TW202307575A - 光阻底層上形成黏附層之方法及含有黏附層之結構 - Google Patents

光阻底層上形成黏附層之方法及含有黏附層之結構 Download PDF

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TW202307575A
TW202307575A TW111114443A TW111114443A TW202307575A TW 202307575 A TW202307575 A TW 202307575A TW 111114443 A TW111114443 A TW 111114443A TW 111114443 A TW111114443 A TW 111114443A TW 202307575 A TW202307575 A TW 202307575A
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photoresist
silicon
layer
metal
reaction chamber
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TW111114443A
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劉澤鋮
吉田嵩高
久保田智廣
福田秀明
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荷蘭商Ａｓｍ Ｉｐ私人控股有限公司
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    • H01J37/32532—Electrodes
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0332—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their composition, e.g. multilayer masks, materials
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Abstract

本發明揭露形成含有一光阻底層與一黏附層的結構之方法、及含有該光阻底層與該黏附層的結構。多個示例性方法包括使用一循環沉積製程形成該光阻底層及形成一黏附層。該黏附層可在用於形成該光阻底層的相同反應腔室內形成。

Description

光阻底層上形成黏附層之方法及含有黏附層之結構
本發明大體上有關結構及有關使用光阻形成結構之方法。更具體地，本發明係關於包括光阻底層或使用光阻底層形成之結構以及形成此類結構之方法。
在電子裝置的製造期間，可藉由圖案化基板表面以及使用例如氣相蝕刻製程從基板表面蝕刻材料，而在基板表面上形成微細的特徵圖案。隨著基板上的裝置密度增加，越來越需要形成具有較小尺寸的特徵。
光阻常用以在蝕刻之前圖案化基板表面。藉由施加一層光阻至基板表面、遮罩光阻表面、使光阻之未經遮罩的部分曝露至輻射（諸如紫外光）、以及移除一部分（例如，未經遮罩或經遮罩部分）的光阻，同時在基板表面上留下一部分光阻而在光阻中形成圖案。
近來，已開發使用極紫外(EUV)波長的技術，以顯影具有相對小圖案特徵（例如，10 nm（奈米）或更小）的圖案。為了使用EUV在基板上形成特徵，可將一光阻底層沉積到基板表面上，然後將一EUV光阻層沉積在光阻底層上面。旋塗式玻璃(SOG)時常用作一底層。旋塗式玻璃底層通常具有約10 nm或更大的厚度。近來，電漿沉積的氧化物已被研究為用於光阻底層的可能材料。然而，此氧化物通常呈現出比（例如，EUV）光阻更高的表面極性。表面極性的差異可能導致圖案崩塌。為了至少這些原因，需要含有一光阻底層之改善結構，諸如，適於連同EUV光阻使用的底層及形成此結構之方法。
本節提出之任何問題及解決方案討論僅為了提供本發明背景脈絡之目的而包括在本發明中，且不應視為承認討論之任何或全部內容在完成本發明時為已知。
本發明的各種實施例係有關含有光阻底層與黏附層之結構、及有關形成該等層與結構之方法。雖然以下更詳細討論本發明的各種實施例解決先前方法與結構的缺點之方式，但通常上，本發明的各種實施例提供可包括具有所需特性（諸如所需蝕刻選擇性、圖案品質、及/或圖案穩定性）的相對較薄、均勻光阻底層之結構。示例性光阻底層可使用一循環製程（諸如原子層沉積）形成，其允許精確控制光阻底層的厚度，無論是在基板表面及不同基板上。此外，如以下更詳細闡述，一附加黏附層可形成以提供所需的表面能，以促成光阻底層與上覆的光阻之間的所需黏合。
根據本發明的示例性實施例，一種形成含有光阻底層的結構之方法，該方法包括在反應腔室內提供一基板、形成上覆於該基板表面的一光阻底層、及形成上覆於該光阻底層的一黏附層。該黏附層可***在該光阻底層與一光阻層兩者之間並接觸光阻底層與光阻層。本發明的多個實例可更包括形成上覆於該黏附層的（例如，EUV）光阻層。可使用一第一循環沉積製程形成該黏附層，該循環沉積製程包括向該反應腔室提供一矽前驅物、向該反應腔室提供一惰性氣體、及使用該惰性氣體形成電漿以形成與矽前驅物或其衍生物起反應的活性物質以形成該黏附層。該光阻底層可包括矽及金屬中之一或多者。例如，該光阻底層可包括氧化矽、碳氧化矽、氮化矽、氮氧化矽、碳氮化矽、氧碳氮化矽、金屬氧化物、金屬氮化物、金屬碳氧化物、金屬氮氧化物、金屬氧碳氮化物、及金屬碳氮化物中之一或多者。當該光阻底層包含矽時，可使用相同或不同的矽前驅物來形成該光阻底層與該黏附層。
該光阻底層可使用一第二循環沉積製程形成，諸如一電漿增強循環（例如，原子層）沉積製程或一熱循環沉積製程。該光阻底層可具有厚度小於10 nm或小於5 nm。該光阻層可為或包括例如正型或負型極紫外光(EUV)微影光阻。
根據本發明的另外示例性實施例，提供含有一光阻底層與一黏附層之結構。該光阻底層及/或黏附層可使用如本文所述方法形成。該光阻底層可包括例如一含有金屬及/或矽的層。該黏附層可包括矽。該黏附層可具有如本文所述的表面能特性。例示性結構亦可包括一層光阻（諸如負型或正型EUV光阻）。
根據本發明的進一步實例，提供一種用於形成黏附層之系統。多個示例性系統包括一反應腔室、一流體耦合到該反應腔室的矽前驅物源、一流體耦合到該反應腔室的惰性氣體源、及一配置成執行如本文所述方法或其部分之控制器。
熟習該項技藝者從下列參考附圖之一些實施例的詳細描述將明白此等及其他實施例。本發明不限制於所揭示任何（多個）具體實施例。
雖然以下揭示一些實施例及實例，但應理解，本發明延伸超出其具體揭示的實施例及/或用途以及其明顯的修改及等效性。因此，所揭露本發明的範疇應不受限於以下所述具體揭露的實施例。
本發明大體上有關形成含有一光阻底層與一黏附層的結構之方法，並有關含有一光阻底層與一黏附層之結構。如以下更詳細描述，多個示例性方法可用於形成具有光阻底層與黏附層的結構，其中提供所需特性，諸如所需的光阻底層厚度（例如，小於10或小於5 nm）、相對低的表面粗糙度、對光阻有良好附著力、所需的蝕刻選擇性、基板內（例如，晶圓）與基板間的所需厚度均勻性、高圖案品質（低缺陷數量與高圖案保真度）、低線寬粗糙度(LWR)、EUV微影製程期間（例如，在任何曝光後烘烤(PEB) 期間）的光阻穩定性、光阻顯影、基板重工(Rework)、合理的EUV靈敏度、及整合兼容性（例如，相對較低的沉積溫度）。
如本文中所使用，術語「基板(substrate)」可指包括及/或在其上可沉積一或多個層的任何（多個）下伏材料。基板可包括塊材（諸如矽（例如單晶矽））、其他IV族材料（諸如鍺）、或化合物半導體材料（諸如GaAs），並可包括上覆或下伏於塊材的一或多層。例如，一基板可包括上覆於該塊材的數個層之圖案化堆疊。圖案化堆疊可根據應用而變化。此外，基板可附加地或替代地包括各種特徵，諸如形成在一基板層的至少一部分內或其上的凹部、線路等。
在一些實施例中，「薄膜(Film)」係指在垂直於厚度方向的方向上延伸的層。在一些實施例中，「層(Layer)」係指一形成於表面上之具有一厚度之材料、或薄膜或非薄膜結構之同義詞。一薄膜或層可由具有一些特性之離散單一膜或層或者由多個膜或層所構成，且相鄰膜或層之間的邊界可清晰或可不清晰，並可或可不基於物理、化學、及/或任何其他特性、形成製程或順序、及/或相鄰膜或層之功能或用途而建立。此外，一層或薄膜可連續或不連續。
在本發明中，「氣體(Gas)」可包括在常溫常壓下為氣體、汽化固體及/或汽化液體的材料，並取決於上下文而可由單一氣體或多個氣體的混合物構成。除了製程氣體以外的氣體（亦即，非通過氣體分配總成（諸如噴灑頭）、其他氣體分配裝置等所引入的氣體）可用於例如密封反應空間，且可包括諸如稀有氣體的密封氣體。
在一些情況下，諸如在材料沉積的上下文中，術語「前驅物(Precursor)」可指參與產生另一化合物的化學反應的化合物，特別是指構成薄膜基質或薄膜主要骨架的化合物，然而術語「反應物(Reactant)」可指在一些情況下有別於前驅物之化合物，該化合物激活前驅物、改性前驅物、或催化前驅物的反應；反應物可對薄膜基質提供元素（諸如O、N、C）並變成薄膜基質的一部分。 在一些情況下，術語前驅物與反應物可互換使用。術語「惰性氣體(Inert gas)」是指在明顯程度上不參與化學反應的氣體及/或當例如施加RF或微波功率時激活前驅物的氣體，但不像反應物，其在明顯程度上可能不會變成薄膜基質的一部分。
術語「循環沉積製程(cyclic deposition process/cyclical deposition process)」可指將前驅物（及/或反應物）循序引入反應腔室中以在基板上方沉積層，並包括處理技術，諸如原子層沉積(ALD)、循環化學氣相沉積（循環CVD)、及包括一ALD組件及一循環CVD組件之混合循環沉積製程。
術語「原子層沉積(Atomic layer deposition)」可指氣相沉積製程，其中沉積循環（通常是複數個連續沉積循環）在製程腔室中實施。當使用（多個）前驅物/（多個）反應性氣體及（多個）沖洗（例如惰性載體）氣體的交替脈衝執行時，如本文中所使用之用語原子層沉積(Atomic layer deposition)亦意指包括由相關用語指稱的製程，諸如化學氣相原子層沉積、原子層磊晶(ALE)、分子束磊晶(MBE)、氣體源MBE、或有機金屬MBE、及化學束磊晶。
通常，對於ALD製程而言，在每個循環期間，前驅物係引入反應腔室並化學吸附到沉積表面（例如，可包括來自先前ALD循環的先前沉積材料或其他材料的基板表面），形成大約不易與附加前驅物起反應（亦即自限反應）的單層或亞單層材料。其後，在一些情況下，可隨後將一反應物（例如，另一前驅物或反應氣體或惰性氣體）引入製程腔室中，用於將化學吸附的前驅物轉換成在沉積表面上的所需材料。反應物/惰性氣體能夠與前驅物進一步起反應或互作用。在一或多個循環期間（例如，在每個循環的每個步驟期間）可利用吹驅步驟，以從製程腔室去除任何過量的前驅物，及/或從反應腔室去除任何過量的反應物及/或反應副產物。
在本發明中，變量之任兩個數字可構成變量之可工作範圍，且所指出之任何範圍可包括或排除端點。附加地，所指出的變量之任何數值（不管該等數值是否以「約」來指示）可指精確值或近似值並包括等效值，且在一些實施例中可指平均值、中間值、代表值、多數值等。此外，在本發明中，在一些實施例中，用語「包括」、「所構成」與「具有」可獨立指「通常或廣泛包含」、「包含」、「基本所組成」或「所組成」。根據本發明之態樣，術語之任何已定義的意義不必然排除該等用語的尋常及慣例意義。
請即參考圖式，圖1示意說明根據本發明的示例性實施例的方法100。方法100包括提供一基板(步驟102)、形成一光阻底層(步驟104)、及形成一黏附層(步驟106)的多個步驟。
步驟102包括提供一基板（諸如本文所述之基板）。該基板可包括一或多個要被蝕刻的層，其包括一或多個材料層。舉例來說，基板可包括欲蝕刻之經沉積的氧化物、天然氧化物、或非晶碳層。基板可包括下伏於欲蝕刻之（多個）材料層的數個層。
在步驟104期間，在基板表面上形成一光阻底層。可使用多種技術形成該光阻底層，包括旋塗式、化學氣相沉積、及循環製程技術。相較於習知的旋塗式玻璃(SoG)，電漿製程處理的SiO與SiOC材料已確認為光阻底層材料的很好選項，因為其具有連續較薄厚度與較低乾蝕刻速率的能力。通常，PEALD被建議作為概念上用於獲得優越的薄膜厚度非均勻性(%NU)的最好方法。
根據方法100的示例性態樣，光阻底層係使用一循環沉積製程形成，諸如一ALD製程，例如PEALD。該循環沉積製程可包括使用活性物質（例如，從（多個）前驅物、（多個）反應物、或者及/或（多個）惰性氣體中之一或多者形成），該等活性物質係使用直接電漿與遠程電漿中之一或多者形成。替代地，步驟104可包括一熱循環沉積製程。使用循環沉積製程可合乎所需，因為其等允許形成具有所欲厚度（例如，小於10 nm或小於或約等於5 nm）、具有改善的厚度均勻性（在基板內及基板之間均是）之光阻底層。使用電漿增強製程可合乎所需，因為相較於熱製程，電漿增強製程允許在相對低的溫度及/或相對高的速率下沉積光阻底層材料。
根據本發明的多個實例，步驟104期間反應腔室內的溫度可小於500℃、小於400℃、小於300℃、或介於約100℃與約500℃、或約150℃與約300℃之間。在步驟104期間反應腔室內的壓力可為約1托(Torr)至約100托、約3托至約50托、或約5托至約20托。
根據本發明的示例性實施例，步驟104包括形成或沉積矽或金屬氧化物、矽或金屬氮化物、及矽或金屬氮氧化物中之一或多者。此類氧化物、氮化物、及/或氮氧化物可亦包括碳。
該光阻底層可包括例如氧化矽、碳氧化矽、氮化矽、氮氧化矽、碳氮化矽、氧碳氮化矽、金屬氧化物、金屬氮化物、金屬碳氧化物、金屬氮氧化物、金屬氧碳氮化物、及金屬碳氮化物中之一或多者。金屬可包括例如一或多個選自由鈦、鉭、鎢、錫、及鉿所組成群組的金屬。在一些情況下，光阻底層包括碳。隨著光阻底層沉積及/或碳處理可應用於光阻底層的表面，碳可結合到光阻底層中。附加地或替代地，一含碳層或其他層可沉積到光阻底層的表面上。該光阻底層的厚度可小於10 nm、小於5 nm、或大於3且小於10 nm。
一用於形成適合步驟104的光阻底層的循環製程在圖2中示意說明（子循環x）。子循環x可包括(A) 將一含金屬或矽的第一前驅物脈衝到反應腔室中（步驟202）；及(B) 將一含氧化劑及/或氮化劑的第二前驅物或反應物脈衝到反應腔室中（步驟206）。在方法100進行步驟106之前，子循環x可重複例如介於約10與約50或約100與約200次之間。
在一些情況下，用於形成光阻底層的循環製程可包括(A) 將一含金屬的第一前驅物脈衝到反應腔室中；(B) 將一含氧化劑及/或氮化劑的第二前驅物或反應物脈衝到反應腔室中；及(C) 將一碳前驅物脈衝到反應腔室中。多個脈衝之每一者可被一吹驅步驟(204、208)分隔。此外，每個脈衝步驟或多個脈衝步驟（例如，脈衝步驟(A)和(B)）的組合可在進行下一步驟之前重複多次，以調整該光阻底層的成分。例如，(AB):C的比率範圍可為約1:1至約1:10。除非另有說明，否則步驟(A)和(B)或步驟(A)、(B)和(C)可採取任何順序進行並可重複所述步驟的各種組合。
根據本發明的多個示例性態樣，提供一含矽的第一前驅物。在一些情況下，該矽前驅物可亦包括碳。多個適用於形成光阻底層的示例性矽前驅物包括本文所述的矽前驅物。
根據本發明的其他示例性態樣，第一前驅物包含一金屬。在這些情況下，第一前驅物可包括一過渡金屬，諸如一或多個選自由鈦、鉭、鎢、錫、及鉿所組成群組的金屬。包含金屬之第一前驅物可亦包括碳（例如，直接或間接鍵結至金屬原子的一或多個有機基團）。舉具體例來說，所述含有金屬的第一前驅物可包括一金屬鹵化物或一金屬有機化合物；或一有機金屬化合物，諸如四（二甲氨基）鈦(TDMAT)、異丙醇鈦(TTIP)、氯化鈦(TiCl)、四（乙基甲基氨基）鉿(TEMAHf)、氯化鉿(HfCl)、三甲基鋁(TMA)、三乙基鋁(TEA)、其他金屬鹵化物、或其他含金屬化合物中之一或多者。
該反應物可包括一氧化反應物、一氮化反應物、或一還原劑，諸如一含氫反應物。氧化及/或氮化反應物包括含氧與氮中之一或多者的反應物。在一些情況下，反應物可包括氮與氧兩者。而且，在一些情況下，兩或多個氧化劑及/或氮化反應物可包括在單一脈衝中。多個示例性氧化劑與氮化劑包括氧(O 2)、水(H 2O)、臭氧(O 3)、過氧化氫(H 2O 2)、氨(NH 3)、二氮烯(N 2H 2)、CO 2、一氧化二氮(N 2O)；多個示例性含氫反應物包括氫(H 2)等。如前述，氧化及/或氮化反應物可暴露於（例如，直接）電漿以形成用於PEALD製程的受激態物質。
當使用時，碳前驅物可包括任何合適的有機化合物，諸如含碳與氧的化合物。在一些情況下，碳前驅物可亦包括氮。碳前驅物可選擇成與例如金屬氧化物的-OH終端表面及/或金屬氮化物的-NH 2終端表面起反應。合適的碳前驅物的多個實例包括有機化合物（諸如酸酐（例如，乙酸酐））、甲苯、二乙二醇、三乙二醇、乙醛、及有機矽化合物（諸如矽烷、及矽氧烷）中之一或多者。多個示例性有機矽化合物包括（n,n-二甲基氨基）三甲基矽烷、三甲氧基（十八烷基）矽烷、六甲基二矽氮烷、三甲氧基（3,3,3-三氟丙基）矽烷、三甲氧基苯基矽烷、三氯（3,3,3-三氟丙基）矽烷及六甲基二矽氮烷。
一旦形成光阻底層，在步驟106期間形成一黏附層。步驟106可在相同反應腔室內且無空氣及/或真空中斷下原位執行。
如圖1所示，步驟106可包括提供一矽前驅物（步驟108）、提供一惰性氣體（步驟110）、及形成電漿（步驟112）的多個子步驟。步驟106可包括一循環沉積製程，諸如一PEALD製程。例如，參考圖2，步驟106可包括將一矽前驅物脈衝到反應腔室（步驟210）、允許該矽前驅物與基板表面起反應、吹驅任何未起反應的前驅物及/或副產物（步驟212）、向該反應腔室提供一惰性氣體、及使用該惰性氣體形成電漿以形成與該矽前驅物或其衍生物起反應的活性物質以形成黏附層（步驟214）、及從該反應腔室吹驅任何過量的反應物質及/或副產物（步驟216）。如圖所示，子循環y可重複多次，例如，介於約30與約40或約50或約60或約70及約120次之間。對於步驟102及/或104，步驟106期間的溫度與壓力可相同或類似。黏附層的厚度大於0且小於2 nm。
在步驟210期間，向該反應腔室提供一矽前驅物。根據本發明的多個實例，矽前驅物不包含氮。無N（氮）前驅物可有利用於形成一黏附層，因為氮認為由於存在N個原子而呈現出毒害效應。根據進一步實例，矽前驅物由或基本上由Si、C、H、及O所組成，其可在載體氣體的輔助下提供給反應腔室。舉例來說，矽前驅物可選自由以下所組成群組中之一或多者：
Figure 02_image001
根據進一步實例，矽前驅物係選自由以下所組成群組中之一或多者：3-甲氧基丙基三甲氧基矽烷、雙（三甲氧基甲矽烷基）甲烷、1,2-雙（甲基二甲氧基甲矽烷基）乙烷、1,2-雙（三乙氧基甲矽烷基）乙烷、1,2-雙（三乙氧基甲矽烷基）乙烯、1,2-雙（二乙氧基甲基甲矽烷基）乙烷、1,2-雙（三甲氧基甲矽烷基）乙烷、1,1,3,3-四甲氧基-1,3-二矽環丁烷、1,1,3,3-四乙氧基-1,3-二矽環丁烷、1,1,3,3,5,5-六甲氧基-1,3,5-三矽環己烷、1,1,3,3,5,5-六乙氧基-1,3,5-三矽環己烷。舉具體例來說，矽前驅物可為或包括3-甲氧基丙基三甲氧基矽烷。在步驟210期間矽前驅物的流動速率可介於約100 sccm與約150 sccm之間。步驟210的持續時間可介於約0.1秒與約0.3秒之間。
在步驟212期間，可從反應腔室吹驅任何過量的矽前驅物及/或任何反應副產物。可藉由向該反應腔室供應一惰性氣體及/或使用一真空源進行吹驅。
在步驟214期間，使用一惰性氣體形成電漿。該惰性氣體可為或包括Ar、He、Ne、Kr、及Xe中之一或多者。形成電漿的功率可為約30W至約1000W。形成電漿之功率的頻率可介於約200 kHz和大約2.45 GHz。該惰性氣體的流動速率可介於約2 slm與約10 slm之間。步驟214的持續時間可介於約0.1秒(s)與約2秒之間。
在步驟216期間，電漿功率被關閉並吹驅任何過量的反應性物質及/或副產物。子循環y可重複多次以形成具有所需厚度的矽基黏附層，例如，大於0且小於約2 nm。
根據本發明的多個方法可亦包括一用於形成上覆於該黏附層並接觸其的光阻層之步驟。光阻可使用例如旋塗式技術予以沉積。光阻層可為或包括正型或負型極紫外光(EUV)微影光阻。
圖3示意說明根據本發明的示例性實施例的結構300。結構300可使用例如方法100及/或200來形成。
如圖所示，結構300包括一基板302、一材料層304、一光阻底層306、一光阻層308、及一***介於光阻底層306與光阻層308之間並接觸其的黏附層310。
基板302可包括如前述的基板。舉例來說，基板302可包括半導體基板，諸如塊材，諸如矽（例如，單晶矽）；其他IV族半導體材料；III-V族半導體材料；及/或II-VI族半導體材料，並可包括一或多個上覆於該塊材的層（例如，圖案化疊層）。此外，如前述，基板302可包括各種拓撲結構，諸如形成在基板層的至少一部分內或其上的凹部、線路等。
材料層304可使用如本文所述的一光阻底層與一光阻層進行圖案化及蝕刻。多個適用於材料層304的示例性材料包括例如氧化物，諸如天然氧化物或場區氧化物。其他示例性材料層304材料包括非晶質碳、氮化物、其他氧化物、矽及附加薄膜（例如，一自聚性單分子膜（例如，六甲基二矽氮烷(HMDS)））。
光阻底層306可包括根據本文所述的方法(例如，方法100)形成的一光阻底層，及/或具有如本文所述的特性及/或材料。示例性光阻底層包括矽或金屬氧化物、矽或金屬氮化物、及矽或金屬氮氧化物中之一或多者，其任一者可包括或不包括碳。例如，光阻底層306可包括氧化矽、碳氧化矽、氮化矽、氮氧化矽、碳氮化矽、氧碳氮化矽、金屬氧化物、金屬氮化物、金屬碳氧化物、金屬氮氧化物、金屬氧碳氮化物、及金屬碳氮化物中之一或多者。
光阻底層306的厚度可取決於材料層304的成分、材料層304的厚度、光阻的類型等。根據本發明的多個實例，光阻底層306的厚度小於10 nm或小於或約5 nm或介於約3 nm與約10 nm之間。如果光阻底層306太厚，則在蝕刻步驟後可能保持殘留的底層材料。如果光阻底層306太薄，則光阻底層306可能無法在蝕刻製程期間提供所需的圖案轉移。
黏附層310理想上呈現出如本文所述的良好黏附性及其他特性。根據本發明的多個實例，黏附層310包括矽並可選擇性包括碳、氫、及氧中之一或多者。如前述，黏附層310可理想上不包括氮。
為在光阻層308與光阻底層306之間提供所需的黏附性，黏附層310可具有或被調整成具有所需的表面化學性質，例如，量化為表面能，其進一步分類為表面能的極性部分與表面能的分散部分。光阻底層306的表面能的極性部分及表面能的分散部分可藉由測量液體（諸如水或CH 2I 2）的接觸角、並使用Owens、Wendt、Rabel和Kaelble(WORK)方法來計算，以確定表面能的極性部分與分散部分。可針對光阻層308測量及計算相同特性。黏附層310的厚度可大於0 nm並小於2 nm。
根據本發明的各種實例，黏附層310的表面能的極性部分的值係介於約5 mN/m至約25 mN/m、或約20 mN/m至約40 mN/m之間。根據進一步實例，黏附層310的表面能的分散部分的值係介於約10 mN/m至約30 mN/m、或約5 mN/m至約25 mN/m、或約20 mN/m至約40 mN/m之間。例如，當光阻層308包含負型光阻時，光阻底層的表面能的極性部分的值可介於約20 mN/m與約40 mN/m之間，及/或光阻底層的表面能的分散部分的值可介於約10 mN/m至約30 mN/m或約20 mN/m至約40 mN/m之間。當光阻層308包括正型光阻時，光阻底層的表面能的極性部分的值可介於約5 mN/m至約25 mN/m，及/或光阻底層的表面能的分散部分的值可介於約10 mN/m至約30 mN/m之間。
舉例來說，隨著利用惰性氣體電漿來形成黏附層310，當將矽前驅物引入薄膜上時，懸浮鍵可能表現為表面反應位點並導致化學吸附。因此，矽前驅物結構中的配位體（例如，CHx配位體）最終可保持在表面上，從而產生所需的表面自由能。黏合劑層本質上可為SiOC，最終是表面碳氫化合物。
光阻層308可為或包括正型或負型（例如，EUV）光阻。
圖4示意說明形成在旋塗式玻璃上的圖案化光阻及形成在具有如本文所述一黏附層的PEALD氧化矽層上的圖案化光阻的掃描電子顯微鏡(SEM)圖像。PEALD 氧化矽層的厚度約為4 nm（使用約50個沉積循環形成），且黏附層的厚度約為1 nm（使用約100個黏附層循環形成）。對於含有該黏附層的結構，全範圍%非均勻性(NU)為1.5%，且在CD (critical dimension) 16 nm中沒有缺陷（圖案崩塌、微橋接、及微斷裂）。此外，線寬粗糙度(LWR)與線邊緣粗糙度(LER)係與10 nm SoG一樣好。
請即參考圖5，其進一步描述配置成執行如本文所述的方法之系統500。系統500包含至少一反應腔室，其配置用於沉積一底層並形成如本文所述的一黏附層。系統500可包含一第一反應腔室511及一第二反應腔室512，其可配置用於沉積一底層並形成如本文所述的一黏附層、或其一部分。如果需要，系統500可包括一第三反應腔室513，其中可執行另一製程，諸如熱或電漿增強後處理。
圖6更詳細示意說明一示例性反應腔室（例如，適合用作反應腔室511或512）。反應器系統600可用於執行如本文所述的一或多個步驟或子步驟，及/或形成如本文所述的一或多個結構或其部分。
反應器系統600在反應腔室3的內部11（反應區）中包括平行且面向彼此的一成對導電平板電極4、2。可藉由從電源25施加例如HRF功率（例如13.56 MHz或27 MHz）至一電極（例如，電極4）並將另一電極（例如，電極2）電氣接地，而在反應腔室3內激發電漿。下層2（下電極）中可設置一溫度調節器，並可將置放其上的基板1的溫度保持在所需的溫度。電極4可用作一氣體分配裝置，諸如一噴淋盤。可分別使用一氣體管線20、一氣體管線21、及一氣體管線22中之一或多者並透過噴淋盤4，將反應氣體、稀釋氣體（如果有）、前驅物氣體、及/或類似物引入反應腔室3中。儘管使用三個氣體管線示出，但是反應器系統600可包括任何合適數量的氣體管線。氣體管線20可耦合到一矽前驅物源29，氣體管線21可耦合到一惰性氣體源27，且氣體管線22可耦合到另一（例如，反應物）氣體源28。
在反應腔室3中，提供具有排氣管線7之圓管13，可通過其排出反應腔室3之內部11中的氣體。此外，經設置在反應腔室3下方之轉移區5設有密封氣體管線24，以經由轉移區5的內部16（傳遞區）將密封氣體引入反應腔室3的內部11中，其中提供用於分開反應區與傳遞區之分隔板14（此圖式省略閘閥，晶圓係通過該閘閥轉移至或移出轉移區5）。轉移區亦具有一排氣管線6。在一些實施例中，沉積與處理步驟在相同的反應空間中進行，使得多個（例如，沉積與黏附層）步驟中之兩者或多者(例如全部)可在沒有將基板暴露於空氣或其他含氧環境的情況下連續進行。
在一些實施例中，惰性或載體氣體至反應腔室3之連續流動可使用流通系統(FPS)來達成，其中載體氣體管線具備具有前驅物儲槽（瓶）的歧路管線，且主管線及歧路管線經切換，其中當僅意欲將載體氣體饋送至反應腔室時，使歧路管線閉合，而當意欲將載體氣體及前驅物氣體兩者饋送至反應腔室時，使主管線閉合且載體氣體流過歧路管線並從瓶與前驅物氣體一起流出。如此，載體氣體可連續流入反應腔室，並可藉由在主管線與歧路管線之間切換，而採取脈衝方式攜帶前驅物氣體，基本上不致對反應腔室的壓力形成波動。
反應器系統600亦包括一或多個控制器26，其係編程或另外配置成執行如本文所述一或多個方法步驟。（多個）控制器26通訊反應器的各種電源、加熱系統、幫浦、機器人與氣體流量控制器、或閥，如熟習該項技藝者所明白。舉例來說，控制器26可配置成控制一矽前驅物與一惰性氣體的氣體流量，以在光阻底層上形成一黏附層。附加地或替代地，控制器可配置成執行多個步驟，以形成如本文所述的一光阻底層。
在一些實施例中，可使用雙腔室反應器（經設置為靠近彼此之用於處理晶圓的兩區段或隔室），其中反應物氣體及稀有氣體可透過共用管線供應，然而前驅物氣體係透過非共用管線供應。
前述本發明的實例實施例並未限制本發明的範疇，既然這些實施例僅為本發明之實施例之實例。任何等效實施例係意欲落入本發明之範疇內。實際上，除本文所示及所描述之實施例外，熟習該項技藝者當可從本說明書明白本發明的各種修改，諸如所描述元件的替代可用組合。此類修改及實施例亦意欲屬於發明申請專利範圍之範疇內。
1:基板 2:電極/下層 3:反應腔室 4:電極/噴淋盤 5:轉移區 6,7:排氣管線 11:內部 13:圓管 14:分隔板 16:內部 20,21,22:氣體管線 24:密封氣體管線 25:電源 26:控制器 27:惰性氣體源 28:氣體源 29:矽前驅物源 100:方法 102:步驟 104:步驟 106:步驟 108:步驟 110:步驟 112:步驟 202:步驟 204:步驟 206:步驟 208:步驟 210:步驟 212:步驟 214:步驟 216:步驟 300:結構 302:基板 304:材料層 306:光阻底層 308:光阻層 310:黏附層 500:系統 511:第一反應腔室 512:第二反應腔室 513:第三反應腔室 600:反應器系統
可在連同下列說明性圖式考慮時，藉由參考實施方式及申請專利範圍而衍生對本發明之例示性實施例的更完整理解。        圖1示意說明根據本發明的示例性實施例之方法。        圖2繪示依據本發明例示性實施例之方法。        圖3示意說明根據本發明的示例性實施例之結構。        圖4示意說明根據本發明的示例性實施例之另一結構。        圖5示意說明配置用於執行如本文所述方法之系統。        圖6示意說明根據本發明的又另外實例之系統。        應瞭解，圖式中的元件是為了簡單與清楚而繪示，且不必然按比例繪製。例如，圖式中之一些元件的尺寸可能相對於其他元素而特別放大，以幫助改善對所繪示本發明實施例的理解。
100:方法
102:步驟
104:步驟
106:步驟
108:步驟
110:步驟
112:步驟

Claims (20)

  1. 一種形成含有光阻底層的結構之方法，該方法包含下列步驟： 在一反應腔室內提供一基板； 形成上覆於該基板之表面的一光阻底層；及 使用一第一循環沉積製程形成一上覆於該光阻底層的黏附層，多個形成該黏附層的步驟包含： 向該反應腔室提供一矽前驅物； 向該反應腔室提供一惰性氣體；及 使用該惰性氣體形成電漿，以形成與該矽前驅物或其衍生物起反應的活性物質，從而形成該黏附層。
  2. 如請求項1所述之方法，其中該光阻底層包含氧化矽、碳氧化矽、氮化矽、氮氧化矽、碳氮化矽、氧碳氮化矽、金屬氧化物、金屬氮化物、金屬碳氧化物、金屬氮氧化物、金屬氧碳氮化物、及金屬碳氮化物中之一或多者。
  3. 如請求項2所述之方法，其中該金屬包含一或多個選自由鈦、鉭、鎢、錫、及鉿所組成群組的金屬。
  4. 如請求項1-3中任一項所述之方法，其更包含一用於形成上覆於並接觸該黏附層的一光阻層之步驟，其中該光阻層包含極紫外光(EUV)微影光阻。
  5. 如請求項1-4中任一項所述之方法，其中該光阻底層的厚度大於3且小於10 nm。
  6. 如請求項1-5中任一項所述之方法，其中該第一循環沉積製程是一原子層沉積製程。
  7. 如請求項1-6中任一項所述之方法，其中該矽前驅物不包含氮。
  8. 如請求項1-7中任一項所述之方法，其中該矽前驅物係選自由以下所組成群組中之一或多者：
    Figure 03_image003
    。
  9. 如請求項1-8中任一項所述之方法，其中該矽前驅物係選自由以下所組成群組中之一或多者：3-甲氧基丙基三甲氧基矽烷、雙（三甲氧基甲矽烷基）甲烷、1,2雙（甲基二甲氧基甲矽烷基）乙烷、1,2-雙（三乙氧基甲矽烷基）乙烷、1,2-雙（三乙氧基甲矽烷基）乙烯、1,2-雙（二乙氧基甲基甲矽烷基）乙烷、1,2-雙（三甲氧基甲矽烷基）乙烷、1,1,3,3-四甲氧基-1,3-二矽環丁烷、1,1,3,3-四乙氧基-1,3-二矽環丁烷、1,1,3,3,5,5-六甲氧基-1,3,5-三矽環己烷、1,1,3,3,5,5-六乙氧基-1,3,5-三矽環己烷。
  10. 如請求項1-9中任一項所述之方法，其中該光阻底層是使用一第二循環沉積製程形成。
  11. 如請求項1-10中任一項所述之方法，其中該光阻底層是使用該矽前驅物形成。
  12. 如請求項11所述之方法，其中該矽前驅物的化學式由Si、C、H、及O所組成。
  13. 如請求項1-12中任一項所述之方法，其中該第一循環沉積製程係重複介於約30與約40或約50或約60或約70及約120次之間。
  14. 如請求項1-13中任一項所述之方法，其中該黏附層的厚度大於0 nm且小於2 nm。
  15. 如請求項1-12中任一項所述之方法，其中該第二循環沉積製程係重複介於約10至約50或約100與約200次之間。
  16. 一種如請求項1-15中任一項所述之方法形成的結構。
  17. 如請求項16所述之結構，其中該光阻底層包含氧化矽、碳氧化矽、氮化矽、氮氧化矽、碳氮化矽、氧碳氮化矽、金屬氧化物、金屬氮化物、金屬碳氧化物、金屬氮氧化物、金屬氧碳氮化物、及金屬碳氮化物中之一或多者。
  18. 如請求項16或17所述之結構，其中該黏附層包含矽。
  19. 如請求項16-18中任一項所述之結構，其更包含上覆於並接觸該黏附層的EUV光阻。
  20. 一種用於形成黏附層之系統，該系統包含： 一反應腔室； 一矽前驅物源，其流體耦合該反應腔室； 一惰性氣體源，其流體耦合該反應腔室；及 一控制器，其配置成執行如請求項1-15中任一項所述之方法。
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