデン系金属膜のエッチング速度低下が発生する。また、基板間のエッチング速度差を誘発してチタニウム系又はモリブデン系金属膜にテーリング(tailing)現象のエッチングを発生させることにより、斑が生ずるおそれがある。上述した範囲を超過すると、ＰＲクラック発生による薬液浸透によってアルミニウム系金属膜とチタニウム系又はモリブデン系金属膜が短絡する現象が発生するおそれがある。さらに、過エッチングによってアルミニウム系金属膜とチタニウム系又はモリブデン系金属膜が消失し、或いは金属配線としての機能を喪失するおそれもある。 The nitric acid is preferably contained at 0.1 to 10% by weight, more preferably 2 to 7% by weight, based on the total weight of the composition. When the content is less than the above range, the etching rate of the aluminum metal film and the titanium or molybdenum metal film is lowered. Further, spots may be generated by inducing a difference in etching rate between the substrates to cause etching of the tailing phenomenon in the titanium-based or molybdenum-based metal film. When the above-mentioned range is exceeded, there is a possibility that a phenomenon in which the aluminum-based metal film and the titanium-based or molybdenum-based metal film are short-circuited due to chemical penetration due to the occurrence of PR cracks may occur. Further, the over-etching may cause the aluminum-based metal film and the titanium-based or molybdenum-based metal film to disappear, or the function as the metal wiring may be lost.
本発明において、含フッ素化合物は、酸化したインジウム系金属膜、酸化したアルミニウム系金属膜、及び下部のチタニウム系又はモリブデン系金属膜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 oxidized indium metal film, oxidized aluminum metal film, and the lower titanium or molybdenum 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。上述した範囲未満で含まれると、アルミニウム系金属膜が低いエッチング速度を有し、基板内で不均一なエッチング特性として誘発できる。上述した範囲を超過して含まれると、アルミニウム系金属膜が過度なエッチング速度によって消失してしまうおそれがあり、下部膜としてのチタニウム系又はモリブデン系金属膜が損傷するおそれがある。 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. If included below the above range, the aluminum-based metal film has a low etching rate and can be induced as non-uniform etching characteristics in the substrate. If the content exceeds the above range, the aluminum-based metal film may disappear due to an excessive etching rate, and the titanium-based or molybdenum-based metal film as the lower film may be damaged.
前記含フッ素化合物は、特に限定されるものではなく、好ましくは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などを使用することができる。これらはそれぞれ単独で又は２種以上混合して使用可能である。 The fluorine-containing compound is not particularly limited, and is preferably a compound that can dissociate into fluorine ions or polyatomic fluorine ions. For example, ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, and potassium bifluoride can be used as the fluorine-containing compound. These can be used alone or in admixture of two or more.
本発明において、水は脱イオン水を意味する。前記水としては、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％となるように残部として含まれる。 In the present invention, water means deionized water. As said water, the thing for semiconductor processes is used, Preferably water of 18 Mohm / cm or more is used. The water is contained as a balance so 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、前記必須成分の他に、リン酸塩化合物をさらに含んでもよい。本発明の組成物がリン酸塩化合物を含む場合には、下部膜がモリブデン系金属膜である三重膜の一括エッチングにさらに適する。 The etching solution composition of the present invention may further contain a phosphate compound in addition to the essential components. When the composition of the present invention contains a phosphate compound, it is more suitable for collective etching of a triple film in which the lower film is a molybdenum-based metal film.
本発明において、リン酸塩化合物は、テーパープロファイルを良好にし、アルミニウム系金属膜及びモリブデン系金属膜のエッチング速度を調節する役目をする。 In the present invention, the phosphate compound serves to improve the taper profile and adjust the etching rate of the aluminum-based metal film and the molybdenum-based metal film.
前記リン酸塩化合物は、組成物の総重量に対して、０．１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。上述した範囲を満足すると、アルミニウム系金属膜及びモリブデン系金属膜のエッチング速度を調節することが容易であり、均一なエッチング特性を実現することができる。 The phosphate compound is preferably included in an amount of 0.1% by weight to 5% by weight, and more preferably 0.1% by weight to 2% by weight, based on the total weight of the composition. When the above range is satisfied, it is easy to adjust the etching rate of the aluminum-based metal film and the molybdenum-based metal film, and uniform etching characteristics can be realized.
前記リン酸塩化合物は、リン酸において水素がアルカリ金属又はアルカリ土金属で１個〜３個置換された塩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が、これに限定されるものではない。具体的に、前記リン酸塩化合物としては、リン酸二水素ナトリウム(sodium dihydrogen phosphate)、リン酸二水素カリウム(potassium dihydrogen phosphate)、及びこれらの組み合わせよりなる群から選択できる。 The phosphate compound is preferably one or more selected from the group consisting of salts in which hydrogen is replaced with 1 to 3 of alkali metal or alkaline earth metal in phosphoric acid, but is limited thereto. Is not to be done. Specifically, the phosphate compound can be selected from the group consisting of sodium dihydrogen phosphate, potassium dihydrogen phosphate, and combinations thereof.
また、本発明のエッチング液組成物は、前述した成分の他に、エッチング調節剤、界面活性剤、金属イオン封鎖剤、腐食防止剤などのその他の添加剤を１種又は２種以上含有することができる。 In addition to the components described above, the etching solution composition of the present invention contains one or more other additives such as an etching regulator, a surfactant, a sequestering agent, and a corrosion inhibitor. Can do.
一方、本発明において、インジウム系金属膜は、透明伝導膜であって、例えばインジウム亜鉛酸化膜（ＩＺＯ）、インジウム錫酸化膜（ＩＴＯ）などを挙げることができる。 On the other hand, in the present invention, the indium metal film is a transparent conductive film, and examples thereof include an indium zinc oxide film (IZO) and an indium tin oxide film (ITO).
また、アルミニウム系金属膜はアルミニウム単一膜、又はアルミニウムを主成分とするアルミニウム合金膜を意味する。前記アルミニウム合金膜はアルミニウム−ランタニウム合金膜であることが好ましい。ここで、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。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。 The aluminum metal film means an aluminum single film or an aluminum alloy film containing aluminum as a main component. The aluminum alloy film is preferably an aluminum-lanthanum alloy film. Here, 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. The other metal (X) is made of Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd, Sn, Fe, Si, Ti, Pt, and C. It is preferable that it is 1 type, or 2 or more types chosen from the group.
また、前記チタニウム系金属膜はチタニウム単一膜又はチタニウム合金膜であることを意味する。 The titanium metal film means a titanium single film or a titanium alloy film.
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。ところが、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８及び比較例１〜比較例７）：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 8 and Comparative Examples 1 to 7): 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、ガラス上にＩＴＯ／Ａｌ−Ｌａ−Ｎｉ／Ｔｉ又はＩＴＯ／Ａｌ−Ｌａ−Ｎｉ／Ｍｏ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。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１〜８及び比較例１〜７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）剥離器(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。
(Test example): Characteristic evaluation of etching solution composition <Etching characteristic evaluation>
As the test substrate, ITO / Al-La-Ni / Ti or ITO / Al-La-Ni / Mo triple-layer film is vapor-deposited on glass, and a photoresist is patterned into a fixed pattern. did. The etching solution compositions of Examples 1 to 8 and Comparative Examples 1 to 7 were charged into a jet etching type experimental equipment (manufactured by SEMES, model name: ETCHER (TFT)), and the temperature was set to 30 ° C. Warmed up. Thereafter, after the temperature reached 30 ± 0.1 °, an etching process was performed. The total etching time was 30% based on EPD. Insert a test piece and start spraying. When etching is completed, the sample is taken out, washed with deionized water, dried using a hot air dryer, and the photoresist is removed 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１〜８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ないエッチング特性を示した。 Referring to Table 2, the etching solution compositions of Examples 1 to 8 were excellent in etching profile and exhibited etching characteristics free from damage and residue of the lower film.
ところが、比較例１及び比較例３のエッチング組成物の場合は、エッチングプロファイルが良くなく、下部膜としてのチタニウム系又はモリブデン系金属膜がエッチングされない結果を得た。また、比較例２及び比較例４のエッチング液組成物の場合は、エッチングプロファイルが良くなく、下部膜の損傷がある良くない結果を得た。比較例５のエッチング液組成物の場合は、硝酸がなくて下部膜の損傷はなかったが、エッチングプロファイルが良くなく、残渣が発生した。比較例６のエッチング液組成物の場合は、下部膜の損傷又は残渣はなかったが、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良くなかった。また、比較例７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かった。
However, in the case of the etching compositions of Comparative Examples 1 and 3, the etching profile was not good, and the result was that the titanium-based or molybdenum-based metal film as the lower film was not etched. Moreover, in the case of the etching liquid composition of the comparative example 2 and the comparative example 4, the etching profile was not good and the bad result with the damage of a lower film was obtained. In the case of the etching solution composition of Comparative Example 5, there was no nitric acid and the lower film was not damaged, but the etching profile was not good and a residue was generated. In the case of the etching solution composition of Comparative Example 6, there was no damage or residue of the lower film, but the etching profile was not very good due to overetching. Further, in the case of the etching solution composition of Comparative Example 7, the damage to the lower film was very large due to an excessive amount of the fluorine-containing compound.
Claims (5)
ＦｅＣｌ３、Ｆｅ（ＮＯ３）３、Ｆｅ２（ＳＯ４）３、ＮＨ４Ｆｅ（ＳＯ４）２、Ｆｅ（ＣｌＯ４）３、ＦｅＰＯ４、およびＦｅ（ＮＨ４）３（Ｃ２Ｏ４）３よりなる群から選ばれる１種又は２種以上である鉄化合物０．１重量％〜１０重量％、
硝酸２重量％〜５重量％、
含フッ素化合物０．０１重量％〜５重量％、
及び残部水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、アルミニウム単一膜又はアルミニウム−ランタニウム合金膜から選択されるアルミニウム系金属膜、及びチタニウム系又はモリブデン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,
FeCl 3 , Fe (NO 3 ) 3 , Fe 2 (SO 4 ) 3 , NH 4 Fe (SO 4 ) 2 , Fe (ClO 4 ) 3 , FePO 4 , and Fe (NH 4 ) 3 (C 2 O 4 ) Iron compound 0.1 wt% to 10 wt%, which is one or more selected from the group consisting of 3 ;
Nitric acid 2 wt% to 5 wt%,
0.01 to 5% by weight of a fluorine-containing compound,
And the balance water,
Indium-based metal film selected from indium zinc oxide film (IZO) and indium-tin oxide film (ITO), aluminum-based metal film selected from aluminum single film or aluminum-lanthanum alloy film, and titanium-based or molybdenum-based metal A batch etching solution composition for a triple film comprising a film.
又はモリブデン系金属膜からなる三重膜用一括エッチング液組成物。 The aluminum-lanthanum alloy film is an aluminum-lanthanum-based alloy film represented by 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) is Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd, Sn, Fe, Si, Ti, Pt, and the like. It is 1 type, or 2 or more types chosen from the group which consists of C, The triple film which consists of an indium type metal film of Claim 1, an aluminum type metal film, and a titanium type or a molybdenum type metal film Bulk etchant composition.
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| KR1020100097748A KR101804572B1 (en) | 2009-11-03 | 2010-10-07 | An etching solution composition |
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| US7358195B2 (en) * | 2003-04-01 | 2008-04-15 | Lg.Philips Lcd Co., Ltd. | Method for fabricating liquid crystal display device |
| KR100575233B1 (en) * | 2003-11-04 | 2006-05-02 | 엘지.필립스 엘시디 주식회사 | Fabrication method of liquid crystal display device |
| KR101264421B1 (en) * | 2005-12-09 | 2013-05-14 | 동우 화인켐 주식회사 | Etchant for metal layer |
| KR101299131B1 (en) * | 2006-05-10 | 2013-08-22 | 주식회사 동진쎄미켐 | Etching composition for tft lcd |
| KR101294968B1 (en) * | 2006-11-20 | 2013-08-09 | 동우 화인켐 주식회사 | Etching solution composition and method of etching using the etching solution composition |
| KR20080045854A (en) * | 2006-11-21 | 2008-05-26 | 동우 화인켐 주식회사 | Method of producing tft array substrate for liquid crystal display |
| JP5559956B2 (en) * | 2007-03-15 | 2014-07-23 | 東進セミケム株式会社 | Etching solution composition for thin film transistor liquid crystal display device |
| KR101284390B1 (en) * | 2007-06-13 | 2013-07-09 | 동우 화인켐 주식회사 | Method for fabricating array substrate for a liquidcrystal display device |
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2010
- 2010-10-07 KR KR1020100097748A patent/KR101804572B1/en active IP Right Grant
- 2010-10-12 CN CN201080050506.3A patent/CN102597163B/en active Active
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| Publication number | Publication date |
|---|---|
| JP2013510425A (en) | 2013-03-21 |
| CN102597163A (en) | 2012-07-18 |
| KR20110049671A (en) | 2011-05-12 |
| CN102597163B (en) | 2014-07-16 |
| KR101804572B1 (en) | 2017-12-05 |
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