TW201224120A - Silicon etching solution and transistor manufacturing method using same - Google Patents
Silicon etching solution and transistor manufacturing method using same Download PDFInfo
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- TW201224120A TW201224120A TW100128020A TW100128020A TW201224120A TW 201224120 A TW201224120 A TW 201224120A TW 100128020 A TW100128020 A TW 100128020A TW 100128020 A TW100128020 A TW 100128020A TW 201224120 A TW201224120 A TW 201224120A
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Classifications
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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
- H01L29/66007—Multistep manufacturing processes
- H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
- H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66409—Unipolar field-effect transistors
- H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
- H01L29/66545—Unipolar field-effect transistors with an insulated gate, i.e. MISFET using a dummy, i.e. replacement gate in a process wherein at least a part of the final gate is self aligned to the dummy gate
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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
- H01L21/30604—Chemical etching
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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
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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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
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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
- H01L21/02041—Cleaning
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- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
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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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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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
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Description
201224120 六、發明說明: 【發明所屬之技術領域】 本,明係關於-種钱刻液及利祕刻液之電晶體之 ^ ί2 刻,選擇構⑽擬閉極之钱 【先前技術】 ^今為止的轉體,係藉峰小電 度丄亦即細微化’而提高性能、成本、絲功率。= 微化,使用氧化矽之習知的閘極絕緣膜中,閘 ίΠί源於隨道電流㈣漏電流將增加,而消耗功‘ 筆記型電腦’ 半導體元件的設備’多半是行動電話、 有率。因此,以減少待機,的洩漏電流為目: 高介顧電晶體_緣材料朗電極之組合,使用 術。此睹屬間極取代習知所使用之氧化石夕與多晶石夕的技 關^擇的金屬之—例,可舉峰(專利文獻D。 樣的與,1 極的製造方法,有人提出各式各 ΐ導ϊΐίΓίΐϋ為ί屬間極。圖1表示使用高介電材料的 刻該多晶石夕時,的電晶體之—部分的剖面示意圖。韻 以及高介電材料2夕日日ff周圍存在有紹、層間絕緣膜、側壁、 不會餘刻㉖、μ⑴,且轉為不祕觸部位。因此,需要一種 的技術? 3曰1、'、邑緣膜、側壁、以及高介電材料,餘刻多晶矽 201224120
=刻多晶石夕的方法’已知有乾式飯刻(專利文獻G 層間絕f膜,故需要於轉層間絕緣 賊。設置保護膜的話,製造步驟將變複雜, 並有可料致良率之下降、製造成本之增加。再者,為了 ^而進行的灰化處理,由於會造雜與相絕緣職傷,故令人 擔心降低電晶體的性能。又’通常以防止微小的残 ,進行較由碎之每單位時間的·量(之後稱為侧速^。)計 异的钕刻處理時間更長之時間侧的過度侧。由於 過度钱刻之際’雜概較_後露出的高介電材料,並^其 變質,故有電晶體之性能下降的情況。 /、 清洗液’已知有種種的驗性清洗 液(非專利文獻2)。但是’該等清洗液不僅會餘刻多 蝕刻鋁(參照比較例1)。 / ^曰 不會蝕刻鋁而蝕刻矽的技術,有人提出一種在氫氧化四 =石夕之_異向性液(專利文獻2)。但是,由於該技術將 於馬溫使帛作為前提,故近年來在濕式侧巾,為了抑制粒 使用半導體製造通常所使狀清洗每―牌晶圓的單片清洗裝置 時,無法提供穩定的侧能力。在單#清洗裝置可使用的溫度下 利用時’由於㈣侧速率過小’故無法使驗包含高介 與$屬閘極的電晶體形成步驟中之矽蝕刻。再者,由於在溫度下 降時產生峨,故無法使肖於如半導體之電晶體部—樣微小的粒 子,殘留也無法料的轉H該技術跡適合細於侧 微里鋁也無法容許之半導體的電晶體形成步驟(參照比較例2)。 、不會蝕刻鋁或鋁合金而可選擇性地僅異向性蝕刻矽的蝕刻劑 組成物,有人提出一種在鹼性水溶液添加還原性化合物盥防蝕 的驗系侧劑組成物(專利文獻3)。但是,該技術由於紹的^ 速率過大,故無法使用於包含高介電材料與金屬閘極的電晶體形 成步驟中之矽蝕刻(參照比較例3)。 尸抑制鋁之蝕刻並去除氯的技術,有人提出一種含有第四級銨 氫氧化物、糖類或是糖醇的水溶液(專利文獻4)。但是,專利文 201224120 f 4為根魏之去除_點而防止|§之侧者,並未言及 刻能力。亦即,專利文獻4與將不_。而敍 2作ί目!!的本發明為不同的技術思想。再者’由於專利文獻4 之刻速率過小’故無法使用於作為本發明 1的包3⑷,電材料與金屬閘極的電晶體 刻(參照比較例4)。 州Τ心广賊 再者,有人提出一種抑制鋁之蝕刻並減弱黏合 =離獻5) °但是,專利文獻5係以不妨礙ί ,膜之^。力的此力之觀點’提出_種防止狀侧的驗性剝離 並未言及該驗性剝離液之石夕的侧能力。因此,專利文^ 5 二將不侧^祕财作為目的的本發縣不_技術。再 ί ’可Ϊ:於,文獻5的剝離液,只要定為呈現鹼性的溶液即 但是’限定於可使用於歡侧之呈現驗性 二r利文獻5,並不容易推測適於本發_ 抑制紹之侧並去除聚酿亞胺定向膜的技術,有人提出 n第四級減氧化物、三烧基胺、醇或_的水溶液(專利文 兔力,ΐ献丨⑦要"'種在藉由去除由#構成的虛擬閘極並取代 方法,製造至少具有由高介電材料膜與鋁金屬二 電晶體的方財,選擇性地去除該虛擬閘極的 先前技術文獻 專利文獻 專利文獻1 :美國專利第7316949號說明書 專利文獻2:日本特開平4 —370932號公報 專利文獻3 :日本特開2〇〇7_214456號公報 專利文獻4 :日本特開平4—48633號公報 專利文獻5 :日本特開2〇〇5_229〇53號公報 201224120 專利文獻6 ·日本特開2006—8932號公報 非專利文獻 非專利文獻1 :應用物理76, 9, 2007, P.l〇06 非專利文獻2 :微機械/MEMS技術大全2〇〇3,p lll 【發明内容】 [發明所欲解決的問題] 肢ίίΓϋ的在於提供""種在藉由去除由賴成的虛擬閘極 齡屬閘極的方法,製造至少具有由高介電材料膜與銘 的疊層體之電晶體的方法中,用於該由_成的虛 7 麵性地去除該㈣構成的虛删極之姓刻液、 以及利用蝕刻液之電晶體之製造方法。 [解決問題之技術手段] 案發明人為了達成前述目的而反覆仔細研究的結果發現: 措由對於岭構成的虛擬祕之_使 發明為基於相關的知識而完成者。亦即, 要曰如下所述。 、土古侧液,制於—電晶體之製造方法,該電晶體之製 造方法具有如下特徵: 使用在基板上至少具有虛擬閘極(dummy gate)叠、 側面予以包覆的側壁、以及設置成將該側壁予 巧之層間絕緣膜的結構體’其巾,該虛擬閘極疊層體,係疊 由矽構成的虛擬閘極而構成;且將該虛擬閘極 取代為鋁金屬閘極; 於該電晶體之製造方法中該岭構成的虛擬 =極之·,並含有(U〜40重量%的選自,於氨、二胺及以通式⑴ 之,少—種的驗性化合物、5〜5G重量%的選自於以 通式⑵表不之多元醇中的至少—種、以及4()〜94 H2N- (CH2CH2NH)m-H ....(1) (m為2〜5的整數); (2) (2)201224120 H- (CH_)n—η ..… (η為3〜6的整數)。 示之2聚第白;^之魏刻液’其中,該二胺及以通式⑴表 二之从為選自於乙二胺、u—丙二胺、u—丙二胺、 月女、以及三伸乙四胺中之至少一種。 ㈣述第1項之魏刻液,其中,該以通式(2)表示之多 组械二^自於甘油、赤蘚糖醇(職〇部麻1)、木糖醇、以及山 梨糖醇中之至少一種。 腔沾利範圍第1項之⑪蝴液,其中,形成高介電材料 電材料為 Hf〇2、HfSi0、HfSi0N、HfLa〇、HfLa0N、
HfTiSiON、HfAISiON、HfZrO、或 A1203 〇 5,一種電晶體之製造方法,其特徵為: 使用在基板上至少具有虛擬閘極叠層體、設置成將該疊層體 =側面予以包覆的側壁、以及設置成將該側壁予以包覆之層間絕 巧的結構體,並包含以下的步驟⑴,其中,該虛擬_疊層體, 層向介電材料膜與由_成的虛擬閘極而構成 閘極取代為鋁金屬閘極; 獄 =驟fl) ’利用含有〇1〜4〇重量%的選自於氨、二胺及以通 式U)表示之聚胺中之至少一種的鹼性化合物、5〜5〇重量%的選 自於以通式(2)表示之多元醇中的至少一種、以及40〜949重量 %的水之餘刻液,將矽蝕刻的步驟; H2N- (CH2CH2NH) m-H ....(1) (m為2〜5的整數); H- (CH (〇H)) n-H ..... (2) (n為3〜6的整數)。 6」如前述第5項之電晶體之製造方法,其中,形成高介電材料 膜的而介電材料為 Hf〇2、HfSi〇、HfSi〇N、HfLa〇、HfLa〇N、
HfTiSiON、HfAlSiON、HfZrO、或 a1203 〇 7·如,述第5項之電晶體之製造方法,其中,該二胺及以通式 (1)表示之聚胺為選自於乙二胺、丙二胺、丙二胺、 201224120 一伸乙二胺、以及三伸乙四胺中之至少一種β 8.如釗述第5項之電晶體之製造方法,其中,該以通式(2) 示之夕元醇為選自於甘油、赤蘚糖醇、木糖醇、以及山 中之至少一種。 /、 [對照先前技術之功效] ^據本發明,在藉由去除由石夕構成的虛擬閘極並取代為鋁金 沾:f的方法’製造至少具有由高介電材制與齡屬閘極構成 j豐層體之電晶體的方法中,可選擇性地去除矽,並可以 率製造高精度、高品質的電蟲體。 【實施方式】 [石夕银刻液] 本發明的矽蝕刻液,係用於一電晶體之製造方法,該電晶體 之製造方法具有如下特徵: 使用在基板上至少具有虛擬閘極疊層體、設置成將該疊層體 之側面予以包覆的側壁、以及設置成將該侧壁予以包覆之層間絕 =臈的結構體,其中,該虛擬閘極疊層體,係疊層高介電材料膜 一由石夕構成的虛擬閘極而構成;且將該虛擬閘極取代為鋁金屬閘 極; 該矽蝕刻液,用於該電晶體之製造方法中該由矽構 間極之餘刻,並含有0.^40重量%的選自於氨、二胺及以通式⑴ 表不之聚胺中之至少一種的鹼性化合物、5〜50重量%的選自於以 通式(2)表示之多元醇中的至少一種、以及4〇〜94 9重量%的水; H2N- (CH2CH2NH) m-H .... (1) (m為2〜5的整數); Η- (CH(OH))n-H …“(2) (η為3〜6的整數)。 本發明所使用的驗性化合物,係為將梦姓刻者,且為撰自於 氨、二胺及以通式⑴表示之聚胺中之至少一種的化合= 於本發明之矽蝕刻液的二胺,尤可舉出乙二胺、1,2—丙二胺、1,3 201224120 通式⑴表示之聚胺’尤可舉出二伸乙三胺、 蝕刻液中之鹼性化合物的濃度,通常為〇1〜4〇 理想,態為〇.2〜40重量% ’更理想之樣態為〇 3〜〇 : 本發_補難之多元醇為選自於叫式 =人 甘油、赤蘚糖醇、木糖醇、山梨糖醇。砰认理^的具體例為 度’即可得到充分_之^腐。 足夠。〃要夕凡醇的浪度為50重量%以下,魏刻能力即為 本發明之報刻液中,視其所需可於 ;二’捧合習知所使用蝴液的界面活性劑== 《結構體》 極之結構體之由梅的虛擬閉 之圖!表示藉由本發明之:刻 = ====基板 置成將該疊層體之侧面覆的側^的^擬間極叠層體、設 予以包覆之層間絕緣膜4的結構體搜1及5又置成將該側壁3 屬間。中虛娜1已被齡 且該金屬·謂由觸有齡屬的金屬閑極, 果的觀點,_含_ ^刺本發明之效 擬間極取料__,而其的中虛 201224120 只要在電晶體之-部分的部位使_,即·^得到不侧該部位, 選擇性地去除形成虛擬閘極的矽之本發明的效果。 再者’圖1表示藉由離子植人等之方法能夠形成的源極/沒 ,、隔離部5,而通常高介電材料膜2係設置於基板7的表面上, 包覆於源極/汲極6之間。 祖ΐΐΪ!本發日月之侧液的結構體中,用於基板7的基板材 之配出f/非晶石夕、多晶石夕、玻璃等’而用於金屬問極等 ίίί 使驗,而1呂以外的材料,例如亦可使用銅、 鶴、鈦-鶴、銘、銘合金、鉻、絡合金等之配線材料。 與5 於層間絕緣膜4的材料,宜使關用高密度電聚化 i Γβ目、Pif化賴(_)、W乙氧基魏(TE〇S )、_石夕玻 =ate Glass; BPSG)等;用於繼3 的材料, 是兮箄!(SlN) D介電材料,宜使用励2、A1203、或 ίΐίΐίίΓ子以及,或是氮原子、以及/或是La、Ti、办 ίί ί=於I於層間絕緣膜4、側壁3、高介電材料膜2的 極1 月的矽蝕刻液’在由矽構成的虛擬閘 絕緣膜^以接、ί 金屬閘極(無圖示)、層間 ㈣侧液,由於具有不會1^ 材斜趙〇 /無圖)、層間絕緣臈4、以及側壁3、以及高介雷 電y曰體之^擇性地侧由鶴成的虛擬_1之特性,故可防止 ί;體之各部位的損傷’並以較佳良率製造高精度、高 《虛擬閘極之钱刻》 度,度’亦即虛擬閘極之刪的溫 更理想之樣料’而較理想之樣態為2G〜7〇。〇, 材料而適當ϋ即可。’且只要根據細的條件或使用的基板 201224120 利用本舍明之砍餘刻液的處理時間’亦即虛擬閘極之钮刻時 間’通常為0.1〜10分鐘左右的範圍,而較理想之樣態為〇.2〜8 分鐘,更理想之樣態為〇·3〜5分鐘,且只要根據餘刻的條件或使 用的基板材料而適當選擇即可。 [電晶體之製造方法] 本發明之電晶體之製造方法,其特徵為: 使用在基板上至少具有虛擬閘極疊層體、設置成將該疊層體 之側面予以包覆的側壁、以及設置成將該側壁予以包覆之層間絕 緣膜的結構體,並包含使用本發明之侧液將報刻的步驟,且 中’該虛擬閘極疊層體,係疊層高介電材料膜與由_成的虛^ 閘極而構成;且將該虛擬閘極取代為鋁金屬閘極,· 該,刻液’含有(U〜4〇重量%的選自於氨、二胺及以通式 中之i少一種的鹼性化合物、5〜50重量%的選自於以 通式(2)表不之多兀醇中的至少一種、以及4〇〜94 H2N- (CH2CH2NH) m-H ....(〇 董以的水, (m為2〜5的整數); H- (CH(〇H))n—Η .…⑵ (η為3〜6的整數)。 述 所述 ίΓ月ίίίίί製造方法中’其結構體、姓刻液係如上所 。使用本s麟的使用溫度、處理時間亦如上 波。去超音 j夠卿’不需使用如醇之類的有:二 === 《其他的步驟》 刻液的要前述本發明之# 驟⑷,在龜上形成高介電__倾;步驟H =該ί .201224120 介電材料膜上形成由矽構成的虛擬閘極,並入* 膜及虛擬間極之疊層體的步驟;步驟(^二=電材料 :),使^述本發明之侧液的虛“極之# 電材料膜上__極,並=包= =膜及銘孟屬閘極之疊層體的步驟。該步驟⑷〜 <石夕自然氧化膜之钱刻(步驟(E)) > 自二:if 製造過程,’因為與空氣接觸而其表面 自然氧化,形成矽自然氧化膜❶因此,本發明 由 發明的蝕刻液之蝕刻虛擬閘極1的步驟(步驟⑴)前, ==然氧化膜較為理想。由於藉由包含如前=, 故可以較佳良率製造高精度、高品f之電晶t有料地以’ 本步驟⑻中,欲蝕刻矽自然氧化膜可使用習知 ,’例如包含氫_等之氟化合物的働等。再者,本^ 侧辟,t結構體的紹金屬閉極(無圖示)、層間絕緣膜4、以及) 即文使用不會使該等部位損傷_刻液較為理想,亦 上有ΐ擇刻㈣然、氧化膜之性能的钱刻液。如前述之5 用含有_〜8重量%之氟化合物、2g〜⑽重量%之= 洛性有機溶劑、以及水的蝕刻液較為理想。 κ ㈣Hi之較理想的具制為氟驗、氟化銨、·氟化銨。 二樣恶為敦化録、酸性氟化敍。本發日月中,該等氟化合物, 可早獨或是組合2種以上而摻合。 水溶性有機溶劑,尤可舉出乙醇、2—丙醇、乙二 二 醇等醇類;二乙二醇單甲峻、二乙二醇單丁_、二丙:醇單^‘ 一丙一醇皁丙醚等二醇醚類;N,N—二甲基曱醯胺、n,n—二甲基 13 201224120 、N—曱基—2—°比17各°定_等酸胺類;二曱亞石風等。該等水 >谷性有機溶劑,可單獨亦可組合2種類以上而使用。 再者’用於本步驟(E)的餘刻液,亦可於5重量%以 ^乾圍添加紐、祕、硫酸、鑛等無機酸;_、丙酸 ^甲俩等有機酸。料酸,可單獨亦可组合2種類以上而使 《電晶體》 、、m atq jj 巧本發明之製造方法轉_電晶體,係為在基板7上至 mmltt 2 ^ f产、§又置成_層體之側面予以包覆的側壁3、嗖置 到的電晶體,且根據本發明之製造方法而得 2,係設置於基板7的表面上,6包高介電材料膜 晶體通常具有得到的電晶體,亦可包含電 的阻隔材料,尤可舉J如緣,。作為形成阻隔層 的絕緣材料,尤可舉出氧化/功氛化鈕等;形成絕緣膜 等。 夕氮化石夕、碳化石夕及該等之街生物 體中,^口(無_而構成的疊層 材料構成的金屬閘極,I!如^層金屬以外之金屬 層。再者’半導體材料尤曰n冉為特性控制臈之機能的 合物半導體、或鉻氧化物等f ^家莖磷、銦-磷等之化 顯本發㈣造方法4=工 篮係為鬲積度、高品 14 201224120 質的電晶體。 實施例 接著,根據實施例而更詳細地説明本發明,但本發明並不限 定於該等例。 評價方法 測定設備: 螢光X;射線分析:使用SII NanoTechnology股份有限公司製、 SEA1200VX 測定。 SEM觀察:使用Hitachi High-Technologies股份有限公司製、 超高解析度電場放射型掃描式電子顯微鏡S —5500觀察。 FIB加工:使用Hitachi High-Technologies股份有限公司製、 聚焦離子束加工裝置FB —2100加工。 STEM觀察:使用Hitachi High-Technologies股份有限公司 製、掃描穿透式電子顯微鏡HD —2300觀察。 判定: (由矽構成的虛擬閘極1之蝕刻狀態) 〇:虛擬閘極1完全地被韻刻。 x:虛擬閘極1之敍刻不足。 (鋁之防蝕能力的評鑑) 〇 :銘之蝕刻速率未滿。 x .紹之钱刻速率為以上。 實施例1〜48 丰難德的祕能力,係以下說明的方 ί所夕晶圓上藉由PVD而堆疊賴_A。在第2 表所不的賴財,於25t:_ 射線分析計測定浸潰前德的胺戶…、又’貝川刀鍾並以螢先X 量。根據算出的蝕刻量I潰;液之鋁膜的蝕刻 率未滿Wmin時,崎侧鱗,_之鞋刻速 接著,以下_斜=,對餘刻液之_防姓能力。 料膜、側壁、及層f魏緣祕舰力與雜高介電材 緣膜的_能力之測試方法。採用石夕晶圓 201224120 =為基板,且該矽晶圓上具有電晶體 y表的u〜u,且準備如圖1所示之剖面圖示於 貫1 ’係使用示於第3表的結構體,而為二二,各 成的虛擬間極1之表面的石夕自然氧化膜,在0.〇ίΪί=石夕構 蝕刻液中,於25°C浸潰2分鐘,並谁杆剎田初^里^氫氟酸的 乾燥氮氣喷射的乾燥。之後,於示於第3表利用 :組成係參照第2表)中’於預定的溫度二g,(=液 用超,水的清洗、利用乾燥氮氣喷射的乾燥。/並進订利 藉由以SEM觀察侧後的電晶體剖面判 閘極卜_3、及層親_4的狀態。滑由矽構成的虛擬 高介電材料膜2係包覆由矽構成的虛擬閘極丨。 刻液去除由石夕構成的虛擬閘極1時,該簡液Ϊ盘古由餘 接觸,故觀察該高介電材料臈2的狀態而&電f斗膜2 電材料膜的損傷。因此,只要是儀刻由石夕構成H擬 況’係使用FIB ’將钱刻後的電晶體進行薄的情 在不於第2表的韻刻液中,係確認浸潰 二 4、以及高介電材料膜2未被則。且於第^ =緣膜 石夕構成的虛擬閘極!之狀態無之钱刻速第率中表示由 關於將不於第2表之侧液應用於本發制、;3 例1〜48,如第3表所示,可知銘之 ^ 法的貫知 選擇性地侧由石夕構成的虛擬閘極1。泣革未滿lnm/麵,且係 比較例1 使用具有電晶體結構1D的結構體,進杆音> ,理後,使用記載於非專敝獻 刻液’可知其無法使用於作為本發明^對2記載的蝕 含有_金制極之電晶體形成步驟中的電材料與 201224120 比較例2 使用具有電晶體結構1B的結構體,推γ者 一 ,理後’使用記載於專利文獻2之包含 與石夕0.1重置%的水溶液(第4表、
進行餘刻處理的結果,如第5表」履:⑴取代儀刻液2G lmn/min,但由石夕構成的虛擬閘極i的;^ _未滿 專利文獻2記載的侧液,可知力不夠。根據則述, 之包含离介雷;0日/$,、無去使用於作為本發明的對象 電晶體形成步驟中的石觸卜 酸處1所示的驗 侧處_絲,如第5 ί:的> ί Wmin以上。』前 對象之勺人的水,讀’可知其無法使驗作為本發明的 刻。匕3同;丨材料與金屬閘極之電晶體形成步驟中的石夕钱 比較例4 酸處用電的結構體’進行實施例1所示的氩敗 :行侧處理的結果,如第(=示 可知其無法使用於作為本發·對象之包 屬閘極之電晶體形成步驟中的石夕侧。 酸處吉構體,進行實施例1所示的氫氣 . 2〇 (5i;t ~ i 17 201224120 lmn/min,但由矽構成的虛擬閘極 前述’專利文獻5記载的剝離力不夠根據 :對象之包含高介電材料與金屬閘極:電 比較例6 使用具有電晶體結構H的結構體 酸處理後,使用記載於專利文獻6 丁只^例1所不的虱虱 甲胺_麵、丙二=重^ 4麵與三 ί ί 未滿inm/min,但由石夕構成的虛擬閘 比較例7 1 間極i的峨力不夠,_:率J= 化合物水溶液’可知其無法使用於作為本 二· 〜3⑧介電材料與金屬閘極之電晶體形成步驟中的 石夕独刻。 比較例8 具f電晶體結構1H的結構體,進行實施例1所示的氫氟 用山祕醇1G重量%的水溶液(第4表、侧液4H) 亥液2G進行_處理的結果,如第5表所示,銘之侧速 ίίί 77111111 ’但由石夕構成的虛擬閘極1的餘刻能力不夠。根 據刖述’多元醇水溶液’可知其無法使用於作為本發明的對象之 包含南介電材料與金屬閘極之電晶體形成步驟中的雜刻。 比較例9 使用具有電晶體結構1Α的結構體,進行實施例i所示的氫氟 18 201224120 f用1,3—丙二胺5重量%與肌醇ig重量%的水溶液 41)取代綱液2G進行侧處^2水= 1η^Γ= 擬間極w_刻,他之_速率為 可知並|法# 恭驗性化合物與環狀多元醇的水溶液, 極之電晶體形成步驟中的石;^對象之包含高介電材料與金屬閉 比較例10 溶: ^表所不,、由石夕構成^虛擬閘極1係祕刻,但銘之侧速率 ^ 。根據則述,驗性化合物與非還原糖的水溶液, I知,法使麟作為本發_對象 ^ 極之電晶體形成步驟中的石夕钱刻。 &…丨电何化、金屬閘 第1表
HDP .利用面逾、度電聚化學法的氧化石 TEOS:四乙氧基石夕烷 BPSG :硼磷梦玻璃 19 201224120 第2表 I虫刻液 驗 多元醇 水 種類 濃度 重量% 種類 濃度 重量% 濃度 重量% 2A 氨 1 山梨糖醇 10 89 2B 乙二胺 1 山梨糖醇 10 89 2C 1,2—丙二胺 1 甘油 30 69 2D 1,3—丙二胺 1 赤蘚糖醇 30 69 2E 1,3 —丙二胺 0.5 木糖醇 30 69.5 2F 1,3 —丙二胺 30 山梨糖醇 10 60 2G 1,3—丙二胺 5 木糖醇 40 55 2H 1,3 —丙二胺 5 山梨糖醇 30 65 21 ' 二伸乙三胺 1 山梨糖醇 10 89 2J 三伸乙四胺 1 山梨糖醇 10 89 第3表 實施例 電晶體結構 融刻液 處理溫度 處理時間 /min 評價 多晶矽蝕刻 狀ΙΪ 鋁防蝕能力 1 1A 2G 25 2 〇 〇 2 1B 2G 25 2 〇 〇 3 1C 2G 25 2 〇 〇 4 1D 2G 25 2 〇 〇 5 1E 2G 25 2 〇 〇 6 1F 2G 25 2 〇 〇 7 1G 2G 25 2 〇 〇 8 1H 2G 25 2 〇 〇 9 11 2G 25 2 〇 〇 10 1A 2H 25 2 〇 〇 11 1B 2H 25 2 〇 〇 12 1C 2H 25 2 〇 〇 13 1D 2H 25 2 〇 〇 14 1E 2H 25 2 〇 〇 15 1F 2H 25 2 〇 〇 16 1G 2H 25 2 〇 〇 17 1H 2H 25 2 〇 〇 18 11 2H 25 2 〇 〇 19 1A 21 25 3 〇 〇 20 1B 21 25 3 〇 〇 21 1C 21 25 3 〇 0 22 1D 21 25 3 〇 〇 23 1E 21 25 3 〇 〇 24 1F 21 25 3 〇 〇
20 201224120 25 1G 21 25 3 〇 〇 26 1H 21 25 3 〇 〇 27 11 21 25 3 〇 〇 28 1A 2A 25 4 〇 〇 29 1A 2B 25 2 〇 〇 30 1A 2C 25 3 〇 〇 31 1A 2D 25 2 〇 〇 32 1A 2E 25 2 〇 〇 33 1A 2F 25 2 〇 〇 34 1A 2J 25 2 〇 〇 35 1B 2A 25 4 〇 〇 36 1B 2B 25 2 〇 〇 37 1B 2C 25 3 〇 〇 38 1B 2D 25 2 〇 〇 39 1B 2E 25 2 〇 〇 40 1B 2F 25 2 〇 〇 41 1B 2J 25 2 〇 〇 42 1C 2A 25 4 〇 〇 43 1C 2B 25 2 〇 〇 44 1C 2C 25 3 〇 〇 45 1C 2D 25 2 〇 〇 46 1C 2E 25 2 〇 〇 47 1C 2F 25 2 〇 〇 48 1C 2J 25 2 〇 〇 第4表 餘刻液 餘刻液之組成(濃度為重量%) 4A 氫氧化四曱銨2%、水98% 4B 氫氧化四曱銨0.5%、矽0.1%、水99.4% 4C 氩氧化四曱銨10%、羥胺10%、 山梨糖醇5%、水75% 4D 氫氧化四曱銨2.4%、山梨糖醇5%、水92.6% 4E 六亞甲基二胺(1,6—己二胺)5%、 山梨糖醇30%、水65% 4F 氫氧化四曱銨4%、三曱胺0.01%、 丙二醇80%、甘油4%、水11.99% 4G 1,3-丙二胺 0.5%、水 99.5% 4H 山梨糖醇10%、水90% 41 1,3 —丙二胺5%、肌醇10%、水85% 4J 1,3 —丙二胺5%、蔗糖10%、水85% 21 201224120 第5表
根據使用本剌的侧液,由於秘麟金屬閘極盘 ,膜、侧壁、以及高介電材料臈,並可選擇性地侧由二2 J擬=極,故可使驗包含高介電㈣膜與 === 電晶體形成步驟,且於產業上十分有用。 U屬閘極的 【圖式簡單說明】 [圖1]石夕去除前之使用高介電材料的電晶體之剖面圖。 【主要元件符號說明】 1 ·虛擬閘極(梦) 2:高介電材料膜 P侧壁 4:層間絕緣膜 5 :隔離部 6:源極/汲極 7 ·基板
Claims (1)
- 201224120 七、申請專利範圍: 係祕—電晶體之製造綠,輯晶體之製造方 詈忐上至少具有虛擬閘極(dummy gate)疊層體、設 以勺舜之側面予以包覆的側壁、以及設置成將該側壁予 展絕緣膜的結構體’其中,該虛擬閘極疊層體,係疊 電膜與由矽構成的虛擬閘極而構成;且將該虛擬閘極 取代為鋁金屬閘極; 刻液’用於該電晶體之製造方法巾該由轉成的虛擬 二一 d ’並含有0.1〜4〇重量%的選自於氨、二胺及以通式(!) 聚胺中之至少—種的驗性化合物、5〜5G重量%的選自於以 k式(2)表不之多元醇中的至少一種、以及40〜94.9重量%的水; H2N- (CH2CH2NH) m-H ....(1) (m為2〜5的整數); H~ (CH (OH)) n-H ..... (2) (n為3〜6的整數)。 申明專利範圍第1項之;刻液,其中,該二胺及以通式⑴ 之聚胺為選自於乙二胺、L2—丙二胺、u_丙二胺、二伸乙 二胺、以及三伸乙四胺中之至少一種。 3.?申„利範11第1項之雜職,其中,該以通式⑵表示 之夕元醇為選自於甘油、赤蘚糖醇、木糖醇、以 及山梨糖Sf·中之至少一種。 ^如申印專利範圍第1項之石夕钱刻液,其中,形成高介電材料膜的 咼介電材料為 Hf02、HfSiO、HfSiON、HflLaO、HfiLaON、HfTiSiON、 HMJSiON、HfZrO、或 A1203。 5·—種電晶體之製造方法,其特徵為: 使用在基板上至少具有虛擬閘極疊層體、設置成將該疊層體 之侧面予以包覆的側壁、以及設置成將該側壁予以包覆之層間絕 ,^的結構體’並包含以下的步驟(I),其中,該虛擬閘極疊層體, 係豐層两介電材料膜與由矽構成的虛擬閘極而構成;且將該虛擬 23 201224120 閘極取代為鋁金屬閘極; ⑴有αΐ〜4G重量%的選自於氨、二胺及以通 白於以、主-之至少一種的鹼性化合物、5〜5〇重量%的選 ο/J»式()表不之多元醇中的至少一種、以及40〜94.9重量 %的水之餘刻液,將矽蝕刻的步驟. H2N- (CH2CH2NH) m—η :⑴ (m為2〜5的整數); H- (CH (OH)) n-H ..…(2) (η為3〜6的整數)。 ^如申請專利翻第5項之電晶體之製造方法,其巾,形成高介電 材料膜的高介電材料為腦2、HfSi〇、腦随、HfLa〇、HfLa〇N、 HfTiSiON、HfAlSiON、HfZrO、或 ai2〇3 〇 7. 如申請專利範圍第5項之電晶體之製造方法,其中,該二胺及以 通式_(1)表示之聚胺為選自於乙二胺、1>2—丙二胺、丙二 胺、一伸乙三胺、以及三伸乙四胺中之至少一種。 8. 如申請專利範圍第5項之電晶體之製造方法,其_,該以通式(2) 表示之多元醇為選自於甘油、赤蘚糖醇、木糖醇、以及山梨糖醇 中之至少一種。 八、圖式: 24
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