TWI277151B - Methods of forming a phosphorus doped silicon dioxide comprising layer, and methods of forming trench isolation in the fabrication of integrated circuitry - Google Patents

Methods of forming a phosphorus doped silicon dioxide comprising layer, and methods of forming trench isolation in the fabrication of integrated circuitry Download PDF

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Publication number
TWI277151B
TWI277151B TW093120255A TW93120255A TWI277151B TW I277151 B TWI277151 B TW I277151B TW 093120255 A TW093120255 A TW 093120255A TW 93120255 A TW93120255 A TW 93120255A TW I277151 B TWI277151 B TW I277151B
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Taiwan
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layer
vapor phase
phosphorus
doped
substrate
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TW093120255A
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English (en)
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TW200509243A (en
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Brian A Vaartstra
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Micron Technology Inc
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C23C16/402—Silicon dioxide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/66—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials
    • H10P14/668—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials
    • H10P14/6681—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials the precursor containing a compound comprising Si
    • H10P14/6684—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H10P14/6686—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0451—Apparatus for manufacturing or treating in a plurality of work-stations
    • H10P72/0468—Apparatus for manufacturing or treating in a plurality of work-stations comprising a chamber adapted to a particular process
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W10/00—Isolation regions in semiconductor bodies between components of integrated devices
    • H10W10/01—Manufacture or treatment
    • H10W10/011—Manufacture or treatment of isolation regions comprising dielectric materials
    • H10W10/014—Manufacture or treatment of isolation regions comprising dielectric materials using trench refilling with dielectric materials, e.g. shallow trench isolations
    • H10W10/0142—Manufacture or treatment of isolation regions comprising dielectric materials using trench refilling with dielectric materials, e.g. shallow trench isolations the dielectric materials being chemical transformed from non-dielectric materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W10/00—Isolation regions in semiconductor bodies between components of integrated devices
    • H10W10/10—Isolation regions comprising dielectric materials
    • H10W10/17—Isolation regions comprising dielectric materials formed using trench refilling with dielectric materials, e.g. shallow trench isolations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H10P14/6336—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H10P14/6339—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD
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    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6921—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon
    • H10P14/69215—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material being a silicon oxide, e.g. SiO2
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    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
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    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6921—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon
    • H10P14/6922—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H10P14/6923—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being boron or phosphorus doped silicon oxides, e.g. BPSG, BSG or PSG

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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Formation Of Insulating Films (AREA)
  • Chemical Vapour Deposition (AREA)
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1277151 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種形成包含磷摻雜二氧化矽層之方法， 及一種於積體電路製造中形成溝渠隔離之方法。 【先前技術】 積體電路製造中的一種常用材料係二氧化矽。其可使用 實質上驅的純度，或與其他材料組合，包括特性修改摻 雜劑。因此，二氧化矽可在形成層時用作與其他材料的混 合物以及可組成或可不組成大部分給定層。示範性材料係 硼磷矽玻璃（borophosphosilicate gIass ; BPSG)、磷矽玻璃 (phosphosiHcate glass ; PSG)及冊矽玻璃（b〇r〇s出c咖 glass; BSG)。通常，此類材料中硼及/或磷原子之原子濃度 皆為1%至4%間的任一點，儘管亦曾使用超過5%的原子百 分比濃度。 隨著半導體裝置繼續在幾何上收縮，此類材料具有產生 水平尺寸大於垂直尺寸之收縮的趨勢…些實财，垂直 尺寸增加。無論如何’其結果係為該裝置的縱橫比（高度比 寬度）增加’使得發展使介電質及其他材料能填充高縱橫比 或增加縱橫比溝渠、通道的程序及其他步驟或結構變得越 來越重要。選擇的典型介電f材料已播雜及/或未摻雜二氧 化石夕’例如其包括上述材料。摻雜劑（例如職旬可有利於 以較高溫度回流沈積層，從而有利於更完全地填充基板上 的開口。形成二氧化矽層時可使用各種反應物先驅物，例 如美國專利第6,300,219號中所揭示的矽烷醇。 94529-95()303.doc 1277151 【發明内容】 本發明揭示-種形成包含磷摻雜二氧化#層之方法，以 及一種於積體電路製造中形成溝渠隔離之方法。一項實施 方案中，一種形成包含磷摻雜二氧化矽層之方法包括 板定位於沈積室内。在對沈積包含磷摻雜二氧化梦層至^ 基板有效的狀況下’在複數個沉積循環中將第一及第二汽 相反應物以交替及時間上分離脈衝方式引入該室内的該基 板。該等第一及第二汽相反應物之—係1>〇(〇汉)3，其中尺係 烴基，該等第一及第二汽相反應物中的另一個係 Si(OR)3OH，其中R係烴基。 一項實施方案中，—種形成包切摻雜二氧切層之方 法包括將基板定位於沈積室内。將第—物種化學吸附至基 板表面，以便從包括P0(0R)3(其中R係煙基）之第一汽^ 應物形成室内基板上第-物種的單層。化學吸㈣㈣— 物種與包括Si(〇R)3〇H(其中轉烴基）之第二汽相反應物接 觸’以便形成包括以及〇的一單層。在對沈積包含磷摻雜二 氧化石夕層至該基板有效的狀況下連續重複化學吸附該第— 物種及將化學吸附的該第—物種與該第二反應物接觸。 本發明亦含有其它方面及實施方案。 【實施方式】 已提交本發明之揭示内容’以促進美國專利法「促 學及貫用技術進步」（第丨章，第8段）的憲法目的。 -項實施方案中’一種形成包含磷摻雜二氧化矽層之方 法包括將需要沈積的基板定位於一沈積室内。在對沈積包 94529-950303.doc 1277151 含碟摻雜二氧化矽層至該基板有效的狀況下，在複數個沉 積循環中將第一及第二汽相反應物以交替及時間上分離脈 衝方式引入該室内的該基板。第一及第二汽相反應物之一 係P〇（OR)3 ’其中r係烴基。第一及第二汽相反應物中的另 個係Si(〇R)3〇H，其中R係烴基。此可藉由原子層沈積. (at〇mic Uyer deposition ; ALD)法（例如包括化學吸附及接 觸法）、藉由化學汽相沈積（chemicai vapor deposition ; CVD) · 法及藉由其他方法以及該等及其他方法之組合來執行。本 · 文使用的CVD及ALD參考2002年4月25曰提出申請的共同 _ 待審美國專利申請案第1〇/133,947號，標題為「原子層沈積 法及化+ &相沈積法」，發明者列為Brjan a· Vaartstra。2002 年4月25日提出申請的此1〇/133,947申請案以提及方式全部 併入本文中，如同該案之全文已在本文揭示一般。應明白 本文提供之較佳及可理解的付諸實施範例主要係原子層沈 積。 P〇（〇R)3之R烴基及Si(〇R)3〇H2R烴基可相同或不同，但 鲁 無⑽如何，一項較佳具體實施例中各材料中的R烴基僅包含 一至五個碳原子。一種較佳及付諸實施]?〇（〇11)3材料包含磷 酉欠一乙S曰。一種較佳示範性及付諸實施Si(〇R)3〇H材料包含 二叔丁基矽烷醇。示範性較佳狀況包含從大約5〇。6至大約 500 C的服度，更佳的係從大約1〇〇。匸至大約3〇〇。匸。示範 性壓力狀況係真空，較佳的係從大約1〇.7 —至大約1〇 Ton佳的係從大約1(r4 丁 〇η，至大約i 丁⑽。狀況可包含 至少第-及第一反應物之一的電漿產生或無第一及第二& * 94529-950303.doc 1277151 應物之電II & n/、 ’座生。若使用電漿產生，此可發生於沈積室内 及/或其外部。 丄^ 咸彳5最佳狀況係無第一及第二反應物之電漿 產生。 該等狀汉士 0 可有效地形成包含二氧化矽層以具有極低磷含 1，例如且古 、 、不大於〇 · 5原子百分比的ί粦，包括更少數量。 或者 5 該裳、 Ζ彳、况可有效地形成包含層之二氧化矽以具有至 少】·〇原子石八， 刀比的磷，其包括（例如）5 〇及更大原子百分比 的石粦。 方法在形成包含磷摻雜二氧化矽層時可不將第一及第 二汽相反應物外的任何汽相反應物引入室内。或者，該方 法可包括—將不同於第一及第二汽相反應物的另一汽相反應 物引入第&第二汽相反應物之至少一些分離脈衝的中 2僅作為範例而言，示範性的另一汽相反應物係氧，包 含（例如）〇2、〇3及/或任何汽相含氧化合物。已決定除Ρ0 (OR)3流外，臭氧脈衝（例如〇2及〇3的混合物）有利於包含更 多的填’例如根據需要大於5原子百分比。 另一示範性汽相反應物包含硼，而包含磷摻雜二氧化矽 層則亦包含硼，例如在製造阶犯或阶犯類材料時。示範 性含硼材料反應物係B(〇R)3。 交替及時間上分離脈衝可包括分離脈衝中間的室泵集及 /或惰性氣體（即N2及/或任何貴氣體）室沖洗之一或其組 合’以移除未反應先驅物/反應物。 一種形成包含二氧化矽層的先前技術在Hausmann等人 所著「高度正形矽奈米層板之快速汽相沈積」中說明，「科 94529-950303.doc 1277151 學雜誌」第298卷第402至406頁（2002)。此一程序最初使用 f基鋁反應物先驅物，例如三乙基鋁或二甲胺鋁，其在基 板上形成初始含鋁層。然後烷氧基矽烷醇，例如三（叔丁氧 基）石夕炫醇’流動至基板。顯然，銘的存在提供了自限性催 化反應’彳《而包含二氧化㈣沈積至某自限性厚度〇_矣 至700埃間的任一點）。換言之’對院氧基錢醇的連續曝 光不會導致包含二氧化石夕層的不斷生長。顯然，二氧化石夕 層自限性生長以某催化方式發生’由於辑曝光/脈衝處 理形成許多個單層其與簡單的則類方式相反。無論如 何，最終層内併入了不需要的鋁。 雖然此處揭示的本發明不排除使用類似取咖_等人 的程序，最佳的係本發明程序在形成包含碌摻雜二氧化石夕 層時不向室中引人任何汽相含紹反應物。根據本發明更佳 的係形成包爾雜二氧化石夕層時基板無銘。 ^ 干U 哎增的万法 ^包括某⑽處理。僅作為範例而言，參考圖！至3說明 範性的此類程序。參考圖卜基板1〇位於任何合適的沈積 (未顯示）内。-項示範性具體實施例中，基板ι〇係半導體 板’例如其包含某材料12,其較佳的係至少包括竿半導 材料，當然㈣括多個驗層。㈣中，= ¥體基板」或「半導電性基板」定義成意 導電性材料之結構，复勺J匕3 其包括但不限於塊狀半導電性材料 例如半導電性晶圓（覃 …… 獨或在包含其他材料之裝配件内）， 及半導體材料層（單猶七★ 早獨或在包含其他材料之裝配件内)。術. 94529-950303.doc 1277151 基板」指任何支撐灶爐 # , #包括但不限於上述半導電性其 板。基板]〇具有表面14，圖中 土
^ u甲”、、員不其係踁基化（具有未決〇H 採用其他對本文上述程序有效的表面終止端。若 此表面可在提供前於沈積室内㈣化，或^ 對7^1工基化。用於經基化表面14之示範性技術包括表面 y錢的曝露。另外，表面可藉由簡單地曝露於周圍大 氣而自然羥基化。 "芬考圖2,化學吸附第一物種以便在室内於經基化表面上 =包含PQ陶3(其中R係烴基）之第—汽相反應物形成第一 種之早層16，如上所述。此係說明為由變數「A」組成， ”構成圖2中層I 6的至少一部分。較佳狀況及其他屬性如以 上茶考第一所述實施方案所述。 /參考圖3，化學吸附的第一物種與包含叫〇从〇h(其中r 係烴基）之第二汽相反應物接觸，以便形成包含以及〇的單 層】8。另外，狀況較佳的係如以上參考第一實施方案所述。 圖3描述包含變數「B」之層]8,化學吸附第一物種單層描 述為「A」’即B對A之化學吸附中a物種之某修改範例，其 中未決定精確較佳及典型物種a&b。無論如何，在對沈積 磷摻雜而包含二氧化矽層至基板有效的狀況下連續重複化 學吸附第一物種及將化學吸附的第一物種與第二反應物接 觸。通常且較佳的係以交替及時間上分離脈衝對基板執行 此類化學吸附及接觸，例如以上第一說明實施方案内所述。 上述實施方案係關於具有P0(0R)3的表面之化學吸附以 及之後的第二汽相反應物曝光（包含Si(〇R)3〇H)，本發明之 94529-950303.doc 10 1277151 覜點藉由其付諸實施，儘管… 孤 < ^ , ί,ν ΨΊ ^ »n ,¾ 〇 '、“何本务明之觀點較佳的係可用於在積體電路穿 造中形成溝渠隔離之方法’例如參考圖4至7所顯示及說 明。圖4顯㈣導體基板26 ’其包括塊狀單晶⑦或其他半導 %性材料基板28。遮罩層3〇形成於半導體基板28上。此係 描述為包含接點氧化層32及覆蓋含氮層Μ，例如氮化石夕。'、 參考圖5’已透過遮罩層3〇將騎溝㈣錢 助6之半，電性材料。可立刻或隨後提供熱氧化層或= 層’例如氮化矽(未顯示)，例如藉由將基板26曝露於埶氧化 狀況提供二氧化矽。 …巩化 /考圖6包各磷摻雜二氧化矽層4〇已形成於半 渠％及Μ内。用於如此執行的示範性技術包括在 — 積循環中以交替及時間上分離脈衝將第—及第二 ^目反應物引人室内基板’如上所述，又例如藉由上述: 觸法。如上所述’沈積可有效地將包含碟摻雜 在隔離溝渠―選擇性地沈康雜之二 4〇、、。此文件中，「選擇性/選擇性地沈積」係指以至少 ==度比率將材料沈積於基板-個區域與另-個區域 上的沈積。 不:效地完全填充隔離溝渠36及38 ’或者如圖6所示 續〜填充員隔離溝渠。沈積處理，例如上述任一種，可繼 此類溝渠，如圖7所示。或者僅藉由範例而言， 了在-遮罩層30移除材料前或後用另一材料 94529-950303.doc Ϊ277151 示範性付諸實施範例使用磷酸三乙酯及三（叔丁氧基）矽 垸醇作為第一及第二個別汽相反應物。使用每個反應物之 個別兩秒反應性脈衝將650埃PSG(8原子百分比磷）正形層 沈積於氮化矽加襯溝渠上，一秒氬沖洗後跟三秒泵集，而 不在反應物脈衝間流動氬。此係在300。C下執行600個完整 循環。不使用臭氧。用於饋送磷酸三乙酯及三（叔丁氧基） 石夕燒醇的個別起泡器/安瓿溫度係50。C及4〇。C。 此處理亦使用溫度為60。C之磷酸三乙酯及70。C之三（叔 丁氧基）矽烷醇來執行。此磷酸三乙酯及三（叔丁氧基）矽烷 醇之一（1)秒及〇·5秒個別脈衝在3〇〇個完整循環後產生65〇 埃膜’提供每循環大約2·2埃的沈積率。此稍高於第一付諸 貫施範例沈積，其係每循環1」埃。沈積膜實質上無碳，磷 含ϊ低於0·5原子百分比。此反應物溫度下的較長磷酸三乙 酯曝光期望產生較高生長率並增加沈積膜之磷含量。 另一付諸實施範例中，將來自6〇。c起泡器/安瓿之磷酸三 乙酯饋送至沈積室内的基板達一秒。此後跟一秒3〇 sccm Ar 級’然後係二秒室泵集，而無將任何氣體流動至室。之後， 將25 sccm之組合〇2/〇3流（〇3體積為5%至12%)流動至室達 兩秒。此後跟一秒3〇 sccm Ar流，然後係三秒泵集，同時無 氣版饋送至至。接著，將三（叔丁氧基）矽烷醇從60。C起泡 ^ /女瓿流動至室兩秒。此後跟一秒3〇 Sam心流，然後再 次係三秒泵集，同時無氣體流動至室。將此程序執行400 们凡正循ί衣，全部處理過程中的壓力從〇.24 丁〇汀至1〇·6 T〇rr 變化。此產生】〇〇0埃厚之層，其中併入5·7原子百分比的構。 94529-950303. doc 1277151 依照條例，本發明已就 予以說明。然而應明白，本發明並不:=-細程度 定特徵，目為本文揭示的構件包含實Hrr明的特 式。因此，本發明之任 务明的較佳形 導内容適當解釋的屬於根據等效物教 ^請專利範圍之合適範嘴内。 =上已麥考以下附圖說明本發明之較佳具體實施例。 略:=據本發明之觀點的程序中半導體晶圓片段之概 圖2係圖丨所示處理步驟後圖I晶圓片段之視圖； 圖3係圖2所示處理步驟後圖2晶圓片段之視圖； 圖4係根據本發明之觀點的程序中半導體晶圓片段之概 略性斷面圖； 【主要元件符號說明】 10 基板 12 材料 14 表面 16 層 18 單層 2 6 半導體基板 28 半導電性材料基板 圖5係圖4所示處理步驟後圖4晶圓片段之視圖； 圖6係圖5所示處理步驟後圖5晶圓片段之視圖； 圖7仏圖6所不處理步驟後圖6晶圓片段之視圖。 94529.950303.doc 1277151 30 遮罩層 32 襯墊氧化層 34 覆蓋含氮層 3 6 隔離溝渠 3 8 隔離溝渠 40 包含磷摻雜二氧化矽層 94529-950303.doc

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1277151 、申請專利範圍： 一種形成包含磷摻雜二氧 乳化石夕層之方法，其包含： 在沈積室内提供基板；以及 在有效沈積包含磷摻雜- 、 雜一虱化矽層至該基板的狀況卞 ’在複數個沈積循環中 ^ 衣τ μ父替及時間上分離脈衝將 及第二汽相反應物引人兮^ 、 j入该至内的該基板，該等第一及第 一 Ά相反應物之一得P fV \ 知P〇(OR)3，其中r係烴基，該等第— 及第一汽相反應物中的η 义 初T的另一個係Si(〇R)3〇H，其中R係烴 基0 2· 3· 4. 5. 6 · 8· 9. 如請求項1之方、、土 ^ , / ，、中呑亥專狀況包含原子層沈積。 如清求項1之方、、么 〇» , /2： ’其中該等狀況係有效地形成具有不大 於〇.5原子百分比磷的該包含二氧化矽層。 如#求項1之方法’其中該等狀況係有效地形成具有至少 1 ·0原子百分比磷的該包含二氧化矽層。 。月/貝1之方法，其在形成該包含磷摻雜二氧化矽層 中不將除該等第一及第二汽相反應物以外的任何汽相 反應物弓丨入該室。 如清求項1之方法，其包含在該等第一及第二汽相反應物 的至少_些該等分離脈衝中間，引入不同於該等第一及 第汽相反應物之另一汽相反應物。 如明求項6之方法，其中該另一汽相反應物係包含氧。 如明求項7之方法，其中該另一汽相反應物包含〇3。 如請求項6之方法，其中該另一汽相反應物係包含硼，該 包含磷摻雜二 氣化石夕層包含石朋 94529.950303.cloc 1277151 ίο. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 如請求項〗夕He μ· 、〈万法，其中該P〇(〇R)d〇R烴基僅包含一至五 個碳原子。 如請求項1、+ β 1、Κ万法，其中該以（〇以)3〇11的R烴基僅包含一至五·個碳原子。 如請求項1 > 士、+ ^ ,、 方法’其中該po(or)3包含麟酸三乙酯。 如請求項1 > 士、+ g，、之方法，其中該Si(OR)3〇H包含三（叔丁氧基） 矽烷醇。 直月^項1之方法，其中該p〇(〇R)3包含磷酸三乙酯，且 其^亥心⑽)3011包含三（叔丁氧基)秒燒醇。 士明求項1之方法，其中該等狀況包含約5G°C至約500〇C 、、W Tyg /BDL ο 如吻求項15之方法，其中該等狀況包 300°C之溫度。 4 士口月求項1之方法，其中該等狀況包含約1 Torr之壓力。 如明求項1之方法，其中該等狀況包含 一反應物之一的電漿產生。 如請求項1之方法， 應物的電漿產生。 如請求項1之方法， 氣體沖洗該室。 如請求項1之方法， 中，該基板上無鋁 如請求項1之方法， 94529-950303.doc 100°C至約 Torr至約1〇 至少該等第一及第 其中該等狀況係無該等第一 及苐二反 其包含在該等分離脈衝中間 ，以惰性 其中在形成該包含磷摻雜二 0 氧化石夕層 其中在形成該包含磷摻雜二 氧化石夕層 1277151 中’不引入任何汽相含鋁反應物至該室。 23· —種形成包含磷摻雜二氧化矽層之方法，其包含： 在沈積室内提供基板； 將弟物種化學吸附至該基板的表面，以便從含 P〇(〇R)3的第一汽相反應物形成第一物種單層至該室内 的該表面上，其中R係烴基； 將經化學吸附之第一物種與包含8^〇幻3〇]9[的第二汽 相反應物接觸，其中R係烴基，以便形成包含^及0的單 層；以及 在有效沈積包含鱗摻雜二氧化矽層至該基板的狀況下 ，連續重複化學吸附該第一物種，並將經化學吸附之第 一物種與該第二反應物接觸。 24·如請求項23之方法，其中至少首先化學吸附該第一物種 的該基板表面係提供為一羥基化表面。 25·如請求項23之#法，纟中該等狀況可有效地形成該包含 二氧化妙層’其具有不大於〇·5原子百分比填。 26. 如請求項23之方法，其中該等狀況可有效地形成該包含 二氧化石夕層’其具有至少1.0原子百分比構。 27. 如請求項24之方法，其在形成該包含磷摻雜二氧化矽層 中’至少於提供該技基化表面後，不將除該等第一及第 二汽相反應物以外的任何汽相反應物引入該室。 28. 如請求項23之方法’其包含引入不同於該等第一及第一 汽相反應物之另一汽相反應物，其在至少一些該等重複 化學吸附及接觸中間。 94529-950303.doc 1277151 29. 30. 3 1 · 32. 33. 34. 35. 36. 37. 38. 39. 40. 4 1 . 如請求項28之方法，其中該另一汽相反應物係包含氧。 如w求項29之方法，其中該另一汽相反應物包含〇3。 如請求項28之方法，其中該另一汽相反應物係包含硼， σ玄包δ私彳爹雜一氧化石夕層包含侧。 如4求項23之方法，其中該p〇(〇R)^^R烴基僅包含一至 五個碳原子。 如4求項23之方法，其中該以（〇11)3〇11的r烴基僅包含一 至五個碳原子。 如请求項23之方法，其中該p〇(〇R)3包含磷酸三乙酯。 如请求項23之方法，其中該Si(OR)3〇H包含三（叔丁氧基） 石夕烧醇。 如睛求項23之方法，其中該p〇(〇R)3包含磷酸三乙酯，且 其中該Si(〇R)3〇H包含三（叔丁氧基）矽烷醇。 士 w求項23之方法，其包含在該等重複化學吸附及接觸 中間，以惰性氣體沖洗該室。 如清求項23之方法’其中在形成該包含卿雜二氧化石夕 層中’該基板上無結。 如请求項23之方法，其中在形成該，包含卿雜二氧化石夕 層中，不引入任何汽相含鋁反應物至該室。 士明求項23之方法’其包含沈積該包含罐摻雜二氧化石夕 層，其形成於該基板之半導電性材料隔離溝渠内。 -種於積體電路製造中形成溝渠隔離之方法，其包括： 在半導體基板上形成遮罩層； 透過該遮罩層將隔離溝渠♦虫刻入該半導體基板之半導 94529-950303.doc 1277151 電性材料中；以及 餘刻該等隔離溝渠後’在對沈積包含碌摻雜二氧化石夕 層至該等溝渠有效的複數個沈積循環中，以交替及時間 上分離脈衝將第-及第二汽相反應物引人該室内的該^ 板，該等第一及第二汽相反應物之一係p〇(〇R)3, i中1 係烴基’該等第一及第二汽相反應物中的另—個係 Si(〇R)3〇H，其中R係烴基。 仏如請求項4]之方法，其中該沈積係有效地填充該等隔離 溝渠。 43. 44. 45. 46. 47· 48· 如請求項4!之方法’其中該沈積並不填充該等隔離溝渠。 如請求項4]之方法’其中該等沈積循環係有效地在該遮 罩層上沈積該包含磷摻雜二氧化矽層。 3长員4 1之方法’其中該等沈積循環不能有效地在該 等隔離溝渠内選擇性地沈積該包含磷摻雜二氧化石夕層。 如請求項4 1之方法，i由呤笪灿7么丄 其中鑪4狀況係有效地形成具有不 大方、0 · 5原子百分比磷的該包含二氧化矽層。 如請求項41之方法，其中該等狀況係有效地形成具有至 少1.〇原子百分比磷的該包含二氧化矽層。 如請求項4 1之方法， 中，不將除該等第一 反應物引入該室。 其在形成該包含磷摻雜二氧化矽層 及第二汽相反應物以外的任何汽相 49.如請求項41之方 汽相反應物之另 相反應物的至少 去’其包含引入不同於該等第一及第二 一汽相反應物，其在該等第一及第二汽 一些該等分離脈衝中間。 94529-950303.doc 1277151 50·如請求項49之方法，其中該另一汽相反應物係包含氧。 5 1 ·如請求項50之方法，其中該另一汽相反應物包含〇3。 5 2 汝明求項49之方法，其中該另一汽相反應物係包含硼， 該包含磷摻雜二氧化矽層包含硼。 ^3·如睛求項41之方法，其中該p〇(〇R)3包含磷酸三乙酯。 54.如請求項41之方法，其中該Si(0R)30H包含三（叔丁氧基） 石夕燒醇。 .求項41之方法’其中該p〇(〇R)3包含嶙酸三乙醋，且 ”中該Si(〇R)3〇H包含三（叔丁氧基）梦院醇。 ★吻求項41之方法，其包含在該等 性氣體沖洗該t。 間以惰 57. 如請求項41之方法，其 層中，該基板上無紹。…包㈣榜雜二氧切 58. ::求項41之方法，其中在形成該 59. = ^引入任何汽相含紹反應物至該室:雜二氧化石夕 口月，項1之方法，其包括形成該包含石粦 〆 為均勻組成。 $雜二氧化石夕層 項23之方法’其包括形成該包含 層為均勻組成。 摻雜二氧化矽 6 1 ·如請求項41之方法，苴 層為均勾組成。 形成該包含罐接雜二氧化石夕 94529-950303.doc 1277151 七、指定代表圖： (一) 本案指定代表圖為：第（6 )圖。 (二) 本代表圖之元件符號簡單說明： 26 半導體基板 2 8 半導電性材料基板 30 遮罩層 32 襯墊氧化層 34 覆蓋含氮層 3 6 隔離溝渠 38 隔離溝渠 40 包含磷摻雜二氧化矽層 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無） 94529-950303.doc
TW093120255A 2003-07-07 2004-07-06 Methods of forming a phosphorus doped silicon dioxide comprising layer, and methods of forming trench isolation in the fabrication of integrated circuitry TWI277151B (en)

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CN100537839C (zh) 2009-09-09
US20050124171A1 (en) 2005-06-09
DE602004016659D1 (de) 2008-10-30
WO2005008746A2 (en) 2005-01-27
WO2005008746A3 (en) 2005-04-07
EP1641958A2 (en) 2006-04-05
CN1860251A (zh) 2006-11-08
ATE408720T1 (de) 2008-10-15
KR100761189B1 (ko) 2007-09-21
TW200509243A (en) 2005-03-01
US7294556B2 (en) 2007-11-13
US7125815B2 (en) 2006-10-24
EP1641958B1 (en) 2008-09-17
US20050009368A1 (en) 2005-01-13
JP2007521658A (ja) 2007-08-02
US7790632B2 (en) 2010-09-07
KR20060037329A (ko) 2006-05-03
US20070161260A1 (en) 2007-07-12

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