JP2013511844A - Ii〜vi半導体のための新規なウェットエッチング剤及び方法 - Google Patents
Ii〜vi半導体のための新規なウェットエッチング剤及び方法 Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 148
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000005530 etching Methods 0.000 claims abstract description 88
- 239000000243 solution Substances 0.000 claims abstract description 56
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011669 selenium Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 claims description 2
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 claims description 2
- 230000009257 reactivity Effects 0.000 abstract description 3
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 8
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- 239000000203 mixture Substances 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 3
- -1 MgSe Chemical compound 0.000 description 3
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 description 1
- LQSJUQMCZHVKES-UHFFFAOYSA-N 6-iodopyrimidin-4-amine Chemical compound NC1=CC(I)=NC=N1 LQSJUQMCZHVKES-UHFFFAOYSA-N 0.000 description 1
- 229910015894 BeTe Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BVTJGGGYKAMDBN-UHFFFAOYSA-N Dioxetane Chemical compound C1COO1 BVTJGGGYKAMDBN-UHFFFAOYSA-N 0.000 description 1
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 1
- 229910017680 MgTe Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- KQNSPSCVNXCGHK-UHFFFAOYSA-N [3-(4-tert-butylphenoxy)phenyl]methanamine Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1=CC=CC(CN)=C1 KQNSPSCVNXCGHK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical class OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229910021476 group 6 element Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- 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
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- 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
- H01L21/34—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 not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
- H01L21/46—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428
- H01L21/461—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/465—Chemical or electrical treatment, e.g. electrolytic etching
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- 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
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Abstract
【選択図】なし
Description
水溶液は、室温で少なくとも1週間安定している。
「上に配置される」とは、下の層と直接接触することを意味する。
「室温」とは、周囲圧力で約25℃の温度を指す。
表1は、使用する化学物質、それらの濃度、並びに供給源情報の一覧を提供する。
所望量の酸を脱イオン(DI)水に加えて所望の濃度(即ち、所望の希釈)の酸を得ることによって、例示されたエッチング液組成物を調製した。室温まで冷却した後(H3PO4の場合には、水による希釈中に熱はほとんど発生しなかった)、所望量のKMnO4を撹拌しながら希酸溶液に加えた。最後に、所望量の界面活性剤(存在する場合)を撹拌しながら添加した。
実施例1では、SC−1半導体及びInP基板試料を、エッチング液A及び比較A、比較B、比較C、比較Dを使用して上記の通りにエッチングした。表3に実施例1のエッチング試験データがまとめられている。
II〜VI半導体を、2.92Mの一定H3PO4濃度と、様々な量のKMnO4濃度とを有する本発明によるエッチング液を使用して、上記プロセスに従ってエッチングした。表4に実施例2のエッチング試験データがまとめられている。
II〜VI半導体を、0.03Mの一定KMnO4濃度と、様々な濃度のH3PO4とを有する本発明によるエッチング液を使用して、上記プロセスに従ってエッチングした。表5に実施例3のエッチング試験データがまとめられている。
エッチング液Aを使用して、様々な組成のII〜VI半導体試料及びInP基板に関して達成されたエッチ速度を、上述された一般的な方法を用いて判定した。結果は表6にまとめられている。
撹拌及び撹拌速度が、様々な量のドデシル硫酸ナトリウム(SDS、C12H25SO3Na)(界面活性剤)で変性されたエッチング液AによるII〜VI半導体(SC−2)のエッチ速度に与える影響を判定するために、実施例5を実施した。撹拌した場合のエッチング実験では、撹拌は、電磁攪拌器(VWR(West Chester,PA)より入手したCorning Magnetic Stirrer Model RCT)及び3.84cmの撹拌子を使用して達成された。「低」撹拌速度とは、撹拌速度が電磁攪拌器の6に設定されたことを意味し、「高」撹拌速度とは、撹拌速度が電磁攪拌器の7に設定されたことを意味する。エッチ速度データが表7にまとめられている。
H3PO4中に大量の界面活性剤と少量のKMnO4とを有する([界面活性剤]/[KMnO4]のモル比>10)エッチング液Aの安定性を調べた。KMnO4に伴う紫色の退色を、エッチング液の不安定性の指標として考えた。1週間以内に紫色を消失した界面活性剤変性エッチング液は、不安定と評価された。表8に様々な界面活性剤で変性されたエッチング液Aの安定性データがまとめられている。
2か月を超える期間にわたって本発明による様々なエッチング液の安定性を実証するために実施例7を実施した。この実施例では、各エッチング液のエッチ速度は、II〜VI半導体試料SC−3に関して上述された方法を用いて判定された。エッチング溶液を実験の期間中(70日超過)周囲実験室条件下で保持した。次に、各エッチング液のエッチ速度を、熟成させた(aged)エッチング液のそれぞれを使用して、同じ方法及び同じII〜VI半導体(SC−3)試料を用いて再度判定した。表9に、本発明による様々なエッチング液組成物に関する初期速度及び最終速度、並びに実験期間がまとめられている。
Claims (22)
- 半導体のエッチング方法において、
II〜VI半導体の表面の少なくとも一部を、過マンガン酸カリウムとリン酸とを含むエッチング液と接触させることと、
前記II〜VI半導体の少なくとも一部を前記エッチング液との接触から取り除いて、エッチングされたII〜VI半導体を形成することと、
前記エッチングされたII〜VI半導体をすすいで前記エッチング液を除去することと、を含む半導体のエッチング方法。 - 前記II〜VI半導体が、室温でエッチングされる、請求項1に記載の半導体のエッチング方法。
- 前記II〜VI半導体が、カドミウム、ベリリウム、マグネシウム、亜鉛、セレン、水銀、テルル、亜鉛、イオウ、又はこれらの組み合わせを含む、請求項2に記載の半導体のエッチング方法。
- 前記II〜VI半導体が、カドミウム、マグネシウム、セレン、亜鉛、又はこれらの組み合わせを含む、請求項3に記載の半導体のエッチング方法。
- 前記エッチング液が、過マンガン酸カリウム及びリン酸の水溶液を含む、請求項2に記載の半導体のエッチング方法。
- 前記エッチング液中のリン酸濃度が、約1.5モル/リットル〜約4.5モル/リットルである、請求項5に記載の半導体のエッチング方法。
- 前記過マンガン酸カリウムの濃度が、約0.01モル/リットル〜約0.1モル/リットルである、請求項5に記載の半導体のエッチング方法。
- 前記過マンガン酸カリウムの濃度が、約0.01モル/リットル〜約0.05モル/リットルである、請求項7に記載の半導体のエッチング方法。
- 前記II〜VI半導体が、約50nm/秒より速い速度でエッチングされる、請求項2に記載の半導体のエッチング方法。
- 前記II〜VI半導体が、水ですすがれる、請求項1に記載の半導体のエッチング方法。
- 前記エッチング液が、界面活性剤を更に含む、請求項1に記載の半導体のエッチング方法。
- 前記界面活性剤が、フッ素化界面活性剤を含む、請求項11に記載の半導体のエッチング方法。
- 前記界面活性剤が、ペルフルオロ酪酸、ペルフルオロブタンスルホン酸、その塩、又はこれらの組み合わせを含む、請求項12に記載の半導体のエッチング方法。
- 半導体のエッチング方法において、
III〜V半導体の上に配置されるII〜VI半導体を用意することと、
前記II〜VI半導体の表面の少なくとも一部を、過マンガン酸カリウムとリン酸とを含むエッチング液と接触させることと、
前記II〜VI半導体の少なくとも一部を前記エッチング液との接触から取り除いて、エッチングされたII〜VI半導体を形成することと、
前記エッチングされたII〜VI半導体をすすいで前記エッチング液を除去することと、を含む半導体のエッチング方法。 - 前記II〜VI半導体のエッチング速度が、前記III〜V半導体のエッチング速度よりも少なくとも10倍速い、請求項14に記載の半導体のエッチング方法。
- 前記II〜VI半導体が、カドミウム、亜鉛、セレン、マグネシウム、又はこれらの組み合わせを含む、請求項15に記載の半導体のエッチング方法。
- 前記III〜V半導体が、InPを含む、請求項16に記載の半導体のエッチング方法。
- 前記エッチング液が、フッ素化界面活性剤を更に含む、請求項14に記載の半導体のエッチング方法。
- 過マンガン酸カリウムとリン酸とを含む水溶液を含むエッチング溶液であって、
前記過マンガン酸カリウムの濃度が、約0.01モル/リットル〜約0.1モル/リットルであり、前記リン酸の濃度が、約1.5モル/リットル〜約4.5モル/リットルであり、
前記水溶液が室温で少なくとも1週間安定している、エッチング液。 - 前記水溶液が、室温で少なくとも75日間安定状態を保つ、請求項19に記載のエッチング溶液。
- 前記エッチング溶液が、室温で少なくとも75日間貯蔵された後に、最初に調製されたときとほぼ同じ速度でII〜VI半導体をエッチングする、請求項19に記載のエッチング溶液。
- フッ素化界面活性剤を更に含む、請求項19に記載のエッチング溶液。
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PCT/US2010/056359 WO2011062835A2 (en) | 2009-11-18 | 2010-11-11 | Novel wet etching agent for ii-vi semiconductors and method |
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WO2011062835A3 (en) | 2011-10-06 |
EP2502263A2 (en) | 2012-09-26 |
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