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TWI421364B - 利用電漿增強化學氣相沉積來沉積共形無定形碳膜層的方法 - Google Patents

利用電漿增強化學氣相沉積來沉積共形無定形碳膜層的方法 Download PDF

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TWI421364B
TWI421364B TW098134833A TW98134833A TWI421364B TW I421364 B TWI421364 B TW I421364B TW 098134833 A TW098134833 A TW 098134833A TW 98134833 A TW98134833 A TW 98134833A TW I421364 B TWI421364 B TW I421364B
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amorphous carbon
substrate
carbon layer
processing chamber
plasma
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TW201026877A (en
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Kwangduk Douglas Lee
Takashi Morii
Yoichi Suzuki
Sudha Rathi
Martin Jay Seamons
Deenesh Padhi
Bok Hoen Kim
Cynthia Pagdanganan
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Applied Materials Inc
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Description

利用電漿增強化學氣相沉積來沉積共形無定形碳膜層的方法
本發明實施例大體而言係有關於積體電路的製造,並且更明確地說,係有關於在一半導體基材上沈積一無定形碳層。
積體電路已演進為可容納數百萬個電晶體、電容器和電阻器在單一個晶片上的複雜元件。晶片設計的進化持續要求更快的電路及更大的電路密度。對於更快的電路以及更大的電路密度之要求也對用來製造此類積體電路的材料加諸相對應的要求。明確地說,隨著積體電路零組件的尺寸縮小至次微米尺寸,不僅必須使用低電阻係數的導電材料,例如銅,以改善元件的電氣效能,並且也必須使用低介電常數絕緣材料,常稱為低k介電材料。低k介電材料一般具有低於3.8的介電常數。
製造具有低k介電材料以及極少或沒有表面缺陷或特徵結構變形的元件是困難的。介電常數低於約3.0的低k介電材料常是多孔且容易在隨後的製程步驟期間刮傷或受損,因此增加缺陷形成在該基材表面上的可能性。此類低k介電材料通常是易碎的且可能在習知研磨製程下變形,例如化學機械研磨(CMP)。一種限制或減少此類低k介電材料的表面缺陷及變形的解決方法是在圖案化及蝕刻之前,先在暴露出的低k介電材料上沈積硬光罩。該硬光罩避免脆弱的低k介電材料損壞及變形。此外,硬光罩層結合習知微影技術可作用為蝕刻光罩,以避免低k介電材料在蝕刻期間被除去。
此外,硬光罩幾乎在積體電路製造製程的每一個步驟中使用,用於前端和後端製程兩者。隨著元件尺寸縮小以及圖案結構日益複雜和難以製造,蝕刻硬光罩更形重要,因為現行光阻無法符合蝕刻抗性要求,並且光阻僅是用來進行影像轉移而非在微影和蝕刻製程中做為蝕刻光罩。反之,接收影像圖案的硬光罩日漸成為在下方層中有效蝕刻圖案的首要材料。
無定形氫化碳是一種可用來做為金屬、無定形矽、以及介電材料,例如二氧化矽或氮化矽材料,除了其他之外,的硬光罩之材料。無定形氫化碳,也稱為無定形碳並可表示為a-C:H或α-C:H,被視為是無長程結晶序的碳材料,且可含有重要的氫含量,例如約10至45的氫原子百分比等級。已觀察到無定形碳擁有化學惰性、光學透明性、以及良好的機械性質。雖然可用若干技術來沈積a-C:H膜,但電漿增強化學氣相沈積(PECVD)因其成本效益及薄膜性質可調性而廣為使用。在一典型PECVD製程中,一碳氫化合物來源,例如承載在一載氣中的氣態碳氫化合物或液態碳氫化合物,係經通入一PECVD腔室內。然後在該腔室內起始電漿,以產生激發的CH-自由基。該等激發的自由基化學性鍵結至設置在該腔室內的基材之表面,在其上形成預期的a-C:H膜。
就硬光罩層係沈積在具有形貌特徵結構的基材上之應用而言,該硬光罩層必須共形覆蓋該形貌特徵結構的所有表面。此外,隨著特徵結構尺寸縮小,由於光波長和圖案尺寸的限制,光阻材料難以正確轉移圖案。因此,日漸需要新的製程和材料來滿足這些挑戰,其中硬光罩對於下世代元件之關鍵尺寸的有效轉移變得不可或缺。硬光罩層沈積共形性在具有下方形貌的基材上是很難實現的,例如用來對準該圖案化製程的對準鍵。第1圖示出具有特徵結構111及形成在其上之非共形無定形碳層112的基材100之概要剖面圖。因為非共形無定形碳層112並非完全覆蓋特徵結構111的側壁114,隨後的蝕刻製程可能造成有害的側壁114腐蝕。側壁114由非共形無定形碳層112完整覆蓋的缺乏也可能造成非共形碳層112下方材料的光阻毒化,其已知會損傷電子元件。
因此,存有對於一種可用於積體電路製造之可共形沈積在具有形貌特徵結構的基材上之材料層的沈積方法之需要。
本發明實施例提供一種處理基材的方法,例如藉由在該基材上沈積一無定形碳層。該方法,根據一第一實施例,包含將一基材設置在一基材處理室內,將碳對氫原子比大於1:2的一碳氫化合物來源通入該處理室,將選自由氫氣、氦氣、氬氣、氮氣、及其組合物所組成的族群之一電漿起始氣體通入該處理室,並且該碳氫化合物來源的體積流速對該電漿起始氣體的體積流速比為1:2或更大,在該處理室內以1瓦/平方公分或更低的RF功率、2托耳或更高的壓力、以及約300℃至約480℃的溫度產生一電漿,以及在該基材上形成一共形無定形碳層。
在另一實施例中,提供一種處理一基材的方法,其包含執行一沈積循環,包含在該基材的一表面上形成一共形無定形碳材料,以及使一淨化氣體流動通過該處理室,以及重複該循環2至50次之間。
在另一實施例中,提供一種處理一基材的方法,其包含將一基材設置在一基材處理室內,將碳對氫原子比大於1:2的一碳氫化合物來源通入該處理室,將選自由氫氣、氦氣、氬氣、氮氣、及其組合物所組成的族群之一電漿起始氣體通入該處理室,並且該碳氫化合物來源的體積流速對該電漿起始氣體的體積流速比為1:2或更大,其中該碳氫化合物來源和該電漿起始氣體係利用設置在距離基材表面400密爾和600密爾之間的一氣體分配器通入該處理室,在該處理室內以1瓦/平方公分或更低的RF功率以及約0℃至約100℃之間的溫度產生一電漿,以及在該基材上形成一共形無定形碳層。
在此所述實施例大體而言提供在一化學氣相沈積系統內沈積具有改善的共形性之無定形碳材料(a-C:H)的方法。一個層的共形性通常是用沈積在一特徵結構側壁上之一層的平均厚度對相同沈積層在該基材範圍,或上表面,上的平均厚度之比例(其可表示為百分比)來量化。觀察到利用在此所述方法沈積的層具有大於約30%,例如70%或更高,約7:10或更大,例如約80%或更高,約4:5或更大,至約100%,約1:1的共形性。例如,會認定第1圖所示之先前技藝非共形無定形碳層112具有0%共形性,因為在側壁114上缺乏層沈積。
明確地說,提供一改善的a-C:H層共形沈積之方法。共形沈積可藉由使用碳對氫比例為1:2或更高的前驅物,例如碳對氫比例為2:3或更高,利用選自由氦氣、氫氣、氮氣、氬氣、或其組合物所組成的族群之電漿起始氣體,以增加的前驅物對電漿起始氣體流速,以增加的沈積壓力,以增加的沈積溫度,以較低的RF功率應用,利用具有降低的沈積速率之電漿環境,藉由在多個層內沈積無定形碳,及其組合來改善。此間沈積製程可在一適合的處理系統內執行。
第3圖係一基材處理系統,系統300,的概要示意圖,其可用來進行根據本發明實施例之無定形碳層沈積。適合系統的範例包含CENTURA系統,其可使用DxZTM 處理室,PRECISION 5000系統,PRODUCERTM 系統,例如PRODUCER SETM 處理室和PRODUCER GTTM 處理室,所有皆可由加州聖塔克拉拉的應用材料公司購得。
系統300包含製程腔室325、氣體分配盤330、控制單元310、及其他硬體零組件,例如電源和真空幫浦。在本發明中使用的系統之一實施例的細節在共同讓渡之2002年4月2號核准之美國專利第6,364,954號之“High Temperature Chemical Vapor Deposition Chamber”中描述,其在此藉由引用的方式併入本文中。
該製程腔室325通常包含基材支撐座350,其係用來支撐一基材,例如一半導體基材390。此基材支撐座350在該製程腔室325內利用連接至支桿360的位移機構(未示出)在垂直方向上移動。取決於製程,可在處理前先將該半導體基材390加熱至一預期溫度。該基材支撐座350係利用一嵌入式加熱器元件370加熱。例如,該基材支撐座350可藉由從一電源供應器306施加電流至該加熱器元件370來阻抗加熱。該半導體基材390轉而由該基材支撐座350加熱。一溫度感應器372,例如一熱電偶,也嵌入在該基材支撐座350內以監控該基材支撐座350的溫度。測得的溫度被用於一回饋迴路中以控制用於該加熱器元件370的電源供應器306。該基材溫度可保持或控制在選用於特定製程應用的溫度下。
使用一真空幫浦302來排空該製程腔室325並在該製程腔室325內維持適當的氣流和壓力。一噴頭320,製程氣體藉其通入製程腔室325內,係設置在該基材支撐座350上方,並且適於提供均勻分佈的製程氣體至製程腔室325內。該噴頭320係連接至一氣體分配盤330,其控制及供應用於該製程程序不同步驟內的各種製程氣體。製程氣體可包含一碳氫化合物來源及一電漿起始氣體,並且在下方結合一例示氬氣稀釋沈積製程之敘述更詳細描述。
該氣體分配盤330也可用來控制及供應各種氣化的液態前驅物。雖未示出,可氣化來自一液態前驅物供應源的液態前驅物,例如,利用一液體注射蒸發器,並在載氣存在下傳送至製程腔室325。該載氣通常是一種惰性氣體,例如氮氣,或一種鈍體,例如氬氣或氦氣。或者,該液態前驅物可利用一熱及/或真空輔助氣相製程從一安瓿氣化。
該噴頭320和基材支撐座350也可形成一對隔開的電極。在該等電極之間產生電場時,通入腔室325內的該等製程氣體被點燃成為電漿392。通常,該電場係利用一匹配網路(未示出)連接該基材支撐座350至一單頻或雙頻的射頻(RF)功率源(未示出)來產生。或者,該RF功率源和匹配網路可連接至該噴頭320,或連接至該噴頭320和該基材支撐座350兩者。電漿輔助化學氣相沈積技術藉由施加電場至靠近該基材表面的反應區域,產生一反應物種電漿來促進反應氣體的激發及/或分解。該電漿內的物種之反應性減少發生一化學反應所需要的能量,實際上降低此種電漿輔助化學氣相沈積製程所需的溫度。
流經該氣體分配盤330的氣體和液體之適當控制及調節係利用質流控制器(未示出)及例如電腦的控制單元310來執行。該噴頭320容許來自該氣體分配盤330的製程氣體均勻地分配及通入該製程腔室325內。例示地,該控制單元310包含一中央處理單元(CPU)312、支撐電路314、以及含有相關控制軟體316的記憶體。此控制單元310負責基材處理所需之眾多步驟的自動控制,例如基材傳輸、氣體流量控制、液體流量控制、溫度控制、腔室排空等等。當該製程氣體混合物離開該噴頭320時,該碳氫化合物的電漿輔助熱分解在該半導體基材390表面395發生,致使一無定形碳層沈積在該半導體基材390上。
沈積製程
本發明態樣提供a-C:H層改善的共形沈積。改善的共形沈積可藉由使用碳對氫比例為1:2或更高的前驅物之製程來實現,例如碳對氫比例為2:3或更高,可利用選自由氦氣、氫氣、氮氣、氬氣、或其組合物所組成的族群之電漿起始氣體來實現,可以增加的前驅物對電漿起始氣體流速來實現,可以增加的沈積壓力實現,可以增加的沈積溫度實現,可以較低的RF功率應用實現,可利用具有降低的沈積速率之電漿環境實現,可利用增加氣體分配盤和基材表面之間的間距來實現,可藉由在多個層內沈積無定形碳來實現,及其組合。咸信在此所述製程提供降低的沈積速率及/或更等向的沈積製程,因此,提供更為共形的沈積製程。
在沈積製程之一態樣中,一a-C:H層係利用一製程來形成,其包含通入一碳氫化合物來源及一電漿起始氣體至一處理室內,例如在上面結合第3圖所述之製程腔室325。該碳氫化合物來源係一或多種碳氫化合物,並且選擇性地例如氬氣之載氣,的混合物。
該一或多種碳氫化合物可包含碳原子對氫原子比為1:2或更高的化合物,例如大於1:2。例如,觀察到2:3或更高的碳對氫(或氫的取代基,例如氟)比例,像從2:3至2:1,例如從約2:3至約3:2,產生具有改善的共形性之無定形碳膜層。咸信具有所述的碳對氫原子比之此類碳氫化合物造成更為等向的沈積製程。
該等碳氫化合物可以部分或完全摻雜,碳氫化合物的衍生物也可受惠於本發明方法。衍生物包含氮-、氟-、氧-、氫氧根-,以及碳氫化合物的含硼衍生物。
一般而言,可包含在該碳氫化合物來源內的碳氫化合物或其衍生物可由式CA HB FC 表示,其中A的範圍在1和24之間,B的範圍在0和50之間,C的範圍在0和50之間,而A對B+C的比例是1:2或更高,例如大於1:2。例如,A對B+C的比例可以是2:3或更高,例如從2:3至2:1,並且在一進一步範例中,從2:3至3:2。在一實施例中,其中C=0,該碳氫化合物來源可具備式CX HY ,並且2/3<=x/y=<3/2,其中x/y是個別的原子數。或者,就氧及/或氮取代化合物而言,該碳氫化合物來源可用式CA HB OC FD NE 表示,其中A的範圍在1和24之間,B的範圍在0和50之間,C的範圍在0和10之間,D的範圍在0和50之間,E的範圍在0和10之間,而A對B+C+D+E的比例是1:2或更高,例如大於1:2。例如,A對B+C+D+E的比例可以是2:3或更高,例如從2:3至2:1,並且在一進一步範例中,從2:3至3:2。
適合的碳氫化合物包含一或多種如下化合物,例如,炔,像乙炔(C2 H2 ),乙烯乙炔及其衍生物,芳香族碳氫化合物,例如苯、苯乙烯、甲苯、二甲苯、吡啶、乙苯、苯乙酮、苯甲酸甲酯、乙酸苯酯、酚、甲酚、呋喃、以及諸如此類,α-松油烯,異丙基甲苯,1,1,3,3,-四甲基丁苯,第三丁醚,甲基丙烯酸甲酯,以及第三丁基糠基醚,具備式C3 H2 和C5 H4 的化合物,鹵化的芳香族化合物,包含氟苯、二氟苯、四氟苯、六氟苯及諸如此類。其它適合的碳氫化合物包含烯,例如乙烯、丙烯、丁烯、戊烯、及諸如此類,二烯,例如丁二烯、異戊二烯、戊二烯、己二烯及諸如此類,以及鹵化的烯,包含氟乙烯、二氟乙烯、三氟乙烯、四氟乙烯、氯乙烯、二氯乙烯、三氯乙烯、四氯乙烯、以及諸如此類。碳原子對氫原子比大於1:2的前驅物之一範例是C4 H2 ,其可以是丁二炔。
此外,本發明預期使用碳原子對氫原子比為3:1或更高的前驅物,像5:1,例如10:1或更高。
咸信隨著碳對氫比例增加,碳原子會在沈積期間與相鄰的碳原子鍵結,藉由形成複雜的三維短程結構網路而造成沈積膜較佳的共形性。
該a-C:H沈積製程包含使用一種電漿起始氣體,其係在該碳氫化合物之前及/或與其同時通入該腔室,並且起始一電漿以開始沈積。該電漿起始氣體可以是一種高游離電位氣體,包含但不限於,氦氣、氫氣、氮氣、氬氣及其組合物,其中氦氣是較佳的。該電漿起始氣體也可以是一種化學惰性氣體,例如氦氣、氮氣、或氬氣是較佳的。適合的氣體游離電位是從約5eV(電子電位)至25eV。該電漿起始氣體可在該碳氫化合物之前通入該腔室內,這容許形成穩定的電漿並降低電弧的可能性。已觀察到使用具有高游離電位的電漿起始氣體可在沈積期間提供較少的薄膜非等向性蝕刻,因此改善無定形碳膜沈積的共形性。做為稀釋氣體或載氣的惰性氣體,例如氬氣,可連同該電漿起始氣體、該碳氫化合物、或其組合物一起通入。
該碳氫化合物和電漿起始氣體可以從約1:100或更高的碳氫化合物對電漿起始氣流比例通入,例如,從約1:100至100:1,像就該無定形碳沈積而言從約1:10至約10:1。在一實施例中,該碳氫化合物對電漿起始氣流比例可從約1:5或更高,像從約1:5至約2:1,例如從約1:2至約1:1,可用於該無定形碳沈積。已觀察到增加碳氫化合物對電漿電漿起始氣流比例可提供優於較低比例的改善之共形性。
該a-C:H層可從該處理氣體沈積,藉由將腔室壓力保持在約2托耳或更高,例如從約2托耳至約20托耳,並且在一實施例中,約7托耳或更高,例如從約7托耳至約9托耳。已觀察到共形性隨著壓力增加而增加,並且咸信離子在抵達該基材之前更為分散,因此喪失一些蝕刻能力,並且更為分散的自由基以更隨機且等向的角度抵達該基材表面,以利更加等向且共形的薄膜沈積。
該a-C:H層可在基材溫度維持在從約0℃至約800℃的腔室內從該碳氫化合物來源沈積,例如在從約0℃至約100℃的溫度下,或在從約300℃至約480℃的溫度下,例如,從約400℃至約450℃。已觀察到在增加的溫度下沈積無定形碳膜層會降低沈積速率,因此改善共形性。此外,在增加的溫度下,吸附的碳前驅物之擴散性或流動性會增加,導致更加等向的沈積和改善的共形性。
此外,該a-C:H層也可以更為共形的方式沈積,當該層係在將基材溫度維持在低於約100℃的腔室內從該碳氫化合物來源沈積時。例如,一a-C:H層係藉由透過與該基材表面隔開310密爾的噴頭提供3800sccm的C2 H2 及6000sccm的氦氣至維持在9托耳壓力以及75℃下的製程腔室,並藉由應用30瓦的高頻功率產生電漿來沈積。分析的沈積層展現出77.8%的共形性(共形性的量度係定義為沈積在一特徵結構的側壁上之無定形碳層的平均厚度S對基材上表面上的無定形碳層的平均厚度T的比例)。同樣地,也觀察到該特徵結構底部上的無定形碳層的厚度對比於基材上表面上的無定形碳層的厚度T的比例是72.2%。
同時驚人且不預期地發現到在降低的氦氣流速下,例如約3000sccm的氦氣,溫度低於100℃的沈積在一特徵結構定義底部上的沈積厚度方面產生實質改善,與在密集的特徵結構定義,即每1600平方奈米約9個特徵結構上之該特徵結構底部上的無定形碳層之厚度對比於基材上表面上的無定形碳層的厚度T之比例是72.2%相比。
也觀察到所沈積的無定形碳層之共形性隨著沈積該層時該噴頭和基材表面間的間距增加而改善,例如介於400密爾和600密爾之間的間距,例如約500密爾的間距。例如,一第二無定形碳層與前段在相同的低溫沈積條件下沈積,但是該噴頭間距為500密爾,與310密爾相較。分析的沈積之第二層展現出90.9%至91.7%的共形性(共形性的量度係定義為沈積在一特徵結構的側壁上之無定形碳層的平均厚度S對基材上表面上的無定形碳層的平均厚度T的比例)。同樣地,也觀察到在具有不同密度的特徵結構圖案上,例如密集的特徵結構定義,即每1600平方奈米約4至20個特徵結構,例如9個特徵結構定義,對比於較不密集的,每1600平方奈米低於4個特徵結構定義,例如1個特徵結構定義,的特徵結構定義,該特徵結構底部上的無定形碳層的厚度對比於基材上表面上的無定形碳層的厚度T的比例是90.9%至91.7%,。
也觀察到該500密爾間距的無定形碳層具有約138埃/分鐘的沈積速率,與該310密爾間距的沈積製程之300埃/分鐘的沈積速率相比。
該碳氫化合物來源及一電漿起始氣體係經通入該腔室內,並且起始一電漿以開始沈積。可用一雙頻RF系統來產生該電漿。咸信一雙頻RF功率應用可提供通量和離子能量的獨立控制,因為咸信衝擊該薄膜表面的該等離子之能量會影響薄膜密度。相信該高頻電漿控制電漿密度,而一低頻電漿控制衝擊該基材表面的離子之動能。具有混合的RF功率之雙頻來源提供範圍從約10MHz至約30MHz的高頻功率,例如約13.56MHz,以及範圍從約10kHz至約1MHz的低頻功率,例如約350kHz。當使用一雙頻RF系統來沈積一a-C:H膜時,該第二RF功率對總混合頻率功率的比例較佳地低於約0.6至1.0(0.6:1)。可基於基材尺寸和所用設備來改變所施加的RF功率和一或多種頻率的使用。可使用一單頻RF功率應用,並且通常是應用如在此所述之高頻功率。
可藉由施加功率密度對基材表面積從約0.01瓦/平方公分至約5瓦/平方公分的RF功率來產生電漿,例如從約0.01至約1瓦/平方公分,例如約0.1瓦/平方公分。就一300毫米的基材而言,該功率應用可從約1瓦至約2000瓦,例如從約10瓦至約200瓦,例如約20瓦。電極間距,即該基材和該噴頭之間的距離,可以是從約200密爾至約1000密爾。
雖未遵循任何特定理論,但相信電漿製程藉由減少能量化離子數目來降低無定形碳沈積速率,使碳氫化合物,即自由基,以更隨機的沈積圖案抵達該基材表面,因此提供所形成的薄膜成長更等向的沈積圖案而改善共形性。也觀察到該降低的電漿沈積可提供較低的沈積速率,其容許吸附的碳前驅物在該基材表面上擴散,而提供更為共形的膜層。
處理300毫米圓形基材之一例示沈積製程運用一種電漿起始氣體,例如氦氣,及一種碳氫化合物來源,例如乙炔(C2 H2 )。該製程可包含供應流速從約400sccm至約8000sccm的電漿起始氣體,例如氦氣,供應流速從約400sccm至8000sccm的碳氫化合物來源,例如乙炔(C2 H2 ),施加從約10瓦至約2000瓦的雙頻RF功率,將腔室壓力維持在從約2托耳至約20托耳,以及將腔室溫度維持在從約25℃至約475℃。此製程範圍提供a-C:H層範圍在約10埃/分鐘至約30000埃/分鐘內的沈積速率以及從約30%至約100%的共形性(沈積在一特徵結構側壁上之一層的平均厚度對相同沈積層在該基材範圍,或上表面,上的平均厚度之比例)。熟知技藝者,在閱讀此間揭示後,可計算出適當的製程參數,以製造沈積速率不同的a-C:H膜。
在該沈積製程之一實施例中,執行複數個獨立的無定形碳沈積以形成一無定形碳層。在該複合沈積製程之一態樣中,一沈積步驟,如在此所述者,之後緊接一暫停步驟,其中電漿起始氣體、一稀釋氣體、及/或前驅物可以降低或無沈積速率的狀態流通。適合的電漿起始氣體、稀釋氣體、及/或前驅物可以從約100sccm至約40000sccm的流速通入該腔室內。若使用該電漿起始氣體即/或一稀釋氣體,可為該暫停步驟起始一電漿。該沈積和暫停步驟然後可重複直到得到預期厚度為止,並且可以循環1至100次,例如循環10至50次,例如循環30次,或者是沈積約1%至約100%之間的無定形碳材料厚度,例如從約2%至約10%的循環,例如約3.3%。一獨立週期的每一次循環可沈積從約1埃至約1000埃厚的無定形碳材料,以形成厚度從約10埃至約15000埃的無定形碳層。該循環沈積製程可使用一或多種上述製程參數調整。
或者,也可抽出氣體,然後在沈積步驟之前或暫停步驟期間再次通入。
咸信一多層沈積方案會降低有效薄膜沈積速率,改善共形性。此外,新沈積的碳原子可在該暫停步驟期間擴散,更進一步改善共形性。一般而言,共形性在一特定無定形碳膜層厚度的層數量增加時(較薄的個別層厚度及較多次重複),並且在暫停步驟時間對沈積步驟時間的比例較大時(低的有效沈積速率)獲得改善。例如,暫停步驟時間對沈積步驟時間的比例可從約100:1至約1:100。藉由調整各別層的厚度和暫停對沈積時間比例,可調整無定形碳膜層的共形性以符合元件需求,因而提供另一種樞紐以改善一特定電漿輔助化學氣相沈積之沈積條件(前驅物、氣體、流速、壓力、溫度、RF功率等)的共形性。
本發明方法之一主要優勢在於優於其他a-C:H沈積製程的共形性增強,如第2圖所示。第2圖示出具有一特徵結構201及一無定形碳層202形成在其上的基材200之概要剖面圖。無定形碳層202示出利用本發明方法沈積之薄膜的典型外觀。就質而言,無定形碳層202係高度共形且完全覆蓋特徵結構201的側壁204和底部203。就量而言,無定形碳層202可擁有從約30%至約100%等級的共形性。例如從約70%至約90%,其中共形性(共形性量度)係定義為沈積在側壁204上的無定形碳層202之平均厚度S對基材200上表面205上的無定形碳層202之平均厚度T的比例。再參見第1圖,非共形之無定形碳層202係經示為具有約5%的共形性。
利用在此所述製程沈積之無定形碳材料的範例如下。
比較範例A:一供比較的無定形碳沈積製程範例包含提供約400sccm的氦氣流速至該處理室,約8000sccm的氬氣流速至該處理室,提供約6000sccm的C3 H6 流速至該處理室,施加約1250瓦的高頻RF功率(13.56MHz),將沈積溫度維持在約300℃,將腔室壓力維持在約4.5托耳,連同約380密爾的間距以在密集區域上以及開放區域階梯覆蓋(共形性量度)產生共形性約20%的無定形碳層。
在一第一範例中,藉由提供約4000sccm的氦氣流速至該處理室,提供約2000sccm的C2 H2 流速至該處理室,施加約50瓦的高頻RF功率(13.56MHz),將沈積溫度維持在約400℃,將腔室壓力維持在約9托耳,連同約300密爾的間距來沈積一無定形碳層,產生187埃/分鐘的沈積速率,並且觀察到達成密集區域約83%至開放區域階梯覆蓋(共形性量度)約96%的共形性。所有範例皆在深寬比約2.1:1的特徵結構上執行。
在一第二範例中,藉由提供約2000sccm的氦氣流速至該處理室,提供約2000sccm的C2 H2 流速至該處理室,施加約100瓦的高頻RF功率(13.56MHz),將沈積溫度維持在約400℃,將腔室壓力維持在約9托耳,連同約300密爾的間距來沈積一無定形碳層,產生516埃/分鐘的沈積速率,並且觀察到達成密集區域約82%至開放區域階梯覆蓋(共形性量度)約86%的共形性。該第一範例及該第二範例皆在深寬比約2.1:1的特徵結構上執行。
在一第三範例中,藉由提供約4000sccm的氦氣流速至該處理室,提供約2000sccm的C2 H2 流速至該處理室,施加約20瓦的高頻RF功率(13.56MHz),將沈積溫度維持在約400℃,將腔室壓力維持在約9托耳,連同約300密爾的間距來沈積一無定形碳層,產生64埃/分鐘的沈積速率,並且觀察到達成密集區域約93%至開放區域階梯覆蓋(共形性量度)約97%的共形性。
在一第四範例中,藉由提供約4000sccm的氦氣流速至該處理室,提供約2000sccm的C2 H2 流速至該處理室,施加約1000瓦的高頻RF功率(13.56MHz),將沈積溫度維持在約400℃,將腔室壓力維持在約7托耳,連同約310密爾的間距來沈積一無定形碳層。
在一第五範例中,利用沈積步驟之後緊接氦氣淨化步驟之14次沈積循環來沈積一無定形碳層。該沈積步驟提供約4000sccm的氦氣流速至該處理室,提供約2000sccm的C2 H2 流速至該處理室,施加約100瓦的高頻RF功率(13.56MHz),將沈積溫度維持在約300℃,將腔室壓力維持在約9托耳,連同約300密爾的間距,產生909埃/分鐘的沈積速率,並且觀察到達成約84%的密集區域覆蓋(共形性量度)。該氦氣淨化步驟係在相同製程參數下執行,除了無C2 H2 流並且無施加RF功率之外。
在一第六範例中,利用沈積步驟之後緊接氦氣淨化步驟之14次沈積循環來沈積一無定形碳層。該沈積步驟提供約400sccm的低氦氣流速至該處理室,提供約400sccm的C2 H2 流速至該處理室,施加約100瓦的高頻RF功率(13.56MHz),將沈積溫度維持在約300℃,將腔室壓力維持在約7托耳,連同約300密爾的間距,產生909埃/分鐘的沈積速率,並且觀察到達成約67%的側壁對頂部共形性,94%的側壁對底部共形性以及72%的底部對頂部共形性。該氦氣淨化步驟係在相同製程參數下執行,除了無C2 H2 流並且無施加RF功率之外。
在一第七範例中,進行在不同功率範圍下沈積的無定形碳層之比較。就兩個製程而言,藉由提供約4000sccm的氦氣流速至該處理室,提供約2000sccm的C2 H2 流速至該處理室,施加約50瓦或20瓦的高頻RF功率(13.56MHz),將沈積溫度維持在約400℃,將腔室壓力維持在約9托耳,連同約300密爾的間距來沈積該無定形碳。該50瓦沈積製程以沈積速率200埃/分鐘產生82%的側壁對頂部共形性,而該20瓦沈積製程以沈積速率64埃/分鐘產生93-97%的側壁對頂部共形性。
在一第八範例中,進行循環相對於單一步驟沈積所沈積出的無定形碳層之比較。就兩個製程而言,藉由提供約4000sccm的氦氣流速至該處理室,提供約2000sccm的C2 H2 流速至該處理室,施加約100瓦的高頻RF功率(13.56MHz),將沈積溫度維持在約400℃,將腔室壓力維持在約9托耳,連同約300密爾的間距來沈積該無定形碳。該單一步驟沈積製程產生51%的側壁對頂部共形性,87%的側壁對底部共形性以及59%的底部對頂部共形性。包含沈積之後緊接一氦氣淨化步驟之14次循環的循環沈積步驟產生71%的側壁對頂部共形性,92%的側壁對底部共形性以及77%的底部對頂部共形性。該氦氣淨化步驟係在相同條件下執行,除了無施加RF功率並且不提供C2 H2 之外。
在一第九範例中,進行兩種循環製程相對於單一步驟沈積所沈積出的無定形碳層之比較。就兩個製程而言,藉由提供約4000sccm的氦氣流速至該處理室,提供約2000sccm的C2 H2 流速至該處理室,施加約50瓦的高頻RF功率(13.56MHz),將沈積溫度維持在約400℃,將腔室壓力維持在約9托耳,連同約300密爾的間距來沈積該無定形碳。該單一步驟沈積製程使用25瓦的RF功率應用並產生密集結構之56%的側壁對頂部共形性及開放結構之87%的側壁對頂部共形性。該第一循環製程之第一循環處理系列使用25次持續7秒、每一者20埃之上述沈積和氦氣冷卻循環,產生密集結構之55%的側壁對頂部共形性及開放結構之82%的側壁對頂部共形性;而該第二系列使用10次持續15秒、每一者50埃之沈積和氦氣循環,產生密集結構之54%的側壁對頂部共形性及開放結構之75%的側壁對頂部共形性。該第二製程之第一循環處理系列使用25次每一者20埃之七秒鐘的沈積循環,產生密集結構之78%的側壁對頂部共形性及開放結構之89%的側壁對頂部共形性;該第二系列使用10次每一者50埃之十五秒鐘的沈積循環,產生密集結構之69%的側壁對頂部共形性及開放結構之89%的側壁對頂部共形性;而該第三系列使用25次每一者20埃之七秒鐘的沈積和13秒鐘的穩定步驟循環,產生密集結構之55%的側壁對頂部共形性及開放結構之92%的側壁對頂部共形性。
第4A-4l圖係使用在此所述之無定形碳層蝕刻一材料層之製程的概要側視圖。在一基材表面(未示出)上沈積一基底材料410,以開始形成一材料堆疊400。該基底材料可以是用來形成半導體元件之一或多種材料,包含矽基材材料、氧化物材料、多晶矽材料、或諸如此類。在該基底材料410上沈積一第一無定形碳層420,並且在該第一無定形碳層420上沈積一第一抗反射層材料430,如第4B圖所示。該無定形碳層可以是能夠從加州聖塔克拉拉的應用材料公司購得之先進曝光圖樣薄膜(APF)材料,或者,如在此所述之無定形碳材料。該第一抗反射層材料430係用來在微影圖案化製程期間控制光線反射。該第一抗反射層材料430可包含二氧化矽、氧氮化矽、氮化矽、或其組合物。該抗反射層材料可以是能夠從加州聖塔克拉拉的應用材料公司購得之DARCTM 材料層。
可在該第一抗反射層材料上依序沈積一第二無定形碳層440和一第二抗反射層材料450,如第4C圖所示。該第二無定形碳層440和該第二抗反射層材料450可以是如沈積層420和第一抗反射層材料430者相同的材料。然後在該第二抗反射層材料450上沈積一光阻層460,例如一光阻劑材料,如第4D圖所示。然後利用一微影製程圖案化該光阻層,產生一圖案化光阻層461,如第4E圖所示。形成在該光阻層461內的第一圖案462係利用一或多個蝕刻製程首先蝕刻該第二抗反射層材料450,然後蝕刻該第二無定形碳層440來轉移至該第二無定形碳層440,而形成一圖案化的第二無定形碳層441。如第4F圖所示。該圖案化的第二無定形碳層441可做為下方材料的硬光罩。該第二抗反射層材料450可利用該一或多個蝕刻製程或利用一分開的製程移除。
在該第一抗反射層材料430和該圖案化的第二無定形碳層441上沈積一共形的無定形碳層470,如第4G圖所示。該共形的無定形碳層可利用在此所述之任何製程沈積。利用一非等向蝕刻製程圖案化該共形的無定形碳層470,以提供側壁無定形碳材料471,如第4H圖所示。該側壁無定形碳材料471的存在容許第二圖案472形成,其具有與否則可在正常情況下利用現行微影製程實現者相比縮小的關鍵尺寸和特徵結構尺寸,即增加的圖案密度。該圖案化的第二無定形碳層441結合該側壁無定形碳材料471可做為下方的第一抗反射層材料430和該第一無定形碳層420的硬光罩層。
然後蝕刻該第一抗反射層材料430以形成具有該第二圖案472之圖案化抗反射層431,如第4I圖所示。在該蝕刻製程期間或利用一後續製程除去該圖案化的第二無定形碳層441和該側壁無定形碳材料471。然後蝕刻該第一無定形碳層420以形成具有欲轉移至下方基底材料410的第二圖案472之圖案化的第一無定形碳層421。然後利用該圖案化的第一無定形碳層421做為硬光罩層來蝕刻該基底材料410,如第4K圖所示,接著除去該圖案化的第一無定形碳層421以提供含有具備該第二圖案472的圖案化基底材料411之基材表面,如第4L圖所示。
在另一實施例中,為第4F-4L圖使用一圖案化光阻材料來取代該圖案化的第二無定形碳層441,因此除去對於第4C-4E圖之該圖案化的第二無定形碳層440和一第二抗反射層材料450以及對應的沈積步驟和蝕刻步驟的需要。
第5A-5H圖係在一空間光罩雙重圖案化製程內使用在此所述之無定形碳層之製程的概要側視圖。在一基材表面上沈積一基底材料510,以開始形成一材料堆疊500。該基底材料可以是用來形成半導體元件之一或多種材料,包含矽基材材料、氧化物材料、多晶矽材料、或諸如此類。在該基底材料510上沈積一第一無定形碳層520,並且在該第一無定形碳層520上形成具有一第一圖案532的圖案化光阻層530,如第5A圖所示。該無定形碳層可以是能夠從加州聖塔克拉拉的應用材料公司購得之先進曝光圖樣薄膜(APF)材料,或者,如在此所述之無定形碳材料。可利用一微影製程來圖案化該光阻層530。然後使該圖案化光阻層530經受一修整製程,藉此窄化該圖案化光阻材料的寬度而形成由該經修整的光阻材料531界定之第二圖案533,如第5B圖所示。然後蝕刻該第一無定形碳層520以轉移該第二圖案533,而形成一圖案化的無定形碳層521,如第5C圖所示。
然後鄰接該圖案化的無定形碳層521結構形成側壁間隙壁540。間隙壁可包含一種蝕刻速率與該第一無定形碳層或共形的無定形碳材料不同的可蝕刻材料。適合的材料包含,例如,二氧化矽、氧氮化矽、氮化矽、或其組合物。然後在該等側壁間隙壁540及圖案化的無定形碳層521結構上沈積共形的無定形碳材料之縫隙填補層550,如第5E圖所示。可利用在此所述之任何製程來沈積該共形的無定形碳材料。較佳的共形的無定形碳材料是蝕刻性質與圖案化的無定形碳層521相似者。然後回蝕該縫隙填補層550以暴露出該等側壁間隙壁540,如第5F圖所示。接著蝕刻該等側壁間隙壁540以暴露出基底材料510,界定出一硬光罩層551,如第5G圖所示。然後可圖案化蝕刻該基底材料510以形成一圖案化基底材料511,如第5H圖所示。
在另一製程中,在如第5D圖所示般鄰接該圖案化的無定形碳層521結構形成該等側壁間隙壁540之後,接著將該圖案化的無定形碳層521從該基材表面去除。該等側壁間隙壁540於是形成一圖案,如第5E’所示,其可用來做為該基底材料510的硬光罩。接著可圖案化蝕刻該基底材料510以形成一圖案化基底材料511。
第6A-6J圖係使用在此所述之無定形碳層來蝕刻一材料層,例如利用低於100度的無定形碳沈積製程,的製程之概要側視圖。在一基材表面(未示出)上沈積一基底材料610,以開始形成一材料堆疊600。該基底材料可以是用來形成半導體元件之一或多種材料,包含矽基材材料、氧化物材料、多晶矽材料、或諸如此類。在該基底材料610上沈積一第一無定形碳層620,並且在該第一無定形碳層620上沈積一抗反射層材料630,如第6B圖所示。該無定形碳層可以是能夠從加州聖塔克拉拉的應用材料公司購得之先進曝光圖樣薄膜(APF)材料,或者,如在此所述之無定形碳材料。該抗反射層材料630係用來在微影圖案化製程期間控制光線反射。該抗反射層材料630可包含二氧化矽、氧氮化矽、氮化矽、或其組合物。該抗反射層材料可以是能夠從加州聖塔克拉拉的應用材料公司購得之DARCTM 材料層。
然後在該抗反射層材料630上沈積一光阻層640,例如一光阻劑材料,如第6C圖所示。接著利用一微影製程圖案化該光阻層,產生一圖案化光阻層641,如第6D圖所示。該圖案化光阻層641形成一第一蝕刻圖案642。
利用在此所述製程及共形性共形地或實質上共形地在該圖案化光阻層641上沈積一第二無定形碳層650,如第6E圖所示。該共形的無定形碳層可利用在此所述之任何製程沈積。在一範例中,該第二無定形碳材料係利用低於100℃的沈積製程沈積。蝕刻並圖案化該第二無定形碳層650以形成一第二蝕刻圖案652,其具有比該第一蝕刻圖案縮小的,例如較窄的,特徵結構尺寸,如第6F圖所示。利用一非等向蝕刻製程圖案化該共形的第二無定形碳層650,以提供側壁無定形碳材料651。
該側壁無定形碳材料651的存在容許第二圖案652形成,其具有與否則可在正常情況下利用現行微影製程實現者相比縮小的關鍵尺寸和特徵結構尺寸,即增加的圖案密度。藉由此製程,形成在該光阻層內之特徵結構定義的尺寸,例如關鍵尺寸,可縮減(“縮小”),以在下方層內提供較精細的特徵結構圖案。該圖案化光阻層641結合該側壁無定形碳材料651可做為下方的抗反射層材料630和該第一無定形碳層620的硬光罩層。
以該側壁無定形碳材料651及該光阻層641形成的第二蝕刻圖案652係利用一或多個蝕刻製程首先蝕刻該抗反射層材料630,如第6G圖般,然後蝕刻該第一無定形碳層620,如第6H圖般,來轉移至該第一無定形碳層620,而形成一圖案化的第一無定形碳層621。該圖案化的第一無定形碳層621可做為下方基底材料610的硬光罩。該抗反射層材料631可在蝕刻該下方材料之前利用該一或多個蝕刻製程或利用一分開的製程移除。
接著蝕刻該第一無定形碳層620以形成具有欲轉移至下方基底材料610的第二蝕刻圖案652之圖案化的第一無定形碳層621,如第6H圖所示。然後利用該圖案化的第一無定形碳層621做為硬光罩層來蝕刻該基底材料610,如第6I圖所示,接著除去該圖案化的第一無定形碳層621以提供含有具備該第二蝕刻圖案652的圖案化基底材料611之基材表面,如第6J圖所示。
第7圖係在此設置在一半導體結構中的無定形碳層的使用之概要側視圖。第7圖揭示利用在此所述製程之一沈積的無定形碳層的使用,其係用來作為倒T形閘極700的犧牲側壁光罩。在該基材710上沈積一通道氧化物層720。在該通道氧化物層上沈積一摻雜的多晶矽層730,並在該摻雜的多晶矽層730上沈積一高熱氧化物(HTO)層740。在該高熱氧化物(HTO)740上沈積一光罩層750。圖案化該光罩層750並蝕刻該氧化物層740和該摻雜的多晶矽層730,以形成特徵結構755。利用在此所述方法之一沈積的無定形碳層760係沈積在該蝕刻基材表面上,以形成所製造的特徵結構755之側壁覆蓋。
雖然前述係針對本發明實施例,但本發明之其他及進一步實施例可在不背離其本範圍下設計出,並且其範圍係由如下申請專利範圍界定。
100、200、710...基材
111、201、755...特徵結構
112、202、420、421、440、441、470、520、521、620、621、650、760...無定形碳層
114、204...側壁
203...底部
205...基材上表面
300...基材處理系統
302...真空幫浦
306...電源供應器
310...控制單元
312...中央處理單元
314...支撐電路
316...控制軟體
320...噴頭
325...製程腔室
330...氣體分配盤
350...基材支撐座
360...支桿
370...加熱器元件
372...溫度感應器
390...基材
392...電漿
395...基材表面
400、500、600...材料堆疊
410、411、510、511、610、611...基底材料
430、431、450、630...抗反射層材料
460、461、530、531、640、641...光阻層
462、532、642...第一圖案
471、651...側壁無定形碳材料
472、533、652...第二圖案
540...側壁間隙壁
550...縫隙填補層
551...硬光罩層
700...閘極
720...通道氧化物層
730...多晶矽層
740...高熱氧化物層
750...光罩層
因此可以詳細暸解上述本發明之特徵結構的方式,即對本發明更明確的描述,簡短地在前面概述過,可藉由參考實施例來得到,其中某些在附圖中示出。但是應注意的是,附圖僅示出本發明之一般實施例,因此不應視為係對其範圍之限制,因為本發明可允許其他等效實施例。
第1圖(先前技藝)係具有一特徵結構及一非共形無定形碳層形成在其上的基材之概要剖面圖。
第2圖係具有一特徵結構及一無定形碳層形成在其上的基材之概要剖面圖。
第3圖係可用來執行根據本發明實施例之無定形碳層沈積的基材處理系統之概要示意圖。
第4A-4L圖係使用在此所述之無定形碳層來蝕刻一材料層的製程之一實施例的概要側視圖。
第5A-5H及5E’圖係在一空間光罩雙重圖案化製程中使用在此所述之無定形碳層的製程之一實施例的概要側視圖。
第6A-6J圖係使用在此所述之無定形碳層來蝕刻一材料層的製程之另一實施例的概要側視圖。
第7圖係在此設置在一半導體結構中的無定形碳層的使用之概要側視圖。
為促進了解,在可能時使用相同的元件符號來表示該等圖式共有的相同元件。預期到一實施例的元件及/或製程步驟可有利地併入其他實施例而不需特別詳述。
200...基材
201...特徵結構
202...無定形碳層
203...底部
204...側壁
205...基材上表面

Claims (17)

  1. 一種在一基材上形成一無定形碳層的方法,至少包含以下步驟:將一基材設置在一基材處理室內;執行一沈積循環,該沉積循環包含以下步驟:將碳對氫原子比大於1:2的一碳氫化合物來源通入該處理室;將選自由氫氣、氦氣、氬氣、氮氣、及它們的組合物所組成的族群之一電漿起始氣體通入該處理室,並且該碳氫化合物來源的體積流速對該電漿起始氣體的體積流速比為1:2或更大;在該處理室內以1瓦/平方公分或更低的RF功率密度、2托耳或更高的壓力、以及約300℃至約480℃的溫度產生一電漿;在該基材上形成一共形無定形碳層;以及在形成該共形無定形碳層之後,藉由使一淨化氣體流動通過該處理室而執行一淨化處理步驟,其中該淨化處理步驟包含一暫停步驟時間且形成該共形無定形碳層包含一沈積步驟時間,其中該暫停步驟時間對該沈積步驟時間的比例從約100:1至約1:100;以及重複該沈積循環2至50次。
  2. 如申請專利範圍第1項所述之方法,其中該沈積循環 更包含將一稀釋氣體通入該處理室內,連同該氫氣前驅物、該電漿起始氣體、或兩者。
  3. 如申請專利範圍第1項所述之方法,其中該碳氫化合物來源的碳對氫原子比為2:3或更高,並且該碳氫化合物來源包含一或多種選自由乙炔、乙烯乙炔、苯、苯乙烯、甲苯、二甲苯、吡啶、苯乙酮、酚、呋喃、C3 H2 、C5 H4 、氟苯、二氟苯、四氟苯、及六氟苯所組成的族群之化合物。
  4. 如申請專利範圍第1項所述之方法,其中該碳氫化合物氣體的體積流速對該電漿起始氣體的體積流速比係從約1:1至約1:2。
  5. 如申請專利範圍第1項所述之方法,其中該RF功率密度係經施加約0.01至約1瓦/平方公分。
  6. 如申請專利範圍第1項所述之方法,其中該壓力係從約2托耳至約20托耳。
  7. 如申請專利範圍第1項所述之方法,其中RF功率係由一雙頻系統提供。
  8. 如申請專利範圍第1項所述之方法,其中該共形無定 形碳層擁有從約30%至約100%的共形性。
  9. 如申請專利範圍第1項所述之方法,其中該淨化氣體包含一惰性氣體或一碳氫化合物來源氣體。
  10. 一種在一基材上形成一無定形碳層的方法,至少包含以下步驟:將一基材設置在一基材處理室內;執行一沈積循環,該沉積循環包含以下步驟:將碳對氫原子比大於1:2的一碳氫化合物來源通入該處理室;將選自由氫氣、氦氣、氬氣、氮氣、及它們的組合物所組成的族群之一電漿起始氣體通入該處理室,並且該碳氫化合物來源的體積流速對該電漿起始氣體的體積流速比為1:2或更大;在該處理室內以1瓦/平方公分或更低的RF功率密度、2托耳或更高的壓力、以及約300℃至約480℃的溫度產生一電漿;在該基材上形成一共形無定形碳層;以及在形成該共形無定形碳層之後,藉由使一淨化氣體流動通過該處理室而執行一淨化處理步驟,其中該淨化氣體被激發成一電漿;以及重複該沈積循環2至50次。
  11. 如申請專利範圍第1項所述之方法,其中每一次沈積循環係沈積2%和50%之間的該共形無定形碳層的厚度。
  12. 一種在一基材上形成一無定形碳層的方法,至少包含以下步驟:將一基材設置在一基材處理室內;將碳對氫原子比大於1:2的一碳氫化合物來源通入該處理室;將由氦氣構成之一電漿起始氣體通入該處理室,並且該碳氫化合物來源的體積流速對該電漿起始氣體的體積流速比為1:2或更大,其中該碳氫化合物來源和該電漿起始氣體係利用設置在距離基材表面400密爾和600密爾之間的一氣體分配器通入該處理室;在該處理室內以1瓦/平方公分或更低的RF功率、9托耳的壓力、以及75℃的溫度產生一電漿;以及在該基材上形成一共形無定形碳層。
  13. 如申請專利範圍第12項所述之方法,其中該共形無定形碳層擁有約72%的共形性。
  14. 如申請專利範圍第13項所述之方法,其中該共形無定形碳層被形成在每1600平方奈米的基材表面的約9個特徵結構定義上。
  15. 如申請專利範圍第12項所述之方法,其中該氣體分配器距離基材表面500密爾。
  16. 如申請專利範圍第15項所述之方法,其中該共形無定形碳層擁有約90%或更高的共形性。
  17. 如申請專利範圍第16項所述之方法,其中該共形無定形碳層被形成在每1600平方奈米的基材表面的介於4至20個特徵結構定義上。
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US8105465B2 (en) 2012-01-31
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