TW201623147A - 利用選擇性氟化硼前驅物之硼離子植入方法,及供植入用 之大群氫化硼之形成方法 - Google Patents
利用選擇性氟化硼前驅物之硼離子植入方法,及供植入用 之大群氫化硼之形成方法 Download PDFInfo
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 203
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 239000002243 precursor Substances 0.000 title claims abstract description 96
- 238000005468 ion implantation Methods 0.000 title claims description 18
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title abstract description 72
- 238000002513 implantation Methods 0.000 title abstract description 20
- 150000001638 boron Chemical class 0.000 title abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title description 9
- 150000002500 ions Chemical class 0.000 claims abstract description 60
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- 239000007943 implant Substances 0.000 claims description 16
- -1 boron ions Chemical class 0.000 claims description 9
- 238000010884 ion-beam technique Methods 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 54
- 239000002019 doping agent Substances 0.000 abstract description 53
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract description 42
- 229910010277 boron hydride Inorganic materials 0.000 abstract description 30
- 229910015900 BF3 Inorganic materials 0.000 abstract description 27
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- WCZAXBXVDLKQGV-UHFFFAOYSA-N n,n-dimethyl-2-(7-oxobenzo[c]fluoren-5-yl)oxyethanamine oxide Chemical compound C12=CC=CC=C2C(OCC[N+](C)([O-])C)=CC2=C1C1=CC=CC=C1C2=O WCZAXBXVDLKQGV-UHFFFAOYSA-N 0.000 description 5
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- AIGRXSNSLVJMEA-FQEVSTJZSA-N ethoxy-(4-nitrophenoxy)-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound O([P@@](=S)(OCC)C=1C=CC=CC=1)C1=CC=C([N+]([O-])=O)C=C1 AIGRXSNSLVJMEA-FQEVSTJZSA-N 0.000 description 2
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical class [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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Abstract
使用比三氟化硼更容易裂解的含氟化硼之摻雜劑物種來植入含硼離子之方法。一種半導體裝置之製造方法包括使用比三氟化硼更容易裂解的含氟化硼之摻雜劑物種來植入含硼離子。也揭示一種供應氫化硼前驅物之系統,及形成氫化硼前驅物之方法,且供應氫化硼前驅物之方法。於本發明之一個實施例中,氫化硼前驅物產生供群簇硼植入之用,用來製造諸如積體電路等半導體製品。
Description
本發明係有關改良式硼植入方法,特別係有關使用比三氟化硼更容易裂解的含氟化硼之摻雜劑物種來植入含硼離子之方法,以及用於該植入方法之組成物。本發明亦係關於一種供應氫化硼前驅物之方法,形成氫化硼前驅物之方法,及氫化硼前驅物之來源。
離子植入係用於積體電路的製造,來將經控制數量之摻雜劑雜質(例如硼)準確導入微電子裝置晶圓內部,且係屬於微電子裝置/半導體製造的關鍵處理程序。於此種植入系統中,離子來源解離期望之摻雜劑元素氣體(「進料」),由該離子來源以具有期望之能量之離子束形式來提取出離子。提取方式係經由跨適當形狀的提取電極來施加高電壓,該提取電極結合可供所提取的離子束通過的孔口。然後離子束係於工作件表面上諸如微電子裝置晶圓表面上導引,俾便將摻雜劑雜質植入
工作件內部,且形成具有期望傳導性的一區。然後,所植入的摻雜劑原子藉退火激化,來形成電激化摻雜區。
目前,於習知裝置的製造上共有10-15個以上的植入步驟。隨著晶圓尺寸的加大、臨界尺寸的縮小及電路複雜度的增加,在更良好的程序控制、低能量之高速電流輸送及平均故障時間(MTBF)縮短方面,對離子植入工具有更大需求。
傳統上三氟化硼(BF3)為硼摻雜劑雜質來源。但BF3之問題在於BF3比其它常用於離子植入的摻雜劑物種(例如As-H=274kJ mole-1及P-H=297kJ mole-1)需要顯著更大能量來打斷B-F鍵結(757kJ mole-1)。結果當植入硼時,離子來源必須於高電弧電壓運轉。高電弧電壓形成高能離子,高能離子碰撞離子來源區的熱燈絲或陰極,結果促成陰極的濺鍍溶蝕與故障。
先前曾經報告名目上供給離子植入器的80% BF3摻雜劑係完好,表示BF3未離子化,或若BF3經離子化則有片段復合。顯然BF3於高電弧電壓的離子化程度低,更佳造成原先已經高度效率不彰的程序益形惡化。
如此,持續需要提供替代的含硼摻雜劑前驅物來用作為硼元素氣體,俾便提高MTBF、處理程序效率、及延長工具壽命,且減少非揮發性物種的累積於離子來源區。
硼群簇植入是一種於比利用三氟化硼植入所需的能量位準更低的能量位準而提高離子植入效率之方法。典型硼群簇植入方法係使用癸硼烷(B10)和十八硼烷(B18)氫化硼前驅物。此等前驅物於室溫為固體,具有相對低的蒸氣壓。此等前驅物的使用,涉及前驅物料由遠端容器昇華,所得蒸氣沿著流體流動管線傳送至一半導體工具來進行群簇植入。此等方法涉及材料流量不足與冷凝等可能的非期望的副效應。為了對抗前者,含固體來源的容器必須加熱至恆定且精確的溫度。為了防止非期望的冷凝,管線係前導至需要接受加熱處理的工具。
利用癸硼烷和十八硼烷作為前驅物之硼群簇植入,造成額外挑戰,包括下列:●熱追蹤固體容器和傳輸管線代價昂貴、繁瑣,於離子植入器的實施困難,難以翻新改進且容易故障;●熱負載不平衡可能導致於冷點冷凝,結果造成堵塞或流速不均;●過度施熱至固體材料,可能導致分解,產生雜質與流速不均;●昇華的材料的流速係依據氣化器上可用的表面積決定。隨著時間的經過,當固體耗盡且再結晶時,氣化器的表面積縮小,結果導致流速隨著進料氣化器的壽命下降;
●測量工具內部材料量極為困難,單純係基於蒸氣壓測量;●材料輸送至工具的控制困難且所費不貲;●癸硼烷和十八硼烷材料昂貴;以及●氣化器安裝於鄰近離子來源經常係為了減少架設熱追蹤傳輸管線於植入器內部的問題,但可能導致安全性與法規上的問題而為危險。
如此,需要有一新穎系統、方法及前驅物來用於群簇硼植入,包括需要有群簇硼植入前驅物輸送至植入工具之改良方法,讓前驅物容易運送至工具,且比傳統含硼離子植入可增加硼離子的植入。
本發明係有關一種使用比三氟化硼更容易裂解的含氟化硼之摻雜劑物種來植入含硼離子之方法。更特別,本發明係有關使用比三氟化硼更易裂解的含硼摻雜劑物種,來改良離子源硬體效率、MTBF及壽命。
於一個態樣中,本發明係關於一種植入含硼離子之方法,包含:於一真空室內,於離子化條件下,離子化經氣化的含硼摻雜劑物種來產生含硼離子;以及藉電場加速含硼離子來將含硼離子植入一裝置基板內,其中該含硼摻雜劑物種主要係由BF3以外之物種所組成。
根據另一個實施例,以含硼摻雜劑物種之總重為基準,含硼摻雜劑物種含有低於20wt%之BF3,較佳低於10wt%,更佳低於5wt%,甚至更佳該含硼摻雜劑物種實質上不含BF3。最佳含硼摻雜劑物種不含三氟化硼。
於另一個態樣中,本發明係關於一種植入含硼離子之方法,包含:於一真空室內,於離子化條件下,離子化經氣化的氟化硼摻雜劑物種來產生含硼離子;以及藉電場加速含硼離子來將含硼離子植入一裝置基板內,其中該氟化硼摻雜劑物種包含選自於由B2F4、B(BF2)3CO、BF2CH3、BF2CF3、BF2Cl、BFCl2、BF(CH3)2、NOBF4、NH4BF4、H2BF7、H2B2F6、H4B4F10、H2BFO2、H2B2F2O3、H2B2F2O6、H2B2F4O2、H3BF2O2、H4BF3O2、H4BF3O3、B8F12、B10F12、及(F2B)3BCO所組成之組群之化合物。
本發明之另一態樣係有關包含含硼摻雜劑物種之組成物或反應劑,其中該組成物或反應劑可用於含硼離子植入。根據一個實施例,以含硼摻雜劑物種之總重為基準,含硼摻雜劑物種含有低於20wt%之BF3,較佳低於10wt%,更佳低於5wt%,甚至更佳該含硼摻雜劑物種實質上不含BF3。最佳含硼摻雜劑物種不含三氟化硼。根據另一個實施例,組成物或反應劑包含易
於低於700kJ/mol,較佳低於650kJ/mol,又更佳低於600kJ/mol裂解之含硼摻雜劑物種。根據一個較佳實施例,氟化硼摻雜劑物種包含選自於由B2F4、B(BF2)3CO、BF2CH3、BF2CF3、BF2Cl、BFCl2、BF(CH3)2、NOBF4、NH4BF4、H2BF7、H2B2F6、H4B4F10、H2BFO2、H2B2F2O3、H2B2F2O6、H2B2F4O2、H3BF2O2、H4BF3O2、H4BF3O3、B8F12、B10F12、及(F2B)3BCO所組成之組群之含硼化合物。
本發明之又另一態樣係有關適合用來將材料輸送至離子植入來源之儲存容器及輸送容器,其中該容器包含根據本發明之含硼摻雜劑物種。根據一個實施例,該容器為汽缸。根據另一個實施例,該容器為低於大氣壓之容器,諸如美國專利第5,518,528號;美國專利第5,704,965號;美國專利第5,704,967號;美國專利第5,935,305號;美國專利第6,406,519號;美國專利第6,204,180號;美國專利第5,837,027號;美國專利第6,743,278號;美國專利第6,089,027號;美國專利第6,101,816號;美國專利第6,343,476號;美國專利第6,660,063號;美國專利第6,592,653號;美國專利第6,132,492號;美國專利第5,851,270號;美國專利第5,916,245號;美國專利第5,761,910號;美國專利第6,083,298號;美國專利第6,592,653號;及美國專利第5,707,424號所述之容器,各案全文以引用方式
併入此處。較佳容器包括但非限於SDS®及VAC®輸送容器(得自ATMI公司,美國康乃迪克州丹伯利市)。根據另一個實施例,容器為安瓿,諸如美國專利第6,868,869號;美國專利第6,740,586號;美國專利申請案第10/201,518號;美國專利申請案第10/858,509號;美國專利申請案第10/625,179號;美國專利申請案第10/028,743號;美國專利申請案第60/662,515號;及美國專利申請案第60/662,396號所述之容器,各案全文以引用方式併入此處。
於又另一態樣中,本發明係關於一種製造微電子裝置之方法,該方法包含於真空室內,於離子化條件下,離子化經氣化之氟化硼摻雜劑物種來產生含硼離子,以及藉電場加速該含硼離子來將含硼離子植入一裝置基板內部,且視需要可將該微電子裝置與該裝置基板組裝,其中該氟化硼摻雜劑物種主要係由BF3以外之物種所組成。更佳,該含硼摻雜劑物種實質上不含BF3,最佳該含硼摻雜劑物種係不含三氟化硼。
本發明之又另一態樣係有關使用此處所述方法之組成物製造的改良式微電子裝置及結合該微電子裝置之製品,且視需要地可將該微電子裝置結合入一製品內部。
本發明亦係關於一種形成氫化硼前驅物之方法,以及供給氫化硼前驅物之方法。更特別,本發明係
有關由含硼氣體所產生之進行群簇硼植入之氫化硼前驅物。此外,本發明係有關氫化硼前驅物來源。
於一個態樣中,本發明提供一種形成供群簇硼植入之氫化硼前驅物之方法。該方法包含提供含硼氣體,且誘導該含硼氣體轉化成為較高階的含硼群簇。
於另一態樣中,本發明提供一種供應用於群簇硼植入之氫化硼前驅物之方法。該方法包含提供含硼氣體,且誘導該含硼氣體轉化成為較高階的含硼群簇,以及供給該較高階含硼群簇至一用於群簇硼植入之工具。於一個實施例中,該轉化係於相鄰工具之反應器內進行。於另一個實施例中,反應器係於該工具內部。
於另一態樣中,本發明係關於一種氫化硼前驅物來源,包含:一含硼氣體來源;一反應器其適合由該含硼氣體來源誘導含硼氣體轉化成為較高階含硼群簇;串流回路,其互連該含硼氣體來源與該反應器;以及視需要地,一質量或壓力控制器於該串流回路內。
於另一態樣中,本發明係關於一種微電子裝置製造設施,包含本發明之氫化硼前驅物來源,以及一微電子裝置製造工具,與該氫化硼前驅物來源耦聯成流動連通。
本發明之另一態樣係有關一種製造一微電子裝置之方法,包含使用藉前述方法所形成之一群簇硼物種來進行群簇硼離子植入。
本發明之又另一態樣係有關一種群簇硼離子植入方法,包含使用藉前述方法所形成之一群簇硼物種。
本發明之其它態樣、特徵及實施例由後文揭示及隨附之申請專利範圍將更為彰顯。
10‧‧‧群簇硼輸送處理系統
12‧‧‧筒形容器
14‧‧‧閥頭總成
16‧‧‧氣體箱
18‧‧‧傳輸管線
20‧‧‧質量或壓力控制器
22‧‧‧反應器
24‧‧‧半導體工具
30‧‧‧進料管線
32‧‧‧氫氣吸氣劑/乙硼烷濃縮器
34‧‧‧反應器
36‧‧‧排放管線
40‧‧‧高壓反應器
42‧‧‧進氣口
44‧‧‧出口路徑
50‧‧‧加熱填充反應器
52‧‧‧內容積
56‧‧‧排放管線
60‧‧‧進氣口
70‧‧‧反應器
72‧‧‧內部同心管
74‧‧‧反應物進料進氣口
76‧‧‧反應區段
80‧‧‧冷/熱反應器
82‧‧‧進氣口
83‧‧‧內容積
84‧‧‧加熱區段
90‧‧‧多階段式加熱反應器
94‧‧‧反應器
95‧‧‧管形入口通道
96‧‧‧電性或電漿放電區
97‧‧‧內容積
98‧‧‧反應器出氣口
圖1為根據本發明之一個實施例之氫化硼前驅物輸送系統之示意代表圖。
圖2為一在線(in-line)乙硼烷濃縮機諸如可用於本發明之實務之濃縮機之示意代表圖。
圖3為高壓反應器之示意代表圖,其中高壓係藉出口路徑的縮窄來形成,讓反應器內部硼群簇的形成反應係於比工具內部壓力更高的壓力下進行。
圖4為一加熱填充反應器諸如可用於實施本發明之反應器之示意代表圖。
圖5為具有同心管設計之反應器諸如可用於實施本發明之反應器之示意代表圖。
圖6為適合用於本發明之系統之冷/熱反應器之示意代表圖。
圖7為用於本發明之系統之多重溫度加熱反應器之示意代表圖。
圖8為適合用於本發明之系統之利用電漿或電性放電之反應器之示意代表圖。
本發明係關於使用比三氟化硼更易裂解之任選的含硼前驅物來製造富含含硼離子之離子束,俾改良效率、MTBF及離子植入器的壽命。
本發明亦係關於形成供群簇離子植入之氫化硼前驅物之方法,以及供給此等前驅物於群簇離子植入使用之方法。此外,本發明亦係關於氫化硼前驅物來源。
本發明之一個實施例係有關一種使用易於低於700kJ/mol,較佳低於650kJ/mol,又更佳低於600kJ/mol之能量裂解的含硼摻雜劑物種,來植入含硼離子之方法。本發明亦係關於含有此種物種之組成物或輸送系統。
如此處使用,「離子來源區」包括真空室、來源電弧室、來源絕緣體、提取電極、阻遏電極、高電壓絕緣體及來源襯套。
如此處使用,「微電子裝置」一詞係與製造來用於微電子用途、積體電路或電腦晶片用途及封裝之半導體基板、平板顯示器、及微機電系統(MEMS)相對應。也須了解「微電子裝置」一詞絕非限制性,反而係包括任何最終將變成微電子裝置或微電子總成之基板。
如此處使用,「前驅物」包括任何先前的分子或結構,且為另一個分子或結構的來源。如此「硼前驅物」為含硼而可用作為各種領域之硼離子來源之前驅物。同理,「氫化硼前驅物」為含有氫化硼而可成為硼離子植入來源之前驅物。
硼離子(B+)典型係植入矽基板來形成p型區,但此處意圖也涵蓋如熟諳技藝人士眾所周知,經由植入含硼分子離子,來製造具有淺p型摻雜區之微電子裝置之方法。例如,可植入諸如BF2 +分子離子而以BF2 +離子的較高提取能達成低而有效的硼提取能。
發明人推定降低含硼摻雜劑化合物的鍵結能,將導致所需弧電壓伴隨的下降,如此延長離子來源的壽命。
如此,本發明之一個實施例係有關一種植入含硼離子之方法,包含使用低於100伏特,較佳低於90伏特,更佳低於80伏特及最佳低於70伏特之電弧電壓,使用習知熱陰離子源,或使用可相媲美的電壓而使用其它離子源,以至少15%的高離子化效率離子化含硼摻雜劑物種。為了達成該項目的,於一個態樣中,本發明係有關一種將含硼離子植入微電子裝置基板內部之方法,該方法包含氣化含硼前驅物進料來產生經氣化之含硼摻雜劑物種(當含硼前驅物進料為液體或固體時),離子化該經氣化之含硼摻雜劑物種來產生含硼離子,以及藉電場加速該含硼離子來將其植入微電子裝置基板,其中該
含硼前驅物進料係不含實質量之三氟化硼。較佳,含硼前驅物包含鹵素物種,包括氟、氯、溴及碘。更佳,含硼前驅物為氟化硼前驅物。需了解於後文述及氟化硼前驅物絕非表示限制性。
此處意圖涵蓋之含硼前驅物包括但非限於B2F4、B(BF2)3CO、BF2CH3、BF2CF3、BF2Cl、BFCl2、BF(CH3)2、NOBF4、NH4BF4、H2BF7、H2B2F6、H4B4F10、H2BFO2、H2B2F2O3、H2B2F2O6、H2B2F4O2、H3BF2O2、H4BF3O2、H4BF3O3、B8F12、B10F12、(F2B)3BCO及其組合。另外,前述含硼前驅物之氟原子可以其它鹵素原子部分或全部取代(例如BCl3、BBr3、B2Cl4等)。於特佳實施例中,含硼前驅物包括B2F4,期望可於比較裂解BF3的B-F鍵結所需電壓更低的電弧電壓於B-B鍵結進行同種裂解。如此,本發明之另一個實施例係有關一種植入含硼離子之方法,包含於B-B鍵結裂解含硼前驅物。本發明之另一個實施例係有關包含有至少一個B-B鍵結之含硼前驅物之組成物或輸送系統。
較佳,替代含硼前驅物種要求解離能於約100kJ mol-1至約650kJ mol-1,更佳300kJ mol-1至約550kJ mol-1之範圍。
於另一個實施例中,本發明係有關一種將含硼離子植入一微電子裝置基板之方法,該方法包含氣化含硼前驅物進料來產生經氣化之含硼摻雜劑物種(當該
含硼前驅物進料為液體或固體時),離子化經氣化之含硼摻雜劑物種來產生含硼離子,以及藉電場加速含硼離子來將其植入微電子裝置基板,其中該含硼前驅物進料包含三氟化硼,及至少一種選自於由B2F4、B(BF2)3CO、BF2CH3、BF2CF3、BF2Cl、BFCl2、BF(CH3)2、NOBF4、NH4BF4、H2BF7、H2B2F6、H4B4F10、H2BFO2、H2B2F2O3、H2B2F2O6、H2B2F4O2、H3BF2O2、H4BF3O2、H4BF3O3、B8F12、B10F12、(F2B)3BCO及其組合所組成之組群之至少一種額外含硼前驅物。另外,前述含硼前驅物之氟原子可以其它鹵素原子部分取代或全部取代(例如BCl3、BBr3、B2Cl4等)。
於另一個實施例中,替代含硼前驅物種包括較高階硼烷類及碳烷類;小型尼朵碳烷類(nido-carboranes)諸如CB5H9、C2B4H8、C3B3H7、C4B2H6、及C2B3H7;開啟籠合碳烷類諸如C2B3H7、CB5H9、C2B4H8、C3B3H7、C4B2H6、C2B7H13;小型克羅梭碳烷類(closo-crboranes)諸如C2B3H5、C2B4H6、C2B5H7、CB5H7、C2B6H8、C2B7H9、C2B8H10、C2B9H11、C2B10H12。此外,此等碳烷類衍生物可用來組合氟來源,修改且最佳化碳烷類之化學性質(亦即蒸氣壓、毒性、反應性)。較高階硼烷類及碳烷類傾向為比含鹵化硼前驅物更穩定之化合物,且可於較低離子植入電弧電壓來提供BxHy片段。任
選地且較佳地,當含硼前驅物種包括高階硼烷類及/或高階碳烷類時,含硼前驅物進料包括至少一種替代氟來源(例如F2)。
於又另一個實施例中,替代含硼前驅物可包括至少一種前述含鹵化硼前驅物及高階硼烷類及/或高階碳烷類,視需要可存在有氟來源。
除了降低解離替代含硼前驅物所需的電弧電壓之外,替代物種較佳係解離成為揮發性副產物,該副產物不會鍍覆真空室內部及其它離子來源區的組件。此外,該替代含硼前驅物較佳具有低碳含量(亦即每分子小於3個碳原子,較佳小於2個,及最佳小於1個),原因在於碳沈積物傾向於縮短離子源組件的壽命。
使用含氟化硼前驅物之優點包括於離子源形成氟基團的產生,該基團與沈積於離子源區組件壁上的硼反應,因而維持該等組件的清潔。為了達成該項目的,含氟物種如F2可於離子化期間導入離子源區,以便當含氟化硼摻雜劑物種無法於離子化期間產生足量氟基團時,輔助組件與真空室的清潔處理。含氟物種相對於含氟化硼摻雜劑物種之用量係由熟諳技藝人士決定。如此,本發明之一個實施例係有關一種使用含硼前驅物及含氟物種(例如F2)植入含硼離子之方法,該含硼前驅物包含選自於由BF3、BCl3、BBr3、B2F4、B2Cl2、B(BF2)3CO、BF2CH3、BF2CF3、BF2Cl、BFCl2、BF(CH3)2、NOBF4、NH4BF4、H2BF7、H2B2F6、
H4B4F10、H2BFO2、H2B2F2O3、H2B2F2O6、H2B2F4O2、H3BF2O2、H4BF3O2、H4BF3O3、B8F12、B10F12、(F2B)3BCO、CB5H9、C2B4H8、C3B3H7、C4B2H6、C2B3H7、C2B3H7、CB5H9、C2B4H8、C3B3H7、C4B2H6、C2B7H13、C2B3H5、C2B4H6、C2B5H7、CB5H7、C2B6H8、C2B7H9、C2B8H10、C2B9H11、C2B10H12、(C12B)3BCO及其組合所組成之組群之含硼摻雜劑物種與一含氟物種(例如F2)。
於本發明之另一個實施例中,鈍氣(noble gas)諸如氖、氬、氟、或氙可與含硼摻雜劑物種共同摻混,或另外可分開饋至真空室來與真空室內的含硼摻雜劑物種混合,藉此形成氣相反應劑組成物。雖然不欲受理論所限,相信鈍氣將與含硼摻雜劑物種碰撞,而輔助於較低電弧電壓時摻雜劑物種的解離。此外,含硼前驅物與鈍氣共同摻混讓操作狀況更為良好。如此,本發明之另一態樣係有關一種使用任一種含硼前驅物(例如BF3或前文列舉之前驅物)及添加鈍氣來提高離子化效率之含硼離子植入方法。較佳用於本發明之此一態樣,含硼前驅物為BF3。
此處也預期,除了此處揭示之替代含硼前驅物之外,進料包括三氟化硼。例如,以進料總重為基準,進料包括約0.01%至約90%重量比之BF3。
實際上,液體及/或固體含硼前驅物進料係使用眾所周知之氣化方法,例如減壓、加熱等於真空室之前或於真空室內氣化,同時氣態前驅物進料直接導入真空室內。經由將電子導入以氣態摻雜劑物種填補的真空室內,離子源產生離子。數種類型之離子源常用於商業離子植入系統,包括Freeman及Bernas型離子源,使用熱電極,藉電弧供電;微波型使用磁控管間接加熱之陰離子源及RF電漿源,各型離子源皆係於真空操作。電子與氣態摻雜劑物種碰撞,結果導致形成由正摻雜劑離子和負摻雜劑離子所形成之離子化電漿。具負偏壓或正偏壓之提取電極,將分別允許正離子或負離子通過孔口,由離子源送出作為準直化離子束,朝向微電子裝置工作件加速。
群簇硼植入允許相對於傳統硼前驅物的使用(諸如三氟化硼、三氟化硼、乙硼烷等)提高離子植入效率。處理過程使用之植入器可於比傳統利用此等硼前驅物之摻雜劑輸送方法更低能量工作。使用群簇技術,允許一次輸送多個硼。於其各個態樣中,本發明提供一種形成氫化硼前驅物之方法、氫化硼前驅物來源、以及輸送該用於硼群簇植入之氫化硼前驅物之方法。
氫化硼乙硼烷(6)為毒性、可燃性、產熱、危險且具有刺鼻氣味的氣體。已知於室溫分解,形成較高階硼烷類諸如BH3、B3H7、B4H8等。分解反應包括下列:
B2H6→2BH3;BH3+B2H6→B3H9;B3H9→B3H7+H2;B3H7+B2H6→B4H10+BH3;B4H10 B4H8+H2;及B4H10 B3H7+BH3。
由於其分解速率高,該氣體通常係以30%或以下的濃度出售。本發明利用此種自然分解程序和較高階硼烷的形成,來產生用於群簇硼植入之氫化硼前驅物。較佳氫化硼前驅物之形成係於接近或在前驅物的使用點進行。
於一個實施例中,本發明提供一種壓力經過控制或流量經控制的硼烷來源,由此來源,硼烷來源材料呈氣體被導入至反應器內於其中反應來形成較高階硼群簇,隨後流至硼群簇植入用工具,如圖1所示。
圖1為根據本發明之一個實施例之群簇硼輸送處理系統10之示意代表圖。硼前驅物含於筒形容器12內,具有一個閥頭總成14固定至容器上部。容器和閥頭總成含於一氣體箱16內,於該氣體箱內,閥頭總成耦聯傳輸管線18。於氣體箱16外部的傳輸管線18含有質量或壓力控制器20來調節硼前驅物蒸氣的流量。
筒形容器12較佳係含有氣態硼來源材料。
另外,但較不佳,容器可含有固態硼來源材料,容器於氣體箱內加熱,讓固體氣化而形成前驅物蒸
氣。容器可以任一種適當方式加熱(未顯示於圖1之加熱元件及/或加熱裝置),例如經由使用加熱夾套加熱、於氣體箱內對流傳熱加熱、或任何其它適合以需要量來產生硼前驅物蒸氣之方式加熱。
傳輸管線18之下游端係耦接至反應器22,於反應器22中,硼前驅物置於處理條件下來產生較高階硼物種例如較高階硼烷類諸如BH3、B3H7、B4H8等。如圖所示,反應器22位置係相鄰於半導體工具24,反應器係與該工具呈流體供應關係,讓較高階硼烷直接從反應器流入工具內部。
於本發明之各個態樣中,反應器的位置可與工具分開、可相鄰於工具、或於工具內部。工具例如包含離子植入器單元,或其它硼前驅物流體利用工具。於較佳實施例中,工具為微電子裝置製造工具。
於較佳實務中,硼烷來源為氣體。此種含硼氣體容易輸送。來源材料亦即含硼氣體於使用前可以業界人士已知之任一種方式儲存。此等儲存方法包括但非限於淨氣體儲存,以稀釋於惰性氣體如氫、氬、氦或氮之氣體儲存。硼烷來源氣體之實例包括但非限於乙硼烷及戊硼烷。
當含硼氣體由供應容器輸送至反應器時,較佳係通過控制器,諸如圖1舉例說明之質量或壓力控制器20。此等控制器可調節質量或壓力,讓氣體維持於其期望的狀態輸送至反應器。此種控制係優於利用固體材料
且流經熱追蹤管線之先前方法。控制器的使用並非本發明所需,但卻高度有利於可提供期望之前驅物氣體流至反應器。
除了含硼烷氣體外,可供應額外反應物。此等額外反應物可於由氣體源至反應器輸送的任一點增加,或可添加至反應器本身。此種反應物例如可用來改良反應動力學,或形成更複雜的高階硼物種。使用反應物允許氫對硼之比的最佳化來形成期望的產物。例如,非揮發性硼聚合物的形成可藉由使用適當氫氣混合物抑制來最大化非堵塞材料的產量。
當乙硼烷為用於本發明之氣體時,乙硼烷氣體濃度係由1000ppm至30%重量比之範圍。大於30%之乙硼烷氣體原始濃度於儲存容器中不穩定而會分解。當期望提供大於30%濃度給反應器時,可於傳輸氣體至反應器的管線上利用濃縮機。
此種濃縮機係示意顯示於圖2所示前驅物輸送系統中,其中於進料管線30的稀乙硼烷進料流流入氫氣吸氣劑/乙硼烷濃縮機32,結果所得濃縮之乙硼烷流至反應器34,用來於其中產生較高階硼烷類,由反應器排放入排放管線36。
當期望高於30%的乙硼烷時,利用濃縮機來減少管線內部的氫氣數量。此種氫氣的減少可藉氫氣吸氣劑或滲透方法達成,例如採用氫氣滲透膜來從較高階硼烷物種中去除氫氣。
本發明之實務中用來產生較高階硼烷類之反應器位置接近所得群簇的使用點。此位置可與群簇使用工具分開、相鄰或於工具內部。於反應器內部,誘導反應而製造存在有多於兩個硼的硼分子。多個實施例中,反應器內之反應溫度可於室溫至400℃之範圍,各實施例中,反應器內之壓力係於真空至1000psi之範圍。
為了達成此項目的,於習知技術範圍內,基於本文揭示可利用各型反應器。任一種可誘導硼群簇的製造之反應器的使用皆係涵蓋於本發明之範圍。可有用地用於本發明之實務之反應器包括但非限於加熱反應器、催化反應器、加熱催化反應器、紫外燈、有電性、微波、或射頻放電或電漿之反應器、填充反應器、多階段加熱式反應器、熱板、高壓反應器及同心管狀反應器。列舉的反應器類型並非彼此互斥,例如加熱的填充的催化反應器(參考圖4)或多階段式加熱的同心反應器(參考圖5)可用於本發明之特定實施例。
於本發明之實務中採用之加熱反應器包括任一種被加熱的反應器。此等反應器可為加熱壁反應器、加熱填充反應器、冷壁反應器、有內部加熱區段之反應器、及整個反應器體積含有多段溫度梯度之反應器。加熱反應器包括其熱量係用來誘導反應的任一種反應器。各類型加熱反應器舉例說明於圖3至8。
催化反應器常用於本發明之實務之催化反應器,包括可加速反應器內部之反應的任一種反應器。可
添加催化劑至反應,或催化劑可成為反應器本身整合一體的一部分。催化劑包括但非限於金屬諸如鐵、鋁、銅、鋁氧、鉑、硼、碳、碳吸附劑及活性碳。若催化劑構成反應器的一部分,則可安裝於反應器結構表面上;呈珠粒或丸粒而填充於反應器內部;或反應器可包括具有任一種已知之流動設計之催化劑含浸的媒體,諸如管、蜂窩或串珠。可採用寬廣多種催化劑反應器。
本發明之方法或系統使用之高壓反應器包括任一種允許於高壓進行反應的反應器。可藉已知之任一種方法產生高壓。例如,經由於反應器的開口區使用孔口或開縫來產生反應器內部壓力,讓壓力積聚於反應器內,供含硼群簇輸送至半導體工具。典型地,當工具為離子植入器時,工具內部壓力為真空,例如低於大氣壓。
圖3為高壓反應器40之示意代表圖,其中高壓係藉出口路徑44的縮窄來形成,讓反應器內部的硼群簇形成反應於比工具內部壓力更高的壓力下進行。反應器有個進氣口42,乙硼烷或硼烷混合物經由該進氣口導入反應器內容積,於內容積內部反應來形成較大型硼群簇從反應器出氣口排放出。於此種反應器體系中,P1和T1係高於P2和T2。
本發明之方法或系統中使用的填充的反應器可包括含填充材料之反應器。填充材料可單純用來增加讓反應發生的表面反應,改良傳熱,或提供催化效果。
封裝材料也包括具有任一種已知設計之經過催化劑含浸之媒體,諸如管、蜂窩或串珠。
圖4為例如可用於實施本發明之經加熱且經填充之反應器50之示意代表圖。反應器有個進氣口60,乙硼烷或硼烷混合物經由該進氣口60被導入反應器的內部容積。內容積52含有表面積反應加強,或內容積填充以催化劑,來產生較大型的硼群簇而於排放管線56中從反應器排放。
本發明使用之同心管反應器包括任一種有多管的反應器。圖5顯示之說明例其中多種氣體於反應器內部組合來反應,反應係發生於加熱區段的臨界點。
圖5之反應器70包括內部同心管72,內部同心管72係與反應器的主殼體同軸,且界定一個環狀通道於其間。環狀通道係與反應物進料之進氣口74做流體連通,其中反應物進入方向係以箭頭B指示。如此,被導入的反應物於內部同心管72的出口端與於箭頭A指示方向流入管72內部的乙硼烷或硼烷混合物混合。熱能或電漿能被導入於個別流體流內,於反應區段76混合,形成更大型的硼群簇,於出氣口從反應器70排放,排放方向以箭頭C指示。
可用於本發明之實務之多階段式加熱反應器包括任一種於反應器之一部分與另一部分之溫度有變化的任一種反應器。此等反應器包括但非限於冷/熱反應器,及有溫度梯度的加熱反應器。此種溫度變化的使用
可最大化群簇轉換率的效率,或以任一種期望方式控制反應。例如,反應器具有一加熱區段位置遠離反應器出口,藉此來最小化可能發生的堵塞。
圖6為適合用於本發明之系統之冷/熱反應器80之示意代表圖。反應器80包括進氣口82,乙硼烷或硼烷混合物通過進氣口82導入反應器的內容積83。內容積83中有個反應區段84,其可選擇性地含有催化劑。於反應器80內部產生的大型硼群簇於出氣口86從反應器中排放。
圖7為用於本發明之系統之多階段式加熱反應器90之示意代表圖。反應器90包括導入乙硼烷或硼烷混合物之進氣口,以箭頭A示意顯示。反應器有多階段式溫度梯度特徵,可進行反應而製造大型硼群簇,其於箭頭B示意指示之出氣口從反應器排放。
圖8為利用電漿或電性、微波、或射頻放電且適合用於本發明系統之反應器94之示意代表圖。反應器94包含內容積97,於其中延伸管狀進氣口通道95,其具有電性或電漿放電區96用來誘導反應,產生大型硼群簇從反應器出氣口98排放。
熱板也可用於本發明之實務作為反應器。此種反應器上,乙硼烷或其它來源氣體係藉表面誘導反應進行快速反應。
一旦形成硼群簇時,硼群簇輸送至用於群簇硼植入的工具。由反應器輸送至工具可以適當方式執
行。當反應器係相鄰於工具或於工具內部時,可單純藉群簇硼串流由反應器送出而進入工具內部來執行輸送。
因此本發明涵蓋一種形成群簇硼植入用之氫化硼前驅物之方法,包含提供含硼氣體至一反應器,且於反應器內部誘導含硼氣體轉化成較高階之含硼群簇。
接受反應來形成較高階硼物種之含硼氣體可選自乙硼烷、戊硼烷、及任何其它適當硼來源試劑,包括其中兩種或更多種來源試劑物種之混合物。
於本發明之各個實施例中,反應器係選自於加熱反應器、催化反應器、加熱催化反應器、紫外燈、含電性、微波或射頻放電或電漿之反應器、填充反應器、多階段式加熱反應器、熱板、高壓反應器、及同心管狀反應器。反應器進一步包含催化劑,例如鐵、鋁、銅、鋁氧、鉑、硼、碳及活性碳。誘導較高階含硼群簇包含於反應器內部加熱含硼氣體,提供熱能或電漿能予反應器內部之含硼氣體,提供多階段式溫度梯度予反應器之含硼氣體,於由室溫至400℃範圍之溫度,及/或於真空至1000psi範圍之壓力,執行反應來誘導較高階含硼群簇。於較高階含硼群簇形成之前或形成的同時,可添加額外反應物至反應器來進行反應。
於一個態樣中,本發明提供一種供應用於群簇硼植入之氫化硼前驅物之方法。該方法包含提供含硼氣體至一反應器,且於反應器內誘導該含硼氣體轉化成
為較高階的含硼群簇,以及供給該高階含硼群簇至一供群簇硼植入之工具。
於另一態樣中,本發明提供一種氫化硼前驅物來源,包括含硼氣體來源、反應器、及將含硼氣體來源與反應器互連之傳輸管線或其它串流回路,視需要可含有一個質量或壓力控制器。
須了解寬廣多種特定配置可用來形成較高階含硼物種供輸送至此種物種的利用設施。利用設施可屬於任一種適當型別,例如包括微電子裝置製造工具,諸如離子植入器、沈積室等。
如此,雖然已經就特定實施例說明本發明,但如熟諳技藝人士已知,本發明非僅囿限於此,而可延伸且涵蓋多項其它修改及實施例。如此,根據隨附之申請專利範圍意圖對本發明做廣義解譯。
10‧‧‧群簇硼輸送處理系統
12‧‧‧筒形容器
14‧‧‧閥頭總成
16‧‧‧氣體箱
18‧‧‧傳輸管線
20‧‧‧質量或壓力控制器
22‧‧‧反應器
24‧‧‧半導體工具
Claims (2)
- 一種用於離子植入的含硼前驅物供應設備,離子植入涉及產生一含硼離子的離子束,該含硼前驅物供應設備包括一儲存與輸送容器;一閥頭總成,固定至該容器的一上部;與該儲存與輸送容器中之一含硼前驅物,該含硼前驅物包括B2F4。
- 如請求項1所述之用於離子植入的含硼前驅物供應設備,耦接至一離子植入器單元或一微電子裝置製造工具,用以將該含硼前驅物輸送至該離子植入器單元或該微電子裝置製造工具。
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TWI720673B (zh) * | 2018-10-31 | 2021-03-01 | 美商恩特葛瑞斯股份有限公司 | 經硼摻雜之非晶形碳硬遮罩及相關方法 |
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