TWI777944B - 半導體基板之製造方法 - Google Patents
半導體基板之製造方法 Download PDFInfo
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- TWI777944B TWI777944B TW106107813A TW106107813A TWI777944B TW I777944 B TWI777944 B TW I777944B TW 106107813 A TW106107813 A TW 106107813A TW 106107813 A TW106107813 A TW 106107813A TW I777944 B TWI777944 B TW I777944B
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- semiconductor substrate
- agent composition
- diffusing agent
- diffusing
- impurity
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- 239000000758 substrate Substances 0.000 title claims abstract description 113
- 239000004065 semiconductor Substances 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
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- 239000000203 mixture Substances 0.000 claims abstract description 57
- 238000000576 coating method Methods 0.000 claims abstract description 55
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 239000012535 impurity Substances 0.000 claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 230000007062 hydrolysis Effects 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 15
- 125000005372 silanol group Chemical group 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 27
- 239000003960 organic solvent Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 14
- 239000010408 film Substances 0.000 description 53
- 238000009792 diffusion process Methods 0.000 description 51
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- 229910000077 silane Inorganic materials 0.000 description 30
- 125000000524 functional group Chemical group 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000005468 ion implantation Methods 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
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- 229910052698 phosphorus Inorganic materials 0.000 description 6
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
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- SFLULBKYTSNESB-UHFFFAOYSA-N methyl tripropyl silicate Chemical compound CCCO[Si](OC)(OCCC)OCCC SFLULBKYTSNESB-UHFFFAOYSA-N 0.000 description 1
- QRBAVICMCJULJS-UHFFFAOYSA-N methyl(tripentoxy)silane Chemical compound CCCCCO[Si](C)(OCCCCC)OCCCCC QRBAVICMCJULJS-UHFFFAOYSA-N 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical group CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical group CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BHXCWWZCEVPINL-UHFFFAOYSA-N pentyl tripropyl silicate Chemical compound CCCCCO[Si](OCCC)(OCCC)OCCC BHXCWWZCEVPINL-UHFFFAOYSA-N 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 1
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- XDGFORICQHRPMI-UHFFFAOYSA-N propan-2-yl 3-methoxypropanoate Chemical class COCCC(=O)OC(C)C XDGFORICQHRPMI-UHFFFAOYSA-N 0.000 description 1
- ILPVOWZUBFRIAX-UHFFFAOYSA-N propyl 2-oxopropanoate Chemical compound CCCOC(=O)C(C)=O ILPVOWZUBFRIAX-UHFFFAOYSA-N 0.000 description 1
- JCMFJIHDWDKYIL-UHFFFAOYSA-N propyl 3-methoxypropanoate Chemical compound CCCOC(=O)CCOC JCMFJIHDWDKYIL-UHFFFAOYSA-N 0.000 description 1
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 238000004151 rapid thermal annealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- PYXXSQFBWMYGEI-UHFFFAOYSA-N tributyl ethyl silicate Chemical compound CCCCO[Si](OCC)(OCCCC)OCCCC PYXXSQFBWMYGEI-UHFFFAOYSA-N 0.000 description 1
- HSDAZXVGQVMFAY-UHFFFAOYSA-N tributyl methyl silicate Chemical compound CCCCO[Si](OC)(OCCCC)OCCCC HSDAZXVGQVMFAY-UHFFFAOYSA-N 0.000 description 1
- QSTQHAMMCFWJFS-UHFFFAOYSA-N tributyl pentyl silicate Chemical compound CCCCCO[Si](OCCCC)(OCCCC)OCCCC QSTQHAMMCFWJFS-UHFFFAOYSA-N 0.000 description 1
- BUZKVHDUZDJKHI-UHFFFAOYSA-N triethyl arsorite Chemical compound CCO[As](OCC)OCC BUZKVHDUZDJKHI-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- QYBKVVRRGQSGDC-UHFFFAOYSA-N triethyl methyl silicate Chemical compound CCO[Si](OC)(OCC)OCC QYBKVVRRGQSGDC-UHFFFAOYSA-N 0.000 description 1
- KVHHJVNRKAZGMT-UHFFFAOYSA-N triethyl pentyl silicate Chemical compound CCCCCO[Si](OCC)(OCC)OCC KVHHJVNRKAZGMT-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- CXZMPNCYSOLUEK-UHFFFAOYSA-N triethyl propyl silicate Chemical compound CCCO[Si](OCC)(OCC)OCC CXZMPNCYSOLUEK-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- OVFCXYRKKOBQMR-UHFFFAOYSA-N trimethoxysilyl dihydrogen phosphate Chemical compound CO[Si](OC)(OC)OP(O)(O)=O OVFCXYRKKOBQMR-UHFFFAOYSA-N 0.000 description 1
- HQNHBYLKGMIFJP-UHFFFAOYSA-N trimethoxysilyl dihydrogen phosphite Chemical compound CO[Si](OC)(OC)OP(O)O HQNHBYLKGMIFJP-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- RZIDDAABTIZZOW-UHFFFAOYSA-N trimethyl pentyl silicate Chemical compound CCCCCO[Si](OC)(OC)OC RZIDDAABTIZZOW-UHFFFAOYSA-N 0.000 description 1
- WKEXHTMMGBYMTA-UHFFFAOYSA-N trimethyl propyl silicate Chemical compound CCCO[Si](OC)(OC)OC WKEXHTMMGBYMTA-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- FVCJARXRCUNQQS-UHFFFAOYSA-N trimethylsilyl dihydrogen phosphate Chemical compound C[Si](C)(C)OP(O)(O)=O FVCJARXRCUNQQS-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
本發明之課題為,提供一種半導體基板之製造方法,其係即使在使用於該表面具備具有奈米級之微小的空隙之三維構造的半導體基板之情況時,亦可包含微小空隙之內表面整面地,於半導體基板之擴散劑組成物所塗佈的部位全體,一面抑制在半導體基板之缺陷的發生,一面良好且均勻地使雜質擴散成分擴散。
本發明之解決手段為,在使用包含雜質擴散成分(A)與可藉由水解生成矽醇基的Si化合物(B)之擴散劑組成物的情況時,使用該擴散劑組成物,於半導體基板之周圍的環境之相對濕度為40%以下的條件中,於半導體基板表面形成30nm以下之膜厚的塗佈膜。
Description
本發明係關於藉由使用包含雜質擴散成分、與可藉由水解生成矽醇基的Si化合物之擴散劑組成物所形成的薄膜,而使雜質擴散成分於半導體基板擴散的半導體基板之製造方法。
電晶體、二極體、太陽能電池等所使用之半導體元件的半導體基板係使磷或硼等之雜質擴散成分於半導體基板擴散而製造。針對該半導體基板,在製造Fin-FET、奈米線FET等之多閘極元件用的半導體基板時,有時會對於該表面具有具備例如奈米級之微小的空隙之三維構造的半導體基板進行雜質的擴散。
在此,作為於半導體基板使雜質擴散成分擴散的方法,例如,已知有離子注入法(例如參照專利文獻1)或CVD法(例如參照專利文獻2)。於離子注入法中係經離子化的雜質擴散成分被打入半導體基板的表面。於CVD法中係在將摻雜有磷或硼等之雜質擴散成分的矽氧化物等之氧化物膜藉由CVD來形成於半導體基板上之
後,將具備氧化物膜的半導體基板藉由電爐等進行加熱,而使雜質擴散成分從氧化物膜擴散於半導體基板。
[專利文獻1]日本特開平06-318559號公報
[專利文獻2]國際公開第2014/064873號
但,於如專利文獻1所記載般之離子注入法中,在將如B(硼)般之輕離子注入半導體基板的情況時,在基板表面附近的區域容易形成點缺陷或點缺陷群聚,在注入如As般之重離子的情況時,在基板表面附近的區域容易形成非晶質區域。例如,於半導體基板藉由離子注入法使雜質擴散成分擴散,而形成如CMOS影像感測器般之CMOS元件的情況,如此之缺陷的發生係直接關係到元件之性能的降低。於CMOS影像感測器中,若產生如此之缺陷,則會產生被稱為白點(White spot)的缺陷。
又,半導體基板,例如,在該表面具有如用以形成具備複數個源極之鰭片、複數個汲極之鰭片、以及與該等鰭片正交的閘極之被稱為Fin-FET之多重閘極元件的立體構造般之奈米級的三維構造之情況,於離子注入法中,對於鰭片或閘極的側面及上面,或鰭片與閘極所包圍
之凹部的內表面整面之均勻的離子之打入係有困難。
並且,於具有奈米級之三維構造的半導體基板,藉由離子注入法使雜質擴散成分擴散的情況,假設即便可均勻的離子之打入,亦具有如下述般之缺陷。例如,在使用具備具有微細的鰭片之立體圖型的半導體基板來形成邏輯LSI裝置等的情況,因離子注入,而矽等之基板材料的結晶容易被破壞。可推測,該結晶的損傷會導致如裝置之特性的變異、或待機洩漏電流的發生般之缺陷。
又,在適用如專利文獻2記載般之CVD法的情況,因懸突現象,而有以包含膜厚均勻的雜質擴散成分之氧化物膜來被覆鰭片與閘極所包圍之凹部的內表面整面係為困難,或因堆積於鰭片與閘極所包圍之凹部的開口部之氧化物而使開口部閉塞的問題。如此般,於離子注入法或CVD法中,係因半導體基板之表面形狀,而難以使雜質擴散成分良好且均勻地於半導體基板擴散。
本發明係鑑於上述之課題而完成者,其目的為,提供一種半導體基板之製造方法,其係即使在使用於該表面具備具有奈米級之微小的空隙之三維構造的半導體基板之情況時,亦可包含微小空隙之內表面整面地,於半導體基板之擴散劑組成物所塗佈的部位全體,一面抑制在半導體基板之缺陷的發生,一面良好且均勻地使雜質擴散成分擴散。
本發明者們係著眼於在將由塗佈型之擴散劑組成物所構成的塗佈膜進行加熱使雜質擴散成分於半導體基板擴散的情況時,可抑制如以離子注入法所產生般之在半導體基板之缺陷的發生,而開始探討。其結果,本發明者們,發現在使用包含雜質擴散成分(A)與可藉由水解生成矽醇基的Si化合物(B)之擴散劑組成物的情況,藉由使用該擴散劑組成物,於半導體基板之周圍的環境之相對濕度為40%以下的條件下,於半導體基板表面形成30nm以下之膜厚的塗佈膜,而可使雜質擴散成分從塗佈膜良好且均勻地擴散於半導體基板,因而完成本發明。
具體而言,本發明係關於一種半導體基板之製造方法,其包含:於作為使雜質擴散成分(A)擴散的對象之半導體基板I上塗佈擴散劑組成物來形成30nm以下之膜厚的塗佈膜、與使擴散劑組成物中之雜質擴散成分(A)於半導體基板I擴散,擴散劑組成物包含雜質擴散成分(A)、與可藉由水解生成矽醇基的Si化合物(B),在將擴散劑組成物進行塗佈時,半導體基板I之周圍的環境之相對濕度為40%以下。
依據本發明,可提供一種半導體基板之製造方法,其係即使在使用於該表面具備具有奈米級之微小的
空隙之三維構造的半導體基板之情況時,亦可包含微小空隙之內表面整面地,於半導體基板之擴散劑組成物所塗佈的部位全體,一面抑制在半導體基板之缺陷的發生,一面良好且均勻地使雜質擴散成分擴散。
本發明之半導體基板之製造方法係包含:於作為使雜質擴散成分(A)擴散的對象之半導體基板I上塗佈擴散劑組成物來形成30nm以下之膜厚的塗佈膜、與使擴散劑組成物中之雜質擴散成分(A)於半導體基板I擴散。
擴散劑組成物係包含雜質擴散成分(A)、與可藉由水解生成矽醇基的Si化合物(B)。
以下,亦將形成30nm以下之膜厚的塗佈膜之步驟記載為「塗佈步驟」,亦將使雜質擴散成分(A)擴散的步驟記載為「擴散步驟」。
以下,針對塗佈步驟、及擴散步驟依序進行說明。
於塗佈步驟中,於半導體基板I上塗佈擴散劑組成物來形成30nm以下之膜厚的塗佈膜。以下,針對塗佈步驟,依擴散劑組成物、半導體基板I、塗佈方法之順序進行說明。
作為擴散劑組成物係包含雜質擴散成分(A)、與可藉由水解生成矽醇基的Si化合物(B)。於本說明書中,亦將可生成矽醇基的Si化合物(B)記載為水解性矽烷化合物(B)。以下,針對擴散劑組成物所包含之必須或任意的成分進行說明。
雜質擴散成分(A)係只要是以往對半導體基板之摻雜中所使用的成分則無特別限定,可為n型摻雜劑,亦可為p型摻雜劑。作為n型摻雜劑係可列舉:磷、砷、及銻等之單質,以及包含此等元素之化合物。作為p型摻雜劑係可列舉:硼、鎵、銦及鋁之單質,以及包含此等元素之化合物。
作為雜質擴散成分(A),就取得之容易性或操作容易的觀點,較佳係磷化合物、硼化合物、砷化合物。作為較佳的磷化合物係可列舉:磷酸、亞磷酸、二亞磷酸、多磷酸、及五氧化二磷、或亞磷酸酯類、磷酸酯類、亞磷酸參(三烷基矽烷基)酯、及磷酸參(三烷基矽烷基)酯等。作為硼化合物係可列舉:硼酸(boric acid)、偏硼酸、硼酸(boronic acid)、過硼酸、次硼酸、及三氧化二硼、或硼酸三烷酯。作為較佳的砷化合物係可列舉:砷酸、及砷酸三烷酯。
作為磷化合物較佳為亞磷酸酯類、磷酸酯
類、亞磷酸參(三烷基矽烷基)酯、及磷酸參(三烷基矽烷基)酯,其中,較佳為磷酸三甲酯、磷酸三乙酯、亞磷酸三甲酯、亞磷酸三乙酯、磷酸參(三甲氧基矽烷基)酯、及亞磷酸參(三甲氧基矽烷基)酯,更佳為磷酸三甲酯、亞磷酸三甲酯、及磷酸參(三甲基矽烷基)酯,特佳為磷酸三甲酯。
作為硼化合物較佳為三甲氧基硼、三乙氧基硼、三甲基硼、三乙基硼、及三乙胺-硼烷。
作為砷化合物較佳為砷、三乙氧基砷、及三-n-丁氧基砷。
擴散劑組成物中之雜質擴散成分(A)之含量係無特別限定。擴散劑組成物中之雜質擴散成分(A)之含量,較佳係雜質擴散成分(A)中所包含之磷、砷、銻、硼、鎵、銦、及鋁等之在半導體基板中發揮摻雜之作用的元素之量(莫耳)成為水解性矽烷化合物(B)中所包含Si之莫耳數的0.01~5倍之量,更佳係成為0.05~3倍之量。
擴散劑組成物係含有水解性矽烷化合物(B)。因此,若將擴散劑組成物塗佈於半導體基板I來形成薄膜,則水解性矽烷化合物會進行水解縮合,而於塗佈膜內形成矽氧化物系之極薄的膜。於塗佈膜內形成矽氧化物系之極薄的膜的情況,可抑制前述之雜質擴散成分(A)往基板
外之外部擴散,即使由擴散劑組成物所構成的膜為薄膜,亦可良好且均勻地使雜質擴散成分(A)於半導體基板擴散。
水解性矽烷化合物(B)係藉由水解而生成羥基,且具有鍵結於Si原子的官能基。作為藉由水解而生成羥基的官能基係可列舉:烷氧基、異氰酸酯基、二甲基胺基及鹵素原子等。作為烷氧基,較佳為碳原子數1~5之直鏈或分支鏈狀之脂肪族烷氧基。作為適宜之烷氧基的具體例係可列舉:甲氧基、乙氧基、n-丙氧基、異丙氧基、及n-丁氧基等。作為鹵素原子,較佳為氯原子、氟原子、溴原子、及碘原子,更佳為氯原子。
作為藉由水解而生成羥基的官能基,就容易迅速地水解,以及水解性矽烷化合物(B)之操作性或取得之容易性的觀點而言,較佳為異氰酸酯基、及碳原子數1~5之直鏈或分支鏈之脂肪族烷氧基,更佳為甲氧基、乙氧基、及異氰酸酯基。
作為具有碳原子數1~5之直鏈或分支鏈狀的脂肪族烷氧基的水解性矽烷化合物(B)之具體例係可列舉:四甲氧基矽烷、四乙氧基矽烷、四-n-丙氧基矽烷、四異丙氧基矽烷、四-n-丁氧基矽烷、四-n-戊氧基矽烷、三甲氧基單乙氧基矽烷、二甲氧基二乙氧基矽烷、單甲氧基三乙氧基矽烷、三甲氧基單-n-丙氧基矽烷、二甲氧基二-n-丙氧基矽烷、單甲氧基三-n-丙氧基矽烷、三甲氧基單-n-丁氧基矽烷、二甲氧基二-n-丁氧基矽烷、單甲氧基
三-n-丁氧基矽烷、三甲氧基單-n-戊氧基矽烷、二甲氧基二-n-戊氧基矽烷、單甲氧基三-n-戊氧基矽烷、三乙氧基單-n-丙氧基矽烷、二乙氧基二-n-丙氧基矽烷、單乙氧基三-n-丙氧基矽烷、三乙氧基單-n-丁氧基矽烷、二乙氧基二-n-丁氧基矽烷、單乙氧基三-n-丁氧基矽烷、三乙氧基單-n-戊氧基矽烷、二乙氧基二-n-戊氧基矽烷、單乙氧基三-n-戊氧基矽烷、三-n-丙氧基單-n-丁氧基矽烷、二-n-丙氧基二-n-丁氧基矽烷、單-n-丙氧基三-n-丙氧基矽烷、三-n-丙氧基單-n-戊氧基矽烷、二-n-丙氧基二-n-戊氧基矽烷、單-n-丙氧基三-n-戊氧基矽烷、三-n-丁氧基單-n-戊氧基矽烷、二-n-丁氧基二-n-戊氧基矽烷、單-n-丁氧基三-n-戊氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三-n-丙氧基矽烷、甲基三-n-丙氧基矽烷、甲基三-n-丁氧基矽烷、甲基三-n-戊氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、乙基三-n-丙氧基矽烷、乙基三-n-丁氧基矽烷、及乙基三-n-戊氧基矽烷。此等之水解性矽烷化合物(B)係可單獨使用1種,亦可將2種以上組合使用。又,上述之烷氧基矽烷化合物的部分水解縮合物亦可作為水解性矽烷化合物(B)使用。
此等之中,較佳為四甲氧基矽烷、四乙氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、及乙基三乙氧基矽烷,特佳為四甲氧基矽烷、及四乙氧基矽烷。
作為具有異氰酸酯基之水解性矽烷化合物
(B),較佳係以下述式(1)所表示之化合物。
R4-nSi(NCO)n...(1)(式(1)中,R為烴基,n為3或4之整數)。
作為式(1)中之R的烴基係在不阻礙本發明之目的的範圍內無特別限定。作為R,較佳係碳原子數1~12之脂肪族烴基、碳原子數1~12之芳香族烴基、碳原子數1~12之芳烷基。
作為碳原子數1~12之脂肪族烴基之適宜的例子係可列舉:甲基、乙基、n-丙基、異丙基、n-丁基、sec-丁基、異丁基、tert-丁基、n-戊基、異戊基、新戊基、環戊基、n-己基、環己基、n-庚基、環庚基、n-辛基、環辛基、n-壬基、n-癸基、n-十一烷基、及n-十二烷基。
作為碳原子數1~12之芳香族烴基之適宜的例子係可列舉:苯基、2-甲基苯基、3-甲基苯基、4-甲基苯基、2-乙基苯基、3-乙基苯基、4-乙基苯基、α-萘基、β-萘基、及聯苯基。
作為碳原子數1~12之芳烷基之適宜的例子係可列舉:苄基、苯乙基、α-萘甲基、β-萘甲基、2-α-萘乙基、及2-β-萘乙基。
於以上所說明之烴基中,較佳為甲基、乙基,更佳為甲基。
於以式(1)所表示之水解性矽烷化合物(B)之中,較佳為四異氰酸酯矽烷、甲基三異氰酸酯矽烷、及乙基三異氰酸酯矽烷,更佳為四異氰酸酯矽烷。
另外,亦可將具有異氰酸酯基之水解性矽烷化合物(B)、與具有碳原子數1~5之直鏈或分支鏈狀之脂肪族烷氧基之水解性矽烷化合物(B)併用。於此情況中,具有異氰酸酯基之水解性矽烷化合物(B)的莫耳數X、與具有碳原子數1~5之直鏈或分支鏈狀之脂肪族烷氧基之水解性矽烷化合物(B)的莫耳數Y之比率X/Y,較佳為1/99~99/1,更佳為50/50~95/5,特佳為60/40~90/10。
擴散劑組成物中之水解性矽烷化合物(B)之含量,作為Si之濃度,較佳為0.001~3.0質量%,更佳為0.01~1.0質量%。藉由擴散劑組成物以如此之濃度含有水解性矽烷化合物(B),而可良好地抑制來自使用擴散劑組成物所形成之薄的塗佈膜之雜質擴散成分(A)的外部擴散,而可使雜質擴散成分良好且均勻地於半導體基板I擴散。
擴散劑組成物通常是為了可形成薄膜之塗佈膜而包含有機溶劑(S)作為溶劑。有機溶劑(S)的種類係在不阻礙本發明之目的的範圍內無特別限定。
又,擴散劑組成物係由於包含水解性矽烷化
合物(B),因此以實質上不含水者為佳。擴散劑組成物中實質上不含水係意味著擴散劑組成物不含有會導致水解性矽烷化合物(B)被水解到阻礙本發明之目的的程度之量的水。
作為有機溶劑(S)之具體例係可列舉:乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚、二乙二醇單苯基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單丙基醚、二丙二醇單丁基醚、二丙二醇單苯基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、三丙二醇單甲基醚、及三丙二醇單乙基醚等之二醇類之單醚;二異戊基醚、二異丁基醚、苄基甲基醚、苄基乙基醚、二噁烷、四氫呋喃、苯甲醚、全氟-2-丁基四氫呋喃、及全氟四氫呋喃等之單醚類;乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丙基醚、乙二醇二丁基醚、丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二丙基醚、丙二醇二丁基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、二丙二醇二甲基醚、二丙二醇二乙基醚、二丙二醇二丙基醚、及二丙二醇二丁基醚等之二醇類之鏈狀二醚類;1,4-二噁烷等之環狀二醚類;1-辛酮、2-辛酮、1-壬酮、2-壬酮、丙酮、2-庚酮、4-庚酮、1-己酮、2-己酮、3-戊酮、二異丁基酮、環己酮、甲基環己
酮、苯基丙酮、甲基乙基酮、甲基異丁基酮、乙基異丁基酮、乙醯丙酮、丙酮基丙酮、紫羅蘭酮、二丙酮基醇、乙醯甲醇、苯乙酮、甲基萘酮、及異佛酮等之酮類;乙酸甲酯、乙酸丁酯、乙酸乙酯、乙酸異丙酯、乙酸戊酯、乙酸異戊酯、甲氧基乙酸乙酯、乙氧基乙酸乙酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丙基醚乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單苯基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、丙二醇單丁基醚乙酸酯、丙二醇單苯基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二醇單丙基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單苯基醚乙酸酯、二乙二醇單丁基醚乙酸酯、2-甲氧基丁基乙酸酯、3-甲氧基丁基乙酸酯、4-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、3-乙基-3-甲氧基丁基乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、2-乙氧基丁基乙酸酯、4-乙氧基丁基乙酸酯、4-丙氧基丁基乙酸酯、2-甲氧基戊基乙酸酯、3-甲氧基戊基乙酸酯、4-甲氧基戊基乙酸酯、2-甲基-3-甲氧基戊基乙酸酯、3-甲基-3-甲氧基戊基乙酸酯、3-甲基-4-甲氧基戊基乙酸酯、4-甲基-4-甲氧基戊基乙酸酯、丙二醇二乙酸酯、甲酸甲酯、甲酸乙酯、甲酸丁酯、甲酸丙酯、碳酸乙酯、碳酸丙酯、碳酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、丙酮酸丁酯、乙醯乙酸甲酯、乙醯乙酸乙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸異丙酯、甲基-3-甲氧
基丙酸酯、乙基-3-甲氧基丙酸酯、乙基-3-乙氧基丙酸酯、丙基-3-甲氧基丙酸酯、及異丙基-3-甲氧基丙酸酯、碳酸丙烯酯、及γ-丁內酯等之酯類;N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、六甲基磷三醯胺(hexamethyl phosphoric triamide)、及1,3-二甲基-2-咪唑啶酮等之不具活性氫原子的醯胺系溶劑;二甲基亞碸等之亞碸類;戊烷、己烷、辛烷、癸烷、2,2,4-三甲基戊烷、2,2,3-三甲基己烷、全氟己烷、全氟庚烷、檸檬烯、及蒎烯等之可包含鹵素之脂肪族烴系溶劑;苯、甲苯、二甲苯、乙基苯、丙基苯、1-甲基丙基苯、2-甲基丙基苯、二乙基苯、乙基甲基苯、三甲基苯、乙基二甲基苯、及二丙基苯等之芳香族烴系溶劑;甲醇、乙醇、n-丙醇、異丙醇、丁醇、異丁醇、2-甲氧基乙醇、2-乙氧基乙醇、3-甲基-3-甲氧基丁醇、己醇、環己醇、苄基醇、及2-苯氧基乙醇等之1元醇類;乙二醇、丙二醇、二乙二醇、及二丙二醇等之二醇類。另外,於上述之較佳的有機溶劑(S)的例示中,包含醚鍵與酯鍵之有機溶劑係被分類為酯類。此等係可單獨使用,亦可將2種以上組合使用。
由於擴散劑組成物包含水解性矽烷化合物(B),因此有機溶劑(S)較佳使用不具與水解性矽烷化合物(B)進行反應之官能基者。尤其,在水解性矽烷化合物(B)具有異氰酸酯基的情況,較佳係使用不具與水解性矽烷化合物(B)進行反應之官能基的有機溶劑(S)
者。
於與水解性矽烷化合物(B)進行反應之官能基中,係包含與可藉由水解生成羥基之基進行直接反應的官能基、以及與藉由水解所生成之羥基(矽醇基)進行反應的官能基雙方。作為與水解性矽烷化合物(B)進行反應之官能基係可列舉例如:羥基、羧基、胺基、鹵素原子等。
作為不具與水解性矽烷化合物(B)進行反應之官能基的有機溶劑之適宜的例子係可列舉上述之有機溶劑(S)之具體例中,作為單醚類、鏈狀二醚類、環狀二醚類、酮類、酯類、不具活性氫原子之醯胺系溶劑、亞碸類、可包含鹵素之脂肪族烴系溶劑、及芳香族烴系溶劑之具體例所列舉的有機溶劑。
擴散劑組成物亦可在不阻礙本發明之目的的範圍內,包含界面活性劑、消泡劑、pH調整劑、黏度調整劑等之各種的添加劑。又,擴散劑組成物亦可在改良塗佈性或製膜性的目的下包含黏合劑樹脂。作為黏合劑樹脂係可使用各種的樹脂,較佳為丙烯酸樹脂。
作為半導體基板I係可無特別限制地使用以往作為使雜質擴散成分擴散之對象所使用的各種基板。作為半導體
基板I,典型而言係使用矽基板。
半導體基板I亦可於擴散劑組成物所塗佈的面上具有立體構造。依據本發明,即使在半導體基板I為於該表面具有如此之立體構造,尤其是具有具備奈米級之微小的圖型之立體構造的情況時,亦可藉由以上所說明之將擴散劑組成物以成為30nm以下之膜厚的方式進行塗佈所形成之薄的塗佈膜形成於半導體基板I上,而使雜質擴散成分對於半導體基板I良好且均勻地擴散。
圖型的形狀並無特別限定,典型而言,可列舉剖面的形狀為矩形之直線狀或曲線狀的線或溝,或除去圓柱或角柱所形成之孔形狀。
在半導體基板I為於該表面具備平行的複數條線被重複配置之圖型作為立體構造的情況,作為線間之寬係可適用於60nm以下、40nm以下、或20nm以下之寬。作為線的高度係可適用於30nm以上、50nm以上、或100nm以上之高度。
擴散劑組成物係以使使用擴散劑組成物所形成之塗佈膜的膜厚成為30nm以下,較佳為0.2~10nm的方式來塗佈於半導體基板I上。
擴散劑組成物之塗佈係於半導體基板I之周圍的環境之相對濕度為40%以下,較佳為30%以下之條件下進行。
針對其機制雖不明確,但藉由在該濕度之環境下形成塗佈膜,而可使雜質擴散成分(A)從使用擴散劑組成物所形成之塗佈膜更良好地擴散至半導體基板I。
擴散劑組成物之塗佈進行時的半導體基板I之周圍的環境之相對濕度的下限,雖只要可將雜質擴散成分(A)良好地擴散則無特別限定,但較佳為5%以上,更佳為10%以上。
於水解性矽烷化合物(B)之水解中,環境中的水分係為必須,若環境之相對濕度過低,則塗佈膜轉換成二氧化矽系被膜之反應無法充分進行,恐有產生雜質擴散成分(A)往半導體基板I外擴散之虞。
調整半導體基板I之周圍的相對濕度之方法係無特別限定。可列舉例如:將塗佈裝置設置在可調濕的室內之方法、或將進行擴散劑組成物對於半導體基板I的塗佈之周圍利用壁或薄片以盡可能無間隙的方式包圍,並且將以市售之調濕裝置圍繞的空間內之相對濕度調整在特定的範圍內之方法。
進行擴散劑組成物之塗佈時之半導體基板I之周圍的環境之溫度較佳係調整為23℃以下者。
有環境之溫度越低,則雜質擴散成分(A)之擴散越良好進行的傾向。
塗佈擴散劑組成物之方法係只要可形成所期望之膜厚的塗佈膜則無特別限定。作為擴散劑組成物之塗佈方法,較佳為旋轉塗佈法、噴墨法、及噴塗法,更佳為
旋轉塗佈法。另外,塗佈膜之膜厚係使用橢圓偏光計所測定之5點以上的膜厚之平均值。
塗佈膜之膜厚係因應於半導體基板I之形狀或任意設定之雜質擴散成分(A)之擴散的程度,而適當設定為30nm以下之任意的膜厚。
較佳係在將擴散劑組成物塗佈於半導體基板I的表面之後,將半導體基板I之表面藉由有機溶劑進行清洗。藉由在塗佈膜之形成後,將半導體基板I之表面進行清洗,而可使塗佈膜之膜厚更均勻。尤其,在半導體基板I為於該表面具有立體構造者的情況,在立體構造之底部(段差部分)塗佈膜之膜厚容易變厚。但,藉由在塗佈膜之形成後將半導體基板I之表面進行清洗,而可使塗佈膜之膜厚均勻化。
作為清洗所使用之有機溶劑,係可使用擴散劑組成物可含有之前述有機溶劑。
於擴散步驟中,係使使用擴散劑組成物形成於半導體基板I上之薄的塗佈膜中之雜質擴散成分(A)於半導體基板I擴散。使雜質擴散成分(A)於半導體基板I擴散的方法係只要是藉由加熱而使雜質擴散成分(A)從由擴散劑組成物所構成之塗佈膜擴散的方法則無特別限定。
作為典型的方法,可列舉將具備由擴散劑組成物所構成的塗佈膜之半導體基板I在電爐等之加熱爐中
進行加熱的方法。此時,加熱條件係只要是雜質擴散成分被擴散達所期望的程度則無特別限定。
通常,在氧化性氣體之環境下將塗佈膜中之有機物進行燒成去除之後,在惰性氣體之環境下將半導體基板I進行加熱,使雜質擴散成分於半導體基板I中擴散。
將有機物進行燒成時之加熱,係於較佳為300~1000℃,更佳為400~800℃左右之溫度下,較佳為進行1~120分鐘,更佳為進行5~60分鐘。
使雜質擴散成分擴散時之加熱,係於較佳為800~1400℃,更佳為800~1200℃左右之溫度下,較佳為進行1~120分鐘,更佳為進行5~60分鐘。
又,在可以25℃/秒以上之昇溫速度將半導體基板I迅速地昇溫至特定的擴散溫度之情況,擴散溫度之保持時間,亦可為如30秒以下、10秒以下、或未達1秒般之極短時間。於此情況中,於半導體基板I之表面的淺區域中,容易以高濃度使雜質擴散成分進行擴散。
依據以上所說明之本發明的方法,即使在使用於該表面具備具有奈米級之微小的空隙之三維構造的半導體基板I之情況時,亦可一面抑制在半導體基板之缺陷的發生,一面於半導體基板I良好且均勻地使雜質擴散成分擴散。
因此,本發明之方法係可適宜適用於具有微小的立體構造之多重閘極元件的製造。本發明之方法係由於可抑制
雜質擴散成分之擴散時在半導體基板之缺陷的發生,因此尤其是可適宜使用於如CMOS影像感測器般之CMOS元件、或邏輯LSI裝置等之製造中。
以下,雖藉由實施例來更具體地說明本發明,但本發明並不限定於以下之實施例。
調製於乙酸n-丁酯中包含四異氰酸酯矽烷0.35質量%與三-n-丁氧基砷0.237質量%的擴散劑組成物。
於具備平坦的表面之矽基板(4吋,P型)的表面,使用旋轉塗佈機,將旋轉塗佈機之周圍的環境調整成表1記載之相對濕度,以23℃,調整旋轉數,而形成表1記載之膜厚的塗佈膜。
另外,在旋轉塗佈後,以乙酸n-丁酯進行清洗。
在如上述方式形成塗佈膜之後,依照以下的方法,來進行雜質擴散成分之擴散處理。
首先,在加熱板上將塗佈膜進行烘烤。接著,使用快速熱退火裝置(燈退火裝置),於流量1L/m之氮環境下,以昇溫速度25℃/秒之條件進行加熱,以1000℃、保持時間5秒之條件進行擴散。擴散結束後,將半導體基板急速地冷卻至室溫。
針對擴散處理後之矽基板,測定25點之薄片電阻
值,並求出薄片電阻值之平均值。將薄片電阻值之平均值記載於表1。
依據實施例1~4與比較例1之比較,得知藉由將塗佈膜形成時之相對濕度調整為40%以下,而可使雜質擴散成分良好地擴散。
如上述般,得知依據實施例1~4之方法,可使雜質擴散成分從例如膜厚10nm以下之極薄的塗佈膜良好地擴散。
如此般,依據實施例1~4方法,即使在使用於該表面具備具有奈米級之微小的空隙之三維構造的半導體基板I之情況時,亦可包含微小空隙之內表面,於基板表面整面均勻地形成極薄的塗佈膜,藉此,可於半導體基板I使雜質擴散成分良好且均勻地擴散。
Claims (6)
- 一種半導體基板之製造方法,其包含:於作為使雜質擴散成分(A)擴散的對象之半導體基板I上塗佈擴散劑組成物來形成30nm以下之膜厚的塗佈膜、與使前述擴散劑組成物中之雜質擴散成分(A)於前述半導體基板I擴散,且前述擴散劑組成物包含前述雜質擴散成分(A)、與可藉由水解生成矽醇基的Si化合物(B),在將前述擴散劑組成物進行塗佈時,前述半導體基板I之周圍的環境之相對濕度為5%以上且30%以下。
- 如請求項1之半導體基板之製造方法,其中,前述環境之溫度為23℃以下。
- 如請求項1或2之半導體基板之製造方法,其中,前述Si化合物(B)為以下式(1)所表示之化合物,R4-nSi(NCO)n...(1)(式(1)中,R為烴基,n為3或4之整數)。
- 如請求項3之半導體基板之製造方法,其中,前述塗佈膜之膜厚為0.2~6nm。
- 如請求項1之半導體基板之製造方法,其中,前述半導體基板I係於塗佈有前述擴散劑組成物之面上具有具備凸部與凹部的立體構造。
- 如請求項1之半導體基板之製造方法,其包含將前述塗佈膜藉由有機溶劑進行清洗。
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JPH06318559A (ja) * | 1993-05-07 | 1994-11-15 | Hitachi Ltd | 高エネルギーイオン注入による半導体装置の製造方法 |
JP2003338632A (ja) * | 2002-05-22 | 2003-11-28 | Sharp Corp | 太陽電池素子の製造方法、その製造方法により得られる太陽電池素子およびその製造方法に用いる太陽電池素子の製造装置 |
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