TW202235581A - 蝕刻組合物、蝕刻方法、半導體裝置之製造方法及環繞式閘極型電晶體之製造方法 - Google Patents
蝕刻組合物、蝕刻方法、半導體裝置之製造方法及環繞式閘極型電晶體之製造方法 Download PDFInfo
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- TW202235581A TW202235581A TW110147702A TW110147702A TW202235581A TW 202235581 A TW202235581 A TW 202235581A TW 110147702 A TW110147702 A TW 110147702A TW 110147702 A TW110147702 A TW 110147702A TW 202235581 A TW202235581 A TW 202235581A
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- etching composition
- mass
- silicon
- etching
- ammonium salt
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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 10
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- 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
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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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- H—ELECTRICITY
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- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
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- H01L21/30608—Anisotropic liquid etching
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- H—ELECTRICITY
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- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract
本發明之蝕刻組合物包含碳數為8以上之四級銨鹽(A),且相對於矽鍺選擇性地溶解矽。本發明之蝕刻組合物亦可進而包含螯合劑(B)。本發明之蝕刻方法係使用該蝕刻組合物來對包含矽與矽鍺之構造體進行蝕刻。本發明提供一種抑制矽鍺溶解並促進矽溶解而使得矽相對於矽鍺之選擇性溶解性優異之蝕刻組合物、使用該蝕刻組合物之蝕刻方法、半導體裝置之製造方法及環繞式閘極型電晶體之製造方法。
Description
本發明係關於一種蝕刻組合物、蝕刻方法、半導體裝置之製造方法及環繞式閘極型電晶體之製造方法。
按照莫耳定律,積體電路之微細化不斷推進。
近年來,不僅在研究減小先前之平面型電晶體之尺寸,還在研究如Fin型電晶體(Fin型FET)或環繞式閘極型電晶體(GAA型FET)般改變結構來提高性能,同時進一步推進微細化或積體化。
Fin型FET中,藉由在相對於矽基板垂直之方向上形成鰭,不僅增加每單位面積之電晶體數量,而且於低電壓時之ON/OFF控制中顯示出優異性能。
為了進一步提高性能,需要花費工夫增大鰭之深寬比等,但若深寬比過大,則存在於用於形成鰭之洗淨步驟或乾燥步驟中鰭倒塌等問題。
GAA型FET中,藉由利用閘極電極覆蓋構成通道之奈米片或奈米線,增加通道與閘極電極之接觸面積,來提高每單位面積之電晶體之性能。
為了形成GAA型FET,需要一種蝕刻組合物,其用於自矽與矽鍺交替地積層而成之構造體,對矽或矽鍺選擇性地進行蝕刻。
作為此類蝕刻組合物,於專利文獻1中揭示有一種組合物,其包含四級氫氧化銨化合物,具體而言包含氫氧化乙基三甲基銨。
[專利文獻1]日本專利特開2019-050364號公報
專利文獻1中所揭示之蝕刻組合物由於未對四級氫氧化銨化合物之種類進行優化、或者未調配有螯合劑,因此矽相對於矽鍺之選擇性溶解性難言充分。
專利文獻1中所揭示之矽與矽鍺交替地積層而成之構造體中,使用結晶性較低之多晶矽作為矽,因此並不明確實際之半導體裝置中常用之結晶性較高之矽是否亦能夠獲得同等之選擇性溶解性。
先前以來,雖然如專利文獻1般研究了包含各種成分之蝕刻組合物,但任一者均難言矽相對於矽鍺之選擇性溶解性充分。
本發明之目的在於提供一種蝕刻組合物,其抑制矽鍺溶解並促進矽溶解而使得矽相對於矽鍺之選擇性溶解性優異。
又,本發明之目的在於提供一種使用該蝕刻組合物之蝕刻方法、半導體裝置之製造方法、及環繞式閘極型電晶體之製造方法。
[解決問題之技術手段]
本發明人等發現,後述之蝕刻組合物抑制矽鍺溶解並促進矽溶解而使得矽相對於矽鍺之選擇性溶解性優異。
即,本發明之主旨如下。
[1]一種蝕刻組合物,其包含碳數為8以上之四級銨鹽(A),且相對於矽鍺選擇性地溶解矽。
[2]如[1]所記載之蝕刻組合物,其中碳數為8以上之四級銨鹽(A)包含選自由氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化四己基銨、氫氧化四辛基銨、及氫氧化苄基三甲基銨所組成之群中之至少一種化合物。
[3]如[1]或[2]所記載之蝕刻組合物,其中碳數為8以上之四級銨鹽(A)包含選自由氫氧化四乙基銨、氫氧化四丙基銨、及氫氧化四丁基銨所組成之群中之至少一種化合物。
[4]如[1]至[3]中任一項所記載之蝕刻組合物,其中在碳數為8以上之四級銨鹽(A)100質量%中,碳數為8以上之四級銨鹽(A)中之4個烷基相同之四級烷基銨鹽之含有率為50質量%以上。
[5]如[1]至[4]中任一項所記載之蝕刻組合物,其中在蝕刻組合物100質量%中,碳數為8以上之四級銨鹽(A)之含有率為10質量%以上。
[6]如[1]至[5]中任一項所記載之蝕刻組合物,其進而包含螯合劑(B)。
[7]如[6]所記載之蝕刻組合物,其中在蝕刻組合物100質量%中,螯合劑(B)之含有率為0.001質量%~25質量%。
[8]如[6]或[7]所記載之蝕刻組合物,其中碳數為8以上之四級銨鹽(A)相對於螯合劑(B)之質量比為5~5000。
[9]如[1]至[8]中任一項所記載之蝕刻組合物,其進而包含水(C)。
[10]如[1]至[9]中任一項所記載之蝕刻組合物,其進而包含水混和性溶劑(D)。
[11]如[10]所記載之蝕刻組合物,其中在蝕刻組合物100質量%中,水混和性溶劑(D)之含有率為15質量%以下。
[12]如[10]或[11]所記載之蝕刻組合物,其中碳數為8以上之四級銨鹽(A)相對於水混和性溶劑(D)之質量比為1以上。
[13]一種蝕刻組合物,其包含碳數為8以上之四級銨鹽(A),且碳數為8以上之四級銨鹽(A)包含選自由氫氧化四乙基銨、氫氧化四丙基銨、及氫氧化四丁基銨所組成之群中之至少一種化合物,在碳數為8以上之四級銨鹽(A)100質量%中,碳數為8以上之四級銨鹽(A)中之4個烷基相同之四級烷基銨鹽之含有率為50質量%以上,在組合物100質量%中,碳數為8以上之四級銨鹽(A)之含有率為10質量%以上。
[14]一種蝕刻方法,其係使用如[1]至[13]中任一項所記載之蝕刻組合物來對包含矽與矽鍺之構造體進行蝕刻。
[15]一種半導體裝置之製造方法,其包括使用如[1]至[13]中任一項所記載之蝕刻組合物來對包含矽與矽鍺之構造體進行蝕刻的步驟。
[16]一種環繞式閘極型電晶體之製造方法,其包括使用如[1]至[13]中任一項所記載之蝕刻組合物來對包含矽與矽鍺之構造體進行蝕刻的步驟。
[發明之效果]
本發明之蝕刻組合物抑制矽鍺溶解並促進矽溶解而使得矽相對於矽鍺之選擇性溶解性優異。
關於使用此類本發明之蝕刻組合物的本發明之蝕刻方法、本發明之半導體裝置之製造方法、及本發明之環繞式閘極型電晶體之製造方法,在蝕刻步驟中,抑制矽鍺溶解並促進矽溶解,藉由矽相對於矽鍺之優異選擇性溶解性,進行高精度之蝕刻,從而能夠以高良率製造所需之製品。
以下,對本發明進行詳細說明。本發明並不受以下實施方式所限定,可於其主旨之範圍內進行各種變更而實施。本說明書中,於使用「~」之表達之情形時,作為包含其前後之數值或物性值之表達來使用。
本發明之蝕刻組合物藉由包含碳數為8以上之四級銨鹽(A)(以下,有時稱為「成分(A)」),而可相對於矽鍺選擇性地溶解矽。
本發明之蝕刻組合物亦可進而包含螯合劑(B)(以下,有時稱為「成分(B)」)、水(C)(以下,有時稱為「成分(C)」)、及水混和性溶劑(D)(以下,有時稱為「成分(D)」)。
<成分(A)>
成分(A)係碳數為8以上之四級銨鹽。藉由在蝕刻組合物中包含碳數為8以上之四級銨鹽,而發揮溶解矽或矽鍺之效果。
基於矽相對於矽鍺之選擇性溶解性優異而言,成分(A)之碳數較佳為8~32,更佳為12~24。成分(A)之碳數為8以上之四級銨鹽例如可例舉:氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化四己基銨、氫氧化四辛基銨、氫氧化苄基三甲基銨等可於烷基具有取代基之氫氧化四烷基銨等四級烷基銨鹽等。
基於矽相對於矽鍺之選擇性溶解性優異而言,作為成分(A)之四級烷基銨鹽較佳為4個烷基相同,尤其是在成分(A)100質量%中,4個烷基相同之四級烷基銨鹽之含量較佳為50質量%以上,更佳為70質量%以上,進而較佳為90質量%以上,4個烷基相同之四級烷基銨鹽之含量最佳為100質量%。
該等碳數為8以上之四級銨鹽可單獨使用1種,亦可併用2種以上。
基於矽相對於矽鍺之選擇性溶解性優異而言,該等碳數為8以上之四級銨鹽之中,較佳為氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化四己基銨、氫氧化四辛基銨、氫氧化苄基三甲基銨,更佳為氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化苄基三甲基銨,進而較佳為氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨,最佳為氫氧化四丁基銨。
基於矽之選擇性溶解性優異而言,在蝕刻組合物100質量%中,成分(A)之含有率較佳為1質量%以上,更佳為10質量%以上,進而較佳為15質量%以上。
基於矽之選擇性溶解性優異而言,在蝕刻組合物100質量%中,成分(A)之含有率較佳為70質量%以下,更佳為55質量%以下,進而較佳為40質量%以下。
根據上述成分(A)之較佳態樣,作為本發明之蝕刻組合物,可例舉如下蝕刻組合物,其包含成分(A),且成分(A)包含選自由氫氧化四丙基銨、及氫氧化四丁基銨所組成之群中之至少一種化合物,在成分(A)100質量%中,成分(A)中之4個烷基相同之四級烷基銨鹽之含有率為50質量%以上,在組合物100質量%中,成分(A)之含有率為10質量%以上。
<成分(B)>
成分(B)係螯合劑。藉由在蝕刻組合物中包含螯合劑,而發揮保護矽鍺之效果。
作為螯合劑,例如可例舉:胺化合物、胺基酸、有機酸等。該等螯合劑可單獨使用1種,亦可併用2種以上。基於矽相對於矽鍺之選擇性溶解性優異而言,該等螯合劑之中,較佳為胺化合物、胺基酸、有機酸,更佳為胺化合物。
作為胺化合物,例如可例舉:乙二胺、1,3-丙二胺、1,4-丁二胺、乙二胺四乙酸、二伸乙三胺五乙酸、三伸乙四胺六乙酸、二伸乙三胺五(甲基膦酸)、乙二胺-N,N'-雙[2-(2-羥基苯基)乙酸]、N,N'-雙(3-胺基丙基)乙二胺、N-甲基-1,3-丙二胺、2-胺基乙醇、N-甲基二乙醇胺、2-胺基-2-甲基-1-丙醇等。該等胺化合物可單獨使用1種,亦可併用2種以上。
基於矽相對於矽鍺之選擇性溶解性優異而言,該等胺化合物之中,較佳為乙二胺、1,3-丙二胺、1,4-丁二胺、乙二胺四乙酸、二伸乙三胺五乙酸、三伸乙四胺六乙酸、二伸乙三胺五(甲基膦酸)、乙二胺-N,N'-雙[2-(2-羥基苯基)乙酸]、N,N'-雙(3-胺基丙基)乙二胺、N-甲基-1,3-丙二胺、2-胺基乙醇、N-甲基二乙醇胺、2-胺基-2-甲基-1-丙醇,更佳為乙二胺、1,3-丙二胺、1,4-丁二胺、乙二胺四乙酸、二伸乙三胺五乙酸、三伸乙四胺六乙酸、二伸乙三胺五(甲基膦酸)、乙二胺-N,N'-雙[2-(2-羥基苯基)乙酸]。
作為胺基酸,例如可例舉:甘胺酸、精胺酸、組胺酸、(2-二羥乙基)甘胺酸等。該等胺基酸可單獨使用1種,亦可併用2種以上。
基於矽相對於矽鍺之選擇性溶解性優異而言,該等胺基酸之中,較佳為甘胺酸、精胺酸、組胺酸、(2-二羥乙基)甘胺酸,更佳為(2-二羥乙基)甘胺酸。
作為有機酸,例如可例舉:草酸、檸檬酸、酒石酸、蘋果酸、2-膦酸基丁烷-1,2,4-三羧酸等。該等有機酸可單獨使用1種,亦可併用2種以上。
基於矽相對於矽鍺之選擇性溶解性優異而言,該等有機酸之中,較佳為草酸、檸檬酸、酒石酸、蘋果酸、2-膦酸基丁烷-1,2,4-三羧酸,更佳為檸檬酸、2-膦酸基丁烷-1,2,4-三羧酸。
基於矽相對於矽鍺之選擇性溶解性優異而言,在蝕刻組合物100質量%中,成分(B)之含有率較佳為0.001質量%以上,更佳為0.005質量%以上,進而較佳為0.01質量%以上。
基於矽相對於矽鍺之選擇性溶解性優異而言,在蝕刻組合物100質量%中,成分(B)之含有率較佳為25質量%以下,更佳為10質量%以下,進而較佳為6質量%以下。
<成分(C)>
本發明之蝕刻組合物較佳為除了包含成分(A)、成分(B)以外,還包含水(C)(成分(C))。
基於容易製造蝕刻組合物而言,在蝕刻組合物100質量%中,成分(C)之含有率較佳為25質量%以上,更佳為40質量%以上,進而較佳為55質量%以上。
基於可提高蝕刻速率而言,在蝕刻組合物100質量%中,成分(C)之含有率較佳為90質量%以下,更佳為85質量%以下,進而較佳為75質量%以下。
<成分(D)>
本發明之蝕刻組合物較佳為除了包含成分(A)、成分(B)以外,還包含水混和性溶劑(D)(成分(D))。藉由在蝕刻液中包含水混和性溶劑,而發揮保護矽鍺之效果。
作為水混和性溶劑(D),只要為水中之溶解性優異者即可,較佳為溶解度參數(SP值)為7.0以上之溶劑。
作為成分(D)之水混和性溶劑,例如可例舉:異丙醇、乙二醇、丙二醇、甲醇、乙醇、丙醇、丁醇、丙三醇、2-(2-胺基乙氧基乙醇)等極性質子性溶劑;丙酮、二甲基亞碸、N,N-二甲基甲醯胺、N-甲基吡咯啶酮、乙腈等極性非質子性溶劑;己烷、苯、甲苯、二乙醚等非極性溶劑等。該等水混和性溶劑可單獨使用1種,亦可併用2種以上。基於矽相對於矽鍺之選擇性溶解性優異而言,該等水混和性溶劑之中,較佳為丙三醇、2-(2-胺基乙氧基乙醇)、乙二醇、丙二醇。
於本發明之蝕刻組合物包含成分(D)之情形時,基於矽相對於矽鍺之選擇性溶解性優異而言,在蝕刻組合物100質量%中,成分(D)之含有率較佳為0.01質量%以上,更佳為0.1質量%以上,進而較佳為1質量%以上。
基於矽相對於矽鍺之選擇性溶解性優異而言,在蝕刻組合物100質量%中,成分(D)之含有率較佳為30質量%以下,更佳為20質量%以下,進而較佳為15質量%以下。
<其他成分>
本發明之蝕刻組合物除了包含成分(A)、成分(B)、成分(C)、成分(D)以外,還可包含其他成分。
作為其他成分,例如可例舉:陰離子型界面活性劑、非離子型界面活性劑、陽離子型界面活性劑等界面活性劑;聚乙烯醇、聚乙二醇、聚丙二醇、聚乙亞胺、聚丙亞胺、聚丙烯酸等水溶性高分子;過氧化氫、過氯酸、過碘酸等氧化劑;抗壞血酸、沒食子酸、鄰苯三酚、鄰苯二酚、間苯二酚、對苯二酚、8-羥基喹啉等還原劑等。該等其他成分可單獨使用1種,亦可併用2種以上。
<各成分之質量比>
於本發明之蝕刻組合物包含成分(A)與成分(B)之情形時,基於矽相對於矽鍺之選擇性溶解性優異而言,本發明之蝕刻組合物中之成分(A)相對於成分(B)之質量比(成分(A)之質量/成分(B)之質量,以下記為「(A)/(B)」)較佳為5~5000,更佳為5~3000,進而較佳為10~3000。
於本發明之蝕刻液包含成分(D)之情形時,基於矽相對於矽鍺之選擇性溶解性優異而言,成分(A)相對於成分(D)之質量比(成分(A)之質量/成分(D)之質量,以下記為「(A)/(D)」)較佳為0.01~1000,更佳為0.1~100。
於本發明之蝕刻液包含成分(D)之情形時,基於矽相對於矽鍺之選擇性溶解性優異而言,成分(B)相對於成分(D)之質量比(成分(B)之質量/成分(D)之質量,以下記為「(B)/(D)」)較佳為2~2000,更佳為5~1000。
<蝕刻組合物之製造方法>
本發明之蝕刻組合物之製造方法並無特別限定,可藉由將成分(A)、視需要之成分(B)、成分(C)、成分(D)、及其他成分加以混合來製造。
混合順序並無特別限定,可一次性混合所有成分,亦可在預先混合部分成分之後,再混合剩餘之成分。
<蝕刻組合物之物性>
基於矽相對於矽鍺之選擇性溶解性優異而言,本發明之蝕刻組合物對矽之蝕刻速率ER
Si較佳為1 nm/分鐘以上,更佳為3 nm/分鐘以上。
基於矽相對於矽鍺之選擇性溶解性優異而言,本發明之蝕刻組合物對矽鍺之蝕刻速率ER
SiGe較佳為1 nm/分鐘以下,更佳為0.8 nm/分鐘以下,進而較佳為0.5 nm/分鐘以下。
基於矽相對於矽鍺之選擇性溶解性優異而言,本發明之蝕刻組合物之矽與矽鍺之溶解選擇比(ER
Si/ER
SiGe)較佳為4以上,更佳為10以上。
蝕刻速率ER
Si、蝕刻速率ER
SiGe、溶解選擇比係利用後述實施例之項中所記載之方法來進行測定、算出。
<蝕刻組合物之蝕刻對象>
本發明之蝕刻組合物抑制矽鍺溶解並促進矽溶解而使得矽相對於矽鍺之選擇性溶解性優異。因此,本發明之蝕刻組合物適於包含矽與矽鍺作為蝕刻對象之構造體、例如半導體裝置,尤其適於形成GAA型FET所需之矽與矽鍺交替地積層而成之構造體。
基於適於利用本發明之蝕刻組合物進行蝕刻而言,在矽鍺100質量%中,成為蝕刻對象之矽鍺中之矽之含有率較佳為10質量%以上,更佳為20質量%以上。
另一方面,基於適於利用本發明之蝕刻組合物進行蝕刻而言,在矽鍺100質量%中,矽鍺中之矽之含有率較佳為95質量%以下,更佳為85質量%以下。
又,基於適於利用本發明之蝕刻組合物進行蝕刻而言,在矽鍺100質量%中,矽鍺中之鍺之含有率較佳為5質量%以上,更佳為15質量%以上。
另一方面,基於適於利用本發明之蝕刻組合物進行蝕刻而言,在矽鍺100質量%中,矽鍺中之鍺之含有率較佳為90質量%以下,更佳為80質量%以下。
關於矽鍺之合金膜,可利用公知方法進行成膜而製造,但基於電晶體形成後電子或電洞之遷移性優異而言,較佳為利用結晶生長法進行成膜而製造。
包含矽與矽鍺之構造體或矽與矽鍺交替地積層而成之構造體中,矽氧化物、矽氮化物、矽碳氮化物等亦可露出。
又,本發明之蝕刻組合物包含成分(A),且成分(A)包含選自由氫氧化四乙基銨、氫氧化四丙基銨、及氫氧化四丁基銨所組成之群中之至少一種化合物,在成分(A)100質量%中,成分(A)中之4個烷基相同之四級烷基銨鹽之含有率為50質量%以上,在組合物100質量%中,成分(A)之含有率為10質量%以上,基於矽相對於矽鍺之選擇性溶解性優異而言,本發明之蝕刻組合物可適宜用於包含矽與矽鍺之構造體。
<蝕刻方法>
本發明之蝕刻方法係使用本發明之蝕刻組合物來對包含矽與矽鍺之構造體進行蝕刻的方法。
蝕刻方式可使用公知方式,例如可例舉:分批式、單片式等。
基於可提高蝕刻速率而言,蝕刻時之溫度較佳為15℃以上,更佳為20℃以上。
基於減少對基板之損害及蝕刻穩定性之觀點而言,蝕刻時之溫度較佳為100℃以下,更佳為80℃以下。
此處,蝕刻時之溫度相當於蝕刻時之蝕刻組合物之溫度。
<用途>
本發明之蝕刻組合物及本發明之蝕刻方法可適宜用於包括對包含矽與矽鍺之構造體進行蝕刻之步驟的半導體裝置之製造,抑制矽鍺溶解並促進矽溶解而使得矽相對於矽鍺之選擇性溶解性優異。因此,本發明之蝕刻組合物及本發明之蝕刻方法尤其可適宜用於包括對包含矽與矽鍺之構造體進行蝕刻之步驟的GAA型FET之製造。
[實施例]
以下,使用實施例進而具體說明本發明。本發明只要不脫離其主旨,則並不限定於以下實施例之記載。
<原料>
在以下之實施例及比較例中,使用如下成分作為蝕刻組合物之製造原料。
成分(A-1):氫氧化四丁基銨
成分(A-2):氫氧化四丙基銨
成分(A'-1):氨
成分(A'-2):氫氧化四甲基銨
成分(A'-3):氫氧化乙基三甲基銨
成分(B-1):乙二胺
成分(B-2):1,3-丙二胺
成分(B-3):乙二胺四乙酸
成分(B-4):二伸乙三胺五乙酸
成分(B-5):二伸乙三胺五(甲基膦酸)
成分(B-6):乙二胺-N,N'-雙[2-(2-羥基苯基)乙酸]
成分(B-7):N,N'-雙(3-胺基丙基)乙二胺
成分(B-8):N-甲基-1,3-丙二胺
成分(B-9):2-膦酸基丁烷-1,2,4-三羧酸
成分(B-10):2-胺基乙醇
成分(B-11):N-甲基二乙醇胺
成分(B-12):2-胺基-2-甲基-1-丙醇
成分(C-1):水
成分(D-1):丙三醇
成分(D-2):2-(2-胺基乙氧基乙醇)
其他成分:8-羥基喹啉(表1中記為「(E-1)」)
<矽之蝕刻速率>
將包含如下構造體之基板於0.5質量%之氟化氫酸水溶液中浸漬30秒鐘,該構造體係膜厚10 nm之矽鍺與膜厚10 nm(浸漬前之矽層之寬度=10 nm)之矽積層而成,然後利用超純水進行沖洗,其後於40℃下在實施例及比較例中所獲得之蝕刻組合物中浸漬15分鐘。利用電子顯微鏡,對浸漬後之基板剖面進行觀察,測定矽層之寬度(nm),使用下述式(1)算出矽之蝕刻速率ER
Si[nm/分鐘]。
ER
Si[nm/分鐘]=(浸漬前之矽層之寬度-浸漬後之矽層之寬度)÷15分鐘 (1)
<矽鍺之蝕刻速率>
將包含如下構造體之基板於0.5質量%之氟化氫酸水溶液中浸漬30秒鐘,該構造體係膜厚10 nm(浸漬前之矽鍺層之寬度=10 nm)之矽鍺與膜厚10 nm之矽積層而成,然後利用超純水進行沖洗,其後於40℃下在實施例及比較例中所獲得之蝕刻組合物中浸漬15分鐘。利用電子顯微鏡,對浸漬後之基板剖面進行觀察,測定矽鍺層之寬度(nm),使用下述式(2)算出矽鍺層之蝕刻速率ER
SiGe[nm/分鐘]。
ER
SiGe[nm/分鐘]=(浸漬前之矽鍺層之寬度-浸漬後之矽鍺層之寬度)÷15分鐘 (2)
<矽與矽鍺之溶解選擇比>
使用下述式(3),算出矽與矽鍺之溶解選擇比。
溶解選擇比=ER
Si[nm/分鐘]÷ER
SiGe[nm/分鐘] (3)
[實施例1]
以在蝕刻組合物100質量%中,成分(A-1)為26質量%、成分(B-1)為0.01質量%、剩餘為成分(C-1)之方式混合各成分,從而獲得蝕刻組合物。
將所獲得之蝕刻組合物之評價結果示於表1中。
[實施例2~22、比較例1~8]
設為表1所示之原料之種類、含有率,且剩餘為成分(C-1),除此以外與實施例1同樣地進行操作,從而獲得蝕刻組合物。
將所獲得之蝕刻組合物之評價結果示於表1中。
[表1]
成分(A) | 成分(B) | 成分(D) | 其他成分 | ER Si[nm/分鐘] | ER SiGe[nm/分鐘] | 溶解選擇比 | |||||
種類 | 含有率[質量%] | 種類 | 含有率[質量%] | 種類 | 含有率[質量%] | 種類 | 含有率[質量%] | ||||
實施例1 | (A-1) | 26.00 | (B-1) | 0.01 | - | - | - | - | 3.4 | 0.3 | 12.8 |
實施例2 | (A-1) | 26.00 | (B-2) | 0.01 | - | - | - | - | 3.8 | 0.3 | 14.3 |
實施例3 | (A-1) | 26.00 | (B-3) | 0.10 | - | - | - | - | 3.4 | 0.2 | 17.0 |
實施例4 | (A-1) | 26.00 | (B-4) | 0.10 | - | - | - | - | 3.3 | <0.07 | >49.0 |
實施例5 | (A-1) | 26.00 | (B-5) | 0.01 | - | - | - | - | 4.1 | 0.3 | 12.2 |
實施例6 | (A-1) | 26.00 | (B-6) | 0.01 | - | - | - | - | 4.7 | 0.4 | 11.8 |
實施例7 | (A-1) | 26.00 | (B-7) | 0.10 | - | - | - | - | 3.6 | 0.3 | 13.5 |
實施例8 | (A-1) | 26.00 | (B-8) | 0.10 | - | - | - | - | 3.3 | 0.1 | 25.0 |
實施例9 | (A-1) | 26.00 | (B-9) | 0.01 | - | - | - | - | 2.9 | 0.1 | 22.0 |
實施例10 | (A-1) | 26.00 | (B-10) | 0.01 | - | - | - | - | 3.9 | 0.3 | 11.8 |
實施例11 | (A-1) | 26.00 | (B-11) | 0.01 | - | - | - | - | 4.0 | 0.3 | 12.0 |
實施例12 | (A-1) | 26.00 | (B-12) | 0.01 | - | - | - | - | 3.3 | 0.2 | 16.3 |
實施例13 | (A-1) | 26.00 | - | - | - | - | - | - | 4.3 | 0.5 | 8.0 |
實施例14 | (A-1) | 5.00 | - | - | - | - | - | - | 3.3 | 0.5 | 6.3 |
實施例15 | (A-1) | 26.00 | (B-2) | 10.00 | - | - | - | - | 4.3 | 0.5 | 8.1 |
實施例16 | (A-1) | 15.00 | - | - | (D-1) | 10.00 | - | - | 4.4 | 0.5 | 8.3 |
實施例17 | (A-1) | 15.00 | - | - | (D-1) | 15.00 | - | - | 2.9 | 0.9 | 3.4 |
實施例18 | (A-1) | 15.00 | - | - | - | - | - | - | 4.4 | 0.2 | 22.0 |
實施例19 | (A-1) | 15.00 | (B-3) | 0.01 | - | - | - | - | 4.8 | 0.5 | 9.0 |
實施例20 | (A-2) | 22.70 | - | - | - | - | - | - | 6.6 | 0.8 | 7.9 |
實施例21 | (A-2) | 15.00 | - | - | - | - | - | - | 8.5 | 1.0 | 8.5 |
實施例22 | (A-2) | 5.00 | - | - | - | - | - | - | 7.6 | 1.3 | 5.7 |
比較例1 | (A'-1) | 10.00 | - | - | - | - | - | - | 0.9 | 0.1 | 7.0 |
比較例2 | (A'-1) | 10.00 | (B-3) | 0.01 | - | - | - | - | 1.0 | 0.2 | 5.0 |
比較例3 | (A'-2) | 15.00 | - | - | - | - | - | - | 4.1 | 3.4 | 1.2 |
比較例4 | (A'-2) | 15.00 | (B-3) | 0.01 | - | - | - | - | 3.3 | 2.3 | 1.4 |
比較例5 | (A'-3) | 15.00 | - | - | - | - | - | - | 4.4 | 3.3 | 1.3 |
比較例6 | (A'-3) | 15.00 | (B-3) | 0.01 | - | - | - | - | 4.8 | 3.2 | 1.5 |
比較例7 | (A'-3) | 15.00 | - | - | (D-1) | 10.00 | - | - | 3.7 | 2.4 | 1.5 |
比較例8 | (A'-3) | 5.00 | - | - | (D-1) | 20.00 | (E-1) | 1.00 | 1.3 | 0.2 | 6.3 |
(D-2) | 35.00 |
根據表1可知,實施例1~22中所獲得之蝕刻組合物抑制矽鍺溶解並促進矽溶解而使得矽相對於矽鍺之選擇性溶解性優異。
另一方面,成分(A)之種類不同於本發明之比較例1~8之中,比較例3~7中所獲得之蝕刻組合物促進矽鍺溶解而使得矽相對於矽鍺之選擇性溶解性差。
比較例1、2及8中,雖然矽相對於矽鍺之選擇性溶解性相對優異,但矽之溶解性差。
使用特定態樣對本發明進行了詳細說明,但本領域技術人員顯而易見可於不脫離本發明之意圖與範圍之情況下進行各種變更。
本申請案基於2021年1月12日提出申請之日本專利申請2021-002880,藉由引用援引其所有內容。
[產業上之可利用性]
本發明之蝕刻組合物及使用該蝕刻組合物之本發明之蝕刻方法抑制矽鍺溶解並促進矽溶解而使得矽相對於矽鍺之選擇性溶解性優異。因此,本發明之蝕刻組合物及使用該蝕刻組合物之本發明之蝕刻方法可適宜用於半導體裝置之製造,尤其是可適宜用於GAA型FET之製造。
Claims (16)
- 一種蝕刻組合物,其包含碳數為8以上之四級銨鹽(A),且相對於矽鍺選擇性地溶解矽。
- 如請求項1之蝕刻組合物,其中碳數為8以上之四級銨鹽(A)包含選自由氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化四己基銨、氫氧化四辛基銨、及氫氧化苄基三甲基銨所組成之群中之至少一種化合物。
- 如請求項1或2之蝕刻組合物,其中碳數為8以上之四級銨鹽(A)包含選自由氫氧化四乙基銨、氫氧化四丙基銨、及氫氧化四丁基銨所組成之群中之至少一種化合物。
- 如請求項1至3中任一項之蝕刻組合物,其中在碳數為8以上之四級銨鹽(A)100質量%中,碳數為8以上之四級銨鹽(A)中之4個烷基相同之四級烷基銨鹽之含有率為50質量%以上。
- 如請求項1至4中任一項之蝕刻組合物,其中在蝕刻組合物100質量%中,碳數為8以上之四級銨鹽(A)之含有率為10質量%以上。
- 如請求項1至5中任一項之蝕刻組合物,其進而包含螯合劑(B)。
- 如請求項6之蝕刻組合物,其中在蝕刻組合物100質量%中,螯合劑(B)之含有率為0.001質量%~25質量%。
- 如請求項6或7之蝕刻組合物,其中碳數為8以上之四級銨鹽(A)相對於螯合劑(B)之質量比為5~5000。
- 如請求項1至8中任一項之蝕刻組合物,其進而包含水(C)。
- 如請求項1至9中任一項之蝕刻組合物,其進而包含水混和性溶劑(D)。
- 如請求項10之蝕刻組合物,其中在蝕刻組合物100質量%中,水混和性溶劑(D)之含有率為15質量%以下。
- 如請求項10或11之蝕刻組合物,其中碳數為8以上之四級銨鹽(A)相對於水混和性溶劑(D)之質量比為1以上。
- 一種蝕刻組合物,其包含碳數為8以上之四級銨鹽(A),且碳數為8以上之四級銨鹽(A)包含選自由氫氧化四乙基銨、氫氧化四丙基銨、及氫氧化四丁基銨所組成之群中之至少一種化合物,在碳數為8以上之四級銨鹽(A)100質量%中,碳數為8以上之四級銨鹽(A)中之4個烷基相同之四級烷基銨鹽之含有率為50質量%以上,在組合物100質量%中,碳數為8以上之四級銨鹽(A)之含有率為10質量%以上。
- 一種蝕刻方法,其係使用如請求項1至13中任一項之蝕刻組合物來對包含矽與矽鍺之構造體進行蝕刻。
- 一種半導體裝置之製造方法,其包括使用如請求項1至13中任一項之蝕刻組合物來對包含矽與矽鍺之構造體進行蝕刻的步驟。
- 一種環繞式閘極型電晶體之製造方法,其包括使用如請求項1至13中任一項之蝕刻組合物來對包含矽與矽鍺之構造體進行蝕刻的步驟。
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