CN102471898B - 用于形成金属线的蚀刻组合物 - Google Patents
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- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title abstract description 13
- 239000002184 metal Substances 0.000 title abstract description 13
- 238000005530 etching Methods 0.000 claims abstract description 69
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 12
- -1 nitrate compound Chemical class 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 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
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
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- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
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- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 150000002475 indoles Chemical class 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 229940001516 sodium nitrate Drugs 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- 239000010936 titanium Substances 0.000 abstract description 40
- 238000000034 method Methods 0.000 abstract description 20
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- 239000000758 substrate Substances 0.000 abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000002356 single layer Substances 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 238000001039 wet etching Methods 0.000 description 8
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- 229910004205 SiNX Inorganic materials 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
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- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
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- 230000003750 conditioning effect Effects 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000009021 linear effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
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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
- 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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- 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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
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- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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Abstract
本发明涉及一种用于形成金属线的蚀刻组合物,能批量湿蚀刻由选自Ti、Ti合金、Al和Al合金组成的组中的至少一种制成的单层膜或多层膜,并能蚀刻很多层从而极大地增加了蚀刻工艺的生产率,且能提高蚀刻速率并防止损坏底层膜和设备,以及能均匀蚀刻图形/非图形从而展示了较好的蚀刻特性;此外由于无需昂贵的设备以及便于形成大面积的栅极和源极/漏极,因此也很经济。
Description
技术领域
本发明涉及一种适合用于平板显示器栅极和源极/漏极的蚀刻组合物,所述蚀刻组合物能批量湿蚀刻由选自Ti、Ti合金、Al和Al合金组成的组中的至少一种制成的单层膜或多层膜。
技术背景
平板显示器基板上形成金属线的典型工艺包括:采用喷溅形成金属层,涂抹光刻胶,进行图片曝光和显影以致光刻胶在选定区域成形,以及进行蚀刻,并在各个这些单个工艺前或后进行清洗。将光刻胶用作掩膜进行蚀刻工艺使得金属层留在选定区域上,蚀刻工艺可包括使用等离子体或类似物的干蚀刻或使用蚀刻溶液的湿蚀刻。
在平板显示器金属层里,导电层由具有低电阻的Al形成,但是这样一个Al层是有问题的因为后续工艺中会产生小丘导致Al层与另一个导电层发生短路现象,并且Al层接触氧化层后会形成绝缘层。因此,在Al的上表面或下表面可形成一种由Mo、Ti、Cr或其合金组成的缓冲层。近来,Ti因具有抗腐蚀性、高硬度和高强度受到了关注。
按照惯例以Ti层作为缓冲层的电极通过使用卤素气体并经由干蚀刻工艺进行蚀刻。虽然干蚀刻工艺因具有各向异性的剖面和较高的蚀刻可控性,与湿蚀刻工艺相比更具优势,但干蚀刻工艺需要昂贵的设备,难以形成大面积的栅极和源极/漏极且降低了蚀刻速率,从而导致较低的生产率。
相应的,已经发展了湿蚀刻这样一种Ti缓冲层的方法。例如,编号为10-1999-0005010,10-1999-0043017的韩国专利申请等揭示了HF作为蚀刻组合物的主要成分用于湿蚀刻钛层。然而,在HF主要用于湿蚀刻的案例中,底层膜和设备会被损坏,因此工艺条件将受到很多限制,进而降低生产率。
发明内容
为此,本发明用以针对上述相关领域的问题,本发明的目的是提供一种蚀刻组合物,所述蚀刻组合物能批量湿蚀刻由选自Ti、Ti合金、Al和Al合金组成的组中的至少一种制成的单层膜或多层膜,并且由于可蚀刻很多层从而极大地增加了蚀刻工艺的生产率;所述蚀刻组合物能提高蚀刻速率以及防止损坏底层膜和设备,并能均匀蚀刻图形/非图形从而展现了较高的蚀刻特性;所述蚀刻组合物无需昂贵的设备并便于形成大面积的栅极和源极/漏极,因此很经济。
本发明一方面提供了一种蚀刻组合物,所述组合物用于蚀刻由选自Ti、Ti合金,Al和Al合金组成的组中的至少一种制成的单层膜或多层膜,包含,基于所述组合物的总重,1~20wt%H2O2,1~7wt%可离解出硝酸根离子的化合物,0.05~2wt%含氟化合物,0.5~6wt%过硫酸盐化合物和余量水。
根据本发明,所述蚀刻组合物可进一步包括0.01~5wt%环状胺化合物。
附图说明
图1是扫描电子显微镜(SEM)图像显示了使用实施例3的蚀刻组合物蚀刻Ti/Al/Ti三层的结果;
图2是SEM图像显示了使用对比例4的蚀刻组合物蚀刻Ti/Al/Ti三层的结果;和
图3和图4是SEM图像,显示了随蚀刻层数而定的蚀刻特性(例如侧蚀刻)的变化,分别使用实施例6和2的蚀刻组合物蚀刻Ti/Al/Ti三层。
具体实施方式
根据本发明,一种蚀刻组合物,用于蚀刻由选自Ti、Ti合金、Al和Al合金组成的组中的至少一种制成的单层膜或多层膜,包含,基于所述组合物的总重,1~20wt%H2O2,1~7wt%可离解出硝酸根离子的化合物,0.05~2wt%含氟化合物,0.5~6wt%过硫酸盐化合物和余量水。
根据本发明蚀刻组合物用于批量蚀刻由选自Ti、Ti合金、Al和Al合金组成的组中的至少一种制成的单层膜或多层膜。在此,多层膜包括两层膜其中Ti或Ti合金层置于Al或Al合金层的之上或之下,也包括三层或更多层膜其中Ti或Ti合金层以及Al或Al合金层交替层合。
根据本发明蚀刻组合物更适宜用于蚀刻一种三层膜包括上层为Ti或Ti合金,中层为Al或Al合金以及底层为Ti或Ti合金。
Ti或Ti合金层定义为包括Ti层或由合金构成的金属层,该合金包含主要成分钛和另一种随该层特性而定的其它金属;Al或Al合金层定义为包括Al层或由合金构成的金属层,该合金包含主要成分Al和另一种随该层特性而定的其它金属。
本发明中,H2O2用于氧化Ti层和Al层的表面,可加入的量为1~20wt%优选5~10wt%,基于所述组合物的总重。如果H2O2的量少于1wt%,Ti层和Al层的蚀刻速率将降低并且图形和非图形之间的蚀刻速率差异会变大,并导致工艺中的问题。相比之下,如果其量超过20wt%,所述图形因Ti层和Al层的过度蚀刻而消失,导致金属线功能的损失。
本发明中,可离解出硝酸根离子的化合物在蚀刻时用于增加由Ti层和Al层所制成的线的线性的作用,可加入的量为1~7wt%基于所述组合物的总重。如果可离解出硝酸根离子的化合物的量少于1wt%,蚀刻的均匀性和线的线性会降低,并形成非均匀的线并导致基板的斑驳问题。相比之下,如果其量超过7wt%,Ti层和Al层的蚀刻速率会增加,导致发生过度蚀刻,且蚀刻的均匀性会降低,以致产生斑点。
可离解出硝酸根离子的化合物的例子包括硝酸盐化合物,例如硝酸铵,硝酸钠,硝酸钾等,它们可单独使用或以其两种或更多种组合使用。此外,因为硝酸在溶液状态下离解成硝酸根离子,因此它可包括在可离解出硝酸根离子的化合物的范围中。
特别有效的是一种可离解出硝酸根离子的化合物,其中硝酸盐化合物和硝酸以重量比为2∶8~8∶2混合。
在本发明中,含氟化合物用于蚀刻氧化的Ti层和Al层的表面,可加入的量为0.05~2wt%优选0.1~0.5wt%,基于所述组合物的总重。如果其量少于0.05wt%,位于顶层和底层的Ti层和Al层的蚀刻速率会降低,导致产生蚀刻残渣,或因不均匀蚀刻导致基板产生斑点。相比之下,如果其量超过2wt%,因蚀刻速率增加过度导致底层被损坏,并且难以控制工艺的速率。
含氟化合物为能从中离解出氟离子或多原子的氟离子的化合物,含氟化合物的例子包括氟化铵(ammonium fluoride)、氟化钠(sodium fluoride)、氟化钾(potassiumfluoride)、氟氢化钠(sodium bifluoride)、氟氢化钾(potassium bifluoride)、氟氢化铵(ammonium bifluoride)、氟化氢(hydrogen fluoride)等,这些化合物可单独使用或以其两种或多种组合使用。
本发明中,过硫酸盐化合物用于在蚀刻时使Ti层和Al层产生倾斜,可加入的量为0.5~6wt%基于所述组合物的总重。如果其量少于1wt%,Ti层和Al层之间的蚀刻速率会出现差异,难以形成倾斜。相比之下,如果其量多于6wt%,Ti层和Al层会被过度蚀刻。
过硫酸盐化合物的例子包括过硫酸铵、过硫酸钠、过硫酸钾等,它们可单独使用或以其两种或多种组合使用。
本发明中,水是适合半导体工艺的去离子水,优选比电阻为18MΩ/cm或更多的水。
根据本发明蚀刻组合物进一步包括环状胺化合物。
当用蚀刻组合物蚀刻时,蚀刻溶液中Ti和Al金属离子将增加。这种金属离子的增加会改变化学溶液中的组合物并且也会降低蚀刻速率,导致蚀刻特性的恶化。
由于环状胺化合物与金属离子反应形成一种稳定的形式,因此它可用来增加基板的处理层数。环状胺化合物可加入的量为0.01~5wt%基于所述组合物的总重。如果环状胺化合物少于0.01wt%,稳定金属离子的效果会变得不显著。相比之下,如果其量多于5wt%,环状胺化合物因低溶解性在制备化学溶液时将难以溶解。
环状胺化合物的例子包括吡咯烷、吡咯啉、吡咯、吲哚、吡唑、咪唑、嘧啶、嘌呤、吡啶、苯并三唑及其衍生物,它们可单独使用或以其两种或更多种组合使用。
除上述成分外,根据本发明蚀刻组合物可进一步包含0.5~10wt%无机酸例如硫酸、盐酸、磷酸和高氯酸,基于所述组合物的总重。在包括此类无机酸的情况下,调节蚀刻速率变得高效简单。
根据本发明蚀刻组合物可进一步包含一种醋酸盐化合物以控制侧蚀刻。醋酸盐化合物可加入的量为0.1~5.0wt%基于所述组合物的总重,以便适当地控制侧蚀刻。
醋酸盐化合物的例子包括醋酸钠(CH3COONa)、醋酸钾(CH3COOK)、醋酸铵(CH3COO(NH4))、醋酸镁(Mg(CH3COO)2)、醋酸钙(Ca(CH3COO)2),它们可单独使用或以其两种或多种组合使用。
根据本发明蚀刻组合物可进一步包括除上述成分之外的常规添加剂,添加剂的例子包括蚀刻调节剂、表面活性剂、螯合剂、抗蚀剂、pH调节剂,等等。
下述实施例用于阐述说明本发明但不能解释为对本发明的限制,下述实施例有助于更好的理解本发明且在本发明的范围内本领域技术人员可进行适当的修改和变化。
实施例1至6和对比例1至4:蚀刻组合物的制备
制备180kg蚀刻组合物所使用的成分和用量显示在以下表1中。
表1
(单位:wt%)
检验实施例
(1)蚀刻特性的评估
用作检验样品的基板包括沉积于玻璃上的SiNx层,成形于SiNx层上的Ti/Al/Ti三层,和光刻胶,该光刻胶成形于Ti/Al/Ti三层之上的预先设定的图形中。
将实施例1至5的各蚀刻溶液放入喷淋式蚀刻机(ETCHER(TFT),SEMES提供)然后加热至设定温度40℃,随后在温度40±0.1℃进行蚀刻工艺。像这样,蚀刻工艺在过度蚀刻条件下进行其中总蚀刻时间比EPD时间增加了30%。随后,将检验样品放入喷淋式蚀刻机中并喷淋各溶液以便蚀刻。蚀刻完成后,将检验样品从蚀刻机中拿出,用去离子水冲洗,用热风干燥机干燥,然后用光刻胶剥离液去除光刻胶。清洗并干燥后,用SEM(S-4700,HITACHI提供)评估检验样品的蚀刻剖面倾斜角度,侧蚀刻(CD(临界尺寸))损失,蚀刻残渣和底层的损坏。结果见下表2。
[蚀刻剖面的评估标准]
◎:优秀(CD偏移:≤1μm,倾斜角度:40~90°)
○:良好(CD偏移:≤1.5μm,倾斜角度:40~90°)
△:一般(CD偏移:≤2μm,倾斜角度:40~90°)
×:较差(图形消失并产生残渣)
表2
由表2可知,当用实施例1~5的蚀刻溶液进行蚀刻时,蚀刻剖面非常好,并且既没有损坏底层也没有产生残渣,具有较好的蚀刻特性(图1)。然而,当用对比例1~4的蚀刻溶液进行蚀刻时,蚀刻剖面总体上很差,部分底层损坏。
具体的在对比例1中,过硫酸盐的量超过了本发明所述的范围,因此蚀刻速率变得太快,难以得到期望的蚀刻剖面。对比例2中,使用了过量的H2O2和可离解出硝酸根离子的化合物,因此蚀刻速率太快从而导致过度蚀刻,难以得到期望的蚀刻剖面。
对比例3和4中,可离解出硝酸根离子的化合物的量超过了本发明所述的范围,于是蚀刻速率增加由此导致过度蚀刻,并且整个光刻胶消失。此外,均匀性较低,并且基板上会产生斑点(图2)。
(2)处理层数的评估
用评估蚀刻特性同样的方法评估实施例6和2的蚀刻组合物蚀刻的层数。同样的,按照过度蚀刻的条件以固定的蚀刻速率进行蚀刻工艺,其中总的蚀刻时间较EPD时间增加了30%,样品层数每次蚀刻增加100层从100至1000层。用SEM(S-4700,由HITACHI提供)对侧蚀刻(CD(临界尺寸))损失的变化进行评估,结果如下表3所示:
表3
如表3所示,与使用实施例6的蚀刻溶液时相比,使用实施例2的蚀刻溶液时侧蚀刻数减少的幅度与蚀刻层数的增加成正比,并且从800层开始发生非蚀刻。但是,直至1000层,实施例6的蚀刻溶液都没有极大地改变侧蚀刻数,而且没有产生非蚀刻。
如上文所述,根据本发明蚀刻组合物可用于批量湿蚀刻由选自Ti、Ti合金,Al和Al合金组成的组中的至少一种制成的单层膜或多层膜,且由于可蚀刻很多层因此能极大地增加蚀刻工艺的生产率。并且,根据本发明,所述蚀刻组合物可增加蚀刻速率以及能防止损坏底层膜和设备,并能均匀蚀刻图形/非图形因此展示了较好的蚀刻特性,此外,无需昂贵的设备并便于形成大面积的栅极和源极/漏极,因此也很经济。
Claims (8)
1.一种蚀刻组合物,用于蚀刻由选自Ti、Ti合金、Al和Al合金组成的组中的至少一种制成的单层膜或多层膜,其中所述组合物包含:
基于所述组合物的总重,
1~20wt%H2O2,1~7wt%硝酸盐化合物和硝酸的混合物,其中硝酸盐化合物和硝酸以重量比为2:8~8:2混合,0.05~2wt%含氟化合物,0.5~6wt%过硫酸盐化合物,0.01~5wt%环状胺化合物,和余量水。
2.根据权利要求1所述蚀刻组合物,其中所述硝酸盐化合物选自硝酸铵、硝酸钠和硝酸钾组成的组中的一种或多种。
3.根据权利要求1所述蚀刻组合物,其中所述含氟化合物为可离解出氟离子或多原子氟离子的化合物。
4.根据权利要求1所述蚀刻组合物,其中所述过硫酸盐化合物选自过硫酸铵、过硫酸钠和过硫酸钾组成的组中的一种或多种。
5.根据权利要求1所述蚀刻组合物,其中所述环状胺化合物选自吡咯烷、吡咯啉、吡咯、吲哚、吡唑、咪唑、嘧啶、嘌呤、吡啶、苯并三唑及其衍生物组成的组中的一种或多种。
6.根据权利要求1所述蚀刻组合物,进一步包含选自硫酸、盐酸、磷酸和高氯酸组成的组中的一种或多种无机酸。
7.根据权利要求1所述蚀刻组合物,进一步包含用于控制侧蚀刻的醋酸盐化合物。
8.根据权利要求3所述蚀刻组合物,其中所述含氟化合物选自氟化铵、氟化钠、氟化钾、氟氢化钠、氟氢化钾、氟氢化铵和氟化氢组成的组中的一种或多种。
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