TWI558850B - 電子零件用處理液及電子零件之製造方法 - Google Patents
電子零件用處理液及電子零件之製造方法 Download PDFInfo
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- TWI558850B TWI558850B TW104104725A TW104104725A TWI558850B TW I558850 B TWI558850 B TW I558850B TW 104104725 A TW104104725 A TW 104104725A TW 104104725 A TW104104725 A TW 104104725A TW I558850 B TWI558850 B TW I558850B
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- CRTUOSFUUJRRBS-UHFFFAOYSA-N oxazepine-3-carboxylic acid Chemical compound OC(=O)C1=NOC=CC=C1 CRTUOSFUUJRRBS-UHFFFAOYSA-N 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- SFLGSKRGOWRGBR-UHFFFAOYSA-N phthalane Chemical compound C1=CC=C2COCC2=C1 SFLGSKRGOWRGBR-UHFFFAOYSA-N 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- GYRUCENCQMAGLO-UHFFFAOYSA-N pyrazine-2,6-diamine Chemical compound NC1=CN=CC(N)=N1 GYRUCENCQMAGLO-UHFFFAOYSA-N 0.000 description 1
- CGGUNVYOABLSQD-UHFFFAOYSA-N pyrazine-2,6-dicarboxylic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=N1 CGGUNVYOABLSQD-UHFFFAOYSA-N 0.000 description 1
- NIPZZXUFJPQHNH-UHFFFAOYSA-N pyrazine-2-carboxylic acid Chemical compound OC(=O)C1=CN=CC=N1 NIPZZXUFJPQHNH-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- GRJJQCWNZGRKAU-UHFFFAOYSA-N pyridin-1-ium;fluoride Chemical compound F.C1=CC=NC=C1 GRJJQCWNZGRKAU-UHFFFAOYSA-N 0.000 description 1
- FVLAYJRLBLHIPV-UHFFFAOYSA-N pyrimidin-5-amine Chemical compound NC1=CN=CN=C1 FVLAYJRLBLHIPV-UHFFFAOYSA-N 0.000 description 1
- LTXJLQINBYSQFU-UHFFFAOYSA-N pyrimidin-5-ol Chemical compound OC1=CN=CN=C1 LTXJLQINBYSQFU-UHFFFAOYSA-N 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- YPOXGDJGKBXRFP-UHFFFAOYSA-N pyrimidine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC=N1 YPOXGDJGKBXRFP-UHFFFAOYSA-N 0.000 description 1
- IIVUJUOJERNGQX-UHFFFAOYSA-N pyrimidine-5-carboxylic acid Chemical compound OC(=O)C1=CN=CN=C1 IIVUJUOJERNGQX-UHFFFAOYSA-N 0.000 description 1
- DDWJFSYHYPDQEL-UHFFFAOYSA-N pyrimidine;1h-pyrrole Chemical class C=1C=CNC=1.C1=CN=CN=C1 DDWJFSYHYPDQEL-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 210000004233 talus Anatomy 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- TVRHRBCLLIUJDG-UHFFFAOYSA-N tetrazin-5-amine Chemical compound NC1=CN=NN=N1 TVRHRBCLLIUJDG-UHFFFAOYSA-N 0.000 description 1
- CKQORTPXQDLZGH-UHFFFAOYSA-N tetrazine-5,6-diamine Chemical compound NC1=NN=NN=C1N CKQORTPXQDLZGH-UHFFFAOYSA-N 0.000 description 1
- 150000004905 tetrazines Chemical class 0.000 description 1
- 125000003831 tetrazolyl group Chemical class 0.000 description 1
- 229960004559 theobromine Drugs 0.000 description 1
- FPCZETWWXSJKED-UHFFFAOYSA-N thieno[3,2-b]furan 4-oxide Chemical compound O1C=CC2=C1C=CS2=O FPCZETWWXSJKED-UHFFFAOYSA-N 0.000 description 1
- OWUUTRXDEVQQRX-UHFFFAOYSA-N thieno[3,2-b]thiophene 4-oxide Chemical compound S1C=CC2=C1C=CS2=O OWUUTRXDEVQQRX-UHFFFAOYSA-N 0.000 description 1
- HBZRBRQKAKCIBF-UHFFFAOYSA-N thieno[3,2-b]thiophene-2,5-dithiol Chemical compound S1C(S)=CC2=C1C=C(S)S2 HBZRBRQKAKCIBF-UHFFFAOYSA-N 0.000 description 1
- URIDZSMHANAERU-UHFFFAOYSA-N thieno[3,2-d][1,2]thiazole Chemical compound C1=NSC2=C1C=CS2 URIDZSMHANAERU-UHFFFAOYSA-N 0.000 description 1
- FZXOORLHDQZVHN-UHFFFAOYSA-N thieno[3,4-b]furan Chemical compound S1C=C2OC=CC2=C1 FZXOORLHDQZVHN-UHFFFAOYSA-N 0.000 description 1
- OLMKSAFIRALYGE-UHFFFAOYSA-N thieno[3,4-d][1,2]thiazole Chemical compound S1C=C2C=NSC2=C1 OLMKSAFIRALYGE-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- VCSJAJFSKJCWFG-UHFFFAOYSA-N triazin-5-amine Chemical compound NC1=CN=NN=C1 VCSJAJFSKJCWFG-UHFFFAOYSA-N 0.000 description 1
- UCAJPHQTEWYXEA-UHFFFAOYSA-N triazine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NN=N1 UCAJPHQTEWYXEA-UHFFFAOYSA-N 0.000 description 1
- DLMDGLJCWXETIS-UHFFFAOYSA-N triazine-5-carboxylic acid Chemical compound OC(=O)C1=CN=NN=C1 DLMDGLJCWXETIS-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
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
- C11D3/187—Hydrocarbons aromatic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2096—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3481—Organic compounds containing sulfur containing sulfur in a heterocyclic ring, e.g. sultones or sulfolanes
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
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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
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
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- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
- Weting (AREA)
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Description
本發明為關於在半導體或顯示器裝置等的電子零件之製造步驟中,可在氧化矽等之除去、蝕刻步驟時選擇性保護含有氮之矽化合物之電子零件用處理液,及使用此處理溶液之電子零件之製造方法。
積體電路(LSI)、或在玻璃基板上形成液晶顯示器用等之薄膜電晶體(TFT)之際,係藉由光阻來形成必需的元件構造或電路構造圖型,再藉由蝕刻步驟來將該不需要之部分除去,而得到所希望的元件構造、電路構造,此技術已樹立。
所形成的元件構造、或電路構造,係依照目的之電子裝置而具有各種之構造,近年來亦檢討著以氮化矽膜作為材料的各種構造物。例如,快閃記憶(flas hmemory)元件般的不揮發性記憶(non-volatile memory)元件之製造步驟中,係於半導體基板上形成閘極絕緣膜圖型及閘極電
極圖型。該閘極電極膜一般為以氮化矽膜或多晶矽膜所形成,此時具有將閘極電極圖型間的半導體基板蝕刻以形成溝槽之步驟。
又,DRAM憶體單元之構造亦為採用氮化矽
膜之構造物。例如,堆疊(stack)型憶體單元之情形時,係於P型矽基板上形成元件分離區域,並形成閘極氧化膜與閘極電極。接著,形成源極/汲極區域,進而藉由CVD法等形成絕緣膜,並對此設置接觸(contact)。接下來,成膜多晶矽使具有導電性,藉由進行圖型成形以形成電容器的下部電極,接著,藉由CVD法將薄的氮化矽膜形成於整面。進而,形成多晶矽膜使具有導電性,進行圖型成形以形成電容器的上部電極。接下來,藉由CVD法來形成BPSG膜(絕緣膜),並將用來與數據讀出用位元線連結的接觸,使用周知的光刻法/蝕刻技術來使其開口。最後形成導電性薄膜、BPSG膜(絕緣膜),而形成堆疊型DRAM憶體單元。
又,具備STI構造之元件分離溝的以往的固
體攝影裝置中,於形成光二極體附近的構造時亦使用氮化矽膜。具體而言,於矽基板上形成由氧化矽膜所構成的絕緣膜,於該絕緣膜上形成由氮化矽膜等所構成的保護。在保護上,於元件分離溝的形成區域形成具有開口的阻劑圖型,將此作為遮罩來進行絕緣膜與保護膜之蝕刻,以將矽基板之上面形成露出的開口部。尚,阻劑圖型在開口部之形成後,藉由灰化等予以除去。接著,將保護膜作為遮罩
來進行矽基板之蝕刻,而形成元件分離溝。
更,液晶顯示器等之顯示器裝置中,像素驅
動用TFT(薄膜電晶體)等亦採用氮化矽膜構造。例如具有,將薄膜電晶體的通道部的歐姆接觸層以乾式蝕刻後,局部成膜氮化矽膜的鈍化層等之構造。
如此般地,在各種電子裝置中,氮化矽膜正
急速地被利用著。作為該理由之一,係與氧化矽等以矽及氧為主體的遮罩材料相比時,在耐腐蝕性能方面具有差異性。利用該性質,例如於半導體元件之製造時,可將氮化矽層作為乾式蝕刻的中止層(stopper layer)、腐蝕防止層、遮罩等使用。又,以Low-k材等為代表的含有氧及氟、碳等的其他元素的氧化矽系低介電率絕緣材料,在與該低介電率絕緣材料共存,並藉由該等來進行圖型成形、或將該等使用作為遮罩時,亦有要求著選擇性蝕刻特性之情形。
但,在如此般的蝕刻步驟或洗淨步驟中,所
使用的蝕刻液、洗淨液在腐蝕前述化合物之際,具有產生亦使含有氮之矽膜某程度地被腐蝕等之問題。特以,近年元件的微細構造化,就算是稍微的腐蝕,亦會表現出顯著的負面影響,故期望著更高度的腐蝕防止技術。
日本國特表2004-528716號,係在氮化矽或
氮氧化矽(silicon oxynitride)等之包含矽及氮之材料之濕式蝕刻步驟中,檢討有關蝕刻選擇比之對於如氧化矽般之材料所造成的負面影響。但,於該文獻中所檢討的是,包
含矽及氮之材料之於蝕刻時之如氧化矽般之材料之蝕刻問題,但對於相反的現象則未有記載或教示。而且,解決該問題之構成,係以在溫度25℃至90℃並包含0.001M至0.1M範圍之濃度之氫氟酸之稀薄的氫氟酸(HF)水溶液中來進行蝕刻而已,僅只規定氫氟酸水溶液之溫度及濃度條件。因而,完全未檢討以導入其他的化合物要素來防止腐蝕。
[專利文獻1]日本國特表2004-528716號
本發明之目的為提供一種水溶液,其係(1)可選擇性保護含有氮之矽化合物不受蝕刻、洗淨等之各種處理中所使用的藥液之腐蝕,(2)同時可蝕刻矽,特別是含有氧、碳之矽,(3)可加大含有氮之矽化合物與含有氧之矽化合物之蝕刻速率之差;以及提供使用該水溶液之電子零件之製造方法。
即,上述目的為藉由以下本發明之構成而達成。
[1].一種電子零件用處理液,其係含有以下述式(1)~(3)所表示之陰離子性界面活性劑1種或2種以上之水溶液,
〔式(1)中,R1~R3係表示氫、或碳數1~4之烷基及伸烷基,X1係表示成為陰離子性之離子之官能基〕。
〔式(2)中,R4係表示氫、或碳數1~4之烷基及伸烷基,X2係表示成為陰離子性之離子之官能基,n係表示2以上之自然數〕。
〔式(3)中,R5係表示氫、或碳數1~4之烷基及伸烷基,X3、X4係表示成為陰離子性之離子之官能基〕。
[2].如上述[1]之電子零件用處理液,其中,前述水溶液為pH2~pH6。
[3].如上述[1]或[2]之電子零件用處理液,其中,含有0.001~50質量%之氫氟酸。
[4].如上述[1]~[3]中任一項之電子零件用處理液,其中,前述氫氟酸為溶解水溶性氟化物鹽而得到。
[5].如上述[1]~[4]中任一項之電子零件用處理液,其中,進而含有佔有面積為較萘環小的環式化合物。
[6].如上述[5]之電子零件用處理液,其中,前述環式化合物為以下述式(4)、(5)、(6)或(7)所表示之化合物,
〔式(4)中,a1、a2、a3、a4及a5係表示至少
1種以上的碳、氮、氧、硫、磷原子之任一者,該等5個構成要素係藉由在接鄰的構成要素間以具有任意的化學鍵結而形成環式構造,並於使用條件下展示出芳香族性之環式化合物,又,a1、a2、a3、a4及a5亦可進而與官能基鍵結,又,亦可為該等之聚合物〕。
〔式(5)中,b1、b2、b3、b4、b5及b6係表
示至少1種以上的碳、氮、氧、硫、磷原子之任一者,該等6個構成係藉由在接鄰的構成要素間以具有任意的化學鍵結而形成環式構造,並於使用條件下展示出芳香族性之環式化合物,又,b1、b2、b3、b4、b5及b6亦可進而與官能基鍵結,又,亦可為該等之聚合物〕。
〔式(6)中,c1、c2、c3、c4、c5、c6、c7、
c8及c9係表示至少1種以上的碳、氮、氧、硫、磷原子之任一者,該等9個構成係藉由在接鄰的構成要素間以具有任意的化學鍵結而形成環式構造,並於使用條件下展示出芳香族性之環式化合物,又,c1、c2、c3、c4、c5、c6、c7、c8及c9亦可進而與官能基鍵結,又,亦可為該等之聚合物〕。
〔式(7)中,d1、d2、d3、d4、d5、d6、d7及
d8係表示至少1種以上的碳、氮、氧、硫、磷原子之任一者,該等8個構成係藉由在接鄰的構成要素間以具有任意的化學鍵結而形成環式構造,並於使用條件下展示出芳香族性之環式化合物,又,d1、d2、d3、d4、d5、d6、d7及d8亦可進而與官能基鍵結〕。
[7].如上述[5]或[6]之電子零件用處理液,其中,含有0.001質量%以上之前述環式化合物。
[8].如上述[1]~[7]中任一項之電子零件用處理液,其中,含有0.001質量%~2質量%之前述陰離子性界面活性劑。
[9].如上述[1]~[8]中任一項之電子零件用處理液,其中,前述水溶液中含有由弱酸與鹼性物質(alkaline species)所構成之緩衝劑。
[10].如上述[1]~[9]中任一項之電子零件用處理液,其中,進而含有能與水混和之有機溶劑。
[11].如上述[1]~[10]中任一項之電子零件用處理液,其中,使用於具有以含有氮之矽化合物作為構成材料之構造物與以不包含氮之矽化合物作為構成材料之構造物之電子零件。
[12].一種電子零件之製造方法,其係具有使用上述[1]~[10]中任一項之電子零件用處理液來進行電子零件之蝕刻或洗淨處理之步驟。
[13].如上述[12]之電子零件之製造方法,其中,前述電
子零件具有以含有氮之矽化合物作為構成材料之構造物與以不包含氮之矽化合物作為構成材料之構造物。
藉由本發明,可提供一種水溶液,其係可選擇性保護含有氮之矽化合物不受藥液乃至處理液(特以含有氟酸等之酸之藥液)之腐蝕,同時可蝕刻含有氧、碳但不含有氮之矽,可加大含有氮之矽化合物與含有氧、碳但不含有氮之矽化合物之蝕刻速率之比,進而亦提供使用該水溶液之電子零件之製造方法。
本發明之電子零件用處理液,其係含有以上述式(1)~(3)所表示之陰離子性界面活性劑1種或2種以上之水溶液。藉由將如此般的處理液使用於蝕刻、洗淨等之電子零件之處理,可選擇性防止含有氮之矽化合物之腐蝕。本發明之處理液,藉由附加賦予因應使用目的之機能之成分,可使用於蝕刻、洗淨、其他所需的各種處理。
對於以式(1)所表示之化合物進行說明。式(1)具有萘骨架,並於各苯環具有分別的取代基R1及R2、R3及X1。式中,R1~R3係表示氫、或碳數1~4之烷基及伸烷基。作為以R1~R3所表示之烷基,較佳為碳數1~4者,可為直鏈狀或具有分支者。又,亦可進而具有取代
基。作為以R1~R3所表示之烷基,具體而言舉例如-CH3、-CH2CH3、-CH2=CH2、-CH(CH3)2、-CH(CH3)3、-CH2CH2CH3等,該等之中較佳為異丙基“-CH(CH3)2”。R1~R3可為相同或相異。
X1係表示成為陰離子性之離子之官能基。亦即,式(1)之化合物藉由上述疏水性的R1~R3、與親水性的X1,而發揮機能作為陰離子系界面活性劑。因此,X係以可機能作為如此般的界面活性劑之官能基為較佳。具體而言,如-SO3 -、-OSO3 -、-COO-、-P(O-)2O、-CH2SO3 -、-CH2COO-之任一者,特佳為-SO3 -、-OSO3 -、-P(O-)2O之任一者。
作為以式(1)所表示之化合物之具體例,舉例如萘磺酸、烷基萘磺酸、烷基萘磺酸鈉、萘羧酸、2-甲基-1-萘羧酸、單異丙基萘磺酸、二異丙基萘磺酸、三異丙基萘磺酸、二丁基萘磺酸等。
對於以式(2)所表示之化合物進行說明。式(2)具有萘骨架之單體,並藉由“-CH2-”來連結各單體並聚合。於萘之一方之苯環具有取代基R4。又,於萘之另一方之苯環具有取代基X2,取代基R4及取代基X2係與上述R1、X1同義。表示重複數的n為2以上之自然數,雖然未特別規定但通常為n=2~50左右。
作為以式(2)所表示之化合物之具體例,舉例如萘磺酸甲醛縮合物(naphthalenesulfonic acid formalin condensate)等。
對於以式(3)所表示之化合物進行說明。式(3)具有二苯基醚骨架,並於各苯環具有分別的取代基R5及X3、X4。取代基R5及X3可相互排他地僅存在於一方,或可存在於雙方的苯環。取代基R5及X3、X4係與上述R1、X1同義,X3、X4可為相同或相異。
作為以式(3)所表示之化合物之具體例,舉例如:烷基二苯基醚磺酸及其鹽(例如,烷基二苯基醚磺酸鈉、烷基二苯基醚二磺酸鈉等)、十二烷基二苯基醚二磺酸及其鹽(例如,十二烷基二苯基醚二磺酸鈣等)。
以式(1)~(3)所表示之化合物,只要是含有至少任一種之1種以上即可,可含有單獨1種,亦可含有任意2種,或亦可含有全部。該等之中特佳為式(1),以式(1)之化合物單獨或式(1)之化合物與其他之化合物之組合為佳。
本發明之以式(1)~(3)表示之化合物,可添加於蝕刻溶液、洗淨溶液、潤濕溶液等的電子裝置之處理液中使用。該添加量,以式(1)~(3)表示之化合物之總量,相對於添加的溶液全量而言為0.001質量%以上,較佳為0.001~2質量%,又較佳為0.001~0.5質量%。添加量少時,防腐蝕效果會降低,過多時雖然不會對於效果造成負面影響,但潤濕所需要的時間會增加,故成本面為不利。
本發明之添加劑,如上述般係添加於電子裝置之處理溶液中使用。作為如此般的處理溶液,較佳為水溶液,特以未滿pH7,又較佳為未滿pH6的酸性水溶液為
佳。作為如此般的酸性水溶液,只要是含有在半導體或液晶裝置等的電子裝置製造步驟中一般所使用之酸之水溶液即可,未有特別限定者。具體而言,舉例如含有氟酸、鹽酸、磷酸、硝酸、及該等酸之組合之1種或2種以上,或將過氧化氫水添加於該等之水溶液。該等酸之濃度,只要是使用於該種處理液之周知濃度範圍即可,以因應所需要的溶液之機能或性能來使用即可。
特以本發明中,以可取得含有氧但不含有氮
之矽化合物、與含有氮之矽化合物之大的蝕刻比為特徵,故較佳為使用於具有該等材料之裝置之處理之處理液。作為如此般的處理液,特佳為含有氟酸之水溶液。作為溶液中的氟酸之含有量,較佳為0.001~50質量%,又較佳為0.01~20質量%。
為使氟酸添加於溶液中,亦可以氟化氫
(hydrogen fluoride)之形態來進行添加,但通常以氫氟酸(hydrofluoric acid)之形態來添加使用。又,亦可使用水溶性氟化鹽等,如此般的鹽之中特佳為氟化銨。氟化銨通常為以NH4F所表示之鹽,但亦可為以(NH4)HF2所表示之氫氟化銨。通常而言,使氟化銨溶解時,於溶液中來自於此的氟酸與銨離子、氨會以等莫耳量存在。氟化銨之含有量較佳為0.00185~40質量%,又較佳為0.00185~37質量%。更,以使氟酸成為過剩之方式,可單獨添加氟酸,亦可添加其他添加物。
本發明中,除了以上述式(1)~(3)表示之陰離
子性界面活性劑以外,以進而含有較式(1)~(3)佔有面積為小的分子,亦即,環狀構造部分之分子面積為較萘之分子面積小的環式化合物為宜。在此所謂的分子面積,係環狀構造部分之佔有面積。如此般地,藉由導入佔有面積為小的化合物,該化合物以填埋佔有面積為較大的式(1)~(3)表示之化合物之間隙之方式,來配置、配列於保護對象物之表面、周圍等,因而認為使得對於藥液之保護作用提昇、並提昇防腐蝕性。當前述分子面積乃至佔有面積為不明確時,只要使用構成基本骨架之元素數量為較萘少的化合物即可。比較大小之對象,可設為作為共存的式(1)~(3)表示之化合物,但以使用與此約略為相同或較此為小的萘為便利。
又,該等之化合物以在使用條件下為展示出
芳香族性者為較佳。該情形時,並非一定要化合物本身為展示出芳香族性,亦可在使用條件下藉由構成化合物之構成元素之一部份或全部之電子狀態產生變化,來展示出芳香族性。電子狀態之變化,不論該過程之種類為何,可任意為釋能過程或吸能過程。一般而言,舉例如:藉由解離所致的離子化、藉由化學反應所致的鍵結變化、外加電壓、或照射光、電子、等離子等。
更,該等之化合物可於環式構造中包含雜原
子,環式構造之構成元素亦可與構成環式構造之其他以外之元素來進行鍵結。亦即,環式化合物可具有官能基,不論該種類為何皆可。假設,即便是藉由導入官能基而成為
欠缺水溶性之情形時,藉由上述化合物(1)~(3)而產生可溶化之可能性為高,倘若仍未能溶解時,可適當添加有機溶劑。
該等之化合物可透過分子構造上的任意元素
或官能基來聚合。聚合物無需在調合溶液之時間點為已形成,亦可於調合後、使用前或使用中藉由任意的化學反應來形成。所謂的任意的化學反應,舉例如脫水縮合或電解聚合等,但不論該化學反應之種類為何皆可。又,該化學反應可任意為釋能過程或吸能過程。
作為如此般的環式化合物,只要是能滿足上
述條件,未有特別限定者,但較佳為5員環單獨之化合物、6員環單獨之化合物、5員環與4員環經縮合之化合物、或5員環與6員環經縮合之化合物,特佳為,具有茚烷骨架的以式(6)所表示之化合物、或以式(4)所表示之化合物。又,視情況亦可使用組合5員環彼此之化合物。
對於式(4)之環式化合物進行說明時,構成要
素之a1、a2、a3、a4及a5係表示至少1種以上的碳、氮、氧、硫、磷原子之任一者,該等元素通常係以單獨而成為各構成要素,但亦可組合2以上的元素。又,各構成要素可為相同或相異者。該等5個構成要素係在接鄰的構成要素間具有化學鍵結,但不論該種類為何皆可。又,a1、a2、a3、a4及a5可進而與官能基鍵結,不論進行鍵結的官能基之種類為何皆可。該化合物係藉由前述5個構成要素而形成環式構造。
式(4)之環式化合物係於使用條件下展示出芳
香族性。作為該化合物展示出芳香族性之條件,例如除了該化合物本身為展示出芳香族性之情形外,可考慮如:a1、a2、a3、a4及a5之元素(原子)之離子化或自由基化;a1、a2、a3、a4及a5之元素(原子)之鍵結種類之變化;a1、a2、a3、a4及a5之元素(原子)上所鍵結的原子或官能基之脫離;a1、a2、a3、a4及a5之元素(原子)上所鍵結的原子或官能基之鍵結種類之變化;a1、a2、a3、a4及a5之元素(原子)上所鍵結的原子之離子化或自由基化;a1、a2、a3、a4及a5之元素(原子)上所鍵結的官能基之離子化或自由基化;a1、a2、a3、a4及a5之元素(原子)上所鍵結的官能基之氧化或還原等的化學變化;來自外界的光、電磁波之照射、外加電壓等,不論該種類及過程為何皆可。
作為以式(4)所表示之環式化合物,相當於吡
咯、吡咯基鹽、吡咯衍生物、苯基吡咯、苯衍生物吡咯加成物、苯吡咯衍生物加成物、吡咯基吡啶、吡咯基嘧啶、吡咯基嗒、吡咯基三嗪、吡啶吡咯衍生物加成物、嘧啶吡咯衍生物加成物、嗒吡咯衍生物加成物、***吡咯衍生物加成物、吡咯吡啶衍生物加成物、吡咯三嗪衍生物加成物、吡咯嘧啶衍生物加成物、吡咯嗒衍生物加成物、吡唑、吡唑基鹽、吡唑衍生物、苯基吡唑、苯衍生物吡唑加成物、吡唑衍生物苯加成物、吡唑基吡啶、吡唑衍生物吡啶加成物、吡啶衍生物吡唑加成物、吡唑基三嗪、吡唑
衍生物三嗪加成物、三嗪衍生物吡唑加成物、吡唑基嘧啶、吡唑衍生物嘧啶加成物、嘧啶衍生物吡唑加成物、吡唑基嗒、吡唑衍生物嗒加成物、嗒衍生物吡唑加成物、咪唑、咪唑基鹽、咪唑衍生物、苯基咪唑、苯衍生物咪唑加成物、咪唑衍生物苯加成物、咪唑基吡啶、咪唑衍生物吡啶加成物、吡啶衍生物咪唑加成物、咪唑基三嗪、咪唑衍生物三嗪加成物、三嗪衍生物咪唑加成物、咪唑基嘧啶、咪唑衍生物嘧啶加成物、嘧啶衍生物咪唑加成物、咪唑基嗒、咪唑衍生物嗒加成物、嗒衍生物咪唑加成物、***、***基鹽、***衍生物、苯基***、苯衍生物***加成物、***衍生物苯加成物、***基吡啶、***衍生物吡啶加成物、吡啶衍生物***加成物、***基三嗪、***衍生物三嗪加成物、三嗪衍生物***加成物、***基嘧啶、***衍生物嘧啶加成物、嘧啶衍生物***加成物、***基嗒、***衍生物嗒加成物、嗒衍生物***加成物、四唑、四唑基鹽、四唑衍生物、苯基四唑、苯衍生物四唑加成物、四唑衍生物苯加成物、四唑基吡啶、四唑衍生物吡啶加成物、吡啶衍生物四唑加成物、四唑基三嗪、四唑衍生物三嗪加成物、三嗪衍生物四唑加成物、四唑基嘧啶、四唑衍生物嘧啶加成物、嘧啶衍生物四唑加成物、四唑基嗒、四唑衍生物嗒加成物、嗒衍生物四唑加成物、五唑、五唑基鹽、五唑衍生物、苯基五唑、苯衍生物五唑加成物、五唑衍生物苯加成物、五唑基吡啶、五唑衍生物吡啶加成物、吡啶衍生物五唑加成物、五
唑基三嗪、五唑衍生物三嗪加成物、三嗪衍生物五唑加成物、五唑基嘧啶、五唑衍生物嘧啶加成物、嘧啶衍生物五唑加成物、五唑基嗒、五唑衍生物嗒加成物、嗒衍生物五唑加成物、呋喃、呋喃衍生物、苯基呋喃、苯衍生物呋喃加成物、呋喃衍生物苯加成物、呋喃基吡啶、呋喃衍生物吡啶加成物、吡啶衍生物呋喃加成物、呋喃基三嗪、呋喃衍生物三嗪加成物、三嗪衍生物呋喃加成物、呋喃基嘧啶、呋喃衍生物嘧啶加成物、嘧啶衍生物呋喃加成物、呋喃基嗒、呋喃衍生物嗒加成物、嗒衍生物呋喃加成物、噻吩、噻吩衍生物、苯基噻吩、苯衍生物噻吩加成物、噻吩衍生物苯加成物、苯硫基吡啶、噻吩衍生物吡啶加成物、吡啶衍生物噻吩加成物、苯硫基三嗪、噻吩衍生物三嗪加成物、三嗪衍生物噻吩加成物、苯硫基嘧啶、噻吩衍生物嘧啶加成物、嘧啶衍生物噻吩加成物、苯硫基嗒、噻吩衍生物嗒加成物、嗒衍生物噻吩加成物、噻吩聚合物、噁唑、噁唑衍生物、苯基噁唑、苯衍生物噁唑加成物、噁唑衍生物苯加成物、噁唑基吡啶、噁唑衍生物吡啶加成物、吡啶衍生物噁唑加成物、噁唑基三嗪、噁唑衍生物三嗪加成物、三嗪衍生物噁唑加成物、噁唑基嘧啶、噁唑衍生物嘧啶加成物、嘧啶衍生物噁唑加成物、噁唑基嗒、噁唑衍生物嗒加成物、嗒衍生物噁唑加成物、噻唑、噻唑衍生物、苯基噻唑、苯衍生物噻唑加成物、噻唑衍生物苯加成物、噻唑基吡啶、噻唑衍生物吡啶加成物、吡啶衍生物噻唑加成物、噻唑基三嗪、噻唑
衍生物三嗪加成物、三嗪衍生物噻唑加成物、噻唑基嘧啶、噻唑衍生物嘧啶加成物、嘧啶衍生物噻唑加成物、噻唑基嗒、噻唑衍生物嗒加成物、嗒衍生物噻唑加成物、噁二唑、噁二唑衍生物、苯基噁二唑、苯衍生物噁二唑加成物、噁二唑衍生物苯加成物、噁二唑基吡啶、噁二唑衍生物吡啶加成物、吡啶衍生物噁二唑加成物、噁二唑基三嗪、噁二唑衍生物三嗪加成物、三嗪衍生物噁二唑加成物、噁二唑基嘧啶、噁二唑衍生物嘧啶加成物、嘧啶衍生物噁二唑加成物、噁二唑基嗒、噁二唑衍生物嗒加成物、嗒衍生物噁二唑加成物等,具體而言可舉例如:1H-咪唑、1-甲基咪唑、2甲基咪唑、1,2-二甲基咪唑、2-苯基咪唑、1H-吡唑、1,2,3-***、1,2,4-***、1,2,3,4-四唑、5-苯基四唑、咪唑咻、組胺酸、三噻吩、聚噻吩等。
將上述所例示的以式(4)所表示之環式化合物
之代表性具體構造表示於下述內容中,但本發明並不限定於該等。
對於式(5)之環式化合物進行說明時,構成要
素之b1、b2、b3、b4、b5及b6係表示至少1種以上的碳、氮、氧、硫、磷原子之任一者,該等元素通常係以單獨而成為各構成要素,但亦可組合2以上的元素。該等6個構成要素係在接鄰的構成要素間具有化學鍵結,但不論該種類為何皆可。其他構成與上述a1、a2、a3、a4及a5為相同。
式(5)之環式化合物,在與上述式(4)之化合物
以相同之使用條件下亦為展示出芳香族性。作為該化合物展示出芳香族性之條件,與上述式(4)之化合物為相同,除了該化合物本身為展示出芳香族性之情形外,可考慮如:b1、b2、b3、b4、b5及b6之元素(原子)之離子化或自由基化;b1、b2、b3、b4、b5及b6之元素之鍵結種類之變化;b1、b2、b3、b4、b5及b6之元素上所鍵結的原子或官能基之脫離;b1、b2、b3、b4、b5及b6之元素上所鍵結的原子或官能基之鍵結種類之變化;1~6位之元素上所鍵結的原子之離子化或自由基化;b1、b2、b3、b4、b5及b6之元素上所鍵結的官能基之離子化或自由基化;b1、b2、b3、b4、b5及b6之元素上所鍵結的官能基之氧化或還原等的化學變化;來自外界的光、電磁波之照射、外加電壓等,不論該種類及過程為何皆可。
作為以式(5)所表示之環式化合物,相當於吡
啶、吡啶鎓鹽、吡啶衍生物、嗒、嗒衍生物、嘧啶、嘧啶衍生物、吡嗪、吡嗪衍生物、三嗪、三嗪衍生物、四嗪、四嗪衍生物、吡喃、吡喃衍生物、戴奧辛、戴奧辛衍
生物、噻喃、噻喃衍生物、二噻(dithiin)、二噻衍生物、氧硫雜環己二烯(oxathiin)、氧硫雜環己二烯衍生物、苯衍生物、苯胺、苯胺衍生物、苯甲酸、苯甲酸衍生物、鄰苯二甲酸、鄰苯二甲酸衍生物、酚、酚衍生物、多元酚、多元酚衍生物、黃烷、類黃酮、類香草素等,具體而言可舉例如:吡啶、嗒、嘧啶、吡嗪、1,2,3-三嗪、1,2,4-三嗪、1,3,5-三嗪、1,2,3,4-四嗪、1,2,4,5-四嗪、1,2,3,5-四嗪、2H-吡喃、1,4-戴奧辛、1,2-戴奧辛、4H-1,3-戴奧辛、2H-噻喃、1,4-二噻、1,2-二噻、4H-1,3-二噻、1,2-氧硫雜環己二烯、1,4-氧硫雜環己二烯、4H-1,3-氧硫雜環己二烯、苯甲酸、菸鹼酸、異菸鹼酸、吡啶-3-胺、吡啶-4-胺、吡啶-3-醇、吡啶-4-醇、3-苯基吡啶、4-苯基吡啶、吡啶氟化物、嗒-4-羧酸、嗒-3-羧酸、嗒-4-胺、嗒-3-胺、嗒-4-醇、嗒-3-醇、3-苯基嗒、4-苯基嗒、嘧啶-4-羧酸、嘧啶-5-羧酸、嘧啶-4-胺、嘧啶-4-胺、嘧啶-5-胺、嘧啶-4-醇、嘧啶-5-醇、4-苯基嘧啶、5-苯基嘧啶、吡嗪-2-羧酸、吡嗪-2,6-二羧酸、吡嗪-2-胺、吡嗪-2,6-二胺、吡嗪-2-醇、吡嗪-2,6-二醇、2-苯基吡嗪、三嗪-4-羧酸、三嗪-5-羧酸、三嗪-5-胺、三嗪-4-胺、三嗪-5-醇、三嗪-4-醇、5-苯基三嗪、4-苯基三嗪、1,2,4-三嗪-3-羧酸、1,2,4-三嗪-6-羧酸、1,2,4-三嗪-5-羧酸、1,2,4-三嗪-3-胺、1,2,4-三嗪-6-胺、1,2,4-三嗪-5-胺、1,2,4-三嗪-3-醇、1,2,4-三嗪-6-醇、1,2,4-三嗪-5-醇、3-苯基-1,2,4-三嗪、6-苯基-1,2,4-三嗪、5-苯基-1,2,4-三嗪、
1,3,5-三嗪-2-羧酸、1,3,5-三嗪-2,4-二羧酸、1,3,5-三嗪-2,4,6-三乙酸、1,3,5-三嗪-2-胺、1,3,5-三嗪-2,4-二胺、1,3,5-三嗪-2-醇、1,3,5-三嗪-2,4-二醇、2-苯基-1,3,5-三嗪、2,4-二苯基-1,3,5-三嗪、2,4,6-三苯基-1,3,5-三嗪、四嗪-5-胺、四嗪-5,6-二胺、四嗪-5-醇、5-苯基四嗪、5,6-二苯基四嗪、1,2,4,5-四嗪-3-羧酸、1,2,4,5-四嗪-3,6-二羧酸、1,2,4,5-四嗪-3-胺、1,2,4,5-四嗪-3,6-二胺、1,2,4,5-四嗪-3-醇、1,2,4,5-四嗪-3,6-二醇、3-苯基-1,2,4,5-四嗪、3,6-二苯基-1,2,4,5-四嗪、1,2,3,5-四嗪-4-羧酸、1,2,3,5-四嗪-4,6-二羧酸、1,2,3,5-四嗪-4-胺、1,2,3,5-四嗪-4,6-二胺、1,2,3,5-四嗪-4-醇、1,2,3,5-四嗪-4,6-二醇、4-苯基-1,2,3,5-四嗪、4,6-二苯基-1,2,3,5-四嗪、2H-吡喃-2-羧酸、2H-吡喃-3-羧酸、2H-吡喃-4-羧酸、2H-吡喃-2,6-二羧酸、2H-吡喃-3,5-二羧酸、2H-吡喃-3,5-二羧酸、2H-吡喃-2-胺、2H-吡喃-2-胺、2H-吡喃-3-胺、2H-吡喃-4-胺、2H-吡喃-2,6-二胺、2H-吡喃-3,5-二胺、2H-吡喃-2-醇、2H-吡喃-3-醇、2H-吡喃-4-醇、2H-吡喃-2,6-二醇、2H-吡喃-3,5-二醇、2-苯基-2H-吡喃、3-苯基-2H-吡喃、4-苯基-2H-吡喃、2,6-二苯基-2H-吡喃、3,5-二苯基-2H-吡喃、1,4-戴奧辛-2-羧酸、1,4-戴奧辛-2,3-二羧酸、1,4-戴奧辛-2,6-二羧酸、1,4-戴奧辛-2-胺、1,4-戴奧辛-2,3-二胺、1,4-戴奧辛-2,6-二胺、1,4-戴奧辛-2-醇、1,4-戴奧辛-2,3-二醇、1,4-戴奧辛-2,6-二醇、2-苯基-1,4-戴奧辛、2,3-二苯基-1,4-戴奧辛、戴奧辛-3-羧酸、戴奧辛-4-羧酸、戴奧辛-3-
醇、4H-1,3-戴奧辛-5-胺、4H-1,3-戴奧辛-5-醇、4-苯基-4H-1,3-戴奧辛、2H-噻喃-3-羧酸、2H-噻喃-4-羧酸、2H-噻喃-6-胺、2H-噻喃-5,6-二胺、2H-噻喃-4-胺、2H-噻喃-6-醇、2H-噻喃-3-醇、2H-噻喃-4-醇、2H-噻喃-4-硫醇基、3-苯基-2H-噻喃、2,6-二苯基-2H-噻喃、1,4-二噻-2-羧酸、1,4-二噻-2,3-二羧酸、2,6-二苯基-1,4-二噻、2,5-二苯基-1,4-二噻、二噻-4-羧酸、二噻-3,4-二羧酸、二噻-3,6-二胺、二噻-4,5-二醇、3,6-二苯基二噻、2-乙烯基-4H-1,3-二噻、氧硫雜環己二烯-3-羧酸、氧硫雜環己二烯-3,4-二胺、6-苯基氧硫雜環己二烯、3,4-二苯基氧硫雜環己二烯、1,4-氧硫雜環己二烯-2-羧酸、2-甲基-1,4-氧硫雜環己二烯、3-甲基-1,4-氧硫雜環己二烯、2-苯基-1,4-氧硫雜環己二烯、3-苯基-1,4-氧硫雜環己二烯、2,3-二苯基-1,4-氧硫雜環己二烯、黃酮、兒茶素、香草醛、香草酸、阿魏酸、乙基香草醛、2,3-二羥基苯甲酸、2,4-二羥基苯甲酸、2,5-二羥基苯甲酸、2,6-二羥基苯甲酸、3,4-二羥基苯甲酸、3,5-二羥基苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、苯-1,3,5-三乙酸、苯-1,2,4-三乙酸、苯-1,2,3-三乙酸、苯甲醛、硝基苯、甲基-2-羥基苯甲酸、2-羥基苯甲酸、苯基乙酸酯、4-胺基苯硫酚、苯磺酸、4-(4-胺基苯基)二磺醯基苯胺、苯基乙醯胺、乙醯基水楊酸、苦味酸、苯胺、苯-1,2-二胺、苯-1,4-二胺、苯-1,3-二胺、苯-1,3,5-三胺、苯-1,2,4-三胺、苯-1,2,3-三胺、酚、苯-1,2-二醇、苯-1,4-二醇、苯-1,3-二
醇、苯-1,3,5-三醇、苯-1,2,4-三醇、苯-1,2,3-三醇、2-胺基酚、4-胺基酚、3-胺基酚、苯基丙胺酸、酪胺酸等。
將上述所例示的以式(5)所表示之環式化合物之代表性具體構造表示於下述內容中,但本發明並不限定於該等。
對於式(6)之環式化合物進行說明時,構成要
素(元素)之c1、c2、c3、c4、c5、c6、c7、c8及c9係表示至少1種以上的碳、氮、氧、硫、磷原子之任一者,該等元素通常係以單獨而成為各構成要素,但亦可組合2以上的元素。構成要素c1、c2及c3、以及構成要素c5、
c6、c7、c8係在接鄰的構成要素彼此間具有化學鍵結,構成要素c4及c9係視為接鄰,在接鄰的3個構成要素間為具有化學鍵結,但不論該等化學鍵結種類為何皆可。然後,藉由該等9個構成要素來形成環式構造,而成為5員環與6員環鍵結之形態。其他構成與上述式(4)及a1、a2、a3、a4及a5為相同。
式(6)之環式化合物,在與上述式(4)之化合物
以相同之使用條件下亦為展示出芳香族性。作為該化合物展示出芳香族性之條件,與上述式(4)之化合物為相同,除了該化合物本身為展示出芳香族性之情形外,可考慮如:c1、c2、c3、c4、c5、c6、c7、c8及c9之元素(原子)之離子化或自由基化;c1、c2、c3、c4、c5、c6、c7、c8及c9之元素之鍵結種類之變化;c1、c2、c3、c4、c5、c6、c7、c8及c9之元素上所鍵結的原子或官能基之脫離;c1、c2、c3、c4、c5、c6、c7、c8及c9之元素上所鍵結的原子或官能基之鍵結種類之變化;c1、c2、c3、c4、c5、c6、c7、c8及c9之元素上所鍵結的原子之離子化或自由基化;c1、c2、c3、c4、c5、c6、c7、c8及c9之元素上所鍵結的官能基之離子化或自由基化;c1、c2、c3、c4、c5、c6、c7、c8及c9之元素上所鍵結的官能基之氧化或還原等的化學變化;來自外界的光、電磁波之照射、外加電壓等,不論該種類及過程為何皆可。
作為以式(6)所表示之環式化合物,相當於苯
并呋喃、苯并呋喃衍生物、二氫苯并呋喃、二氫苯并呋喃
衍生物、四氫苯并呋喃、四氫苯并呋喃衍生物、吲哚、吲哚衍生物、二氫吲哚、二氫吲哚衍生物、四氫吲哚、四氫吲哚衍生物、苯并噻吩、苯并噻吩衍生物、二氫苯并噻吩、二氫苯并噻吩衍生物、四氫苯并噻吩、四氫苯并噻吩衍生物、吲、吲衍生物、苯并咪唑、苯并咪唑衍生物、吲唑、吲唑衍生物、苯并二氧環(benzodioxole)、苯并二氧環衍生物、苯并二吩(benzodithiole)、苯并二吩衍生物、苯并噁唑、苯并噁唑衍生物、二氫苯并噁唑、二氫苯并噁唑衍生物、苯并噻唑、苯并噻唑衍生物、二氫苯并噻唑、二氫苯并噻唑衍生物、苯并氧硫雜環戊烷(benzoxathiole)、苯并氧硫雜環戊烷衍生物、二氫苯并氧硫雜環戊烷、二氫苯并氧硫雜環戊烷衍生物、苯并***、苯并***衍生物、二氫苯并***、二氫苯并***衍生物、四氫苯并***、四氫苯并***衍生物、苯并噁二唑、苯并噁二唑衍生物、二氫苯并噁二唑、二氫苯并噁二唑衍生物、四氫苯并噁二唑、四氫苯并噁二唑衍生物、苯并噻二唑、苯并噻二唑衍生物、二氫苯并噻二唑、二氫苯并噻二唑衍生物、四氫苯并噻二唑、四氫苯并噻二唑衍生物、嘌呤、嘌呤衍生物、鄰苯二甲醯亞胺、鄰苯二甲醯亞胺衍生物、鄰苯二甲酸酐、鄰苯二甲酸酐衍生物等,具體而言可舉例如:1-苯并呋喃、2-苯并呋喃、2,3-二氫-1-苯并呋喃、1,3-二氫-2-苯并呋喃、2,3,3a,7a-四氫-1-苯并呋喃、1,3,3a,7a-四氫-2-苯并呋喃、1H-吲哚、2H-異吲哚、色胺酸、2,3-二氫-1H-吲哚、2,3-二氫-1H-異吲哚、2,3,3a,7a-
四氫-1H-吲哚、2,3,3a,7a-四氫-1H-異吲哚、1-苯并噻吩、2-苯并噻吩、2,3-二氫-1-苯并噻吩、1,3-二氫-2-苯并噻吩、2,3,3a,7a-四氫-1-苯并噻吩、1,3,3a,7a-四氫-2-苯并噻吩、吲、1H-苯并咪唑、1H-吲唑、1,3-苯并二氧環、3H-1,2-苯并二氧環、1,3-苯并二吩、3H-1,2-苯并二吩、1,3-苯并噁唑、1,2-苯并噁唑、2,1-苯并噁唑、2,3-二氫-1,3-苯并噁唑、2,3-二氫-1,2-苯并噁唑、1,3-二氫-2,1-苯并噁唑、1,3-苯并噻唑、1,2-苯并噻唑、2,1-苯并噻唑、2,3-二氫-1,3-苯并噻唑、2,3-二氫-1,2-苯并噻唑、1,3-二氫-2,1-苯并噻唑、1,3-苯并氧硫雜環戊烷、3H-2,1-苯并氧硫雜環戊烷、3H-1,2-苯并氧硫雜環戊烷、3a,7a-二氫-1,3-苯并氧硫雜環戊烷、3a,7a-二氫-3H-2,1-苯并氧硫雜環戊烷、3a,7a-二氫-3H-1,2-苯并氧硫雜環戊烷、1H-苯并***、1-羥基苯并***、3a,7a-二氫-1H-苯并***、2,3,3a,7a四氫-1H-苯并***、2,1,3-苯并噁二唑、1,2,3-苯并噁二唑、1,3-二氫-2,1,3-苯并噁二唑、3a,7a-二氫-1,2,3-苯并噁二唑、1,3,3a,7a-四氫-2,1,3-苯并噁二唑、2,3,3a,7a-四氫-1,2,3-苯并噁二唑、2,1,3-苯并噻二唑、1,2,3-苯并噻二唑、1,3-二氫-2,1,3-苯并噻二唑、3a,7a-二氫-1,2,3-苯并噻二唑、1,3,3a,7a-四氫-2,1,3-苯并噻二唑、2,3,3a,7a-四氫-1,2,3-苯并噻二唑、9H-嘌呤、腺嘌呤、鳥嘌呤、次黃嘌呤、黃嘌呤、可可鹼、咖啡因、尿酸、異鳥嘌呤、鄰苯二甲醯亞胺、鄰苯二甲酸酐等。
將上述所例示的以式(6)所表示之環式化合物
之代表性具體構造表示於下述內容中,但本發明並不限定於該等。
對於式(7)之環式化合物進行說明時,構成要素(元素)之d1、d2、d3、d4、d5、d6、d7及d8係表示至少1種以上的碳、氮、氧、硫、磷原子之任一者,該等元素通常係以單獨而成為各構成要素,但亦可組合2以上的元素。構成要素d1、d2、d4、d5、d6及d8係在接鄰的構成要素彼此間具有化學鍵結,構成要素d3及d7係視為接鄰,在接鄰的3個構成要素間為具有化學鍵結,但不論該等化學鍵結種類為何皆可。然後,藉由該等8個構成要素來形成環式構造,而成為5員環與5員環鍵結之形態。其他構成與上述式(4)及a1、a2、a3、a4及a5為相同。
式(7)之環式化合物,在與上述式(4)之化合物以相同之使用條件下亦為展示出芳香族性。作為該化合物展示出芳香族性之條件,與上述式(4)之化合物為相同,除了該化合物本身為展示出芳香族性之情形外,可考慮如:d1、d2、d3、d4、d5、d6、d7及d8之元素(原子)之離子化或自由基化;d1、d2、d3、d4、d5、d6、d7及d8之元素之鍵結種類之變化;1~8位之元素上所鍵結的原子或官能基之脫離;d1、d2、d3、d4、d5、d6、d7及d8之元素上所鍵結的原子或官能基之鍵結種類之變化;d1、d2、d3、d4、d5、d6、d7及d8之元素上所鍵結的原子之離子化或自由基化;d1、d2、d3、d4、d5、d6、d7及d8之元素上所鍵結的官能基之離子化或自由基化;d1、d2、d3、d4、d5、d6、d7及d8之元素上所鍵結的官能基之氧化或還原等的化學變化;來自外界的光、電磁波之照射、
外加電壓等,不論該種類及過程為何皆可。
作為以式(7)所表示之環式化合物,相當於二氫吡咯并吡咯、二氫吡咯并吡咯衍生物、四氫吡咯并吡咯、四氫吡咯并吡咯衍生物、呋喃并吡咯、呋喃并吡咯衍生物、二氫環戊基吡咯、二氫環戊基吡咯衍生物、四氫環戊基吡咯、四氫環戊基吡咯衍生物、二氫噻吩并吡咯、二氫噻吩并吡咯衍生物、呋喃并咪唑、呋喃并咪唑衍生物、咪唑并噁唑、咪唑并噁唑衍生物、二氫咪唑并咪唑、二氫咪唑并咪唑衍生物、呋喃、呋喃衍生物、二氫呋喃、二氫呋喃衍生物、噻吩并呋喃、噻吩并呋喃衍生物、噻吩并吡咯、噻吩并吡咯衍生物、噻吩并咪唑、噻吩并咪唑衍生物、噻吩并噻吩、噻吩并噻吩衍生物、二氫噻吩并噻吩、二氫噻吩并噻吩衍生物、二氫吡咯并吡唑、二氫吡咯并吡唑衍生物、二氫吡唑并吡唑、二氫吡唑并吡唑衍生物、環戊基噻吩、環戊基噻吩衍生物、環戊基呋喃、環戊基呋喃衍生物、呋喃并噁唑、呋喃并噁唑衍生物、噻吩并噻唑、噻吩并噻唑衍生物、噻吩并噻唑、噻吩并噻唑衍生物、噁唑并噁唑、噁唑并噁唑衍生物、噻唑并噻唑、噻唑并噻唑衍生物等,具體而言可舉例如:具體而言,2-呋喃并[3,2-b]吡咯-4-基乙醯胺、3-甲基-4H-呋喃并[3,2-b]吡咯、6-碘基-5-甲基-4H-呋喃并[3,2-b]吡咯、N-乙基呋喃并[3,2-b]吡咯-4-胺、N-甲基-1H-吡咯并[3,2-b]吡咯-4-胺、N-丙烷-2-基-1H-吡咯并[3,2-b]吡咯-4-胺、[1,2]噁唑并[3,4-d][1,2]噁唑、[1,2]噻唑并[3,4-d][1,2]噻唑、1,2,3,4-四氫吡咯并
[3,2-b]吡咯、1,2,3,5-四氫吡咯并[3,4-c]吡咯、1,2-二氫吡咯并[3,4-c]吡唑、1,4,5,6-四氫環戊基[b]吡咯、1,4,5,6-四氫吡咯并[3,4-b]吡咯、1,4-二氫環戊基[b]吡咯、1,4-二氫吡唑并[4,3-c]吡唑-6-胺、1,4-二氫吡唑并[4,3-c]吡唑、1,4-二氫吡咯并[3,2-b]吡咯-5-胺、1,4-二氫吡咯并[3,2-b]吡咯、1,4-二甲基吡咯并[3,2-b]吡咯-6-胺、1,4-二甲基吡咯并[3,2-b]吡咯、1,5-二氫吡咯并[3,4-b]吡咯、1,5-二甲基-4H-吡咯并[3,2-b]吡咯、1,6-二氫環戊基[b]吡咯、1,6-二氫咪唑并[4,5-d]咪唑、1,6-二氫吡咯并[3,4-b]吡咯、1-呋喃并[3,2-b]吡咯-4-基乙酮、1H-呋喃并[2,3-d]咪唑-2-胺、1H-呋喃并[2,3-d]咪唑-2-基乙醇、1H-呋喃并[2,3-d]咪唑-5-胺、1H-呋喃并[2,3-d]咪唑-5-醇、1H-呋喃并[2,3-d]咪唑、1H-呋喃并[2,3-d]咪唑-2,5-二胺、1H-呋喃并[3,4-b]吡咯、1H-呋喃并[3,4-d]咪唑、1H-吡咯并[3,2-b]吡咯-4-胺、1H-吡咯并[3,2-b]吡咯-4,6-二胺、1H-吡咯并[3,2-b]吡咯-4-羧酸、1H-噻吩并[2,3-d]咪唑-2-胺、1H-噻吩并[2,3-d]咪唑-5-胺、1H噻吩并[2,3-d]咪唑、1H-噻吩并[3,4-b]吡咯、1H-噻吩并[3,4-d]咪唑、1-羥基-4H-吡咯并[3,2-b]吡咯-6-胺、1-羥基噻吩并[2,3-d]咪唑、1-甲基呋喃并[2,3-d]咪唑-2-胺、1-甲基呋喃并[2,3-d]咪唑-5-胺、1-甲基呋喃并[2,3-d]咪唑、1-甲基噻吩并[2,3-d]咪唑-2-胺、1-甲基噻吩并[2,3-d]咪唑、1-乙烯基噻吩并[2,3-d]咪唑、2-(1H-呋喃并[2,3-d]咪唑-2-基)乙醇、2-(2-甲基丙基)-4H-呋喃并[3,2-b]吡咯、2-(2-嗎福林-4-基乙基)-4H-呋喃并[3,2-b]吡咯、2-
(4H-呋喃并[3,2-b]吡咯-2-基)乙醇、2-(4H-呋喃并[3,2-b]吡咯-2-基)-N,N-二甲基乙基胺、2-(4H-噻吩并[3,2-b]吡咯-6-基)乙基胺、2-(氧戊烷-2-基甲基)-4H-呋喃并[3,2-b]吡咯、2,3-二氫呋喃并[3,2-b]呋喃、2,3-二氫噻吩并[3,2-b]噻吩、2,5-雙(甲基磺醯基)噻吩并[3,2-b]噻吩、2,6-二氫吡咯并[3,4-c]吡咯、2-[(5-胺基-1H-呋喃并[2,3-d]咪唑-2-基)胺基]乙醇、2-丁基-4H-呋喃并[3,2-b]吡咯、2-氯-4H-噻吩并[3,2-b]吡咯、2-乙氧基-1H-呋喃并[2,3-d]咪唑、2-乙氧基-4H-呋喃并[3,2-b]吡咯、2-庚基-4H-呋喃并[3,2-b]吡咯、2-甲氧基-1H-呋喃并[2,3-d]咪唑、2-甲氧基-1H-噻吩并[2,3-d]咪唑、2-甲氧基-1-甲基呋喃并[2,3-d]咪唑、2-甲氧基-4H-呋喃并[3,2-b]吡咯、2-甲基-1H-呋喃并[2,3-d]咪唑、2-甲基-1H-噻吩并[2,3-d]咪唑、2-甲基-4H-呋喃并[3,2-b]吡咯、2-甲基-4H-噻吩并[3,2-b]吡咯、2-甲基噻吩并[3,2-b]呋喃、2-N-乙基-1H-呋喃并[2,3-d]咪唑-2,5-二胺、2-N-甲基-1H-呋喃并[2,3-d]咪唑-2,5-二胺、2-N-甲基-1H-噻吩并[2,3-d]咪唑-2,5-二胺、2-丙基-4H-呋喃并[3,2-b]吡咯、3,4-二氫-2H-噻吩并[3,2-b]吡咯、3,4-二甲基呋喃并[3,2-b]吡咯、3,6-二甲基-4H-呋喃并[3,2-b]吡咯、3-溴-4H-噻吩并[3,2-b]吡咯、3H-噻吩并[2,3-d]咪唑-4-氧化物、3-羥基呋喃并[2,3-d]咪唑、3-甲基-1,4-二氫環戊基[b]吡咯、3-甲基-4H-環戊基[b]呋喃、3-甲基-4H-噻吩并[3,2-b]吡咯、3-甲基-4-亞甲基環戊基[b]呋喃、3-甲基呋喃并[2,3-d]咪唑、3-甲基噻吩并[2,3-d]咪唑、3-甲基噻吩并[3,2-b]呋
喃、4,5,6-三甲基-1H-吡咯并[3,2-b]吡咯、4,5-二甲基-1H-咪唑并[4,5-d]咪唑、4,6-二氫-1H-噻吩并[3,4-b]吡咯、4-乙氧基-1H-吡咯并[3,2-b]吡咯、4H-環戊基[b]呋喃、4H-呋喃并[3,2-b]吡咯-2-胺、4H-呋喃并[3,2-b]吡咯-2-醇、4H-呋喃并[3,2-b]吡咯-6-醇、4H-呋喃并[3,2-b]吡咯、4H-咪唑并[4,5-d][1,3]噁唑、4H-吡咯并[3,2-b]吡咯-1,6-二胺、4H-噻吩并[3,2-b]吡咯-2-胺、4H-噻吩并[3,2-b]吡咯、4H-噻吩并[3,2-b]吡咯-1-氧化物、4-羥基-1H-吡咯并[3,2-b]吡咯-6-胺、4-羥基-1H-吡咯并[3,2-b]吡咯、4-羥基呋喃并[3,2-b]吡咯-3-胺、4-甲氧基-1H-吡咯并[3,2-b]吡咯、4-甲氧基呋喃并[3,2-b]吡咯-3-胺、4-甲基-1H-吡咯并[3,2-b]吡咯-6-胺、4-甲基呋喃并[3,2-b]吡咯、4-甲基噻吩并[3,2-b]吡咯、4-N,4-N-二乙基呋喃并[3,2-b]吡咯-3,4-二胺、4-丙烷-2-基氧基-1H-吡咯并[3,2-b]吡咯、5-溴-1,4,5,6-四氫吡咯并[3,2-b]吡咯、5-乙炔基噻吩并[3,2-b]噻吩、5-乙氧基-1H-呋喃并[2,3-d]咪唑、5-乙氧基呋喃并[3,2-b]呋喃、5-乙氧基噻吩并[3,2-b]呋喃、5-乙基呋喃并[3,2-b]呋喃、5-乙基噻吩并[3,2-b]呋喃、5-乙基噻吩并[3,2-b]噻吩、5-己基噻吩并[3,2-b]噻吩、5-碘基噻吩并[3,2-b]噻吩、5-甲氧基-1H-呋喃并[2,3-d]咪唑、5-甲氧基呋喃并[3,2-b]呋喃、5-甲氧基噻吩并[3,2-b]呋喃、5-甲基-1,4-二氫吡咯并[3,2-b]吡咯、5-甲基-4,6-二氫-1H-吡咯并[3,4-b]吡咯、5-甲基-4H-呋喃并[3,2-b]吡咯、5-甲基-4H-噻吩并[3,2-b]吡咯、5-甲基-6H-環戊基[c]呋喃、5-甲基-6H-環戊基[c]噻吩、5-甲基
呋喃并[3,2-b]呋喃、5-甲基磺醯基噻吩并[3,2-b]呋喃、5-甲基磺醯基噻吩并[3,2-b]噻吩、5-甲基噻吩并[3,2-b]呋喃、5-甲基噻吩并[3,2-b]噻吩、5-N-乙基-1H-呋喃并[2,3-d]咪唑-2,5-二胺、5-N-甲基-1H-呋喃并[2,3-d]咪唑-2,5-二胺、5-N-甲基-1H-噻吩并[2,3-d]咪唑-2,5-二胺、5-辛基噻吩并[3,2-b]噻吩、5-丙-2-烯基-6H-環戊基[c]呋喃、5-丙-2-烯基-6H-環戊基[c]噻吩、6-(1,2,3,6-四氫吡啶-4-基)-4H-噻吩并[3,2-b]吡咯、6-氟-5-甲基-4H-呋喃并[3,2-b]吡咯、6H-環戊基[c]呋喃、6H-環戊基[c]噻吩、6H-呋喃并[3,2-b]呋喃-5-酮、6H-呋喃并[3,2-b]吡咯、6H-噻吩并[3,2-b]吡咯、6H-噻吩并[3,4-c]吡咯、6-甲基-1,4-二氫吡咯并[3,2-b]吡咯、6-甲基-1H-呋喃并[2,3-d]咪唑、6-甲基-4H-噻吩并[3,2-b]吡咯、6-甲基呋喃并[3,2-b]呋喃、6-甲基噻吩并[3,2-b]呋喃、6-甲基噻吩并[3,2-b]噻吩、6-丙烷-2-基-4H-噻吩并[3,2-b]吡咯、呋喃并[3,2-b]呋喃、呋喃并[3,2-b]呋喃-5-醇、呋喃并[3,2-b]吡咯-3,4-二胺、呋喃并[3,4-d][1,2]噁唑、N,N-二乙基-2-(4H-呋喃并[3,2-b]吡咯-2-基)乙基胺、N,N-二甲基-1-(4H-噻吩并[3,2-b]吡咯-6-基)甲基胺、N,N-二甲基-2-(4H-噻吩并[3,2-b]吡咯-6-基)乙基胺、N-乙基-1H-吡咯并[3,2-b]吡咯-4-胺、N-甲基-1H-噻吩并[2,3-d]咪唑-2-胺、噻吩并[3,2-b]呋喃、噻吩并[3,2-b]呋喃-4-氧化物、噻吩并[3,2-b]噻吩、噻吩并[3,2-b]噻吩-4-氧化物、噻吩并[3,2-b]噻吩-2,5-二硫醇、噻吩并[3,2-d][1,2]噻唑、噻吩并[3,4-b]呋喃、噻吩并[3,4-d][1,2]噻唑、三甲基(4H-
噻吩并[3,2-b]吡咯-6-基甲基)銨氮等。
作為上述環式化合物之添加量,依照一併添
加的以式(1)~(3)所表示之化合物之種類、或環式化合物本身之種類而異,但相對於添加的溶液全量而言只要含有0.001質量%以上即可。作為該上限未特別規定,但較佳為2質量%左右。
為了使處理液調整為合適的pH值,或使pH
值成為一定值,亦可含有由弱酸與任意的鹼性物質所構成之緩衝劑。作為如此般的緩衝劑之含有量,只要是調整至對於目的之pH調整而言為所需之量即可,但以對於主劑之上述界面活性劑與阻止劑之作用為不會產生負面影響之方式來調整量。
作為構成緩衝劑之弱酸,未有特別限定者,
可列舉例如:磷酸、縮合磷酸、聚磷酸、偏磷酸等之磷酸類、或檸檬酸、丙二酸、蘋果酸等之含有羧基之有機酸、胺基酸等。又,作為鹼性物質,不論是氨、胺等種類皆可。
處理液中亦可含有有機溶劑。有機溶劑係用
以調整處理液之比介電率、或提高處理性能而被添加。作為如此般的有機溶劑,可列舉例如:異丙醇、N-甲基吡咯烷酮、二甲基亞碸、二甲基甲醯胺、甲醇、乙醇、丁醇、丙醇、乙二醇等,但不限定於該等,只要是能與水混和者即可,可從任意周知之材料中選擇使用。作為有機溶劑之含有量,相對於處理液而言,通常為0.1~90質量%,較
佳為未滿30質量%。
本說明書中有將上述界面活性劑、或上述界
面活性劑與上述環式化合物之組合之添加劑稱為抑制劑乃至阻止劑之情形。本發明之添加劑(阻止劑:Inhibitor)為藉由添加於如上述般的處理溶液中,可選擇性保護含有氮之矽化合物不受蝕刻乃至腐蝕。在此,本發明中所謂的「含有氮之矽化合物」,係指氮化矽(SiNx)、氧化氮化矽(SiOxNy、(x>y>0))、氮化氧化矽(SiNxOy、(x>y>0))等之含有氮與矽、及進而的其他元素之化合物之總稱。該等之化合物亦可多少超出該化學計量之組成。
又,作為與如此般的含有氮之矽化合物為一起浸漬於處理液中並成為蝕刻或洗淨之對象之材料,較佳為含有氧、碳之矽化合物。該含有氧或碳之矽化合物,係包含氧化矽(SiOx)、碳化矽(SiCN)、SiOF(亦稱為FSG)、SiOC、SiOH、TEOS(TetraEthOxySilane)、及含有該等作為材料或組合該等的稱為PSG(Phosphorus Silicon Glass)、BPSG(Boron Phosphor Silicate Glass)、SOG(Spin on Glass:SiO2)、Low-k等的半導體構造物或絕緣材所使用的材料。該等之化合物亦可多少超出該化學計量之組成。
在本發明中,如上述般為可抑制氮化矽之蝕
刻,但以氮化矽化合物對氧化矽之蝕刻速率所表示之指標定義為選擇比。具體而言,將氟酸水溶液中的熱氧化矽與CVD-氮化矽之蝕刻速率之比(CVD-氮化矽蝕刻速率/熱氧化矽蝕刻速率)設為選擇比。該選擇比為將包含上述界面
活性劑等之發明構成要素之溶液、與僅氟酸之參考用樣品相比較時,為未滿1,較佳為0.8以下,又較佳為0.5以下。
具有本發明之添加劑之處理液,通常在形成
於Si晶圓、Si薄膜構造物上之大規模積體電路、或形成於玻璃基板上之液晶顯示器用薄膜電晶體中,較佳被適用於前述含有氧、碳之矽化合物與含有氮之矽化合物為露出並存在之處理步驟。特以適合於,使用氟酸來將作為絕緣、鈍化構造或蝕刻殘渣而存在的含有氧、碳之矽化合物進行蝕刻、洗淨之步驟。
在該使用之際,不論是噴霧式單片裝置、浸
漬式浴槽裝置、噴霧式批次裝置皆可。又,就防止元件表面之氧化之觀點而言,處理時的氣氛亦有使用氮等的惰性氣體之情形。
處理條件為依照所使用的絕緣膜之種類而
異,一般而言為以20~70℃、0.5~40分鐘左右。但,依對象物之蝕刻條件、添加劑之濃度等最佳條件亦有所不同,故只要因應所需設定最適合的處理條件即可。
又,以處理液進行處理後,可直接以水進行
潤濕,長時間之浸漬亦可。尚,本說明書中所謂的「水」,係包含純水、超純水等,可因應所需選擇使用。
以下為表示實施例,對於具體的發明之實施
形態進行說明。
準備1質量%濃度的氟酸水溶液,於此水溶液中分別添加0.05質量%的作為以式(1)所表示之化合物之樣品1:(1)-1異丙基萘磺酸、樣品2:(1)-3二異丙基萘磺酸、樣品3:(1)-4二丁基萘磺酸、樣品4:作為以式(2)所表示之化合物之(2)-1萘磺酸甲醛縮合物,來調整處理液。又,亦準備未含有界面活性劑的僅氟酸水溶液的「比較樣品0」。
於8吋大小的矽晶圓上形成1000nm的熱氧化矽(Th-SiO2)膜,再藉由CVD法成膜氮化矽(SiN)膜600nm,並使其做為試片。尚,各膜之形成條件等為使用一般慣用之手法來成膜,故予以省略。將所得到的試片浸漬於以上述所調整的處理液中,測定分別的膜之蝕刻速率。此時之處理溫度為25℃、處理時間為10min~30min。又,求得:作為與比較樣品(未含有界面活性劑)之蝕刻速率之比之「蝕刻速率比」;與,作為氮化矽之蝕刻速率/熱氧化矽之蝕刻速率之「選擇比」。將結果表示於表1中。
由表1之結果可得知,不論是添加何種的界
面活性劑的樣品,對於氮化矽而言可得到一定的防腐蝕效果。又,可得知特別以樣品(1)-4為得到優異的防腐蝕效果。
與實施例1為相同地準備1質量%濃度的氟酸水溶液,於此水溶液中添加0.05質量%的作為以式(1)所表示之化合物之(1)-1異丙基萘磺酸,進而分別添加0.1質量%的如表2中所表示的環式化合物,來調整樣品21-26之各處理液。又,亦準備未添加環式化合物的參考用的「比較樣品20」。
於所得到的各處理液中浸漬與實施例1為相
同的試片,測定分別的膜之蝕刻速率。又,與實施例1為相同地從各蝕刻速率求得蝕刻速率比與選擇比。將結果表示於表2中。
由表2之結果可得知,相較於實施例1,全部
的樣品皆得到優異的結果。又,樣品23、24為特別優異。
在實施例2中,將環式化合物中的樣品24之苯并咪唑以分別添加如表3中所示:0.001質量%(樣品31)、0.005質量%(樣品32)、0.01質量%(樣品33)、0.05質量%(樣品34)、0.1質量%(樣品35),來調整樣品31-35之各處理液。又,亦準備未添加環式化合物的參考用的「比較樣品30」。
於所得到的各處理液中浸漬與實施例1為相
同的試片,測定分別的膜之蝕刻速率。又,與實施例1為相同地從各蝕刻速率求得蝕刻速率比與選擇比。將結果表示於表3中。
由表3之結果可得知,即使是0.001質量%的
樣品31亦具有效果,0.005質量%的樣品32可更提昇效果,0.01質量%以上的樣品33-35為呈現橫向狀態。
準備添加有苯并咪唑(Benzimidazole)的1質量%濃度的氟酸水溶液,於此水溶液中如表4所示般分別添加0.001質量%(樣品41)、0.005質量%(樣品42)、0.01質量%(樣品43)、0.02質量%(樣品44)、0.03質量%(樣品45)、0.05質量%(樣品46)、0.1質量%(樣品47)的作為以式(1)所表示之化合物之(1)-1異丙基萘磺酸,來調整樣品41-47之各處理液。又,亦準備未添加界面活性劑的參考用的「比較樣品40」。
於所得到的各處理液中浸漬與實施例1為相
同的試片,測定分別的膜之蝕刻速率。又,與實施例1為相同地從各蝕刻速率求得蝕刻速率比與選擇比。將結果表
示於表4中。
由表4之結果可得知,在界面活性劑之添加
量0.005質量%則可表現出防腐蝕效果,在0.02質量%以上為變得顯著。
作為濃度相異的氟酸水溶液,分別準備0.1質量%(樣品51)、0.5質量%(樣品52)、2質量%(樣品53)、5質量%(樣品54)、10質量%(樣品55)、15質量%(樣品56)。對於在該等各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜之蝕刻速率,來求得阻止劑之有無之蝕刻速率比。作為阻止劑,係添加0.05質量%的以式(1)所表示之化合物之樣品1:(1)-1異丙基萘磺酸,作為環式化合物,係添加0.01質量%的苯并咪唑。又,氮化
矽膜之試片,係準備與實施例1為相同者。處理條件等亦依照實施例1。將結果表示於表5中。
由表5之結果可明確得知般,在氟酸濃度2
質量%的樣品53之蝕刻速率比為最降低,並得到良好結果。
與實施例5相同地,作為濃度相異的氟酸水溶液準備樣品61~樣品66,對於在各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜與氧化矽膜之蝕刻速率,來求得阻止劑之有無之選擇比。阻止劑為使用與實施例5為相同者。又,氮化矽膜/氧化矽膜之試片,係準備與實施例1為相同者。處理條件等亦依照實施例1。將結果表示於表6中。
由表6之結果可明確得知般,在氟酸濃度2
質量%的樣品63之阻止劑添加時之選擇比為最降低,並得到良好結果。
調整含有10質量%磷酸銨及1質量%氟酸的水溶液之pH,如表7所表示般準備pH2~6的樣品71~樣品75。pH之調整為藉由氨水來進行。對於在該等各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜之蝕刻速率,來求得阻止劑之有無之蝕刻速率比。阻止劑為使用與實施例5為相同者。又,氮化矽膜之試片,
係與實施例1為相同地準備僅氮化矽膜者。處理條件等亦依照實施例1。將結果表示於表7中。
由表7之結果可明確得知般,在pH2之樣品
71的蝕刻速率比為最降低,隨著pH之上昇蝕刻速率比亦變高,得知pH4以上時則未有變化。
與實施例7為相同地調整pH,如表8所表示般準備pH2~6之樣品81~樣品85。對於在該等各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜與氧化矽膜之蝕刻速率,來求得阻止劑之有無之選擇比。阻止劑為使用與實施例5為相同者。又,氮化矽膜/氧化矽膜之試片,係準備與實施例1為相同者。處理條件等亦依照實施例1。將結果表示於表8中。
由表8之結果可明確得知般,在pH2之樣品
81的阻止劑添加時的選擇比為最降低,得知隨著pH之上昇選擇比亦變高。
調整含有如表9所表示的10質量%弱酸‧鹼性物質的緩衝液、與1質量%氟酸的水溶液,並如表9所表示般準備各樣品91~樣品94。對於在該等各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜之蝕刻速率,來求得阻止劑之有無之蝕刻速率比。阻止劑為使用與實施例5為相同者。又,氮化矽膜之試片,係與實施例1為相同地準備僅氮化矽膜者。處理條件等亦依照實施例1。將結果表示於表9中。
由表9之結果可明確得知般,添加有蘋果酸
銨的樣品94之蝕刻速率比為最低,接著是樣品93,進而以樣品91與92之蝕刻速率比為變高。
與實施例9相同地使用各緩衝液,並準備如表10所表示的各樣品101~樣品104。對於在該等各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜與氧化矽膜之蝕刻速率,來求得阻止劑之有無之選擇比。阻止劑為使用與實施例5為相同者。又,氮化矽膜/氧化矽膜之試片,係準備與實施例1為相同者。處理條件等亦依照實施例1。將結果表示於表10。
由表10之結果可明確得知般,在添加有磷酸
銨的樣品101、添加有丙二酸銨的樣品103、及添加有蘋果酸銨的樣品104的阻止劑添加時的蝕刻速率比為最低。
在含有1質量%氟酸的水溶液中,混合0~50質量%的有機溶劑之二甲基亞碸(DMSO),使能成為如表11所表示的濃度,並調製如表11所表示的各樣品110~樣品115。對於在該等各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜之蝕刻速率,來求得阻止劑之有無之蝕刻速率比。阻止劑為使用與實施例5為相同者。又,氮化矽膜之試片,係與實施例1為相同地準備僅氮化矽膜者。處理條件等亦依照實施例1。將結果表示於表11。
由表11之結果可明確得知般,在未添加有機
溶劑(0%)之樣品110的蝕刻速率比為最低,接著,與有機溶劑之含有量成比例關係蝕刻速率比為變高,且以30%之樣品114的蝕刻速率為達到1。
與實施例11相同地,調製如表12所表示的各樣品120~樣品125。對於在該等各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜與氧化矽膜之蝕刻速率,來求得阻止劑之有無之選擇比。阻止劑為使用與實施例5為相同者。又,氮化矽膜/氧化矽膜之試片,係準備與實施例1為相同者。處理條件等亦依照實施例1。將結果表示於表12。
由表12之結果可明確得知般,未添加有機溶
劑(0%)之樣品120的阻止劑添加時選擇比為最低,接著,與有機溶劑之含有量成比例關係選擇比為變高,且不論是否含有阻止劑,在有機溶劑30%之樣品124的選擇比為相同。又,在有機溶劑50%之樣品125中,不論是何種的蝕刻速率都更為降低。
在含有1質量%氟酸的水溶液中,混合0~50質量%的有機溶劑之N-甲基吡咯烷酮(NMP),使能成為如表13所表示的濃度,並調製如表13所表示的各樣品130~樣品135。對於在該等各樣品中為添加有阻止劑之情形、及
未添加有阻止劑之情形,調查氮化矽膜之蝕刻速率,來求得阻止劑之有無之蝕刻速率比。阻止劑為使用與實施例5為相同者。又,氮化矽膜之試片,係與實施例1為相同地準備僅氮化矽膜者。處理條件等亦依照實施例1。將結果表示於表13。
由表13之結果可明確得知般,在未添加有機
溶劑(0%)之樣品130的蝕刻速率比為最低,接著,與有機溶劑之含有量成比例關係蝕刻速率比為變高,且在30%之樣品134的蝕刻速率為達到1。
與實施例13相同地,調製如表14所表示的各樣品140~樣品145。對於在該等各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜與氧化矽膜之蝕刻速率,來求得阻止劑之有無之選擇比。阻止劑為
使用與實施例5為相同者。又,氮化矽膜/氧化矽膜之試片,係準備與實施例1為相同者。處理條件等亦依照實施例1。將結果表示於表14。
由表14之結果可明確得知般,在未添加有機
溶劑(0%)之樣品140的阻止劑添加時選擇比為最低,接著,與有機溶劑之含有量成比例關係選擇比為變高,且不論是否含有阻止劑,在有機溶劑30%之樣品144的選擇比為相同。又,在有機溶劑50%之樣品145中,不論是何種的蝕刻速率都更為降低。
在含有1質量%氟酸的水溶液中,混合0~50質量%的有機溶劑之乙二醇,使成為如表11所表示的濃度,並調製如表15所表示的各樣品150~樣品155。對於在該等各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜之蝕刻速率,來求得阻止劑之有無之蝕刻速率比。阻止劑為使用與實施例5為相同者。又,氮化矽膜之試片,係與實施例1為相同地準備僅氮化矽膜者。
處理條件等亦依照實施例1。將結果表示於表15。
由表15之結果可明確得知般,在未添加有機
溶劑(0%)之樣品150的蝕刻速率比為最低,接著,與有機溶劑之含有量成比例關係蝕刻速率比為變高,且在50%之樣品155的蝕刻速率為達到1。
與實施例15相同地,調製如表16所表示的各樣品
160~樣品165。對於在該等各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜與氧化矽膜之蝕刻速率,來求得阻止劑之有無之選擇比。阻止劑為使用與實施例5為相同者。又,氮化矽膜/氧化矽膜之試片,係準備與實施例1為相同者。處理條件等亦依照實施例1。將結果表示於表16。
由表16之結果可明確得知般,在未添加有機
溶劑(0%)之樣品160的阻止劑添加時選擇比為最低,接著,與有機溶劑之含有量成比例關係選擇比為變高,且不論是否含有阻止劑,在有機溶劑50%之樣品165的選擇比為相同。
在含有1質量%氟酸的水溶液中,混合0~50質量%的有機溶劑之異丙醇(IPA),使能成為如表17所表示的濃度,並調製如表17所表示的各樣品170~樣品175。對於在該等各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜之蝕刻速率,來求得阻止劑之有無之蝕刻速率比。阻止劑為使用與實施例5為相同者。
又,氮化矽膜之試片,係與實施例1為相同地準備僅氮化矽膜者。處理條件等亦依照實施例1。將結果表示於表17。
由表17之結果可明確得知般,在未添加有機
溶劑(0%)之樣品170的蝕刻速率比為最低,接著,與有機溶劑之含有量成比例關係蝕刻速率比為變高,且20%之樣品173的蝕刻速率已經達到1。
與實施例17相同地,調製如表18所表示的各樣品180~樣品185。對於在該等各樣品中為添加有阻止劑之情形、及未添加有阻止劑之情形,調查氮化矽膜與氧化矽膜之蝕刻速率,來求得阻止劑之有無之選擇比。阻止劑為使用與實施例5為相同者。又,氮化矽膜/氧化矽膜之試片,係準備與實施例1為相同者。處理條件等亦依照實施例1。將結果表示於表18。
由表18之結果可明確得知般,在未添加有機
溶劑(0%)之樣品180的阻止劑添加時選擇比為最低,接著,與有機溶劑之含有量成比例關係選擇比為變高,且不
論是否含有阻止劑,在有機溶劑20%之樣品183的選擇比為相同。又,有機溶劑從30%到50%之至樣品185為止中,不論是何種的蝕刻速率皆與含有量成比例關係且更為降低。
本發明之添加劑、及添加有此者之處理液,係可合適使用於記憶元件、處理元件、邏輯元件其他LSI等之半導體元件、或液晶、有機EL等之顯示元件等之電子零件之製造步驟中。特別是於具有含有氮之矽化合物與含有氧、碳之矽化合物為混合存在構造之裝置之製造步驟中,若需要選擇性保護含有氮之矽化合物時將非常有用。
Claims (13)
- 一種電子零件用處理液,其係含有以下述式(1)~(3)所表示之陰離子性界面活性劑1種或2種以上之水溶液,
- 如請求項1之電子零件用處理液,其中,前述水溶液為pH2~pH6。
- 如請求項1或2之電子零件用處理液,其中,含有0.001~50質量%之氫氟酸。
- 如請求項3之電子零件用處理液,其中,前述氫氟酸為溶解水溶性氟化物鹽而得到。
- 如請求項1或2之電子零件用處理液,其中,進而含有佔有面積為較萘環小的環式化合物。
- 如請求項5之電子零件用處理液,其中,前述環式化合物為以下述式(4)、(5)、(6)或(7)所表示之化合物,
- 如請求項6之電子零件用處理液,其中,含有0.001質量%以上之前述環式化合物。
- 如請求項1或2之電子零件用處理液,其中,含有0.001質量%~2質量%之前述陰離子性界面活性劑。
- 如請求項1或2之電子零件用處理液,其中,前述水溶液中含有由弱酸與鹼性物質所構成之緩衝劑。
- 如請求項1或2之電子零件用處理液,其中,含有進而能與水混和之有機溶劑。
- 如請求項1或2之電子零件用處理液,其中,使用於具有以含有氮之矽化合物作為構成材料之構造物與以不包含氮之矽化合物作為構成材料之構造物之電子零件。
- 一種電子零件之製造方法,其係具有使用請求項1~10中任一項之電子零件用處理液來進行電子零件之蝕刻或洗淨處理之步驟。
- 如請求項12之電子零件之製造方法,其中,前述電子零件具有以含有氮之矽化合物作為構成材料之構造物與以不包含氮之矽化合物作為構成材料之構造物。
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JP6526460B2 (ja) | 2019-06-05 |
US9812315B2 (en) | 2017-11-07 |
US20150279654A1 (en) | 2015-10-01 |
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