TWI814971B - 蝕刻液,及半導體元件之製造方法 - Google Patents
蝕刻液,及半導體元件之製造方法 Download PDFInfo
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- TWI814971B TWI814971B TW108147496A TW108147496A TWI814971B TW I814971 B TWI814971 B TW I814971B TW 108147496 A TW108147496 A TW 108147496A TW 108147496 A TW108147496 A TW 108147496A TW I814971 B TWI814971 B TW I814971B
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- Prior art keywords
- etching
- acid
- processed
- sige
- etching liquid
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- 238000005530 etching Methods 0.000 title claims abstract description 184
- 238000000034 method Methods 0.000 title claims description 46
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- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- YPPQYORGOMWNMX-UHFFFAOYSA-L sodium phosphonate pentahydrate Chemical compound [Na+].[Na+].[O-]P([O-])=O YPPQYORGOMWNMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000391 spectroscopic ellipsometry Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- YNJQKNVVBBIPBA-UHFFFAOYSA-M tetrabutylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+](CCCC)(CCCC)CCCC YNJQKNVVBBIPBA-UHFFFAOYSA-M 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 description 1
- LUVHDTDFZLTVFM-UHFFFAOYSA-M tetramethylazanium;chlorate Chemical compound [O-]Cl(=O)=O.C[N+](C)(C)C LUVHDTDFZLTVFM-UHFFFAOYSA-M 0.000 description 1
- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 0.000 description 1
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 description 1
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
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-
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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
- 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
- H01L21/30612—Etching of AIIIBV compounds
-
- 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
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- C—CHEMISTRY; METALLURGY
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- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
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- H01L21/02381—Silicon, silicon germanium, germanium
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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
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Abstract
一種蝕刻液,其係相對於Si、Ge及此等之氧化物,用以將通式Si1-x
Gex
表示之化合物(惟,x為超過0且未達1)予以選擇性地蝕刻處理之蝕刻液,其含有過碘酸與氟化物。
Description
本發明係關於蝕刻液,及半導體元件之製造方法。
本案係基於2018年12月27日於日本申請的日本特願2018-244958號主張優先權,其內容援用於此。
自以往起,積體電路內之構成的尺度,係已可進行半導體晶片上之功能單元的高密度化。例如,電晶體尺寸的縮小,係可將更多之記憶體元件整合於晶片上,達成容量經增加的製品之製造。
用於積體電路裝置之場效電晶體(FET)之製造中,作為矽以外之半導體結晶材料,係使用Ge。Ge係具備高的電荷載體(電洞)移動度、能帶間隙偏移(band gap offset)、不同的晶格常數,及成為與矽的合金而生成SiGe之半導體二元合金的能力等,依情況而較矽為有利的數個特徵。
但是,對Ge材料(特別是通式Si1-x
Gex
表示之化合物。惟,x為超過0且未達1。以下有僅稱為「SiGe化合物」者)之選擇性高的蝕刻液係有各種提案。
例如專利文獻1中,記載含有至少1個二醇化合物、至少1個氟化物種及至少1個氧化物種之蝕刻組成物。
又,專利文獻2中,記載含有過乙酸、氟化酸及氧化物之蝕刻組成物。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特表2018-519674號公報
[專利文獻2]美國專利第7176041號說明書
[發明所欲解決之課題]
但是,如專利文獻1或2記載之以往的蝕刻液係化學上不安定,可能有隨時間經過,對SiGe化合物之蝕刻速率變動的情況,製程之控制可能有困難的情況。
本發明係有鑑於上述實情而為者,其課題為提供對通式Si1-x
Gex
表示之化合物之蝕刻速率的經時安定性經提高之蝕刻液,以及使用前述蝕刻液之被處理體之處理方法及半導體元件之製造方法。
[用以解決課題之手段]
為了解決上述課題,本發明採用以下之構成。
本發明之第1態樣,為一種相對於Si、Ge及此等之氧化物,用以將通式Si1-x
Gex
表示之化合物(惟,x為超過0且未達1)予以選擇性地蝕刻處理之蝕刻液,其含有過碘酸與氟化物。
本發明之第2態樣,為一種被處理體之處理方法,其特徵為包含使用前述蝕刻液,將含有通式
Si1-x
Gex
表示之化合物的被處理體進行蝕刻處理之步驟。
本發明之第3態樣,為一種半導體元件之製造方法,其特徵為包含使用前述蝕刻液,將含有通式
Si1-x
Gex
表示之化合物的被處理體進行蝕刻處理之步驟。
[發明之效果]
依照本發明,可提供對通式Si1-x
Gex
表示之化合物的蝕刻速率之經時安定性經提高的蝕刻液,以及使用前述蝕刻液之被處理體之處理方法及半導體元件之製造方法。
(蝕刻液)
本發明之第1態樣之蝕刻液,含有過碘酸與氟化物。本態樣之蝕刻液,係相對於Si、Ge及此等之氧化物,用以將通式Si1-x
Gex
表示之化合物(以下有僅稱為「SiGe化合物」者)予以選擇性地蝕刻處理。
<過碘酸>
本實施形態之蝕刻液含有過碘酸。過碘酸可為正過碘酸(H5
IO6
)、偏過碘酸(HIO4
)之任意者,較佳為正過碘酸(H5
IO6
)。
SiGe化合物可藉由氧化而成為能夠溶解。過碘酸為釋出用以將SiGe化合物氧化之氧原子的氧化劑,過碘酸之氧化還原電位,由於具有足夠將SiGe化合物氧化之電位,因此可效率良好地將SiGe化合物氧化。
本實施形態之蝕刻液中之過碘酸之含量,並無特殊限定,例如,相對於蝕刻液之總質量而言,例示有0.02~5質量%,較佳為0.05~4.5質量%、更佳為0.1~4質量%、又更佳為0.20~3質量%。
過碘酸之含量若為前述範圍內,容易提高對SiGe化合物之蝕刻速率的經時安定性。
<氟化物>
本實施形態之蝕刻液含有氟化物。
氟化物,並無特殊限定,可列舉六氟鈦酸、六氟矽酸、六氟鋯酸、四氟硼酸、三氟甲磺酸四丁基銨、四氟硼酸四丁基銨等之四氟硼酸四烷基銨(NR1
R2
R3
R4
BF4
)、六氟磷酸四烷基銨(NR1
R2
R3
R4
PF6
)、氟化四甲基銨等之氟化四烷基銨(NR1
R2
R3
R4
F)(其無水物或水合物)、氟化氫銨、氟化銨(式中,R1
、R2
、R3
、R4
,可互為相同亦可相異地選自由氫、直鏈或分支鏈之C1
-C6
烷基(例如甲基、乙基、丙基、丁基、戊基、己基)、C1
-C6
烷氧基(例如羥基乙基、羥基丙基),或取代或非取代之芳基(例如苄基)所成之群)等。
其中,氟化物尤以氫氟酸(DHF)及/或氟化銨(NH4
F)為佳。
本實施形態之蝕刻液中,氟化物可1種單獨使用、亦可合併使用2種以上。
本實施形態之蝕刻液中之氟化物之含量,並無特殊限定,例如,相對於蝕刻液之總質量而言,例示有0.02~5質量%,較佳為0.025~3.00質量%、更佳為0.03~2.50質量%、又更佳為0.04~2.00質量%。氟化物之含量為前述範圍內時,對SiGe化合物之蝕刻速率容易更加提高。
又,本實施形態之蝕刻液的氟離子濃度,並無特殊限定,例如,例示有0.005~2.50mol/L,較佳為0.007~1.50mol/L、更佳為0.008~1.25mol/L、又更佳為0.010~1.00mol/L。氟離子濃度為前述範圍內時,對SiGe化合物之蝕刻速率容易更加提高。
<其他成分>
本實施形態之蝕刻液,在不損及本發明之效果的範圍,於上述成分以外亦可含有其他成分。其他成分例如可列舉水、水溶性有機溶劑、pH調整劑、氧化劑、鈍化劑、界面活性劑等。
・水
本實施形態之蝕刻液,較佳含有水作為上述成分之溶劑。水亦可含有不可避免地混入的微量成分。本實施形態之蝕刻液所用之水,較佳為蒸餾水、離子交換水,及超純水等之實施過淨化處理的水;更佳為使用一般使用於半導體製造之超純水。
本實施形態之蝕刻液中之水之含量,並無特殊限定,較佳為80質量%以上、更佳為90質量%以上、又更佳為94質量%以上。又,上限值並無特殊限定,較佳為未達99.95質量%、更佳為99.9質量%以下、又更佳為99.5質量%以下。本實施形態之蝕刻液,較佳為含有過碘酸及氟化物之水溶液。
・水溶性有機溶劑
本實施形態之蝕刻液,在不損及本發明之效果的範圍,亦可含有水溶性有機溶劑。水溶性有機溶劑,可列舉醇類(例如甲醇、乙醇、乙二醇、丙二醇、甘油、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、二乙二醇、二丙二醇、呋喃甲醇,及2-甲基-2,4-戊二醇等)、二甲基亞碸、醚類(例如乙二醇二甲基醚、二乙二醇二甲基醚、三乙二醇二甲基醚、四乙二醇二甲基醚、丙二醇二甲基醚)等。
本實施形態之蝕刻液中,水溶性有機溶劑可1種單獨使用、亦可合併使用2種以上。
本實施形態之蝕刻液含有水溶性有機溶劑時,水溶性有機溶劑之含量,相對於水之量與水溶性有機溶劑之量的合計而言,較佳為50質量%以下、更佳為30質量%以下、又更佳為10質量%以下。
・pH調整劑
為了更加提高對SiGe化合物之蝕刻速率,本實施形態之蝕刻液亦可含有pH調整劑。
pH調整劑,較佳為選自由酸及其鹽所成之群的至少1種。具體而言,可列舉甲磺酸、三氟甲磺酸、草酸二水合物、檸檬酸、酒石酸、吡啶甲酸、琥珀酸、乙酸、乳酸、磺琥珀酸、安息香酸、丙酸、甲酸、丙酮酸、馬來酸、丙二酸、富馬酸、蘋果酸、抗壞血酸、苦杏仁酸、庚酸、丁酸、戊酸、戊二酸、鄰苯二甲酸、次磷酸、水楊酸、5-磺水楊酸、鹽酸、乙磺酸、丁磺酸、p-甲苯磺酸、二氯乙酸、二氟乙酸、單氯乙酸、單氟乙酸、三氯乙酸、三氟乙酸、氫溴酸(62重量%)、硫酸、乙酸銨、乙酸鈉、乙酸鉀、乙酸四甲基銨及其他之乙酸四烷基銨、乙酸鏻、丁酸銨、三氟乙酸銨、碳酸銨、氯化銨、硫酸銨、磷酸、磷酸氫二銨、磷酸二氫銨、磷酸氫雙(四甲基銨)、磷酸氫二鈉、磷酸二氫鈉、磷酸氫二鉀、磷酸二氫鉀、磷酸氫二-四烷基銨、磷酸二氫二-四烷基銨、磷酸氫二鏻、磷酸二氫鏻、膦酸銨、膦酸四烷基銨、膦酸鈉、膦酸鉀、膦酸鏻、艾提壯酸,及此等之鹽等。
其中,作為酸之pH調整劑,尤以甲磺酸或草酸為佳。
又,本實施形態之蝕刻液,亦可含有鹼性化合物作為pH調整劑。如此的鹼性化合物,可使用有機鹼性化合物及無機鹼性化合物,有機鹼化合物,可列舉以有機四級銨氫氧化物為首的四級銨鹽、三甲胺及三乙胺等之烷基胺及其衍生物之鹽作為適合的例子。
又,無機鹼性化合物,可列舉包含鹼金屬或鹼土類金屬之無機化合物及其鹽。例如可列舉氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化銣及氫氧化銫等。
本實施形態之蝕刻液中,pH調整劑可1種單獨使用、亦可合併使用2種以上。
本實施形態之蝕刻液含有pH調整劑時,例如,相對於蝕刻液之總質量而言,例示有0.01~10質量%,較佳為0.02~4.5質量%、更佳為0.03~4質量%、又更佳為0.05~3質量%。pH調整劑之含量為前述範圍內時,對SiGe化合物之蝕刻速率容易更加提高。
・氧化劑
本實施形態之蝕刻液,除了過碘酸以外,亦可含有其他氧化劑。
氧化劑例如可列舉過氧化氫、FeCl3
、FeF3
、Fe(NO3
)3
、Sr(NO3
)2
、CoF3
、MnF3
、過氧一硫酸氫鉀複合鹽(2KHSO5
・KHSO4
・K2
SO4
)、碘酸、氧化釩(V)、氧化釩(IV、V)、釩酸銨、過氧一硫酸銨、亞氯酸銨、氯酸銨、碘酸銨、硝酸銨、過硼酸銨、過氯酸銨、過碘酸銨、過硫酸銨、次氯酸銨、次溴酸銨、鎢酸銨、過硫酸鈉、次氯酸鈉、過硼酸鈉、次溴酸鈉、碘酸鉀、過錳酸鉀、過硫酸鉀、硝酸、過硫酸鉀、次氯酸鉀、亞氯酸四甲基銨、氯酸四甲基銨、碘酸四甲基銨、過硼酸四甲基銨、過氯酸四甲基銨、過碘酸四甲基銨、過硫酸四甲基銨、過氧一硫酸四丁基銨、過氧一硫酸、硝酸鐵(III)、過氧化脲、過乙酸、甲基-1,4-苯醌(MBQ)、1,4-苯醌(BQ)、1,2-苯醌、2,6-二氯-1,4-苯醌(DCBQ)、甲醌、2,6-二甲基-1,4-苯醌(DMBQ)、四氯苯醌、四氧嘧啶、N-甲基嗎啉N-氧化物、三甲胺N-氧化物等。
本實施形態之蝕刻液中,氧化劑可1種單獨使用、亦可合併使用2種以上。
本實施形態之蝕刻液含有氧化劑時,例如,相對於蝕刻液之總質量而言,較佳為0.01~10質量%、更佳為0.1~7質量%。
・鈍化劑
本實施形態之蝕刻液,亦可含有用於鍺之鈍化劑。
鈍化劑可列舉抗壞血酸、L(+)-抗壞血酸、異抗壞血酸、抗壞血酸衍生物、硼酸、二硼酸銨、硼酸鹽(例如五硼酸銨、四硼酸鈉及二硼酸銨)、丙胺酸、精胺酸、天門冬醯胺、天門冬胺酸、半胱胺酸、麩胺酸、麩醯胺、組胺酸、異白胺酸、白胺酸、離胺酸、甲硫胺酸、苯基丙胺酸、脯胺酸、絲胺酸、蘇胺酸、色胺酸、酪胺酸、纈胺酸、溴化鈉、溴化鉀、溴化銣、溴化鎂、溴化鈣、具有式NR1
R2
R3
R4
Br(式中,R1
、R2
、R3
及R4
,係可互為相同或亦可相異地,選自由氫,及分支鏈或直鏈之C1
-C6
烷基(例如甲基、乙基、丙基、丁基、戊基、己基)所成之群)之溴化銨等。
本實施形態之蝕刻液中,鈍化劑可1種單獨使用、亦可合併使用2種以上。
本實施形態之蝕刻液含有鈍化劑時,例如,相對於蝕刻液之總質量而言,較佳為0.01~5質量%、更佳為0.1~1質量%。
・界面活性劑
以調整蝕刻液對被處理體之濕潤性為目的等,本實施形態之蝕刻液,亦可含有界面活性劑。界面活性劑,可使用非離子界面活性劑、陰離子界面活性劑、陽離子界面活性劑,或兩性界面活性劑,亦可合併使用此等。
非離子界面活性劑,例如可列舉聚環氧烷烷基苯基醚系界面活性劑、聚環氧烷烷基醚系界面活性劑、包含聚環氧乙烷與聚環氧丙烷之嵌段聚合物系界面活性劑、聚氧化烯二苯乙烯化苯基醚系界面活性劑、聚伸烷基三苄基苯基醚系界面活性劑、乙炔聚環氧烷系界面活性劑等。
陰離子界面活性劑,例如可列舉烷基磺酸、烷基苯磺酸、烷基萘磺酸、烷基二苯基醚磺酸、脂肪酸醯胺磺酸、聚氧乙烯烷基醚羧酸、聚氧乙烯烷基醚乙酸、聚氧乙烯烷基醚丙酸、烷基膦酸、脂肪酸之鹽等。「鹽」可列舉銨鹽、鈉鹽、鉀鹽、四甲基銨鹽等。
陽離子界面活性劑,例如可列舉4級銨鹽系界面活性劑,或烷基吡啶鎓系界面活性劑等。
兩性界面活性劑,例如可列舉甜菜鹼型界面活性劑、胺基酸型界面活性劑、咪唑啉型界面活性劑、胺氧化物型界面活性劑等。
此等之界面活性劑一般而言可商業上獲得。界面活性劑可1種單獨使用、亦可合併使用2種以上。
<被處理體>
本實施形態之蝕刻液,係用於SiGe化合物之蝕刻者,係以含有SiGe化合物之被處理體為蝕刻處理的對象。被處理體只要係含有SiGe化合物者則無特殊限定,可列舉具有含有SiGe化合物之層(含有SiGe化合物之膜)的基板等。前述基板並無特殊限定,可列舉半導體晶圓、光罩用玻璃基板、液晶顯示用玻璃基板、電漿顯示用玻璃基板、FED(Field Emission Display)用基板、光碟用基板、磁碟用基板、光磁碟用基板等之各種基板。前述基板較佳為用於製作半導體裝置之基板。前述基板,於含有SiGe化合物之層及基板之基材以外,亦可適當具有各種層或結構,例如金屬配線、閘極結構、源極結構、汲極結構、絕緣層、強磁性層,及非磁性層等。又,基板之裝置面的最上層不必要為含有SiGe化合物之層,例如,多層結構之中間層亦可為含有SiGe化合物之層。
基板之大小、厚度、形狀、層結構等,並無特殊限制,可依目的來適當選擇。
前述含有SiGe化合物之層,較佳為含有SiGe化合物之層、更佳為SiGe化合物膜。基板上之含有SiGe化合物之層的厚度並無特殊限定,可依目的來適當選擇。含有SiGe化合物之層的厚度,例如可列舉1~500nm或1~300nm之範圍。
本實施形態之蝕刻液,可用於進行基板中之含有SiGe化合物之層的微細加工、可用於去除基板上附著的含有SiGe化合物之附著物、亦可用於自表面具有含有SiGe化合物之層的被處理體去除粒子等之雜質。
依照以上說明之本實施形態之蝕刻液,由於含有過碘酸作為氧化劑,因此可提高對SiGe化合物之蝕刻速率的經時安定性。其理由雖不確定,但其係推測由於過碘酸作為氧化劑係非常安定,故本實施形態之蝕刻液,對SiGe化合物之蝕刻速率不會經時劣化。例如,本實施形態之蝕刻液,即使於室溫保存3日以上或7日以上之後,對SiGe化合物之蝕刻速率亦幾乎不變化。因此,推測藉由本實施形態之蝕刻液,可安定地控制包含SiGe化合物之蝕刻步驟的製程。
(被處理體之處理方法)
本發明之第2態樣之被處理體之處理方法,其特徵為包含使用上述第1態樣之蝕刻液,將含有SiGe化合物之被處理體進行蝕刻處理之步驟。
含有SiGe化合物之被處理體,可列舉與上述「(蝕刻液)」中之「<被處理體>」所說明的為相同者,較佳例示具有含有SiGe化合物之層的基板。於基板上形成含有SiGe化合物之層的方法並無特殊限定,可使用公知之方法。該方法例如可列舉濺鍍法、化學氣相沈積(CVD:Chemical Vapor Deposition)法、分子束磊晶(MBE:Molecular Beam Epitaxy)法,及原子層沈積法(ALD:Atomic layer deposition)等。於基板上形成含有SiGe化合物之層時所用的含有SiGe化合物之層的原料亦無特殊限定,可依成膜方法適當選擇。
<將被處理體進行蝕刻處理之步驟>
本步驟為使用上述第1態樣之蝕刻液將含有SiGe化合物之被處理體進行蝕刻處理之步驟,其包含使前述蝕刻液接觸於前述被處理體之操作。蝕刻處理之方法並無特殊限定,可使用公知之蝕刻方法。該方法例如例示有噴霧法、浸漬法、浸液法等,但不限定於此等。
噴霧法中,例如將被處理體向特定方向搬送或旋轉,對其空間噴射上述第1態樣之蝕刻液,使前述蝕刻液接觸於被處理體。亦可依需要,一邊使用旋轉塗佈器使基板旋轉一邊噴霧前述蝕刻液。
浸漬法中,係於上述第1態樣之蝕刻液中浸漬被處理體,使前述蝕刻液接觸於被處理體。
浸液法中,係於被處理體上盛裝上述第1態樣之蝕刻液,使被處理體與前述蝕刻液接觸。
此等之蝕刻處理之方法,可依被處理體之結構或材料等適當選擇。噴霧法或浸液法的情況時,前述蝕刻液對被處理體之供給量,只要係被處理體之被處理面被前述蝕刻液充分浸濕的量即可。
蝕刻處理之目的並無特殊限定,可為被處理體之含有SiGe化合物之被處理面(例如基板上之含有SiGe化合物之層)的微細加工、可為附著於被處理體(例如具有含有SiGe化合物之層的基板)的含有SiGe化合物之附著物的去除、亦可為被處理體之含有SiGe化合物之被處理面(例如基板上之含有SiGe化合物之層)的洗淨。
蝕刻處理之目的為被處理體之含有SiGe化合物之被處理面的微細加工時,通常,係於將不欲被蝕刻之部位藉由蝕刻遮罩被覆後,使被處理體與蝕刻液接觸。
蝕刻處理之目的,為附著於被處理體之含有SiGe化合物之附著物的去除時,係藉由使上述第1態樣之蝕刻液接觸於被處理體,使含有SiGe化合物之附著物溶解,可自被處理體去除SiGe化合物附著物。
蝕刻處理之目的,為處理體之含有SiGe化合物之被處理面的洗淨時,係藉由使上述第1態樣之蝕刻液接觸於被處理體,使前述被處理面迅速溶解,於短時間自被處理體之表面去除附著於被處理體之表面的粒子等之雜質。
進行蝕刻處理之溫度並無特殊限定,只要係SiGe化合物會溶解於前述蝕刻液的溫度即可。蝕刻處理之溫度例如可列舉15~60℃。噴霧法、浸漬法,及浸液法的所有情況,均藉著提高蝕刻液之溫度,蝕刻速率會上昇,但亦可考慮將蝕刻液之組成變化抑制在低水準,或作業性、安全性、成本等,來適當選擇處理溫度。
進行蝕刻處理之時間,只要依蝕刻處理之目的、藉由蝕刻所去除之SiGe化合物之量(例如含有SiGe化合物之層的厚度、SiGe化合物附著物之量等),及蝕刻處理條件,來適當選擇即可。
依照以上說明的本實施形態之被處理體之處理方法,係使用含有過碘酸之上述第1態樣之蝕刻液作為氧化劑,來進行被處理體之蝕刻處理。該蝕刻液由於對SiGe化合物之蝕刻速率的經時安定性高,因此可安定地控制包含SiGe化合物之蝕刻步驟的製程。
(半導體元件之製造方法)
本發明之第3態樣之半導體元件之製造方法,其特徵為包含使用上述第1態樣之蝕刻液,將含有SiGe化合物之被處理體進行蝕刻處理之步驟。
將含有SiGe化合物之被處理體進行蝕刻處理之步驟,可與上述「(被處理體之處理方法)」中所說明的方法同樣地進行。含有SiGe化合物之被處理體,較佳為具有含有SiGe化合物之層的基板。前述基板可使用半導體元件之製作通常所使用的基板。
<其他步驟>
本實施形態之半導體元件之製造方法,於上述蝕刻處理步驟以外,亦可包含其他步驟。其他步驟並無特殊限定,可列舉於製造半導體元件時所進行的公知步驟。該步驟例如可列舉金屬配線、閘極結構、源極結構、汲極結構、絕緣層、強磁性層,及非磁性層等之各結構之形成步驟(層形成、上述蝕刻處理以外之蝕刻、化學機械研磨、變換等)、阻劑膜形成步驟、曝光步驟、顯影步驟、熱處理步驟、洗淨步驟、檢查步驟等,但不限定於此等。此等之其他步驟,可依需要於上述蝕刻處理步驟之前或後適當進行。
依照以上說明的本實施形態之半導體元件之製造方法,使用含有過碘酸之上述第1態樣之蝕刻液作為氧化劑,來進行被處理體之蝕刻處理。
該蝕刻液由於對SiGe化合物之蝕刻速率的經時安定性高,因此可安定地控制包含SiGe化合物之蝕刻步驟的製程。
[實施例]
以下藉由實施例以更詳細說明本發明,但本發明不限定於此等之例子。
<蝕刻液之配製>
(實施例1~4、比較例1~3)
混合表1所示之各成分,配製各例之蝕刻液。
表1中,各縮寫係分別具有以下意義。[ ]內之數值為摻合量(質量%)。
DHF:氫氟酸
NH4
F:氟化銨
PAA:過乙酸
PIA:過碘酸(H5
IO6
)
AA:乙酸
MSA:甲磺酸
<被處理體之蝕刻處理(1)>
於矽基板上使SiGe膜進行磊晶沈積,得到形成有SiGe膜之被處理體(1)。由所得之被處理體(1)切出試驗片,藉由螢光X射線分析測定SiGe膜之膜厚後,膜厚為50nm。
將各例之蝕刻液置入燒杯,藉由於室溫(23℃)將前述試驗片浸漬於各例之蝕刻液中5分鐘,進行蝕刻處理。前述蝕刻處理後,將試驗片吹氮氣乾燥,藉由螢光X射線分析測定SiGe膜之膜厚。由蝕刻處理前後之SiGe膜之膜厚,算出對SiGe之蝕刻速率(Å/min)。結果示於表2。
<被處理體之蝕刻處理(2)>
由SOI(100)基板切出試驗片,得到被處理體(2)。將所得之被處理體(2),藉由橢圓偏振光譜儀(spectroscopic ellipsometry)測定Si膜之膜厚後,膜厚為100nm。
將各例之蝕刻液置入燒杯,藉由於室溫(23℃)將前述試驗片浸漬於各例之蝕刻液中5分鐘,進行蝕刻處理。前述蝕刻處理後,將試驗片吹氮氣乾燥,藉由橢圓偏振光譜儀測定Si膜之膜厚。由蝕刻處理前後之Si膜之膜厚,算出對Si之蝕刻速率(Å/min)。結果示於表2。
<被處理體之蝕刻處理(3)>
藉由化學蒸鍍法(CVD)於矽基板上將矽氧化膜製膜,得到被處理體(3)。由所得之被處理體(3)切出試驗片,藉由橢圓偏振光譜儀測定矽氧化膜之膜厚後,膜厚為100nm。
將各例之蝕刻液置入燒杯,藉由於室溫(23℃)將前述試驗片浸漬於各例之蝕刻液中5分鐘,進行蝕刻處理。前述蝕刻處理後,將試驗片吹氮氣乾燥,藉由橢圓偏振光譜儀測定矽氧化膜之膜厚。由蝕刻處理前後之矽氧化膜之膜厚,算出對Si之蝕刻速率(Å/min)。結果示於表2。
<蝕刻選擇比之評估>
基於上述「被處理體之蝕刻處理(1)」、「被處理體之蝕刻處理(2)」及「被處理體之蝕刻處理(3)」所得之蝕刻速率的結果,算出被處理體(1)/被處理體(2)之蝕刻選擇比及被處理體(1)/被處理體(3)之蝕刻選擇比。結果示於表2。
由表2所示之結果,確認到實施例1~4之蝕刻液,得到與比較例1~3之蝕刻液為同等以上之SiGe蝕刻選擇比。
特別是確認到摻合了pH調整劑之實施例3及4之蝕刻液,相較於比較例1~3之蝕刻液而言,SiGe蝕刻選擇比有所提高。
<SiGe蝕刻速率之經時安定性之評估>
分別將實施例2之蝕刻液及比較例3之蝕刻液保管於瓶中,對於保管開始起3日後之各蝕刻液,藉由與上述「被處理體之蝕刻處理(1)」同樣之操作,算出對SiGe之蝕刻速率ER3(Å/min)。
又,對於保管開始起7日後之各蝕刻液,藉由與上述「被處理體之蝕刻處理(1)」同樣之操作,算出對SiGe之蝕刻速率ER7(Å/min)。
將上述「被處理體之蝕刻處理(1)」所得之蝕刻速率,作為保管開始起0日後之對SiGe之蝕刻速率ER0。
對於蝕刻速率ER3及蝕刻速率ER7,各自算出距蝕刻速率ER0之變動率(%)。結果示於表3。
由表3所示之結果,確認到實施例2之蝕刻液,即使保管開始起經過7日後,對SiGe之蝕刻速率亦幾乎不變動。
以上,說明了本發明之較佳實施例,但本發明不限定於此等實施例。在不脫離本發明之要旨的範圍,可進行構成之附加、省略、取代,及其他變更。本發明不限定於前述說明,僅被所附的申請專利範圍所限定。
Claims (2)
- 一種蝕刻液,其係相對於Si、Ge及此等之氧化物,用以將通式Si1-xGex表示之化合物(惟,x為超過0且未達1)予以選擇性地蝕刻處理之蝕刻液,其含有過碘酸、氟化物與pH調整劑,且不含有二醇化合物。
- 一種半導體元件之製造方法,其包含使用如請求項1之蝕刻液,將含有通式Si1-xGex表示之化合物的被處理體進行蝕刻處理之步驟。
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