TWI782893B - 選擇性地移除鍺化矽材料之方法、套組及組成物 - Google Patents
選擇性地移除鍺化矽材料之方法、套組及組成物 Download PDFInfo
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- TWI782893B TWI782893B TW105121538A TW105121538A TWI782893B TW I782893 B TWI782893 B TW I782893B TW 105121538 A TW105121538 A TW 105121538A TW 105121538 A TW105121538 A TW 105121538A TW I782893 B TWI782893 B TW I782893B
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- acid
- ammonium
- germanium
- silicon
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
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- H01L29/66409—Unipolar field-effect transistors
- H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
- H01L29/66568—Lateral single gate silicon transistors
- H01L29/66613—Lateral single gate silicon transistors with a gate recessing step, e.g. using local oxidation
- H01L29/66621—Lateral single gate silicon transistors with a gate recessing step, e.g. using local oxidation using etching to form a recess at the gate location
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- 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
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Abstract
本發明係關於可用於自其上具有下列該等材料之微電子裝置相對於含鍺材料及含矽材料選擇性移除矽鍺材料之組成物。該等移除組成物包括至少一種二醇且係可調整以達成所需的SiGe:Ge移除選擇性及蝕刻速率。
Description
本發明係關於一種相對於含鍺材料及含Si材料選擇性地蝕刻矽鍺材料之組成物及方法。
過去數十年來,積體電路中之特徵的縮放使得可在半導體晶片上提高功能性單元的密度。舉例來說,縮小電晶體尺寸容許在晶片上併入增加數目的記憶體裝置,從而導致製得具有增加容量的產品。
在用於積體電路裝置之場效電晶體(FET)的製造中,除矽外之半導電結晶材料可能為有利的。一此種材料的實例係Ge,其提供許多相對於矽的潛在有利特徵,諸如,但不限於,高電荷載體(電洞)移動率、帶隙偏移、不同晶格常數、及與矽合金化形成SiGe之半導電二元合金的能力。
於新型電晶體設計中使用Ge的一個問題係目前針對這些年來積極縮放之矽FET所達成的極細特徵(例如,22nm及以下)現於Ge中難以達成,當以較不積極縮放的形式實施時通常使潛在基於材料的效能增益重新開始。縮放的困難係與Ge的材料性質相關,且更特定言之係與蝕刻通常在Ge活性層(例如,電晶體通道層)與下層矽基板材料之間用作中間層之SiGe的困難相關。當前,
SiGe係使用氫氧化四甲銨(TMAH)於90℃下蝕刻,但SiGe/Ge選擇性差且蝕刻條件(即較高溫度及TMAH之毒性)不理想。
本發明之一目的係提供用於相對於含鍺材料及含Si材料選擇性移除矽鍺材料,同時使存在於微電子裝置上之其他材料之移除或腐蝕減至最小的組成物。
本發明之具體例大致係關於用於自包含下列該等材料之微電子裝置相對於含鍺材料及含矽材料選擇性地蝕刻矽鍺材料之組成物及方法。
在一具體例中,描述一種自微電子裝置之表面相對於含鍺材料及含矽材料選擇性地移除鍺化矽材料之方法,該方法包括使一組成物與微電子裝置之表面以相對於含鍺材料及含矽材料選擇性地移除鍺化矽材料所需之時間及溫度接觸,其中該組成物包含至少一種二醇化合物、至少一種氟化物物質、及至少一種氧化物質。
在另一具體例中,描述一種套組,該套組包括存於一或多個容器中之一或多種適於形成用於自微電子裝置之表面相對於含鍺材料及含矽材料選擇性地移除鍺化矽材料之組成物的組分,其中一容器包含至少一種氧化劑及第二容器包含至少一種二醇、至少一種氟化物、水、視需要之至少一種緩衝劑、及視需要之至少一種鍺鈍化劑,其用於在工廠或使用點處組合。
在又另一具體例中,描述另一種套組,該套組包括存於一或多個容器中之一或多種適於形成用於自微電子裝置之表面相對於含鍺材料及含矽材料選擇性地移除鍺化矽材料之組成物的組分,其中一容器包含至少一種氧化劑及至少一種二醇及第二容器
包含至少一種氟化物、水、視需要之至少一種緩衝劑、及視需要之至少一種鍺鈍化劑,其用於在工廠或使用點處組合。
在又另一具體例中,描述一種組成物,該組成物包含至少一種二醇化合物、至少一種氟化物物質、至少一種氧化物質、視需要之至少一種緩衝物質、視需要之至少一種鍺鈍化物質、及水。
在另一具體例中,描述一種用於自微電子裝置之表面相對於含鍺材料及含矽材料選擇性地移除矽鍺材料之組成物,該組成物包含下列各項之組合:(a)包含至少一種二醇化合物、至少一種氟化物物質、視需要之至少一種緩衝物質、視需要之至少一種鍺鈍化物質、及水之濃縮物,及(b)至少一種氧化劑。
本發明之其他態樣、特徵及具體例將可由隨後之揭示內容及隨附之申請專利範圍而更完整明瞭。
一般而言,本發明係關於相對於含鍺材料及含Si材料選擇性地移除矽鍺材料,且因此可用作自微電子裝置至少部分移除矽鍺材料之蝕刻劑的組成物。本發明揭示組成物可如何用來相對於含Ge材料及含Si材料移除矽鍺材料。
為容易參考起見,「微電子裝置」係對應於經製造用於微電子、積體電路、能量收集或電腦晶片應用中之半導體基板、平板顯示器、相變記憶體裝置、太陽能面板及包括太陽能電池裝置、光伏打元件、及微機電系統(MEMS)的其他產品。應瞭解術語「微電子裝置」、「微電子基板」及「微電子裝置結構」不具任何限
制意味,且包括任何最終將成為微電子裝置或微電子組件的基板或結構。微電子裝置可為圖案化、毯覆式、控制及/或測試裝置。
「矽」係經定義為包括Si、多晶Si、及單晶Si。矽可包含於可用作(例如)諸如FET及積體電路之電子裝置之基板或部分基板的絕緣體上矽(silicon-on-insulator;SOI)晶圓中。其他類型的晶圓亦可包含矽。
如本文中所使用,「含矽材料」包括,但不限於,矽;p型摻雜矽;n型摻雜矽;氧化矽,包括閘極氧化物(例如,熱或化學生長之SiO2)及TEOS;氮化矽;熱氧化物;SiOH;SiCOH;矽化鈦;矽化鎢;矽化鎳;矽化鈷;及低k介電材料。如本文所定義,「低k介電材料」係相當於任何在層狀微電子裝置中使用作為介電材料的材料,其中該材料具有小於約3.5之介電常數。低k介電材料較佳包括低極性材料諸如含矽有機聚合物、含矽之有機/無機混合材料、有機矽酸鹽玻璃(OSG)、TEOS、氟化矽酸鹽玻璃(FSG)、二氧化矽、及摻碳氧化物(CDO)玻璃。應明瞭低k介電材料可具有不同密度及不同孔隙度。應明瞭針對本申請案之目的,含矽材料不包含實質量的鍺,即含矽材料包含低於5重量%鍺,較佳低於2重量%鍺。
如本文所述,「氧化矽」或「SiO2」材料係相當於自氧化物前體來源沉積之材料,例如,TEOS、熱沉積氧化矽、或使用市售前體諸如SiLKTM、AURORATM、CORALTM、或BLACK DIAMONDTM沉積之摻碳氧化物(CDO)。針對本說明之目的,「氧化矽」意欲廣泛地包括SiO2、CDO、矽氧烷及熱氧化物。氧化矽或SiO2材料係相當於純氧化矽(SiO2)以及於結構中包括雜質的不純氧
化矽。
如本文所用,「氟化物」物質係相當於包括離子氟化物(F-)或共價鍵結氟之物質。應明瞭氟化物物質可作為氟化物物質包含或於原位產生。
如本文所定義,「含鍺材料」可為塊狀鍺晶圓、n型摻雜鍺、p型摻雜鍺、絕緣體上鍺(GOI)晶圓(在此情況該層係形成於基板頂部上之介電層上的鍺層)、基板上之鍺層、以及鍺化合物諸如鍺化鈦、鍺化鎢、鍺化鎳、及鍺化鈷。含鍺材料可為至少部分延伸於基板上方之連續層或可分割成個別區域。應明瞭針對本申請案之目的,含鍺材料不包含實質量的矽,即含鍺材料包含低於5重量%矽,較佳低於2重量%矽。
矽-鍺(SiGe)合金為技藝中所知曉且具有通式Si1-xGex。針對當前揭示內容之目的,將使用式SiGe來表示待移除的矽鍺材料。
如本文所使用,「約」係意指相當於所述值之±5%。
應明瞭一些化學組分當在其最低能量(即穩定)狀態中,特定言之在商業購得時,即自然包括可忽略量的水。針對本說明之目的,自然存在的水不被視為「添加水」。
本發明之組成物可以如更完整說明於下文之相當多樣的特定配方具體實施。
在所有該等組成物中,當參照包括零下限之重量百分比範圍論述組成物之特定組分時,當明瞭在組成物之各種特定具體例中可存在或不存在該等組分,且在存在該等組分之情況中,其可以基於其中使用該等組分之組成物之總重量計低至0.001重量百分
比之濃度存在。
在第一態樣中,描述一種自微電子裝置之表面相對於含鍺材料及含矽材料選擇性地移除鍺化矽材料之組成物及一種使用該組成物之方法,該組成物包含至少一種二醇化合物、至少一種氟化物物質、及至少一種氧化物質,由其等所組成,或基本上由其等所組成。在另一具體例中,該組成物包含至少一種二醇化合物、至少一種氟化物物質、至少一種氧化物質、及水,由其等所組成,或基本上由其等所組成。在又另一具體例中,該組成物包含至少一種二醇化合物、至少一種氟化物物質、至少一種氧化物質、至少一種緩衝物質、及水,由其等所組成,或基本上由其等所組成。在又另一具體例中,該組成物包含至少一種二醇化合物、至少一種氟化物物質、至少一種氧化物質、至少一種鍺鈍化物質、及水,由其等所組成,或基本上由其等所組成。在另一具體例中,該組成物包含至少一種二醇化合物、至少一種氟化物物質、至少一種氧化物質、至少一種緩衝物質、至少一種鍺鈍化物質、及水,由其等所組成,或基本上由其等所組成。
本文涵蓋的二醇物質包括脂族二醇,包括,但不限於,乙二醇、新戊二醇、1,2-丙二醇(propylene glycol)、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,2-戊二醇、1,3-戊二醇、1,4-戊二醇、2,3-丁二醇、3-甲基-1,2-丁二醇、1,5-戊二醇、2-甲基-1,3-戊二醇、2,4-戊二醇、2-甲基-2,4-戊二醇、2,3-戊二醇、1,2-己二醇、2-乙基-1,3-己二醇、2,5-二甲基-2,5-己二醇、1,2-辛二醇及其組合。亦涵蓋包含超過兩個羥基之物質,諸如三醇(例如,甘油),及其中存在兩個有效羥基且第三個經酯化或醚化之物質(例如,辛酸甘油酯、癒創木酚甘
油醚)。較佳地,該至少一種二醇物質包括1,2-丁二醇及/或乙二醇。二醇物質之量係在約30重量%至約99重量%,較佳約30重量%至約60重量%之範圍內。
涵蓋的氟化物物質包括,但不限於,六氟鈦酸、六氟矽酸、六氟鋯酸、四氟硼酸、三氟甲磺酸四丁銨、四氟硼酸四烷基銨(NR1R2R3R4BF4)諸如四氟硼酸四丁基銨、六氟磷酸四烷基銨(NR1R2R3R4PF6)、氟化四烷基銨(NR1R2R3R4F)(其無水或水合物)諸如氟化四甲基銨、氟化氫銨、氟化銨,其中R1、R2、R3、R4可彼此相同或不同且係選自由氫、直鏈或分支鏈C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)、C1-C6烷氧基(例如,羥乙基、羥丙基)、經取代或未經取代之芳基(例如,苄基)所組成之群。氟化物物質較佳包括氫氟酸及/或氟化銨。氟化物物質之量係在約0.01重量%至約5重量%之範圍內,較佳約0.1重量%至1重量%。
本文涵蓋之氧化物質包括,但不限於,過氧化氫、FeCl3、FeF3、Fe(NO3)3、Sr(NO3)2、CoF3、MnF3、發氧方(oxone)(2KHSO5˙KHSO4˙K2SO4)、過碘酸、碘酸、氧化釩(V)、氧化釩(IV、V)、釩酸銨、過氧單硫酸銨、亞氯酸銨、氯酸銨、碘酸銨、硝酸銨、過硼酸銨、過氯酸銨、過碘酸銨、過硫酸銨、次氯酸銨、次溴酸銨、鎢酸銨、過硫酸鈉、次氯酸鈉、過硼酸鈉、次溴酸鈉、碘酸鉀、過錳酸鉀、過硫酸鉀、硝酸、過硫酸鉀、次氯酸鉀、亞氯酸四甲銨、氯酸四甲銨、碘酸四甲銨、過硼酸四甲銨、過氯酸四甲銨、過碘酸四甲銨、過硫酸四甲銨、過氧單硫酸四丁銨、過氧單硫酸、硝酸鐵、尿素過氧化氫、過乙酸、甲基-1,4-苯醌(MBQ)、1,4-苯醌(BQ)、1,2-苯醌、2,6-二氯-1,4-苯醌(DCBQ)、甲苯醌、2,6-
二甲基-1,4-苯醌(DMBQ)、四氯苯醌、四氧嘧啶(alloxan)、N-甲基啉N-氧化物、三甲胺N-氧化物、及其組合。氧化物質可在製造商處、在將組成物引入至裝置晶圓之前、或者於裝置晶圓處(即於原位)引入至組成物。氧化物質較佳包含醌化合物(例如,DCBQ)、過氧化氫、過乙酸、碘酸銨、或其任何組合。當存在時,氧化物質之量係在約0.01重量%至約10重量%之範圍內,較佳約0.1重量%至1重量%。
若使用醌作為氧化劑,則可使用醌於抗氧化、較佳非質子性溶劑(例如四氫噻吩碸、四甘醇二甲醚、及其組合)中之濃溶液(例如5-15%)作為待於使用前方才添加至配方的醌來源。舉例來說,醌可為DCBQ且可將其溶解於四氫噻吩碸及四甘醇二甲醚之混合物中。醌/非質子性溶劑混合物(例如,DCBQ/四氫噻吩碸/四甘醇二甲醚混合物)可被視為針對本文所述之組成物、套組、及方法之目的的「至少一種氧化劑」。
當存在時,至少一種緩衝物質係經添加來將溶液之pH維持於約1至約5,較佳約1.5至約4之範圍內。涵蓋的緩衝物質包括,但不限於,甲磺酸、二水合草酸、檸檬酸、酒石酸、2-吡啶甲酸、琥珀酸、乙酸、乳酸、磺基琥珀酸、苯甲酸、丙酸、甲酸、丙酮酸、順丁烯二酸、丙二酸、反丁烯二酸、蘋果酸、抗壞血酸、苦杏仁酸、庚酸、丁酸、戊酸、戊二酸、酞酸、次磷酸、水楊酸、5-磺基水楊酸、氫氯酸、乙磺酸、丁磺酸、對甲苯磺酸、二氯乙酸、二氟乙酸、單氯乙酸、單氟乙酸、氫氯酸、三氯乙酸、三氟乙酸、氫溴酸(62重量%)、硫酸、乙酸銨、乙酸鈉、乙酸鉀、乙酸四甲銨及其他乙酸四烷基銨、乙酸鏻、丁酸銨、三氟乙酸銨、磷酸、磷酸
單氫二銨、磷酸二氫銨、磷酸單氫雙(四甲基銨)、磷酸單氫二鈉、磷酸二氫鈉、磷酸單氫二鉀、磷酸二氫鉀、磷酸單氫二-四烷基銨、磷酸二氫二-四烷基銨、磷酸單氫二鏻、磷酸二氫鏻、膦酸銨、膦酸四烷基銨、膦酸鈉、膦酸鉀、膦酸鏻、其鹽、及其組合。該至少一種緩衝物質較佳包含二水合草酸。當存在時,緩衝物質之量係在約0.01重量%至約10重量%之範圍內,較佳約0.1重量%至3重量%,但熟悉技藝人士當明瞭該量係取決於所選擇使用的緩衝物質而定。
文中描述之組成物的一可選組分係至少一種針對鍺的鈍化劑。鈍化劑可包括,但不限於,抗壞血酸、L(+)-抗壞血酸、異抗壞血酸、抗壞血酸衍生物、硼酸、硼酸氫銨、硼酸鹽(例如,五硼酸銨、四硼酸鈉、及硼酸氫銨)、丙胺酸、精胺酸、天冬醯胺酸、天冬胺酸、半胱胺酸、麩胺酸、麩醯胺酸、組胺酸、異白胺酸、白胺酸、離胺酸、甲硫胺酸、***酸、脯胺酸、絲胺酸、蘇胺酸、色胺酸、酪胺酸、纈胺酸、溴化鈉、溴化鉀、溴化銣、溴化鎂、溴化鈣、具有式NR1R2R3R4Br之溴化銨(其中R1、R2、R3及R4可彼此相同或不同且係選自由氫及分支鏈或直鏈C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)組成之群)。該至少一種鍺鈍化劑較佳包含組胺酸。當存在時,鈍化劑之量係在約0.01重量%至約5重量%之範圍內,較佳約0.1重量%至1重量%。
應明瞭可調整組成物以改變矽鍺材料相對於含鍺材料及含矽材料之蝕刻速率,此係熟悉技藝人士所可輕易地明瞭及決定。最佳地,在25℃下矽鍺:含鍺化合物(SiGe:Ge)之選擇性係大於5:1,更佳大於10:1,及最佳等於或大於15:1,其中矽鍺材
料蝕刻速率大於約10埃/分鐘,更佳大於50埃/分鐘。
當明瞭一般實務係製造濃縮形式的組成物以在使用之前稀釋。舉例而言,組成物可以更為濃縮的形式製造,其後再在製造商處、在使用前、及/或在工廠在使用期間以水、額外的水、至少一種氧化劑、至少一種二醇、或額外的二醇稀釋。稀釋比率可在約0.1份稀釋劑:1份組成物濃縮物至約100份稀釋劑:1份組成物濃縮物範圍內。或者,濃縮物可包含至少一種二醇化合物、至少一種氟化物物質、視需要之至少一種緩衝物質、視需要之至少一種鍺鈍化物質、及水,且可在使用點前或使用點處與至少一種氧化劑組合。濃縮物對至少一種氧化劑之比率係在約100:1至約10:1之範圍內,較佳約50:1至約30:1。
文中所述之組成物係經由簡單地添加各別成分及混合至均勻狀態而容易地調配得。此外,可輕易地將組成物調配為單一包裝配方或在使用點處或使用點前混合的多份配方,較佳係多份配方。可將多份配方之個別份於工具處或於混合區域/範圍(諸如線上混合器)或於工具上游之儲槽中混合。涵蓋多份配方之各個份可包含成分/組分之任何組合,其當混合在一起時形成期望的組成物。各別成分的濃度可在組成物的特定倍數內寬廣地改變,即更稀或更濃,且當明瞭組成物可變化及替代地包含與本文之揭示內容一致之成分的任何組合,由其等所組成,或基本上由其等所組成。
因此,第二態樣係關於一種套組,其包括存於一或多個容器中之一或多種適於形成文中所述之組成物的組分。套組之容器必需適於儲存及運送該等組成物組分,例如,NOWPak®容器(Entegris,Inc.,Billerica,Mass.,USA)。較佳地,一個容器包含至少
一種氧化劑及第二容器包含其餘組分,例如,至少一種二醇、至少一種氟化物、水、視需要之至少一種緩衝劑、及視需要之至少一種鍺鈍化劑,其用於在工廠或使用點處組合。舉例來說,在一具體例中,一個容器包含至少一種氧化劑及第二容器包含其餘組分,例如,至少一種二醇、至少一種氟化物、水、至少一種緩衝劑、及至少一種鍺鈍化劑,其用於在工廠或使用點處組合。在另一具體例中,一個容器包含至少一種氧化劑及至少一種二醇及第二容器包含其餘組分,例如,至少一種氟化物、水、視需要之至少一種緩衝劑、及視需要之至少一種鍺鈍化劑,其用於在工廠或使用點處組合。容納組成物之組分的一或多個容器較佳包括用於使該一或多個容器中之組分流體相通,以進行摻混及配送的構件。舉例來說,參照NOWPak®容器,可對該一或多個容器中之襯裡的外側施加氣體壓力,以導致襯裡之至少一部分的內容物排出,且因此可流體相通而進行摻混及配送。或者,可對習知之可加壓容器的頂部空間施加氣體壓力,或可使用泵於達成流體相通。此外,系統較佳包括用於將經摻混之組成物配送至製程工具的配送口。
較佳使用實質上化學惰性、不含雜質、可撓性及彈性的聚合膜材料,諸如高密度聚乙烯,於製造該一或多個容器的襯裡。理想的襯裡材料不需要共擠塑或障壁層來進行加工,且不含任何會不利影響待置於襯裡中之組分之純度需求的顏料、UV抑制劑、或加工劑。理想襯裡材料的清單包括含純粹(無添加劑)聚乙烯、純粹聚四氟乙烯(PTFE)、聚丙烯、聚胺基甲酸酯、聚二氯亞乙烯、聚氯乙烯、聚縮醛、聚苯乙烯、聚丙烯腈、聚丁烯等等的膜。此等襯裡材料的較佳厚度係在約5密爾(mil)(0.005英吋)至約30密爾
(0.030英吋)之範圍內,例如,20密爾(0.020英吋)之厚度。
關於套組之容器,將以下專利及專利申請案之揭示內容的各別全體併入本文為參考資料:美國專利第7,188,644號,標題「使超純液體中之顆粒產生減至最小的裝置及方法(APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS)」;美國專利第6,698,619號,標題「可回收及再利用的桶中袋流體儲存及配送容器系統(RETURNABLE AND REUSABLE,BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM)」;及2008年5月9日提出申請之PCT/US08/63276,標題「材料摻混及分佈用的系統及方法(SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION)」。
在第三態樣中,本發明係關於使用文中所述之組成物之方法。舉例來說,涵蓋一種使用該組成物自微電子裝置之表面相對於含鍺材料及含矽材料選擇性地移除矽鍺材料之方法。
在移除應用中,組成物係以任何適當方式施用至微電子裝置之表面,例如,經由將組成物噴塗於裝置之表面上,經由(於靜態或動態體積之組成物中)浸泡裝置,經由使裝置與已於其上吸收組成物之另一材料(例如,墊、或纖維吸收性塗布器元件)接觸,經由使裝置與循環的組成物接觸,或藉由任何其他藉以使組成物與矽鍺材料及含鍺材料進行移除接觸之適當手段、方式或技術。該應用可係於批式或單一晶圓裝置中用於動態或靜態清洗。
在使用文中所述之組成物時,典型上使該組成物與裝置結構在約20℃至約100℃範圍內,較佳約25℃至約70℃之溫度
下接觸約1分鐘至約200分鐘,較佳約5分鐘至約60分鐘之足夠時間。該等接觸時間及溫度係為說明性,可使用任何其他可有效地達成所需之移除選擇性的適宜時間及溫度條件。
於達成期望的蝕刻作用後,可輕易地將組成物自其先前經施用的微電子裝置移除,例如,藉由可能係在本發明組成物的給定最終應用中所期望且有效的沖洗、洗滌、或其他移除步驟。舉例來說,裝置可經包括去離子水的沖洗溶液沖洗及/或乾燥(例如,旋轉乾燥、N2、蒸氣乾燥等)。若鍺或高鍺膜經暴露,則較佳的沖洗係實質上非水性,例如,異丙醇(IPA)。
本發明之又另一態樣係關於根據文中所述方法製得之經改良的微電子裝置及包含此等微電子裝置之產品。
本發明之另一態樣係關於一種製造物件,其包括以下各物,由其等所組成或基本上由其等所組成:微電子裝置基板、矽鍺材料、含鍺材料、及如文中所述之組成物。
又另一態樣係關於一種自微電子裝置之表面相對於含鍺材料及含矽材料選擇性地移除矽鍺材料之組成物,該組成物包含下列各項之組合:(a)包含至少一種二醇化合物、至少一種氟化物物質、視需要之至少一種緩衝物質、視需要之至少一種鍺鈍化物質、及水之濃縮物,及(b)至少一種氧化劑。
本發明之特徵及優點由以下論述的說明性實施例作更完整展示。
為確保最大儲存壽命,如下製備兩種溶液且在使用前混合:
容器A:0.1-5重量%二水合草酸、0.1-2重量%氟化銨、0.1-2重量%組胺酸、30-55重量%乙二醇及其餘的水。
容器B:5-15重量% 2,6-二氯-1,4-苯醌(DCBQ),其餘為具有9:1重量百分比比率的四氫噻吩碸:四甘醇二甲醚。
在使用前將90-95份容器A與5-10份容器B混合。所得pH為2.9且所得組成物之浴液壽命超過8小時且容器A及B中之組成物的儲存壽命超過六個月。
經由將各者之試樣於組合溶液中在室溫下浸泡測得22:1之Si(0.4)Ge(0.6)相對於Ge的蝕刻選擇性。經測得Si(0.4)Ge(0.6)蝕刻速率為8.3nm/分鐘。此外,於4分鐘後,測得氧化矽及氮化矽之蝕刻損耗分別為1.3nm及5nm。
為確保最大儲存壽命,如下製備兩種溶液且在使用前混合:
容器C:0.1-2重量%氟化銨、0.1-2重量%氫氟酸、及其餘的水。
容器D:5-15重量% 2,6-二氯-1,4-苯醌(DCBQ),其餘為乙二醇。
在使用前將40-60份容器A與60-40份容器B混合。所得pH為4.7且所得組成物之浴液壽命超過6小時且容器C及D中之組成物的儲存壽命超過八星期。
經由將各者之試樣於組合溶液中在室溫下浸泡測得5.9:1之Si(0.4)Ge(0.6)相對於Ge的蝕刻選擇性。經測得Si(0.4)Ge(0.6)蝕刻速率為13.8nm/分鐘。此外,於4分鐘後,測得氧化矽及氮化矽之蝕刻損耗分別為2.8nm及7.4nm。
雖然本發明已參照本發明之特定態樣、特徵及說明具
體例說明於文中,但當明瞭本發明之效用並不因此受限,而係可延伸至涵蓋熟悉本發明領域人士基於文中揭示內容所可明白的許多其他變化、修改及替代具體例。因此,後文所主張之發明意欲經廣泛解釋及詮釋為包括在其精神及範疇內的所有此等變化、修改及替代具體例。
Claims (9)
- 一種自微電子裝置之表面相對於含鍺材料及含矽材料選擇性地移除鍺化矽材料之方法,該方法包括使一組成物與微電子裝置之表面接觸以相對於含鍺材料及含矽材料選擇性地移除該鍺化矽材料,其中該組成物包含30wt%至99wt%之至少一種二醇化合物、0.01wt%至5wt%之至少一種氟化物物質、0.01wt%至10wt%之至少一種氧化物質、及水。
- 如請求項1之方法,其中,該至少一種二醇物質包括選自由下列所組成之群之物質:乙二醇、新戊二醇、1,2-丙二醇(propylene glycol)、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,2-戊二醇、1,3-戊二醇、1,4-戊二醇、2,3-丁二醇、3-甲基-1,2-丁二醇、1,5-戊二醇、2-甲基-1,3-戊二醇、2,4-戊二醇、2-甲基-2,4-戊二醇、2,3-戊二醇、1,2-己二醇、2-乙基-1,3-己二醇、2,5-二甲基-2,5-己二醇、1,2-辛二醇及其組合。
- 如請求項1或2之方法,其中,該至少一種氟化物物質包括選自由下列所組成之群之物質:氫氟酸、六氟鈦酸、六氟矽酸、六氟鋯酸、四氟硼酸、三氟甲磺酸四丁銨、四氟硼酸四烷基銨(NR1R2R3R4BF4)、六氟磷酸四烷基銨(NR1R2R3R4PF6)、氟化四烷基銨(NR1R2R3R4F)、氟化氫銨、氟化銨、及其組合,其中R1、R2、R3、R4可彼此相同或不同且係選自由氫、直鏈或分支鏈C1-C6烷基、C1-C6烷氧基、或經取代或未經取代之芳基所組成之群。
- 如請求項1或2之方法,其中,該至少一種氧化物質包括選自由下列所組成之群之物質:過氧化氫、FeCl3、FeF3、Fe(NO3)3、Sr(NO3)2、CoF3、MnF3、發氧方(2KHSO5˙KHSO4˙K2SO4)、過碘 酸、碘酸、氧化釩(V)、氧化釩(IV、V)、釩酸銨、過氧單硫酸銨、亞氯酸銨、氯酸銨、碘酸銨、硝酸銨、過硼酸銨、過氯酸銨、過碘酸銨、過硫酸銨、次氯酸銨、次溴酸銨、鎢酸銨、過硫酸鈉、次氯酸鈉、過硼酸鈉、次溴酸鈉、碘酸鉀、過錳酸鉀、過硫酸鉀、硝酸、過硫酸鉀、次氯酸鉀、亞氯酸四甲銨、氯酸四甲銨、碘酸四甲銨、過硼酸四甲銨、過氯酸四甲銨、過碘酸四甲銨、過硫酸四甲銨、過氧單硫酸四丁銨、過氧單硫酸、硝酸鐵、尿素過氧化氫、過乙酸、甲基-1,4-苯醌(MBQ)、1,4-苯醌(BQ)、1,2-苯醌、2,6-二氯-1,4-苯醌(DCBQ)、甲苯醌、2,6-二甲基-1,4-苯醌(DMBQ)、四氯苯醌、四氧嘧啶(alloxan)、N-甲基啉N-氧化物、三甲胺N-氧化物、及其組合。
- 如請求項1或2之方法,其進一步包含至少一種選自由下列所組成之群之緩衝物質:甲磺酸、二水合草酸、檸檬酸、酒石酸、2-吡啶甲酸、琥珀酸、乙酸、乳酸、磺基琥珀酸、苯甲酸、丙酸、甲酸、丙酮酸、順丁烯二酸、丙二酸、反丁烯二酸、蘋果酸、抗壞血酸、苦杏仁酸、庚酸、丁酸、戊酸、戊二酸、酞酸、次磷酸、水楊酸、5-磺基水楊酸、氫氯酸、乙磺酸、丁磺酸、對甲苯磺酸、二氯乙酸、二氟乙酸、單氯乙酸、單氟乙酸、氫氯酸、三氯乙酸、三氟乙酸、氫溴酸(62重量%)、硫酸、乙酸銨、乙酸鈉、乙酸鉀、乙酸四甲銨及其他乙酸四烷基銨、乙酸鏻、丁酸銨、三氟乙酸銨、磷酸、磷酸單氫二銨、磷酸二氫銨、磷酸單氫雙(四甲基銨)、磷酸單氫二鈉、磷酸二氫鈉、磷酸單氫二鉀、磷酸二氫鉀、磷酸單氫二-四烷基銨、磷酸二氫二-四烷基銨、磷酸單氫二鏻、磷酸二氫鏻、膦酸銨、膦酸四烷基銨、膦酸鈉、膦酸鉀、膦酸鏻、其鹽、及其組合。
- 如請求項1或2之方法,其進一步包含至少一種選自由下列所組成之群之鈍化劑:抗壞血酸、L(+)-抗壞血酸、異抗壞血酸、抗壞血酸衍生物、硼酸、硼酸氫銨、硼酸鹽、丙胺酸、精胺酸、天冬醯胺酸、天冬胺酸、半胱胺酸、麩胺酸、麩醯胺酸、組胺酸、異白胺酸、白胺酸、離胺酸、甲硫胺酸、***酸、脯胺酸、絲胺酸、蘇胺酸、色胺酸、酪胺酸、纈胺酸、溴化鈉、溴化鉀、溴化銣、溴化鎂、溴化鈣、具有式NR1R2R3R4Br之溴化銨(其中R1、R2、R3及R4可彼此相同或不同且係選自由氫及分支鏈或直鏈C1-C6烷基組成之群)。
- 一種套組,其包括存於一或多個容器中之一或多種適於形成用於自微電子裝置之表面相對於含鍺材料及含矽材料選擇性地移除鍺化矽材料之組成物的組分,其中一容器包含0.01wt%至10wt%之至少一種氧化劑及第二容器包含30wt%至99wt%之至少一種二醇、0.01wt%至5wt%之至少一種氟化物、水、視需要之至少一種緩衝劑、及視需要之至少一種鍺鈍化劑,其用於在工廠或使用點處組合。
- 一種套組,其包括存於一或多個容器中之一或多種適於形成用於自微電子裝置之表面相對於含鍺材料及含矽材料選擇性地移除鍺化矽材料之組成物的組分,其中一容器包含0.01wt%至10wt%之至少一種氧化劑及30wt%至99wt%之至少一種二醇及第二容器包含0.01wt%至5wt%之至少一種氟化物、水、視需要之至少一種緩衝劑、及視需要之至少一種鍺鈍化劑,其用於在工廠或使用點處組合。
- 一種相對於含鍺材料及含矽材料選擇性地移除鍺化矽材料之 組成物,其包含30wt%至99wt%之至少一種二醇化合物、0.01wt%至5wt%之至少一種氟化物物質、0.01wt%至10wt%之至少一種氧化物質、視需要之至少一種緩衝物質、視需要之至少一種鍺鈍化物質、及水。
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JP2018519674A (ja) | 2018-07-19 |
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KR102092720B1 (ko) | 2020-03-24 |
TW201704538A (zh) | 2017-02-01 |
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KR20180019237A (ko) | 2018-02-23 |
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