CN100350570C - Etching method for aluminum-molybdenum laminate film - Google Patents
Etching method for aluminum-molybdenum laminate film Download PDFInfo
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- CN100350570C CN100350570C CNB028209869A CN02820986A CN100350570C CN 100350570 C CN100350570 C CN 100350570C CN B028209869 A CNB028209869 A CN B028209869A CN 02820986 A CN02820986 A CN 02820986A CN 100350570 C CN100350570 C CN 100350570C
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- metal film
- wet etching
- molybdenum
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000005530 etching Methods 0.000 title abstract description 26
- 239000005001 laminate film Substances 0.000 title abstract 3
- UNQHSZOIUSRWHT-UHFFFAOYSA-N aluminum molybdenum Chemical compound [Al].[Mo] UNQHSZOIUSRWHT-UHFFFAOYSA-N 0.000 title 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 34
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 28
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 24
- 238000001039 wet etching Methods 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011733 molybdenum Substances 0.000 claims abstract description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 57
- 239000000758 substrate Substances 0.000 claims description 22
- 235000011054 acetic acid Nutrition 0.000 claims description 19
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 12
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 235000003704 aspartic acid Nutrition 0.000 claims description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000768 polyamine Chemical class 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 229960005137 succinic acid Drugs 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000000291 glutamic acid group Chemical group N[C@@H](CCC(O)=O)C(=O)* 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000010408 film Substances 0.000 description 75
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 20
- 229910001182 Mo alloy Inorganic materials 0.000 description 20
- 239000000908 ammonium hydroxide Substances 0.000 description 20
- 239000003870 refractory metal Substances 0.000 description 15
- 229910000838 Al alloy Inorganic materials 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 238000011010 flushing procedure Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- -1 Hydroxyl tricarboxylic acids Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical class OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- H01L21/3063—Electrolytic etching
-
- 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
- C23F1/26—Acidic compositions for etching refractory metals
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- ing And Chemical Polishing (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
An etching method which comprises contacting a laminate film comprising at least one aluminum based metal film and at least one molybdenum based high melting point metal film with a wet etching solution comprising an aqueous solution containing phosphoric acid, nitric acid, an organic acid and a cation-generating component, while maintaining the water content of the etching solution in a range of 10 to 30 wt %. The method allows the laminate film to be etched so as to have a good normal taper form.
Description
Technical field
The present invention relates to the formation method of the stacked distribution that is used for signal wiring of a kind of liquid crystal indicator etc., in more detail, the engraving method that relates to the stacked film of high melting point metal layers such as aluminum-based metal layer on a kind of substrate and molybdenum relates to a kind of formation method of stacked distribution of high confidence level.
Background technology
On glass substrate, rectangular ground assortment ITO transparent pixel electrodes such as (Indium Tin Oxide), with the active array type LCD of TFT (Thin Film Transition), usually adopt the gate electrode that on the same glass substrate, is formed with drive TFT and the TFT panel construction of the gate wirings that prolongs from this gate electrode or data wiring etc. with its driving.
Describe with reference to profile shown in Figure 1 summary the most general contrary irregular type TFT panel construction.
Normal cone shape ground forms gate electrode 2 on glass substrate 1, is situated between by gate insulating film 3 and i type semiconductor layer 4, n type semiconductor layer 5, and source electrode 6 and drain electrode 7 are disposed in opposite directions with gate electrode 2, forms TFT thus.Usually i type semiconductor layer 4 is formed by the a-Si of non-doping, and n type semiconductor layer 5 is by the n that contains n type impurity
+A-Si forms.Gate electrode 2 is that metal etc. constitutes by Al, guarantees the distribution coating of the i type semiconductor layer 4 that its upper strata forms, and in order to improve the insulating properties of gate insulating film 3, the normal cone shape is processed in its side.
In the past in the method for Cai Yonging, in order to make by Al is that the gate electrode 2 that constitutes such as metal or the gate wirings that prolongs thus are processed into the normal cone shape, utilizing splash etc. 1 whole of glass substrate is gone up to form Al is metal level, after optionally forming resist pattern thereon, isotropically carry out wet etching as mask with this resist pattern.
But, in recent years, in order to form the connector that Al is metal wiring and ITO film, prevent that Al from being the low mound (hillock) of metal wiring, adopt of TFT panel is the stacked distribution structure of the upper strata stacked molybdenum refractory metal distributions (Mo is a gate electrode) 22 such as (Mo) of metal wiring (Al is a gate electrode) 21 at low resistance Al as shown in Figure 2, perhaps be the upper strata of metal wiring 21 as shown in Figure 3 at low resistance Al, on the lower floor two sides, the stacked distribution structure of stacked molybdenum refractory metal distributions 22 such as (Mo), can improve insulating properties by the normal cone shape is processed in the side of refractory metal distributions 22 such as Mo in this case.
As Al the wet etching solution (spy open flat 7-176500 communique, spy are opened flat 7-176525 communique, the spy opens flat 9-127555 communique) of metal film with phosphoric acid, nitric acid, the mixed nitration mixture of acetic acid in the past.But, when stating nitration mixture in the use, because the standard electrode potential of Al and stacked metal is different, cell reaction etc. takes place in the wet etching operation, be that the stepped construction of metal film and high melting point metal film is processed into very difficulty of normal cone shape with Al.
But the spy opens flat 6-104241 communique and is described below, and is stacked film as using above-mentioned nitration mixture to carry out the means of wet etching with Mo/Al, can control the Film Thickness Ratio of stacked film, but not tackle the problem at its root.
According to above situation, wish that exploitation can be etched into above-mentioned stacked film the good engraving method of good normal cone shape.
Summary of the invention
The objective of the invention is to solve the variety of issue that exists in the above-mentioned prior art, provide a kind of with the aluminum-based metal film, particularly the aluminum-based metal film becomes the wet etch process of good normal cone shape with the stacked film wet etching of refractory metal films such as molybdenum.
The inventor has carried out research in depth in order to achieve the above object, found that, at the etching solution that constitutes with the aqueous solution that contains phosphoric acid, nitric acid, organic acid and cation constituent, to containing at least a aluminum-based metal film and at least a molybdenum is that the stacked film of high melting point metal film is when carrying out etching, by the moisture in the etching solution is maintained between 10~30 weight %, can become good normal cone shape by wet etching, until finishing the present invention.
The present invention relates to engraving method, it is characterized in that, make that to be formed on the substrate be that stacked film that high melting point metal film constitutes contacts by containing the wet etching solution that the aqueous solution that phosphoric acid, nitric acid, organic acid and cation generate composition constitutes by being formed at aluminum-based metal film and molybdenum on being formed at this aluminum-based metal film on the substrate, keep moisture simultaneously at 15~20 weight %.
The invention still further relates to engraving method, it is characterized in that, make be formed on the substrate be high melting point metal film by being formed at molybdenum on the substrate, to be formed at this molybdenum be the aluminum-based metal film on the high melting point metal film and to be formed at molybdenum on this aluminum-based metal film be the stacked film contact that constitutes of high melting point metal film by containing the wet etching solution that the aqueous solution that phosphoric acid, nitric acid, organic acid and cation generate composition constitutes, and keeps moisture simultaneously at 18~23 weight %.
Description of drawings
Fig. 1 is general contrary irregular type TFT panel construction summary section.
Fig. 2 is illustrated in the skeleton diagram of stepped construction that low-resistance Al is the stacked high-melting-point distribution in upper strata of metal wiring.
Fig. 3 is illustrated on upper strata that low-resistance Al is a metal wiring, the lower floor two sides, and stacked Mo is the skeleton diagram of the stepped construction of refractory metal distribution.
Fig. 4 is that the Al of expression formation normal cone shape is that metal wiring/Mo is the process chart of refractory metal wiring layer stack structure situation.
Fig. 5 is that the Al of the non-cone shape of expression formation is that metal wiring/Mo is the skeleton diagram of refractory metal wiring layer stack structure.
Fig. 6 is that the Mo of expression formation normal cone shape is that refractory metal distribution/Al is that metal wiring/Mo is the process chart of refractory metal wiring layer stack structure situation.
Fig. 7 is that the Mo of the non-cone shape of expression formation is that refractory metal distribution/Al is that metal wiring/Mo is the skeleton diagram of refractory metal wiring layer stack structure.
Embodiment
The wet etching solution that the present invention uses is the aqueous solution that contains phosphoric acid, nitric acid, organic acid and cation constituent.
Concentration of phosphoric acid is 50~80 weight % of wet etching solution, preferred 60~75 weight %.Phosphoric acid is that metal film carries out etching to Al mainly, and during less than 50 weight %, Al is that the metal film etching speed is slow, and when surpassing 80 weight % in addition, Al is that the metal film etching speed is too fast, and is not preferred.Al described in the present invention is that metal film is meant that aluminium film and aluminium content are the above aluminium alloy films of 80 weight % in addition.Alloying element for example has Nd, Zr, Cu, Si etc.
The concentration of nitric acid is 0.5~10 weight % of etching solution, preferred 1~8 weight %.Nitric acid mainly is to be the high melting point metal film etching to Mo, and during less than 0.5 weight %, Mo is that the etching speed of high melting point metal film is slow, and when surpassing 10 weight %, Mo is that the etching speed of high melting point metal film is too fast, and is not preferred.Mo described in the present invention is that high melting point metal film is meant that molybdenum film and molybdenum content are the above molybdenum alloy films of 80 weight % in addition.Alloying element for example has W etc.
Organic acid for example has: monocarboxylic acid classes such as formic acid, acetic acid, propionic acid, butyric acid; Omega-dicarboxylic acids such as oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, phthalic acid; Tricarboxylic acids such as trimellitic acid etc.; Hydroxyl monocarboxylic acid classes such as hydroxacetic acid, lactic acid, salicylic acid; Hydroxydicarboxylic acid such as malic acid, tartaric acid; Hydroxyl tricarboxylic acids such as citric acid; Aminocarboxylic such as aspartic acid, glutamic acid acids.
Organic acid concentration is 0.5~10 weight % of etching solution, preferred 5~8 weight %.Organic acid concentration can be according to the concentration of phosphoric acid, nitric acid, and perhaps etching condition etc. is suitably determined.
Cation generates composition for example to be had: ammonia; Ammonium salts such as ammonium hydroxide; Fatty amines such as methyl amine, dimethyl amine, Trimethylamine, ethylamine, diethylamide, triethylamine, propyl group amine, dipropylamine, tripropylamine, butylamine, dibutylamine, tri-butylamine; Alkanol amines such as monoethanolamine, diethanol amine, triethanolamine; Polyamines classes such as ethylenediamine, propane diamine, trimethylene diamines, tetra-methylenedimine; Cyclammonium classes such as pyrroles, pyrrolin, pyrrolidones, morpholine; And quaternary ammonium base such as tetramethyl-ammonium hydroxide, tetraethyl ammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide.Outside described ammonia, amine, quaternary ammonium base, alkali metal salts such as NaOH, potassium hydroxide also can be used as cation and generate composition in addition.Generate preferred especially ammonium salt in the composition at above-mentioned cation.
The concentration that above-mentioned cation generates composition is 0.1~20 weight % of wet etching solution, preferred 1~10 weight %.During less than 0.1 weight %, the etching solution life-span is short, and when surpassing 20 weight %, Mo is that metal film, Al are that the etching speed of metal film is slow, not preferred.
The moisture optimum content of wet etching solution among the present invention is owing to form intrinsic scope according to kind, the composition of etched metal film, and the metal film of each actual uses is carried out suitably selecting common preferred 10~30 weight % scopes.Moisture when for example refractory metal film/Al such as wet etching Mo is metal film is 15~20 weight %, preferred 16~19 weight %; Moisture when refractory metal film/Al such as wet etching Mo are refractory metal films such as metal film/Mo is 18~23 weight %, preferred 19~22 weight %.
Etching condition is not particularly limited, and can adopt existing known condition.For example make 0.5~3 fen kind of metal film contact wet etching solution under the normal temperature (20~25 ℃)~50 ℃.Etching condition can suitably be selected according to researchs such as the kind of the stacked film that uses, thickness.
Use Fig. 4 (a)~(c) be elaborated.At first splash aluminium alloy (99.1 weight %Al, 0.9 weight %Zr), splash molybdenum alloy (85 weight %Mo, 15 weight %W) then form the stacked film (Fig. 4 (a)) of molybdenum alloy film 22 (750 )/aluminium alloy films 21 (750 ) on TFT glass substrate 1.Coating photoresist 23 on the stacked film of molybdenum alloy/aluminium alloy, behind pre-prepd figure mask exposure, video picture forms specific resist pattern (Fig. 4 (b)).
Use the substrate of above-mentioned Fig. 4 (b), utilize
(1) phosphoric acid 65 weight %, nitric acid 9 weight %, acetic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 19 weight %,
(2) phosphoric acid 66 weight %, nitric acid 9 weight %, acetic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 18 weight %,
(3) phosphoric acid 67 weight %, nitric acid 9 weight %, acetic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 17 weight % and
(4) phosphoric acid 68 weight %, nitric acid 9 weight %, acetic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 16 weight %
4 kinds of etching solutions, under 45 ℃, be etched to optimal etch, after the water flushing, drying is that stripper is peeled off photoresist 23 with amine again, uses electron microscope (SEM) to observe afterwards.The result obtains the stacked film of the molybdenum alloy/aluminium alloy with good normal cone shape shown in Fig. 4 (c).
Comparative example 1
Use the substrate of above-mentioned Fig. 4 (b), utilize
(5) phosphoric acid 62 weight %, nitric acid 9 weight %, acetic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 22 weight % and
(6) phosphoric acid 71 weight %, nitric acid 9 weight %, acetic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 13 weight %
2 kinds of etching solutions, under 45 ℃, be etched to optimal etch, after the water flushing, drying is that stripper is peeled off photoresist 23 with amine again, uses electron microscope (SEM) to observe afterwards.The result obtains the non-cone shape stacked film that has shown in Fig. 5 (c), can not obtain the stacked film of molybdenum alloy/aluminium alloy of the normal cone shape shown in Fig. 4 (c).
Use Fig. 6 (a)~(c) be elaborated.At first splash molybdenum alloy (85 weight %Mo, 15 weight %W), aluminium alloy (99.1 weight %Al, 0.9 weight %Zr), splash molybdenum alloy (85 weight %Mo, 15 weight %W) then forms the stacked film (Fig. 6 (a)) of molybdenum alloy film 22 (750 )/aluminium alloy films 21 (1500 )/molybdenum alloy film 22 (750 ) on TFT glass substrate 1.Coating photoresist 23 on stacked film, behind pre-prepd figure mask exposure, video picture forms specific resist pattern (Fig. 6 (b)).
Use the substrate of above-mentioned Fig. 6 (b), utilize
(7) phosphoric acid 64 weight %, nitric acid 7 weight %, acetic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 22 weight %,
(8) phosphoric acid 65 weight %, nitric acid 7 weight %, acetic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 21 weight %,
(9) phosphoric acid 66 weight %, nitric acid 7 weight %, acetic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 20 weight % and
(10) phosphoric acid 67 weight %, nitric acid 7 weight %, acetic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 19 weight %
4 kinds of etching solutions, under 45 ℃, be etched to optimal etch, after the water flushing, drying is that stripper is peeled off photoresist 23 with amine again, uses electron microscope (SEM) to observe afterwards.The result obtains the molybdenum alloy/aluminium alloy with the good normal cone shape/molybdenum alloy stacked film shown in Fig. 6 (c).
Use the substrate of above-mentioned Fig. 6 (b), utilize
(11) phosphoric acid 63 weight %, nitric acid 8 weight %, propionic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 22 weight %,
(12) phosphoric acid 64 weight %, nitric acid 8 weight %, propionic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 21 weight %,
(13) phosphoric acid 65 weight %, nitric acid 8 weight %, propionic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 20 weight %,
(14) phosphoric acid 66 weight %, nitric acid 8 weight %, propionic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 19 weight %
4 kinds of etching solutions, under 45 ℃, be etched to optimal etch, after the water flushing, drying is that stripper is peeled off photoresist 23 with amine again, uses electron microscope (SEM) to observe afterwards.The result obtains the molybdenum alloy/aluminium alloy with the good normal cone shape/molybdenum alloy stacked film shown in Fig. 6 (c).
Use the substrate of above-mentioned Fig. 6 (b), utilize
(15) phosphoric acid 62 weight %, nitric acid 8 weight %, acetic acid 5 weight %, NaOH 3 weight %, moisture 22 weight %,
(16) phosphoric acid 63 weight %, nitric acid 8 weight %, acetic acid 5 weight %, NaOH 3 weight %, moisture 21 weight %,
(17) phosphoric acid 64 weight %, nitric acid 8 weight %, acetic acid 5 weight %, NaOH 3 weight %, moisture 20 weight %,
(18) phosphoric acid 65 weight %, nitric acid 8 weight %, acetic acid 5 weight %, ammonium hydroxide 3 weight %, moisture 19 weight %
4 kinds of etching solutions, under 45 ℃, be etched to optimal etch, after the water flushing, drying is that stripper is peeled off photoresist 23 with amine again, uses electron microscope (SEM) to observe afterwards.Structure obtains the molybdenum alloy/aluminium alloy with the good normal cone shape/molybdenum alloy stacked film shown in Fig. 6 (c).
Comparative example 2
Use the substrate of above-mentioned Fig. 6 (b), utilize
(19) phosphoric acid 61 weight %, nitric acid 7 weight %, acetic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 25 weight %,
(20) phosphoric acid 70 weight %, nitric acid 7 weight %, acetic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 16 weight %
2 kinds of etching solutions, under 45 ℃, be etched to optimal etch, after the water flushing, drying is that stripper is peeled off photoresist 23 with amine again, uses electron microscope (SEM) to observe afterwards.The result obtains non-cone shape stacked film as shown in Figure 7, can not obtain the molybdenum alloy/aluminium alloy/molybdenum alloy stacked film of the normal cone shape shown in Fig. 6 (c).
Comparative example 3
Use the substrate of above-mentioned Fig. 6 (b), utilize
(21) phosphoric acid 60 weight %, nitric acid 8 weight %, propionic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 25 weight %,
(22) phosphoric acid 69 weight %, nitric acid 8 weight %, propionic acid 5 weight %, ammonium hydroxide 2 weight %, moisture 16 weight %
2 kinds of etching solutions, under 45 ℃, be etched to optimal etch, after the water flushing, drying is that stripper is peeled off photoresist 23 with amine again, uses electron microscope (SEM) to observe afterwards.The result obtains non-cone shape stacked film as shown in Figure 7, can not obtain the molybdenum alloy/aluminium alloy/molybdenum alloy stacked film of the normal cone shape shown in Fig. 6 (c).
Use wet etch process of the present invention, can be with the aluminum-based metal film, particularly the aluminum-based metal film becomes good normal cone shape with the stacked film wet etching of refractory metal films such as molybdenum.
Claims (8)
1, a kind of engraving method, it is characterized in that, make that to be formed on the substrate be that stacked film that high melting point metal film constitutes contacts by containing the wet etching solution that the aqueous solution that phosphoric acid, nitric acid, organic acid and cation generate composition constitutes by being formed at aluminum-based metal film and molybdenum on being formed at this aluminum-based metal film on the substrate, keep moisture simultaneously at 15~20 weight %.
2, a kind of engraving method, it is characterized in that, make be formed on the substrate be high melting point metal film by being formed at molybdenum on the substrate, to be formed at this molybdenum be the aluminum-based metal film on the high melting point metal film and to be formed at molybdenum on this aluminum-based metal film be the stacked film contact that constitutes of high melting point metal film by containing the wet etching solution that the aqueous solution that phosphoric acid, nitric acid, organic acid and cation generate composition constitutes, and keeps moisture simultaneously at 18~23 weight %.
3, engraving method as claimed in claim 1 or 2 is characterized in that, described concentration of phosphoric acid is 50~80 weight % of wet etching solution.
4, engraving method as claimed in claim 1 or 2 is characterized in that, concentration of nitric acid is 0.5~10 weight % of wet etching solution.
5, engraving method as claimed in claim 1 or 2, it is characterized in that described organic acid is at least a acid that is selected from the group that formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, phthalic acid, trimellitic acid, hydroxacetic acid, lactic acid, salicylic acid, malic acid, tartaric acid, citric acid, aspartic acid, glutamic acid form.
6, engraving method as claimed in claim 1 or 2 is characterized in that, described organic acid concentration is 0.5~10 weight % of wet etching solution.
7, engraving method as claimed in claim 1 or 2 is characterized in that, it is at least a compound that is selected from the group that ammonia, ammonium salt, aliphat amine, alkanol amine, polyamines class, cyclammonium class, quaternary ammonium base, alkali metal salt forms that described cation generates composition.
8, engraving method as claimed in claim 1 or 2 is characterized in that, the concentration that described cation generates composition is 0.1~20 weight % of wet etching solution.
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US20210254224A1 (en) * | 2018-09-18 | 2021-08-19 | Samsung Electronics Co., Ltd. | Etching composition, a method of etching a metal barrier layer and a metal layer using the same, and method of manufacturing semiconductor device using the same |
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KR20040029289A (en) | 2003-11-14 | 2004-04-06 | 동우 화인켐 주식회사 | Etchant composition for aluminum or aluminum alloy single layer and multi layers |
KR101131832B1 (en) * | 2004-10-15 | 2012-07-17 | 동우 화인켐 주식회사 | Etchant composition for single layer and multi layers consisting of aluminum or aluminum alloy or/and molybdenum or molybdenum alloy |
KR101171175B1 (en) * | 2004-11-03 | 2012-08-06 | 삼성전자주식회사 | Etchant for conductive material and method for manufacturing a thin film transistor array panel using the etchant |
JP4741343B2 (en) * | 2004-11-29 | 2011-08-03 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor device |
US7547627B2 (en) | 2004-11-29 | 2009-06-16 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing semiconductor device |
KR101216651B1 (en) * | 2005-05-30 | 2012-12-28 | 주식회사 동진쎄미켐 | etching composition |
CN100376721C (en) * | 2005-09-21 | 2008-03-26 | 中国海洋大学 | Chemical etching solution for molybdenum |
JP4855968B2 (en) * | 2007-02-16 | 2012-01-18 | 株式会社 日立ディスプレイズ | PATTERN FORMING METHOD AND METHOD FOR MANUFACTURING LIQUID CRYSTAL DISPLAY DEVICE USING THE PATTERN FORMING METHOD |
KR101393599B1 (en) * | 2007-09-18 | 2014-05-12 | 주식회사 동진쎄미켐 | Etchant composition for patterning circuits in thin film transistor-liquid crystal devices |
JP2009103732A (en) * | 2007-10-19 | 2009-05-14 | Sony Corp | Display unit and method of manufacturing the same |
JP5484853B2 (en) * | 2008-10-10 | 2014-05-07 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor device |
CN102471688A (en) * | 2009-08-13 | 2012-05-23 | 东友Fine-Chem股份有限公司 | Etchant composition for forming copper interconnects |
KR101728553B1 (en) * | 2010-12-21 | 2017-04-20 | 동우 화인켐 주식회사 | Etching solution composition for ohmic contact layer |
CN102392248B (en) * | 2011-10-18 | 2013-08-21 | 绵阳艾萨斯电子材料有限公司 | Etchant of molybdenum and/ or aluminum containing metal film for OLED (Organic Light Emitting Diode) and preparation method thereof |
CN103409753B (en) * | 2013-07-23 | 2015-08-19 | 苏州羽帆新材料科技有限公司 | Metal etchants and preparation method thereof |
CN117867501B (en) * | 2024-03-12 | 2024-06-11 | 芯越微电子材料(嘉兴)有限公司 | Molybdenum-aluminum dual-purpose etching solution and preparation method of substrate patterning metal layer |
CN118477556A (en) * | 2024-07-16 | 2024-08-13 | 合肥中聚和成电子材料有限公司 | Preparation method of aluminum etching solution |
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- 2002-10-21 KR KR1020047005396A patent/KR100944300B1/en active IP Right Grant
- 2002-10-21 WO PCT/JP2002/010871 patent/WO2003036707A1/en active Search and Examination
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US5150233A (en) * | 1990-02-26 | 1992-09-22 | Canon Kabushiki Kaisha | Liquid crystal device and display apparatus with a three-layered electrode of ito, molybdenum, and aluminum |
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US11795550B2 (en) * | 2018-09-18 | 2023-10-24 | Samsung Electronics Co., Ltd. | Etching composition, a method of etching a metal barrier layer and a metal layer using the same, and method of manufacturing semiconductor device using the same |
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JPWO2003036707A1 (en) | 2005-02-17 |
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