TW201917777A - 擴散劑組成物及半導體基板之製造方法 - Google Patents
擴散劑組成物及半導體基板之製造方法 Download PDFInfo
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- TW201917777A TW201917777A TW107126440A TW107126440A TW201917777A TW 201917777 A TW201917777 A TW 201917777A TW 107126440 A TW107126440 A TW 107126440A TW 107126440 A TW107126440 A TW 107126440A TW 201917777 A TW201917777 A TW 201917777A
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- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明之課題係提供一種擴散劑組成物,其可有效率地(例如藉由1次的成膜)形成較以往能以高濃度來使雜質擴散成分擴散至半導體基板中的薄膜,以及提供使用該擴散劑組成物的半導體基板之製造方法。 解決課題之手段之本發明之擴散劑組成物,其係用於對半導體基板的雜質擴散的擴散劑組成物,其特徵為, 包含雜質擴散成分(A)與矽烷偶合劑(B), 前述矽烷偶合劑(B)具有藉由水解而能生成矽烷醇基之基與烷基, 前述烷基之至少1個係於鏈中及/或末端具有選自由一級胺基、二級胺基以及三級胺基所成之群中之至少1個的胺基。
Description
本發明為關於使雜質擴散成分擴散至半導體基板而被使用的擴散劑組成物,與使用該擴散劑組成物的半導體基板之製造方法。
電晶體、二極體、太陽電池等的半導體元件中所使用的半導體基板,係使磷或硼等的雜質擴散成分對半導體基板進行擴散而製造。關於該半導體基板,在製造Fin-FET、奈米線FET等的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微小空隙的三維構造的半導體基板進行雜質的擴散。
於此,作為使雜質擴散成分擴散至半導體基板之方法,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)。離子注入法中,係將經離子化的雜質擴散成分打入半導體基板的表面。CVD法中,係將摻雜有磷或硼等的雜質擴散成分而成的矽氧化物等的氧化物膜藉由CVD來形成於半導體基板上後,將具備氧化物膜的半導體基板藉由電爐等進行加熱,來使雜質擴散成分從氧化物膜擴散至半導體基板。 [先前技術文獻] [專利文獻]
[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
[發明所欲解決之課題]
然而,如專利文獻1所記載般之離子注入法,在對半導體基板注入如B(硼)之輕離子的情形時,易於基板的表面附近區域形成點缺陷或點缺陷團簇(Cluster)。例如藉由離子注入法使雜質擴散成分擴散至半導體基板,形成如CMOS影像感測器之元件的情形時,此種缺陷的產生會直接導致元件性能的降低。
又,半導體基板,例如於其表面具有如立體構造之奈米級三維構造(該三維構造係用來形成具備複數個源極(Source)的鰭片(Fin)、複數個汲極(Drain)的鰭片及與該等鰭片正交之閘極(Gate),且被稱為Fin-FET的多閘極元件)的情形,於離子注入法時,係不易對鰭片或閘極之側面及上面、或由鰭片與閘極所包圍之凹部的內表面整面均勻地打入離子。 對於具有奈米級三維構造之半導體基板的雜質擴散的不均勻性,亦成為使如前述CMOS影像感測器般的元件的性能降低之因素。
而且,藉由離子注入法來使雜質擴散成分擴散至具有奈米級三維構造之半導體基板時,假設即使是可均勻地打入離子,仍有如下述的不良狀況。例如,使用具備具有微細鰭片之立體圖型的半導體基板來形成邏輯LSI裝置等時,容易因離子注入導致破壞矽等的基板材料的結晶。該結晶的損壞,係認為會導致如裝置特性的參差不齊、或待機洩漏電流的產生之問題。
又,適用如專利文獻2所記載般之CVD法時,因外伸(Overhang)現象而具有下述般之問題:不易將由鰭片與閘極所包圍之凹部的內表面整面,以膜厚呈均勻的包含雜質擴散成分的氧化物膜被覆、或因堆積於由鰭片與閘極所包圍之凹部的開口部之氧化物而堵塞了開口部。如此般地,離子注入法或CVD法時,隨著半導體基板之表面形狀不同,不易使雜質擴散成分良好且均勻地於半導體基板擴散。
於其表面具有奈米級三維構造之半導體基板中,為了提高雜質擴散成分的擴散均勻性,係認為會使用塗佈型的擴散劑組成物。 於其表面具備具有奈米級微小空隙的三維構造之基板中,只要是可將塗佈型的擴散劑組成物均勻地塗佈至包含微小空隙的內表面整面的全表面的話,可使硼等的雜質在該具有立體表面之半導體基板中均勻地擴散。
然而,即使是使用塗佈型的擴散劑組成物,隨著擴散劑組成物的組成不同,具有難以使雜質擴散成分良好地於半導體基板擴散之情形。
本發明係有鑑於上述課題而完成之發明,以提供一種能將雜質擴散成分良好地擴散至半導體基板中的擴散劑組成物及使用該擴散劑組成物的半導體基板之製造方法為目的。 [解決課題之手段]
本發明人發現,藉由在包含雜質擴散成分(A)的擴散劑組成物中,使含有具有至少1個的胺基而成的具有烷基的矽烷偶合劑,可解決上述課題,終至完成本發明。即,本發明如同下述。
本發明之第一樣態為一種擴散劑組成物,其係用於對半導體基板的雜質擴散的擴散劑組成物, 包含雜質擴散成分(A)與矽烷偶合劑(B), 前述矽烷偶合劑(B)具有藉由水解而能生成矽烷醇基之基與烷基, 前述烷基之至少1個係於鏈中及/或末端具有選自由一級胺基、二級胺基以及三級胺基所成之群中之至少1個的胺基。
本發明之第二樣態為一種半導體基板之製造方法,其包含: 藉由將第一樣態相關的擴散劑組成物塗佈至半導體基板上來形成塗佈膜;與 使擴散劑組成物中的雜質擴散成分(A)擴散至半導體基板中。 [發明之效果]
依據本發明,可提供一種能將雜質擴散成分良好地擴散至半導體基板中的擴散劑組成物及使用該擴散劑組成物的半導體基板之製造方法。
[實施發明之形態]
以下為對於本發明之實施樣態進行詳細說明,但本發明並不受下述實施樣態任何限定,在本發明之目的範圍內,可加以適當變更來予以實施。
≪擴散劑組成物≫ 其係用於對半導體基板的雜質擴散的擴散劑組成物,且包含雜質擴散成分(A)與矽烷偶合劑(B)。 以下為對於擴散劑組成物所包含的必須或任意的成分進行說明。
[雜質擴散成分(A)] 雜質擴散成分(A)係只要是以往的對半導體基板之摻雜所使用的成分即可並無特別限定,可為p型摻雜劑、亦可為n型摻雜劑。作為p型摻雜劑係可舉出硼、鎵、銦及鋁等的單質、以及包含該等元素的化合物。作為n型摻雜劑係可舉出磷、砷及銻等的單質、以及包含該等元素的化合物。
以下,藉由硼化合物及磷化合物來分別進行說明。
(硼化合物) 作為硼化合物,只要是展現出本案發明之效果的化合物即可,並無特別限定。作為較佳的硼化合物,可舉出選自由下述式(a1)~(a4)所表示之化合物所成之群中之1種以上的硼化合物:(式(a1)中,Ra1
係分別獨立為氫原子、碳原子數1以上10以下的烴基,Ra2
為氫原子或碳原子數1以上10以下的烴基,但Ra1
及Ra2
之至少一方為烴基,Ra3
為碳原子數1以上10以下的2價脂肪族烴基; 式(a2)中,Ra4
為碳原子數1以上10以下的烴基,Ra5
為氫原子或碳原子數1以上10以下的烴基,Ra6
為碳原子數1以上10以下的2價脂肪族烴基; 式(a3)中,Ra7
係分別獨立為碳原子數1以上10以下的烴基,Ra8
係分別獨立為氫原子或碳原子數1以上10以下的烴基,Ra9
為碳原子數1以上10以下的2價的烴基,p為0或1; 式(a4)中,Ra10
係分別獨立為氫原子、碳原子數1以上10以下的烴基,Ra11
係分別獨立為氫原子或碳原子數1以上10以下的烴基,但Ra10
及Ra11
之至少一方為烴基,Ra12
係分別獨立為碳原子數1以上10以下的2價的烴基)。
(式(a1)所表示之化合物) 式(a1)中,Ra1
係分別獨立為氫原子、碳原子數1以上10以下的烴基,Ra2
為氫原子或碳原子數1以上10以下的烴基,Ra3
為碳原子數1以上10以下的2價脂肪族烴基。但Ra1
及Ra2
之至少一方為烴基。 作為Ra1
及Ra2
之碳原子數1以上10以下的烴基之方面,可以是脂肪族烴基、也可以是芳香族烴基、也可以是組合該等之基。 作為烴基的適合的具體例,可舉出甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基、n-己基、n-庚基、n-辛基、2-乙基己基、n-壬基及n-癸基等的烷基;環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基及環癸基等的環烷基;乙烯基、芳基(2-丙烯基)、3-丁烯基、4-戊烯基及5-己烯基等的烯基;苯基、萘-1-基、萘-2-基等的芳香族烴基;苄基及苯乙基等的芳烷基;o-甲苯基、m-甲苯基、p-甲苯基、o-乙基苯基、m-乙基苯基及p-乙基苯基等的經烷基取代的芳香族烴基。 作為Ra1
係以甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、苯基及苄基為較佳。作為Ra2
係以氫原子、甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、苯基及苄基為較佳。
作為Ra3
的脂肪族烴基,可以是直鏈狀、也可以是支鏈狀,但以直鏈狀者為較佳。作為R3
的適合例子有亞甲基、乙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、辛烷-1,8-二基、壬烷-1,9-二基及癸烷-1,10-二基。 作為Ra3
係以乙烷-1,2-二基及丙烷-1,3-二基為較佳。
(式(a2)所表示之化合物) 式(a2)中,Ra4
為碳原子數1以上10以下的烴基,Ra5
為氫原子或碳原子數1以上10以下的烴基,Ra6
為碳原子數1以上10以下的2價脂肪族烴基。 作為Ra4
及Ra5
之碳原子數1以上10以下的烴基的適合例子之方面,係與Ra1
及Ra2
的適合例子為相同。作為Ra4
係以甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、苯基及苄基為較佳。作為Ra5
係以氫原子、甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、苯基及苄基為較佳。 作為Ra6
之碳原子數1以上10以下的2價脂肪族烴基的適合例子之方面,係與Ra3
的適合例子為相同。作為Ra6
係以丙烷-1,3-二基及丁烷-1,4-二基為較佳。
(式(a3)所表示之化合物) 式(a3)中,Ra7
係分別獨立為碳原子數1以上10以下的烴基,Ra8
係分別獨立為氫原子或碳原子數1以上10以下的烴基,Ra9
為碳原子數1以上10以下的2價的烴基,p為0或1。p係以1為較佳。 作為Ra7
及Ra8
之碳原子數1以上10以下的烴基的適合例子之方面,係與Ra1
及Ra2
的適合例子為相同。作為Ra7
係以甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、苯基及苄基為較佳,以tert-丁基及苄基為又較佳。作為Ra8
係以氫原子、甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、苯基及苄基為較佳,以甲基、乙基、n-丙基為又較佳。 作為Ra9
之碳原子數1以上10以下的2價脂肪族烴基的適合例子之方面,係與Ra3
的適合例子為相同。作為Ra9
係以乙烷-1,2-二基、丙烷-1,3-二基及丁烷-1,4-二基為較佳。
(式(a4)所表示之化合物) 式(a4)中,Ra10
係分別獨立為氫原子、碳原子數1以上10以下的烴基,Ra11
係分別獨立為氫原子或碳原子數1以上10以下的烴基,但Ra10
及Ra11
之至少一方為烴基,Ra12
係分別獨立為碳原子數1以上10以下的2價的烴基。 作為Ra10
及Ra11
之碳原子數1以上10以下的烴基的適合例子之方面,係與Ra1
及Ra2
的適合例子為相同。作為Ra10
係以甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、苯基及苄基為較佳,以tert-丁基及苄基為又較佳。作為Ra11
係以氫原子、甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、苯基及苄基為較佳,以甲基、乙基、n-丙基為又較佳。 作為Ra12
之碳原子數1以上10以下的2價脂肪族烴基的適合例子之方面,係與Ra3
的適合例子為相同。作為Ra12
係以亞甲基及乙烷-1,2-二基為較佳,以亞甲基為又較佳。
以上說明之式(a1)~式(a4)所表示之化合物中,就易於合成或取得之觀點、或易於良好地擴散雜質擴散成分而言,以式(a1)所表示之化合物為較佳。
作為式(a1)所表示之化合物的具體例,可舉出以下之化合物。
(磷化合物) 作為磷化合物,可舉出磷酸參(三烷基甲矽烷基)酯、亞磷酸參(三烷基甲矽烷基)酯、亞磷酸酯類、磷酸酯類等。該等之中,以磷酸參(三甲基甲矽烷基)酯(tris(trimethylsilyl)phosphate)、亞磷酸參(三甲基甲矽烷基)酯(tris(trimethylsilyl)phosphite)、磷酸三甲酯、磷酸三乙酯、亞磷酸三甲酯及亞磷酸三乙酯為又較佳。
若雜質擴散成分(A)包含磷化合物之情形時,雜質擴散成分係以包含磷酸參(三甲基甲矽烷基)酯及/或亞磷酸參(三甲基甲矽烷基)酯者為較佳。
擴散劑組成物中的雜質擴散成分(A)的含量並無特別限定。相對於擴散劑組成物的全質量,雜質擴散成分(A)的含量係以0.1質量%以上30質量%以下為較佳,以0.5質量%以上20質量%以下為又較佳,以1質量%以上15質量%以下為特佳。
[矽烷偶合劑(B)] 擴散劑組成物係包含矽烷偶合劑(B)。 矽烷偶合劑(B)具有藉由水解而能生成矽烷醇基之基與烷基,且該烷基之至少1個係於鏈中及/或末端具有選自由一級胺基、二級胺基以及三級胺基所成之群中之至少1個的胺基。 藉由使用包含該矽烷偶合劑(B)之擴散劑組成物,使得雜質擴散成分能良好地從使用擴散劑組成物所形成的塗佈膜擴散至半導體基板中。此係認為是,因為分子中的胺基的影響,使得矽烷偶合劑(B)彼此的水解縮合變得可易於良好地進行,而可使塗佈膜的膜厚變厚,因而可容易地使雜質擴散成分(A)以高濃度來進行導入之故。
本說明書中,所謂上述「於鏈中及/或末端」具有該等的胺基,具體而言係指下述含意:於烷基(以下,本段落中稱為-Cn
H2n + 1
(n為整數)所表示之通常含意的烷基)的鏈中嵌入選自由二級胺基及三級胺基所成之群中之至少1個的胺基;胺基鍵結於烷基的鏈中的二級碳原子或三級碳原子;以及/或胺基(-NH2
;一級胺基)鍵結於烷基的末端的碳原子。若三級胺基嵌入於烷基的鏈中之情形時,係相當於在烷基的鏈中嵌入的二級胺基中的氫原子被烷基所取代之構造。
作為胺基係以一級胺基及二級胺基為較佳。 就達成本發明之效果之觀點而言,矽烷偶合劑每1分子中的胺基係較佳為1個以上5個以下,但又較佳為1個以上3個以下,即使是僅只1個亦可達成本發明之效果。
作為矽烷偶合劑(B)所具有的「藉由水解而能生成矽烷醇基之基」,可舉出與矽烷偶合劑(B)的矽原子鍵結的烷氧基、異氰酸酯基、二甲基胺基、鹵素原子等。作為烷氧基係以碳原子數1以上5以下的直鏈或支鏈狀的脂肪族烷氧基為較佳。作為適合的烷氧基的具體例,可舉出甲氧基、乙氧基、n-丙氧基、異丙氧基及n-丁氧基等。作為鹵素原子係以氯原子、氟原子、溴原子及碘原子為較佳,以氯原子為又較佳。
作為藉由水解而能生成矽烷醇基之基,就能容易快速地水解、以及矽烷偶合劑(B)的操作性或取得的容易性之觀點而言,以碳原子數1以上5以下的直鏈或支鏈狀的脂肪族烷氧基或異氰酸酯基為較佳,以甲氧基、乙氧基或異氰酸酯基為又較佳。
矽烷偶合劑(B)係以包含下述式(1)所表示之矽烷偶合劑者為較佳:(式(1)中,R1
為伸烷基,作為R1
的伸烷基,可被選自二級胺基及三級胺基之1個以上的胺基中斷,R2
為藉由C-Si鍵而鍵結於矽原子的1價有機基,R3
為烷基,m為0以上2以下之整數)。
作為關於R1
的可被選自二級胺基及三級胺基之1個以上的胺基中斷的伸烷基,可舉出可被選自二級胺基及三級胺基之1個以上(例如1或2)的胺基中斷的碳原子數1以上10以下的伸烷基。該伸烷基的碳原子數係以1以上8以下為較佳,以1以上7以下為又較佳。作為R1
,係以可被選自二級胺基及三級胺基之1個以上(例如1或2)的胺基中斷的碳原子數1以上6以下的伸烷基為特佳。 作為R1
的適合的具體例,可舉出亞甲基、乙烷-1,2-二基、丙烷-1,3-二基及丁烷-1,4-二基、或將此等的2價基與1或2個的胺基予以組合而構成的2價基等。
作為關於R2
的藉由C-Si鍵而鍵結於矽原子的1價有機基,在不妨礙本發明之目的之範圍內,並無特別限定。作為該有機基的適合例子,可舉出烴基等。烴基的碳原子數係以1以上20以下為較佳。 其中,以鏈狀或環狀的烷基、芳香族烴基或芳烷基為又較佳。
作為鏈狀或環狀的烷基,可舉出碳原子數1以上12以下的鏈狀或環狀的烷基,具體而言可舉出甲基、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、n-十二烷基等。
作為芳香族烴基,可舉出碳原子數1以上12以下的芳香族烴基,具體而言可舉出苯基、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、聯苯基等。
作為芳烷基,可舉出碳原子數1以上12以下的芳烷基,具體而言可舉出苄基、苯乙基、α-萘基甲基、β-萘基甲基、2-α-萘基乙基及2-β-萘基乙基。 作為關於R2
的藉由C-Si鍵而鍵結於矽原子的1價有機基,以甲基或乙基為較佳,以甲基為又較佳。 作為關於R3
的烷基,可舉出碳原子數1以上12以下的鏈狀或環狀的烷基,具體而言可舉出甲基、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、n-十二烷基等。 m係以0或1為較佳,m係以0為又較佳。
作為矽烷偶合劑(B)的較佳的具體例,可舉出下述式(a)~(f)之各別所表示之3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三乙氧基矽烷、3-[2-(2-胺基乙基胺基乙基胺基)丙基]三甲氧基矽烷等。 該等之矽烷偶合劑(B)係可使用單獨1種、或可組合2種以上來使用。又,該等化合物的部分水解縮合物亦可使用作為矽烷偶合劑(B)。
於矽烷偶合劑(B)的質量中上述式(1)所表示之矽烷偶合劑的質量係以50質量%以上為較佳,以70質量%以上為又較佳,以90質量%以上為特佳,以100質量%為最佳。
擴散劑組成物中的矽烷偶合劑(B)的含量並無特別限定,但相對於擴散劑組成物的全質量,以0.01質量%以上5.0質量%以下為較佳,以0.03質量%以上3.0質量%以下為又較佳,以0.05質量%以上2.0質量%以下為特佳。藉由以如此般的濃度來使擴散劑組成物含有矽烷偶合劑(B),可容易地將雜質擴散成分(A)良好地從使用擴散劑組成物所形成的塗佈膜擴散至半導體基板中。
[有機溶劑(S)] 藉由塗佈從而容易形成所期望的膜厚的塗佈膜之觀點而言,擴散劑組成物係以包含有機溶劑(S)來作為溶媒為較佳。有機溶劑(S)的種類,在不妨礙本發明之目的之範圍內,並無特別限定。
又,由於擴散劑組成物包含矽烷偶合劑(B),故實質上以不包含水為較佳。所謂擴散劑組成物中實質上不包含水,係指擴散劑組成物中不含有會使矽烷偶合劑(B)水解至無法得到藉由該矽烷偶合劑(B)之添加所能期望之效果之程度的水量之含意。
作為溶劑(S)的具體例,可舉出乙二醇單甲基醚、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的乙二醇類的單醚;二異戊基醚(二異戊醚)、二丁基醚、二異丁基醚、tert-丁基甲基醚、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的單醚類;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的乙二醇類的鏈狀二醚類;1,4-二噁烷等的環狀二醚類;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、甲基萘基酮及異佛酮等的酮類;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、碳酸伸丙酯及γ-丁內酯等的酯類;N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、六甲基磷酸三醯胺及1,3-二甲基-2-咪唑啉酮等的不具有活性氫原子的醯胺系溶劑;二甲基亞碸等的亞碸類;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、檸檬烯及蒎烯等的可包含鹵素的脂肪族烴系溶劑;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的芳香族烴系溶劑;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-苯氧基乙醇等的1價醇類;乙二醇、丙二醇、二乙二醇及二丙二醇等的乙二醇類。尚,上述之較佳的有機溶劑(S)的例中,包含醚鍵與酯鍵的有機溶劑係分類為酯類。該等係可單獨使用、或可組合2種以上來使用。
由於擴散劑組成物包含矽烷偶合劑(B),故有機溶劑(S)係較佳使用不具有與矽烷偶合劑(B)反應的官能基者。特別是若矽烷偶合劑(B)具有異氰酸酯基之情形時,以使用不具有與矽烷偶合劑(B)反應的官能基的有機溶劑(S)者為較佳。
會與矽烷偶合劑(B)反應的官能基係包含:與藉由水解而能生成羥基之基會直接反應的官能基、和、與藉由水解所生成的羥基(矽烷醇基)會反應的官能基之兩者。作為與矽烷偶合劑(B)會反應的官能基,可舉出例如羥基、羧基、胺基、鹵素原子等。
作為不具有與矽烷偶合劑(B)反應的官能基的有機溶劑的適合例子,上述之有機溶劑(S)的具體例中,可舉出例如作為單醚類、鏈狀二醚類、環狀二醚類、酮類、酯類、不具有活性氫原子的醯胺系溶劑、亞碸類、可包含鹵素的脂肪族烴系溶劑及芳香族烴系溶劑之具體例的有機溶劑。
[其他的成分] 擴散劑組成物在不妨礙本發明之目的之範圍內,也可包含界面活性劑、消泡劑、pH調整劑、黏度調整劑等的各種的添加劑。又,擴散劑組成物係依改良塗佈性、或製膜性之目的下也可包含黏合劑樹脂。作為黏合劑樹脂係可使用各種的樹脂,以丙烯酸樹脂為較佳。
藉由將分別指定量的以上說明的成分均勻地混合,從而可製造擴散劑組成物。
≪半導體基板之製造方法≫ 半導體基板之製造方法係包含: 藉由塗佈前述之擴散劑組成物來形成塗佈膜;與使擴散劑組成物中的雜質擴散成分(A)擴散至半導體基板中。 以下,亦將形成塗佈膜之步驟記載為「塗佈步驟」,將使雜質擴散成分(A)擴散至半導體基板中之步驟記載為「擴散步驟」。以下,對於塗佈步驟及擴散步驟依序來進行說明。
[塗佈步驟] 塗佈步驟係在半導體基板上塗佈擴散劑組成物來形成塗佈膜。以下,對於塗佈步驟依照擴散劑組成物、半導體基板、塗佈方法之順序來進行說明。
(半導體基板) 作為半導體基板,可無特別限制地使用以往以來作為使雜質擴散成分擴散之對象而被使用的各種基板。作為半導體基板,典型上係可使用矽基板。
半導體基板係可在塗佈擴散劑組成物的面上具有立體構造。依據本發明,即使是半導體基板於其表面上具有如此般的立體構造(特別是具備奈米級之微小圖型的立體構造)時,以成為例如1nm以上100nm以下的膜厚之方式來塗佈上述說明之擴散劑組成物,並將所形成的薄型塗佈膜形成在半導體基板上,藉此可使雜質擴散成分對於半導體基板呈良好且均勻地擴散。
圖型的形狀並無特別限定,但典型上可舉出斷面形狀為矩形的直線狀或曲線狀的線或溝、或孔洞形狀。
若半導體基板在其表面上具備重複配置的平行的複數條線之圖型來作為立體構造時,作為線間的寬能夠適用於1μm以下、100nm以下、60nm以下或20nm以下的寬度。作為線的高度能夠適用於30nm以上、100nm以上、1μm以上或5μm以上的高度。
(塗佈方法) 使用擴散劑組成物所形成的塗佈膜的膜厚並無特別限定。擴散劑組成物之使用擴散劑組成物所形成的塗佈膜的膜厚,就兼具雜質擴散劑成分(A)之良好的擴散、與於擴散後殘留的膜為容易剝離之觀點而言,以5nm以上100nm以下為較佳,以10nm以上80nm以下為又較佳,以15nm以上50nm以下為特佳。 尚,所謂塗佈膜的膜厚,係指提供於擴散步驟的塗佈膜的膜厚。例如,於擴散步驟之前若進行以有機溶劑之淋洗時,將淋洗後的膜厚設為塗佈膜的膜厚。
擴散劑組成物的塗佈係以半導體基板的周圍環境的相對濕度為40%以下為宜,較佳以30%以下的條件下來進行。 關於機制尚未明確,但藉由在該濕度的環境來形成塗佈膜,可使雜質擴散成分(A)更加良好地從使用擴散劑組成物所形成的塗佈膜擴散至半導體基板中。
進行擴散劑組成物的塗佈時,半導體基板的周圍環境的相對濕度的下限,只要是可使雜質擴散成分(A)良好地擴散即可,並無特別限定,但就使矽烷偶合劑(B)的藉由水解之縮合可良好地進行之觀點而言,以5%以上為較佳,以10%以上為又較佳。
調整半導體基板的周圍的相對濕度之方法並無特別限定。例如,將塗佈裝置設置在能夠調濕的室內之方法;或,將對於半導體基板之擴散劑組成物之塗佈之周圍,利用牆壁或薄片並以盡可能無間隙之方式來包圍外,以市售的調濕裝置來將所圍繞的空間內的相對濕度調整在指定的範圍內之方法。
塗佈膜係100℃以上300℃以下,較佳係可被加熱至150℃以上250℃以下左右的溫度。加熱時間並無特別限定,但例如為60秒以上180秒以下左右。認為是藉由進行該加熱,從而使得膜的穩定性有提升之傾向。
塗佈擴散劑組成物之方法,只要是可形成所期望的膜厚的塗佈膜即可,並無特別限定。作為擴散劑組成物的塗佈方法係以旋塗法、噴墨法及噴塗法為較佳,以旋塗法為又較佳。
塗佈膜的膜厚係可因應半導體基板的形狀、或任意所設定的雜質擴散成分(A)的擴散程度,來做適當設定為任意的膜厚。
於擴散劑組成物的對於半導體基板表面的塗佈中,亦以藉由有機溶劑來淋洗半導體基板的表面者為較佳。在塗佈膜之形成中,藉由淋洗半導體基板的表面,從而可使塗佈膜的膜厚呈更加均勻。特別是,若半導體基板為在其表面上具有立體構造者時,在立體構造的底部(高低差部分)的塗佈膜的膜厚將容易變厚。但,藉由在塗佈膜之形成後淋洗半導體基板的表面,從而可使塗佈膜的膜厚均勻化。
作為使用於淋洗的有機溶劑,可使用擴散劑組成物亦能含有的前述的有機溶劑。
[擴散步驟] 擴散步驟係將使用擴散劑組成物而在半導體基板上所形成的薄型塗佈膜中的雜質擴散成分(A)擴散至半導體基板中。使雜質擴散成分(A)擴散至半導體基板中之方法,只要是藉由加熱而能使雜質擴散成分(A)從塗佈膜(其係由擴散劑組成物所構成者)擴散之方法即可,並無特別限定。
作為典型的方法,可舉出將具備由擴散劑組成物所構成的塗佈膜的半導體基板在電爐等的加熱爐中進行加熱之方法。此時,加熱條件係只要是能使雜質擴散成分(A)依照所期望的程度來進行擴散即可,並無特別限定。
通常,在包含氧的環境下將塗佈膜中的有機物予以燒成除去後,在惰性氣體的環境下將半導體基板加熱,從而使雜質擴散成分(A)擴散至半導體基板中。 將有機物進行燒成時的加熱,較佳為300℃以上1000℃以下,又較佳為400℃以上800℃以下左右的溫度下,較佳為進行1秒以上10分以下,又較佳為5秒以上5分鐘以下。 使雜質擴散成分(A)擴散時的加熱,較佳為700℃以上1400℃以下,又較佳為700℃以上未滿1200℃的溫度下,較佳為進行1分以上120分以下,又較佳為5分以上60分鐘以下。
又,在能以25℃/秒以上的昇溫速度來使半導體基板快速地昇溫至指定的擴散溫度之情形時,擴散溫度的保持時間也可以是60秒以下、30秒以下、10秒以下或未滿1秒之極短時間。此情形時,在半導體基板表面較淺的區域中,可容易使雜質擴散成分(A)以高濃度進行擴散。
依據以上說明之方法,可使用前述之擴散劑組成物在半導體基板上形成較佳的薄膜,藉此可使雜質擴散成分良好地擴散至半導體基板中。 [實施例]
以下為藉由實施例更具體地說明本發明,但本發明並非被限定於以下之實施例中。
[實施例1~4及比較例1~9] 作為雜質擴散成分((A)成分)為使用下述式所表示之N,N’-二-tert-丁基-1,3-二氮雜硼環戊烷。
作為矽烷偶合劑((B)成分)為使用下述B1~B7的矽烷偶合劑。 B1:3-胺基丙基三乙氧基矽烷 B2:3-胺基丙基三甲氧基矽烷 B3:甲基三乙氧基矽烷 B4:二甲基二乙氧基矽烷 B5:苯基三甲氧基矽烷 B6:3-縮水甘油氧基丙基三甲氧基矽烷
以(A)成分的濃度成為5質量%、(B)成分的濃度成為表1所記載之濃度之方式,將(A)成分、與表1所記載之種類的(B)成分溶解至丙二醇單甲基醚乙酸酯(PGMEA)中,從而得到各實施例及比較例之擴散劑組成物。尚,比較例1中未使用(B)成分。
作為擴散對象的基板,準備已施予藉由濃度0.5質量%的氫氟酸水溶液之洗淨、與藉由離子交換蒸餾水之洗淨後,經乾燥的具備平坦表面的矽基板(6吋、n型)。 以30%的相對濕度條件下,使用旋轉塗佈機,將各實施例及比較例的擴散劑組成物分別塗佈至矽基板的表面上後,以丙二醇單甲基醚乙酸酯(PGMEA)來進行淋洗,從而形成塗佈膜。將所形成的塗佈膜的膜厚記載於表1中。 尚,關於比較例9的擴散劑組成物,由於在淋洗後幾乎不殘留膜,故不進行擴散試驗。
在塗佈膜之形成後,根據以下之方法來進行雜質擴散成分的擴散處理。 使用快速熱退火裝置(燈退火裝置),在流量1L/m的氮環境下,以昇溫速度25℃/秒之條件來進行加熱,並藉以擴散溫度1050℃及擴散時間10秒之條件來進行擴散處理。擴散時間的起點係基板的溫度到達指定的擴散溫度之時間點。在擴散之結束後,將矽基板急速地冷卻至室溫。
將擴散後的矽基板利用濃度0.5質量%的氫氟酸水溶液來進行5分鐘處理,以剝離擴散處理後的矽基板上所殘留的膜。接下來,在進行藉由離子交換蒸餾水之洗淨與乾燥後,測定矽基板的薄片電阻值。將薄片電阻值的測定結果記載於表1中。
依據實施例1~4可得知,藉由使用組合包含作為雜質擴散成分(A)的硼化合物、與包含胺基的指定構造的矽烷偶合劑(B)的擴散劑組成物,從而可使雜質擴散成分(A)良好地擴散至半導體基板中。 另一方面,依據比較例1~9可得知,若擴散劑組成物係以含有不包含胺基的烷氧基矽烷、或不含有相當於矽烷偶合劑(B)的成分,來替代包含胺基的指定構造的矽烷偶合劑(B)之情形時,根本而言連塗佈膜之良好的形成都為困難、或難以將雜質擴散成分(A)良好地擴散至半導體基板中。
[實施例5~10及比較例10] 作為雜質擴散成分((A)成分)為使用磷酸參(三甲基甲矽烷基)酯。 作為矽烷偶合劑((B)成分)為使用前述之B1(3-胺基丙基三乙氧基矽烷)及B2(3-胺基丙基三甲氧基矽烷)。
以(A)成分的濃度成為表2所記載之濃度、(B)成分的濃度成為表2所記載之濃度之方式,將(A)成分、與表2所記載之種類的(B)成分溶解至丙二醇單甲基醚乙酸酯(PGMEA)中,從而得到各實施例及比較例之擴散劑組成物。尚,比較例10中未使用(B)成分。
作為擴散對象的基板,準備已施予藉由濃度0.5質量%的氫氟酸水溶液之洗淨、與藉由離子交換蒸餾水之洗淨後,經乾燥的具備平坦表面的矽基板(6吋、p型)。 以30%的相對濕度條件下,使用旋轉塗佈機,將各實施例及比較例的擴散劑組成物分別塗佈至矽基板的表面上後,以丙二醇單甲基醚乙酸酯(PGMEA)來進行淋洗,從而形成塗佈膜。將所形成的塗佈膜的膜厚記載於表2中。 尚,關於比較例10的擴散劑組成物,由於在淋洗後幾乎不殘留膜,故不進行擴散試驗。
在塗佈膜之形成後,根據以下之方法來進行雜質擴散成分的擴散處理。 使用快速熱退火裝置(燈退火裝置),在流量1L/m的氮環境下,以昇溫速度25℃/秒之條件來進行加熱,並藉以擴散溫度1050℃及擴散時間10秒之條件來進行擴散處理。擴散時間的起點係基板的溫度到達指定的擴散溫度之時間點。在擴散之結束後,將矽基板急速地冷卻至室溫。
將擴散後的矽基板利用濃度0.5質量%的氫氟酸水溶液來進行5分鐘處理,以剝離擴散處理後的矽基板上所殘留的膜。接下來,在進行藉由離子交換蒸餾水之洗淨與乾燥後,測定矽基板的薄片電阻值。將薄片電阻值的測定結果記載於表2中。
對於使用實施例6的擴散劑組成物並施予擴散處理的矽基板,使用四極型二次離子質譜分析(Q-SIMS)裝置,測定磷濃度(atoms/cc)、與擴散深度。其結果,在使用實施例7的擴散劑組成物並對於矽基板來進行雜質擴散之情形時,可使深度10nm或20nm的較淺區域中的磷濃度為超過1020
(atoms/cc)的高濃度,得知為可良好地擴散雜質擴散成分。
依據實施例5~10可得知,即使是使用作為雜質擴散成分(A)的磷化合物之情形時,藉由使用組合包含作為雜質擴散成分(A)的磷化合物、與包含胺基的指定構造的矽烷偶合劑(B)的擴散劑組成物,亦能使雜質擴散成分(A)良好地擴散至半導體基板中。 另一方面,依據比較例10可得知,若擴散劑組成物不含有相當於矽烷偶合劑(B)的成分之情形時,根本而言連塗佈膜之良好的形成都為困難。
Claims (9)
- 一種擴散劑組成物,其係用於對半導體基板的雜質擴散的擴散劑組成物,其特徵為, 包含雜質擴散成分(A)與矽烷偶合劑(B), 前述矽烷偶合劑(B)具有藉由水解而能生成矽烷醇基之基與烷基, 前述烷基之至少1個係於鏈中及/或末端具有選自由一級胺基、二級胺基以及三級胺基所成之群中之至少1個的胺基。
- 如請求項1之擴散劑組成物,其中,前述矽烷偶合劑包含下述式(1)所表示之矽烷偶合劑,(式(1)中,R1 為伸烷基,作為R1 的伸烷基,可被選自二級胺基及三級胺基之1個以上的胺基中斷,R2 為藉由C-Si鍵而鍵結於矽原子的1價有機基,R3 為烷基,m為0以上2以下之整數)。
- 如請求項1之擴散劑組成物,其中,前述雜質擴散成分(A)為硼化合物或磷化合物。
- 如請求項3之擴散劑組成物,其中,前述雜質擴散成分(A)包含下述式(a1)所表示之硼化合物,(式(a1)中,Ra1 係分別獨立為氫原子、碳原子數1以上10以下的烴基,Ra2 為氫原子或碳原子數1以上10以下的烴基,但Ra1 及Ra2 之至少一方為烴基,Ra3 為碳原子數1~10的2價脂肪族烴基)。
- 如請求項3之擴散劑組成物,其中,前述雜質擴散成分(A)包含磷酸參(三甲基甲矽烷基)酯及/或亞磷酸參(三甲基甲矽烷基)酯。
- 一種半導體基板之製造方法,其特徵為包含: 藉由將請求項1~5中任1項之擴散劑組成物塗佈至半導體基板上來形成塗佈膜;與 使前述擴散劑組成物中的雜質擴散成分(A)擴散至前述半導體基板中。
- 如請求項6之半導體基板之製造方法,其中,在前述擴散劑組成物的塗佈中或塗佈後,藉由有機溶劑來進行淋洗。
- 如請求項6或7之半導體基板之製造方法,其中,供給於前述雜質擴散成分(A)之擴散的前述塗佈膜之膜厚為5nm以上100nm以下。
- 一種請求項1之擴散劑組成物之應用,其係對半導體基板之雜質擴散。
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