TW201417173A - 矽-碳-氮化物之選擇性蝕刻 - Google Patents
矽-碳-氮化物之選擇性蝕刻 Download PDFInfo
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- 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
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- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
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- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
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- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
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Abstract
茲描述蝕刻圖案化異質結構上曝露的含-矽-氮-和-碳材料的方法,該方法包括由含氟前驅物和含氧前驅物形成的遠端電漿蝕刻。來自遠端電漿的電漿流出物流入基板處理區域,在基板處理區域該電漿流出物與含-矽-氮-和-碳材料的曝露區域反應。該電漿流出物與該圖案化異質結構反應,以選擇性地從該曝露的含-矽-氮-和-碳材料區域去除含-矽-氮-和-碳材料,同時非常緩慢地去除選定的其他曝露材料。
Description
本專利申請案主張於2012年09月20日提出申請且標題為「矽-碳-氮化物之選擇性蝕刻(SILICON-CARBON-NITRIDE SELECTIVE ETCH)」的美國臨時專利申請案第61/703,612號的優先權權益,為了所有的目的將該申請案以引用方式全部併入本文中。
本發明係關於矽-碳-氮化物之選擇性蝕刻。
積體電路能夠被製作出係藉由在基板表面上產生錯綜複雜的圖案化材料層的製程。在基板上產生圖案化材料需要控制的方法,以去除曝光的材料。化學蝕刻被用於各式各樣的目的,包括將光阻中的圖案轉入下面的層,即已經存在表面上的薄化層或特徵的薄化橫向尺寸。往往理想的是擁有一種蝕刻一種材料的速度比蝕刻另一種材料的速度更快的蝕刻製程,以有助於例如圖案轉移製程進行。這樣的蝕刻製程即所謂的對第一種材料有選擇性。材料、電路及製程具有多樣性的結果是,已經開發出具有對各種材料的選擇性之蝕刻
製程。然而,對於選擇性地蝕刻矽碳氮化物仍有一些選擇。
乾蝕刻製程對於選擇性地從半導體基板去除材料往往是理想的。此理想性源自於以最小的物理干擾和緩地從微型結構去除材料的能力。乾式蝕刻製程也允許藉由去除氣相試劑來突然停止蝕刻速率。某些乾式蝕刻製程牽涉到將基板曝露於由一或更多個前驅物形成的遠端電漿副產物。例如,當電漿流出物流入基板處理區域時,氨和三氟化氮的遠端電漿激發使得氧化矽可被選擇性地從圖案化基板去除。某些選擇性的遠端電漿蝕刻製程會產生固體副產物,當基板材料被去除時該固體副產物生長在基板的表面上。當後續基板的溫度升高時,該固體副產物經由昇華被去除。產生固體副產物的結果是,SiconiTM蝕刻製程會使在被蝕刻材料的曝露區域中或附近形成的微細剩餘結構變形。
一種理想地選擇性去除矽-碳-氮化物的氣相方法,且不會形成固體副產物。
茲描述蝕刻圖案化異質結構上曝露的含-矽-氮-和-碳材料的方法,該方法包括由含氟前驅物和含氧前驅物形成的遠端電漿蝕刻。來自遠端電漿的電漿流出物流入基板處理區域,在基板處理區域該電漿流出物與含-矽-氮-和-碳材料的曝露區域反應。該電漿流出物與該圖案化異質結構反應,以選擇性地從該曝露的含-矽-氮-和-碳材料區域去除含-矽-氮-和-碳材料,同時非常緩慢地去除選定的其他曝露材料。含-矽-氮-和-碳材料的選擇性是遠端電漿和基板處理區域之間存
在離子抑制元素所致。該離子抑制元素控制到達基板的離子性帶電物種之數量。可以使用該方法來選擇性地以比曝露的氧化矽或曝露的氮化矽更快的速率去除含-矽-氮-和-碳材料。
本發明之實施例包括在基板處理腔室之基板處理區域中蝕刻圖案化基板的方法。該圖案化基板具有曝露的含-矽-氮-和-碳區域。該方法包含使含氟前驅物和含氧前驅物中之每一者流入流體耦接至該基板處理區域的遠端電漿區域,同時在該電漿區域中形成電漿,以產生電漿流出物。該方法進一步包括藉由使該電漿流出物經由噴灑頭中的通孔流入該基板處理區域而蝕刻該曝露的含-矽-氮-和-碳區域。
在以下的部分描述中提出另外的實施例與特徵,而且對於本技術領域中具有通常知識者而言,在檢視本說明書之後,部分的該等實施例與特徵將變得顯而易見,或者是可藉由實施揭示的實施例而學習部分的該等實施例與特徵。藉由說明書中描述的手段、組合以及方法可實現及獲得揭示的實施例之特徵與優點。
110‧‧‧操作
120‧‧‧操作
125‧‧‧操作
130‧‧‧操作
135‧‧‧操作
145‧‧‧操作
1001‧‧‧基板處理腔室
1010‧‧‧遠端電漿系統
1011‧‧‧氣體入口組件
1012‧‧‧第一通道
1013‧‧‧第二通道
1020‧‧‧腔室電漿區域
1021‧‧‧蓋體
1024‧‧‧絕緣環
1026‧‧‧長度
1050‧‧‧通孔的最小直徑
1051‧‧‧中空容積
1053‧‧‧噴灑頭
1055‧‧‧小孔
1056‧‧‧通孔
1070‧‧‧基板處理區域
1100‧‧‧系統
1102‧‧‧FOUP
1104‧‧‧機器人手臂
1106‧‧‧低壓保持區域
1108a‧‧‧處理腔室
1108b‧‧‧處理腔室
1108c‧‧‧處理腔室
1108d‧‧‧處理腔室
1108e‧‧‧處理腔室
1108f‧‧‧處理腔室
1110‧‧‧第二機器人手臂
1155‧‧‧氣體處理系統
1157‧‧‧系統控制器
藉由參照本說明書的剩餘部分及圖式可以實現對揭示的實施例之本質與優點的進一步瞭解。
第1圖為依據所揭示實施例的碳化矽選擇性蝕刻製程之流程圖。
第2A圖圖示依據本發明之實施例的基板處理腔室。
第2B圖圖示依據本發明之實施例的基板處理腔室之噴灑頭。
第3圖圖示依據本發明之實施例的基板處理系統。
在附圖中,相似的組件及/或特徵可以具有相同的參考標號。此外,相同類型的各個組件可以藉由在該參考標號之後接續破折號和第二標號來進行區分,該第二標號可以在類似的組件之間進行區分。假使只在說明書中使用第一參考標號,則該描述係適用於任何一個具有相同第一參考標號的類似組件,而與第二參考標號無關。
茲描述蝕刻圖案化異質結構上曝露的含-矽-氮-和-碳材料的方法,該方法包括由含氟前驅物和含氧前驅物形成的遠端電漿蝕刻。來自遠端電漿的電漿流出物流入基板處理區域,在基板處理區域該電漿流出物與含-矽-氮-和-碳材料的曝露區域反應。該電漿流出物與該圖案化異質結構反應,以選擇性地從該曝露的含-矽-氮-和-碳材料區域去除含-矽-氮-和-碳材料,同時非常緩慢地去除選定的其他曝露材料。含-矽-氮-和-碳材料的選擇性是遠端電漿和基板處理區域之間存在離子抑制元素所致。該離子抑制元素控制到達基板的離子性帶電物種之數量。可以使用該方法來選擇性地以比曝露的氧化矽或曝露的氮化矽更快的速率去除含-矽-氮-和-碳材料。
離子抑制元素的功能是減少或消除從電漿產生區域前往基板的離子性帶電物種。不帶電的中性和自由基物種可以通過離子抑制器中的開口,以在基板發生反應。應該注意的是,完全消除基板周圍的反應區域中的離子性帶電物種並非總是所期望的目標。在許多情況下,需要離子物種到達基
板,以進行蝕刻及/或沉積製程。在這些情況下,離子抑制器有助於將反應區域中的離子物質濃度控制在可協助製程的水平。
依據本發明的一些實施例,可以使用如示例性的設備部分中描述的離子抑制器來提供用於選擇性地蝕刻基板的自由基及/或中性物種。例如在一個實施例中,使用離子抑制器來提供含氟和氧的電漿流出物,以選擇性地蝕刻含-矽-氮-和-碳材料。使用電漿流出物可以得到高達約4000:1或以上的含-矽-氮-和-碳材料對氧化矽的蝕刻速率選擇性。可以使用離子抑制器來提供自由基濃度比離子更高的反應氣體。因為電漿的大部分帶電粒子被離子抑制器過濾或去除,所以在蝕刻製程過程中基板通常沒有偏壓。使用自由基和其他中性物種的這種製程與傳統包括濺射和轟擊的電漿蝕刻製程相比可以減少電漿損傷。本發明的實施例也優於傳統的濕式蝕刻製程,傳統的濕式蝕刻製程中液體的表面張力會導致小的特徵彎曲和剝離。
為了更好地瞭解和理解本發明,現在參照第1圖,第1圖為依據所揭示實施例的碳化矽選擇性蝕刻製程之流程圖。矽碳氮化物是含-矽-氮-和-碳材料的實例。在第一操作之前,圖案化基板中形成了結構。該結構具有矽碳氮化物和氧化矽的個別曝露區域。然後基板被輸送到處理區域(操作110)。
三氟化氮的流動被引入與處理區域分開的電漿區域(操作120)。可以使用其他來源的氟來增加或取代三氟化
氮。一般情況下,可以使含氟前驅物流入電漿區域,並且該含氟前驅物包含至少一選自於由原子氟、雙原子氟、三氟化溴、三氟化氯、三氟化氮、氟化氫、六氟化硫及二氟化氙所組成之群組的前驅物。甚至可以將含碳前驅物,例如四氟化碳、三氟甲烷、二氟甲烷、氟甲烷及類似者添加到已列出的群組中。使用含碳前驅物通常需要流量增加的本文所述含氧前驅物。本文中可以將分離的電漿區域稱為遠端電漿區域,而且該分離的電漿區域可以在與處理腔室不同的模組內或在該處理腔室內的隔室內。也使氧氣(O2)流入電漿區域(操作125),其中氧氣在電漿中與三氟化氮一起被激發。一般來說,可以使含氧前驅物流入電漿區域,並且該含氧前驅物可以包含至少一選自O2、O3、N2O、NO、NO2或類似者的前驅物。
本發明的實施例保持高的氧(O)對氟(F)原子流動速率,以實現含-矽-氮-和-碳薄膜本身在製造中使用的蝕刻速率。本質上,氧的存在有助於從含-矽-氮-和-碳薄膜清除碳。在一個實施例中,發現在1:1和4:1之間的氣體流量比(O2:NF3),或更一般的是在2:3和8:3之間的原子流量比(O:F)實現了50-100/分鐘或更高的可製造蝕刻速率。在不同的實施例中,本發明也可以利用在約0.5:1或以上的O:F比、在約1:1或以上的O:F比或在約2:1或以上的O:F比。在本發明的實施例中,O:F原子流量比可以為低於或約10:1、低於或約6:1、低於或約5:1或低於或約4:1。原子流量比的上限可以與下限組合,以形成其他的實施例。更高的範圍通常
用於含有碳的含氟前驅物。更一般的O:F原子流量比係計算自每個前驅物氣體的氣體流動速率和每個分子中每個原子的總數。在一個前驅物是O2且另一個前驅物是NF3的實施例中,每個氧分子包括兩個氧原子,而每個三氟化氮分子包括3個氟原子。使用質量流量控制器來保持例如1:1以上的氣體流量比將產生2:3以上的原子流量比。在另一個實施例中,前驅體氣體包括至少一種同時含有氧和氟的氣體。計算原子流量比時係包括所有貢獻者的原子流動速率。
然後遠端電漿區域中形成的電漿流出物流入基板處理區域(操作130)。圖案化基板被選擇性地蝕刻(操作135),使得曝露的矽碳氮化物被以比曝露的氧化矽大至少20倍的速率去除。反應性化學物種被從基板處理區域去除,然後從處理區域移出基板(操作145)。進入電漿中的氧氣流(O2)和產生的進入基板處理區域的含氧激發物種流使得電漿流出物中的含氟激發物種去除矽碳氮化物。進入基板處理區域的含氧激發物種流對氧化矽的曝露區域影響不大,所以含氟激發物種基本上無法蝕刻氧化矽區域。在蝕刻操作過程中,該基板處理區域是無電漿的,以確保含-矽-氮-和-碳層的高蝕刻選擇性。
使用含氧前驅物增加了矽碳氮化物的蝕刻速率,且對氧化矽的蝕刻速率有最小的影響。含氟前驅物及/或含氧前驅物可以進一步包括一或更多種相對惰性的氣體,例如He、N2、Ar或類似者。可以使用惰性氣體來改善電漿的穩定性。可以使用不同氣體的流動速率和比例來控制蝕刻速率和蝕刻
選擇性。在一實施例中,含氟氣體包括流動速率在約5sccm和300sccm之間的NF3、流動速率在約5sccm和1500sccm之間的O2、流動速率在約0sccm和3000sccm之間的He以及流動速率在約0sccm和3000sccm之間的Ar。本技術領域中具有通常知識者將理解的是,其他氣體及/或流量的使用可以取決於數個因素,包括處理腔室的架構、基板的尺寸、幾何形狀及被蝕刻特徵的佈局以及類似者。一些含氫前驅物也可以與其他的前驅物相結合或個別流入電漿區域,然而應保持低的濃度。氫可以在電漿中與含氟前驅物相互作用以形成前驅物,而藉由在氧化物表面上形成固體殘餘副產物來去除氧化矽。與曝露的氧化矽區域相比,此反應降低曝露的矽碳氮化物區域的選擇性。在一些實施例中,雖然引入一些氫可能是有用的,但在揭示的實施例中,在蝕刻製程的過程中也可能沒有或基本上沒有含氫前驅物流入電漿區域。在本發明的實施例中,含氟前驅物和電漿流出物可以是基本上沒有氫的。
該方法還包括當含氟前驅物和含氧前驅物在遠端電漿區域中時施加能量給含氟前驅物和含氧前驅物來產生電漿流出物。如本技術領域中具有通常知識者可理解的,電漿可以包括許多帶電的和中性的物種,包括自由基和離子。可以使用習知的技術(例如射頻(RF)、電容耦合、感應耦合及類似者)來產生電漿。在一實施例中,能量係使用源功率在約10瓦和2000瓦之間且壓力在約0.2托和30托之間的電容耦合電漿單元來施加。電容耦合電漿單元可以位於處理腔室之
氣體反應區域的遠端。例如,電容耦合電漿單元和電漿產生區域可以藉由離子抑制器與氣體反應區域分離。
一些可能機制的討論可以證明是有效益的,但不希望申請專利範圍的涵蓋面受到可能是或可能不是完全正確的理論機制所限制。藉由輸送含氟前驅物和含氧前驅物進入遠端電漿區域來同時產生自由基-氟前驅物和自由基-氧前驅物。申請人假設產生某濃度的自由基-氟片段、氟離子及原子並將該等自由基-氟片段、氟離子及原子輸入基板處理區域。申請人進一步假設自由基-氧物種被同時輸送到基板處理區域。自由基-氧物種可以在近表面區域與碳反應,以在矽碳氮化物區域的曝露表面附近產生富含矽的區域。在此反應過程中可能產生的揮發性物種可能包括二氧化碳(CO2),然後可以經由流體耦接至基板處理區域的排氣系統抽出二氧化碳。矽碳氮化物的富含矽近表面區域可以被基板處理區域內同時可用的自由基-氟前驅物蝕刻。氧化矽區域基本上不受自由基-氧影響。自由基-氟前驅物對矽具有高度的選擇性,而留下基本上未被蝕刻的氧化矽。結果,本文概述的蝕刻方法對含-矽-氮-和-碳材料實現了選擇性。一般來說,本文提出的蝕刻方法之選擇性可以具有大於或約50:1、大於或約100:1、大於或約150:1或大於或約250:1的選擇性(含-矽-氮-和-碳材料:氧化矽)。該選擇性、非局部電漿、控制的離子濃度及沒有固體副產物中的每個皆使這些蝕刻製程非常適用於以極少的變形來去除或修整微細的含-矽-氮-和-碳材料結構,並且同時去除極少的氧化矽或未去除氧化矽。這些選擇性也普遍適用於不久
將要描述的含-矽-氮-和-碳材料。
除了或取代曝露的氧化矽區域,在本文的蝕刻操作過程中也可以是圖案化基板上曝露的氮化矽區域。在本發明的實施例中,蝕刻操作的選擇性(曝露的含-矽-氮-和-碳區域:曝露的氮化矽區域)可以是大於或約2:1、大於或約3:1或大於或約4:1。使用本文揭示的蝕刻製程,碳化矽和矽碳氮化物的蝕刻速率較相似,而氮化矽和矽被蝕刻地較緩慢,如以上所量化。
基板的溫度通常可以在約-30℃和約150℃之間。已經發現在此範圍內的較低溫度下蝕刻速率較高。在實施例中,在本文所述的蝕刻過程中,基板的溫度可以是約0℃或更高、約5℃或更高、或約10℃或更高。在不同的實施例中,基板溫度可以是小於或約50℃、小於或約30℃、小於或約20℃、小於或約15℃或小於或約10℃。該數據進一步顯示蝕刻速率的增加為製程壓力的函數。基板處理區域內的壓力係低於或約50托、低於或約30托、低於或約20托、低於或約10托或低於或約5托。在本發明的實施例中,壓力可以是高於或約0.1托、高於或約0.2托、高於或約0.5托或高於或約1托。溫度或壓力的任何上限可以與下限組合,以形成另外的實施例。一般來說,可以使用本文所述的製程來蝕刻含有矽和碳(不只是碳化矽)的薄膜。遠端電漿蝕刻製程可以去除包括約30%或更高矽原子濃度的含-矽-氮-和-碳材料。在本發明的實施例中,含-矽-氮-和-碳材料中的碳原子濃度可以是大於或約10%、大於或約15%或大於或約20%。
類似地,在本發明的實施例中,含-矽-氮-和-碳材料中的氮原子濃度可以是大於或約10%、大於或約15%或大於或約20%。除了雜質和摻雜劑之外,含-矽-氮-和-碳材料也可以僅由矽、氮及碳所組成。當然,在本發明的實施例中,含-矽-氮-和-碳材料可以是矽碳氮化物。
其他的製程參數係揭示於描述示例性處理腔室和系統的過程中。
可以實施本發明之實施例的處理腔室可以被包括在處理平台內,該處理平台例如CENTURA®和PRODUCER®系統,皆可向美國加州聖克拉拉市的應用材料公司(Applied Materials,Inc.of Santa Clara,Calif.)取得。可以與本發明的示例性方法一起使用的基板處理腔室之實例可以包括在2006年05月30日提出申請、標題為「用於介電質間隙填充的處理腔室(PROCESS CHAMBER FOR DIELECTRIC GAPFILL)」且共同受讓給Lubomirsky等人的美國臨時專利申請案第60/803,499號中所圖示和描述者,為了所有的目的將該專利申請案之全部內容以引用方式併入本文中。另外的示例性系統可以包括美國專利第6,387,207號和第6,830,624號中所圖示和描述者,為了所有的目的將該等專利以引用方式併入本文中。
第2A圖為依據所揭示實施例的基板處理腔室1001。遠端電漿系統1010可以處理含氟前驅物,然後該含氟前驅物經由氣體入口組件1011前進。可以在氣體入口組件
1011內看到兩個截然不同的氣體供應通道。第一通道1012攜帶通過遠端電漿系統(RPS)1010的氣體,而第二通道1013繞過遠端電漿系統1010。在實施例中可以將任一個通道使用於含氟前驅物。另一方面,第一通道1012可用於製程氣體,並且第二通道1013可用於處理氣體。圖示蓋體(或導電頂部)1021和穿孔的分隔板1053之間具有絕緣環1024,絕緣環1024使得AC電勢可被相對於穿孔的分隔板1053施加到蓋體1021。AC電勢在腔室電漿區域1020中擊發電漿。製程氣體經由第一通道1012進入腔室電漿區域1020,並且製程氣體可以在單獨的或與遠端電漿系統1010組合的腔室電漿區域1020中被電漿激發。假使製程氣體(含氟前驅物)流經第二通道1013,則只有腔室電漿區域1020用於激發。本文中可以將腔室電漿區域1020及/或遠端電漿系統1010的組合稱為遠端電漿系統。穿孔的分隔板(也可稱為噴灑頭)1053將腔室電漿區域1020與噴灑頭1053下方的基板處理區域1070分隔。噴灑頭1053允許電漿存在於腔室電漿區域1020中,以避免在基板處理區域1070中直接激發氣體,同時還允許激發的物種從腔室電漿區域1020進入基板處理區域1070。
噴灑頭1053被定位在腔室電漿區域1020和基板處理區域1070之間,並允許遠端電漿系統1010及/或腔室電漿區域1020內產生的電漿流出物(前驅物或其他氣體的激發衍生物)通過複數個通孔1056,通孔1056穿過板材的厚度。噴灑頭1053還具有一或更多個中空容積1051,中空容積1051可以被蒸氣或氣體形式的前驅物填滿,並通過小孔1055進入
基板處理區域1070,但不是直接進入腔室電漿區域1020。可以將中空容積1051用於不需要被電漿激發的前驅物,以實現特定的製程。在此揭示的實施例中,噴灑頭1053的厚度比通孔1056的最小直徑1050之長度更長。為了保持顯著濃度的激發物種從腔室電漿區域1020滲透到基板處理區域1070,可以藉由形成部分貫穿噴灑頭1053的通孔1056之較大直徑部分來限制通孔的最小直徑1050之長度226。在揭示的實施例中,通孔1056的最小直徑1050之長度可以與通孔1056的最小直徑屬於相同數量級或更短。
如第2A圖所圖示,可以設置噴灑頭1053來提供離子抑制器的效用。或者,可以包括分離的處理腔室元件(未圖示),該處理腔室元件抑制流入基板處理區域1070的離子濃度。蓋體1021和噴灑頭1053可以分別發揮作為第一電極和第二電極的功能,所以蓋體1021和噴灑頭1053可以接收不同的電壓。在這些架構中,可以將電功率(例如RF功率)施加於蓋體1021、噴灑頭1053或上述兩者。例如,可以將電功率施加於蓋體1021,同時將噴灑頭1053(作為離子抑制器)接地。基板處理系統可以包括RF產生器,RF產生器提供電功率到蓋體及/或噴灑頭1053。施加於蓋體1021的電壓可以促進腔室電漿區域1020內有均勻分佈的電漿(例如減少局部化電漿)。為了能夠在腔室電漿區域1020中形成電漿,絕緣環1024可以將蓋體1021與噴灑頭1053電絕緣。絕緣環1024可以由陶瓷製作並且可以具有高的崩潰電壓,以避免放電。方才所述靠近電容耦合電漿組件的部分基板處理腔室1001可
以進一步包括冷卻單元(未圖示),該冷卻單元包括一或更多個冷卻流體通道,以使用循環冷卻劑(例如水)冷卻曝露於電漿的表面。
在圖示的實施例中,噴灑頭1053可以(經由通孔1056)分配製程氣體,該製程氣體含有氧、氟及/或氮及/或該製程氣體在腔室電漿區域1020中被電漿激發之後的電漿流出物。在實施例中,被引入遠端電漿系統1010及/或腔室電漿區域1020的製程氣體可以含有氟(例如F2、NF3或XeF2)。該製程氣體還可以包括載送氣體,例如氦氣、氬氣、氮氣(N2)等。電漿流出物可以包括製程氣體的離子化或中性衍生物,而且本文中還可以將電漿流出物稱為自由基-氟前驅物,以指稱引入的製程氣體之原子組份。
通孔1056設以抑制離子化帶電物種遷移出腔室電漿區域1020,同時允許未帶電的中性或自由基物種通過噴灑頭1053進入基板處理區域1070。這些未帶電的物種可以包括高度反應性物種,該等高度反應性物種被以反應性較低的載送氣體經由通孔1056輸送。如以上所注意的,可以減少離子物種經由通孔1056的遷移,而且在一些例子中可以完全抑制離子物種經由通孔1056遷移。控制離子物種通過噴灑頭1053的量對於被帶入而與下方的晶圓基板接觸的氣體混合物提供了增加的控制,進而增加了對於氣體混合物之沉積及/或蝕刻特性的控制。例如,調整氣體混合物的離子濃度可以明顯改變氣體混合物的蝕刻選擇性(例如SiCx:SiOx的蝕刻比)。
在實施例中,通孔1056的數量可以在約60和約2000
之間。通孔1056可以具有各種不同的形狀,但最容易製作成圓形。在揭示的實施例中,通孔1056的最小直徑1050可以在約0.5mm和約20mm之間,或在約1mm和約6mm之間。在選擇通孔的橫截面形狀上也有緯度之分,該橫截面形狀可以是圓錐形、圓柱形或上述兩種形狀之組合。在不同的實施例中,用於將未激發前驅物導入基板處理區域1070的小孔1055之數量可以在約100和約5000之間,或在約500和約2000之間。小孔1055的直徑可以在約0.1mm和約2mm之間。
通孔1056可設以控制電漿活化氣體(例如離子、自由基及/或中性物種)通過噴灑頭1053。例如,可以控制孔的深寬比(例如孔徑對長度)及/或孔的幾何形狀,使得通過噴灑頭1053的活化氣體中離子化帶電物種的流量減少。噴灑頭1053中的通孔1056可以包括面向腔室電漿區域1020的錐形部分以及面向基板處理區域1070的圓柱形部分。可以訂製該圓柱形部分的比例和尺寸,以控制通過進入基板處理區域1070的離子物種流量。還可以施加可調整的電偏壓到噴灑頭1053,以作為控制通過噴灑頭1053的離子物種流量的額外工具。
或者,通孔1056可以在朝向噴灑頭1053的頂部表面處具有較小的內徑(ID)並且在朝向噴灑頭1053的底部表面處具有較大的內徑。此外,可以將通孔1056的底部邊緣去角,以助於在電漿流出物離開噴灑頭時在基板處理區域1070中均勻地分配電漿流出物,藉以促進電漿流出物和前驅物氣
體的均勻分佈。可以沿著通孔1056將較小的內徑放在各個位置,並且仍允許噴灑頭1053減少基板處理區域1070內的離子密度。離子密度的減少是在進入基板處理區域1070之前增加與牆壁的碰撞次數的結果。每個碰撞提高了離子因從牆壁取得或喪失電子而被中和的可能性。一般來說,通孔1056的較小內徑可以在約0.2mm和約20mm之間。在其他實施例中,該較小內徑可以在約1mm和約6mm之間或在約0.2mm和約5mm之間。此外,通孔1056的深寬比(即較小內徑對孔長度)可以為約1至20。通孔的較小內徑可以是沿著通孔的長度找到的最小內徑。通孔1056的橫截面形狀通常可以是圓柱形的、圓錐形的或上述之任意組合。
第2B圖為依據揭示的實施例用於處理腔室的噴灑頭1053之仰視圖。噴灑頭1053與第2A圖中圖示的噴灑頭一致。描繪的通孔1056在噴灑頭1053的底部具有較大的內徑(ID),而且在噴灑頭1053頂部具有較小的內徑。小孔1055大致上均勻地分佈在噴灑頭的表面上,即使在通孔1056之間亦然,這有助於提供比本文所述的其他實施例更均勻的混合。
當含氟電漿流出物和含氧電漿流出物經由噴灑頭1053中的通孔1056到達時,示例性的圖案化基板可以由基座(未圖示)支撐在基板處理區域1070內。雖然可以在基板處理區域1070裝設支援用於其他製程(例如固化)的電漿之配備,但在本發明的實施例中,在圖案化基板的蝕刻過程中並無電漿存在。
電漿可以在噴灑頭1053上方的腔室電漿區域1020
中或噴灑頭1053下方的基板處理區域1070中被點燃。腔室電漿區域1020中存在電漿,以從含氟前驅物的進入流產生自由基-氟前驅物。在處理腔室的導電性頂部(蓋體1021)和噴灑頭1053之間施加通常在射頻(RF)範圍中的交流電壓,以在沉積過程中在腔室電漿區域1020中點燃電漿。RF電源產生13.56MHz的高射頻頻率,但也可能會產生單獨的其他頻率或與13.56MHz頻率結合的其他頻率。
當開啟基板處理區域1070中的底部電漿以固化薄膜或清洗鄰接基板處理區域1070的內表面時,可以使頂部電漿停留在很低或無功率下。藉由在噴灑頭1053和基座或腔室底部之間施加交流電壓來點燃基板處理區域1070中的電漿。可以在電漿存在的同時將清洗氣體引入基板處理區域1070。
基座可以具有熱交換通道,熱交換流體經由該熱交換通道流入,以控制基板的溫度。這種架構允許基板溫度被冷卻或加熱,以保持相對低溫(從室溫到約120℃)。熱交換流體可以包含乙二醇和水。可以使用以平行同心圓形式配置成兩個圈的嵌入式單迴路嵌入式加熱器元件來電阻式加熱基座的晶圓支撐盤(較佳為鋁、陶瓷或上述物質之組合),以實現相對高溫(約120℃至約1100℃)。加熱器元件的外部可以與支撐盤的周邊相鄰,而加熱器元件的內部係沿著具有較小外徑的同心圓路徑。接到加熱器元件的接線通過基座的底桿。
基板處理系統係由系統控制器所控制。在示例性的實施例中,該系統控制器包括硬碟磁碟機、軟碟磁碟機及處
理器。該處理器包含單板電腦(SBC)、類比和數位輸入/輸出板、介面板及步進馬達控制器板。CVD系統的各種部件符合Versa模件歐洲(Versa Modular European,VME)標準,VME標準定義板、卡片機架以及連接器的尺寸和類型。VME標準還定義具有16位元數據匯流排和24位元定址匯流排的匯流排結構。
系統控制器控制蝕刻腔室的所有活動。該系統控制器執行系統控制軟體,該系統控制軟體為儲存在電腦可讀媒體中的電腦程式。較佳地,該媒體為硬碟磁碟機,但該媒體也可以是其他種類的記憶體。該電腦程式包括指令組,該指令組指示時間、氣體混合物、腔室壓力、腔室溫度、RF功率水平、基座位置以及其他特定製程的參數。也可以使用其他儲存在其他記憶體裝置(包括例如軟碟或其他適當的磁碟機)的電腦程式來指示系統控制器。
可以使用由系統控制器執行的電腦程式產品來實施在基板上沉積薄膜堆疊的製程或用於清洗腔室的製程。可以用任何現有的電腦可讀程式語言來撰寫電腦程式譯碼:例如68000組合語言、C、C++、Pascal、Fortran或其他的電腦可讀程式語言。使用現有的文本編輯器將適當的程式譯碼輸入單一檔案或多個檔案中,並儲存或體現於電腦可用媒體中,例如電腦的記憶體系統。假使輸入的譯碼內文屬於高階語言,則編譯該譯碼,然後將產生的編譯譯碼與預編譯的微軟視窗®(Microsoft Windows®)程式館常式之目標譯碼聯結。為了執行該經聯結、編譯的目標譯碼,系統使用者喚起目標
譯碼,致使電腦系統載入記憶體中的譯碼。然後CPU讀取並執行譯碼,以進行程式中確認的任務。
使用者與控制器之間的介面可包含平板觸摸感應式監視器。在較佳的實施例中使用二個監視器,一個組裝於潔淨室牆壁上供操作員使用,而另一個組裝於牆壁外面供服務技師使用。該二個監視器可同時顯示相同的資訊,在任一情況中在同一時間只有一個監視器接受輸入。為了要選擇特殊的畫面或功能,操作員可觸碰觸摸感應式監視器的指定區域。經觸碰的區域會改變其彰顯的顏色,或者會顯示出新的選單或畫面,以確認操作員與觸摸感應式監視器之間的溝通。可以使用其他的裝置(如鍵盤、滑鼠或其他的指向或溝通裝置)來取代該觸摸感應式監視器,或是除了該觸摸感應式監視器之外可同時使用該等其他的裝置,以容許使用者與系統控制器溝通。
可以將腔室電漿區域或遠端電漿系統中的區域稱為遠端電漿區域。在實施例中,自由基前驅物(例如自由基-氟前驅物和自由基-氧前驅物)係形成於遠端電漿區域中並進入基板處理區域,在該基板處理區域中此組合優先蝕刻含-矽-氮-和-碳材料。在實施例中,基本上可以將電漿功率僅施加於遠端電漿區域,以確保自由基-氟前驅物和自由基-氧前驅物在基板處理區域中不會被進一步激發。
在採用腔室電漿區域的實施例中,該激發的電漿流出物係於基板處理區域的分區中產生,該基板處理區域係從沉積區域分割出。沉積區域(本文中亦已知為基板處理區域)
是電漿流出物混合和反應以蝕刻圖案化基板(例如半導體晶圓)之處。該激發的電漿流出物還可以伴隨有惰性氣體(在示例性案例中為氬氣)。在圖案化基板的蝕刻過程中,本文可以將基板處理區域描述為「無電漿」的。「無電漿」並不一定意指該區域是沒有電漿的。由於通孔1056的形狀和尺寸,電漿區域內產生的相對低濃度離子化物種和自由電子確實會通過隔板(噴灑頭/離子抑制器)中的細孔(縫隙)。在一些實施例中,除了無法避免的、無處不在的非故意輻射來源之外,基板處理區域內並無離子化物種和自由電子濃度。在腔室電漿區域中,電漿的邊界是很難界定的,並且可能會經由噴灑頭中的孔侵入該基板處理區域。在感應耦合電漿的情況中,可能會在該基板處理區域內直接激起少量的離子化。此外,可以在該基板處理區域中形成低強度的電漿,而不損害形成的薄膜之理想特徵。在激發的電漿流出物的形成過程中,所有離子密度遠比腔室電漿區域(或對於該事件為遠端電漿區域)低的電漿之起因皆未偏離本文所用的「無電漿」之範圍。
在不同的實施例中,可以使三氟化氮(或另一個含氟前驅物)以約25sccm和約200sccm之間、約50sccm和約150sccm之間或約75sccm和約125sccm之間的速率流入腔室電漿區域1020。在不同的實施例中,可以使氧氣(O2)以約25sccm和約200sccm之間、約50sccm和約150sccm之間或約75sccm和約125sccm之間的速率流入腔室電漿區域1020。
進入腔室的含氟前驅物和含氧前驅物之結合流動速
率可以佔整體氣體混合物的0.05%至約20%體積;其餘的是載送氣體。在實施例中使含氟前驅物和含氧前驅物流入遠端電漿區域,但電漿流出物具有相同的體積流量比。在含氟前驅物的案例中,在該等含氟前驅物氣體穩定遠端電漿區域內的壓力之前可以先使吹洗或載送氣體進入遠端電漿區域。
電漿功率可以有各種的頻率或多種頻率的組合。在示例性的處理系統中,電漿係由蓋體1021和噴灑頭1053之間輸送的RF功率提供。在不同的實施例中,RF功率可以在約10瓦和約2000瓦之間、約20瓦和約1500瓦之間或約50瓦和約500瓦之間。在不同的實施例中,該示例性的處理系統中施加的RF頻率可以是小於約200kHz的低RF頻率、在約10MHz和約15MHz之間的高RF頻率或大於或約1GHz的微波頻率。
在載送氣體和電漿流出物流入基板處理區域1070的過程中,可以將基板處理區域1070保持在各種壓力下。基板處理區域內的壓力為低於或約50托、低於或約30托、低於或約20托、低於或約10托或低於或約5托。在本發明的實施例中,該壓力可以為高於或約0.1托、高於或約0.2托、高於或約0.5托或高於或約1托。可以將壓力的下限與壓力的上限組合,以實現本發明的進一步實施例。
在一或更多個實施例中,可以將基板處理腔室1001整合於各種多處理平台中,該等多處理平台包括可向美國加州聖克拉拉市的應用材料公司取得的ProducerTM GT、CenturaTM AP及EnduraTM平台。這樣的處理平台能夠執行幾
種處理操作而不會破真空。可以實施本發明之實施例的處理腔室除了其他類型的腔室之外還可以包括介電質蝕刻腔室或各種化學氣相沉積腔室。
可以將沉積系統之實施例結合到更大的製造系統中,以製造積體電路晶片。第3圖圖示依據所揭示實施例的一個這樣的沉積、蝕刻、烘烤及固化腔室系統1101。在該圖中,一對FOUP(前開式晶圓傳送盒)1102供應基材基板(例如直徑300毫米(mm)的晶圓),該基板由機器人手臂1104接收,並在被放入其中一個晶圓處理腔室1108a-f之前被放入低壓保持區域1106。可以使用第二機器人手臂1110來在低壓保持區域1106和晶圓處理腔室1108a-f之間來回運送基板晶圓。可以整體配備每個晶圓處理腔室1108a-f,以進行數種基板處理操作,除了循環層沉積(CLD)、原子層沉積(ALD)、化學氣相沉積(CVD)、物理氣相沉積(PVD)、蝕刻、預清洗、除氣、定向及其他的基板製程之外,該基板處理操作還包括本文所述的乾蝕刻製程。
晶圓處理腔室1108a-f可以包括一或更多個系統組件,用於沉積、退火、固化及/或蝕刻基板晶圓上的流動性介電質薄膜。在一個架構中,可以使用兩對處理腔室(例如1108c-d和1108e-f)來在基板上沉積介電質材料,並且可以使用第三對處理腔室(例如1108a-b)蝕刻沉積的介電質。在另一個架構中,可以配置全部的三對腔室(例如1108a-f)來在基板上蝕刻介電質薄膜。可以在與不同的實施例中所圖示的製造系統分離的腔室中進行所描述的任一或更多種製程。
使用系統控制器1157來控制馬達、閥、流量控制器、電源及進行本文所述製程流程所需的其他功能。也可以藉由系統控制器1157來控制氣體處理系統1155,以將氣體引入一個或全部的晶圓處理腔室1108a-f。系統控制器1157可以依賴光感測器的反饋來決定並調整可移動機械組件在氣體處理系統1155及/或晶圓處理腔室1108a-f中的位置。機械組件可以包括在系統控制器1157的控制下由馬達移動的機器人手臂、節流閥及基座。
在示例性的實施例中,系統控制器1157包括硬碟磁碟機(記憶體)、USB接口、軟碟磁碟機及處理器。系統控制器1157包括類比和數位輸入/輸出板、介面板及步進馬達控制器板。含有基板處理腔室1001的多腔室處理系統1101之各種部件係受到系統控制器1157的控制。該系統控制器執行系統控制軟體,該系統控制軟體的形式為儲存在電腦可讀媒體中的電腦程式,該電腦可讀媒體例如硬碟、軟碟或快閃記憶體拇指磁碟機。也可以使用其他類型的記憶體。該電腦程式包括指令組,該指令組指示時間、氣體混合物、腔室壓力、腔室溫度、RF功率水平、基座位置以及其他特定製程的參數。
可以使用由控制器執行的電腦程式產品來實施在基板上蝕刻、沉積或以其他方式處理薄膜的製程或用於清洗腔室的製程。可以用任何現有的電腦可讀程式語言來撰寫電腦程式譯碼:例如68000組合語言、C、C++、Pascal、Fortran或其他的電腦可讀程式語言。使用現有的文本編輯器將適當的程式譯碼輸入單一檔案或多個檔案中,並儲存或體現於電
腦可用媒體中,例如電腦的記憶體系統。假使輸入的譯碼內文屬於高階語言,則編譯該譯碼,然後將產生的編譯譯碼與預編譯的微軟視窗®(Microsoft Windows®)程式館常式之目標譯碼聯結。為了執行該經聯結、編譯的目標譯碼,系統使用者喚起目標譯碼,致使電腦系統載入記憶體中的譯碼。然後CPU讀取並執行譯碼,以進行程式中確認的任務。
使用者與控制器之間的介面可以經由觸摸感應式監視器,並且還可以包括滑鼠和鍵盤。在一個實施例中使用二個監視器,一個組裝於潔淨室牆壁上供操作員使用,而另一個組裝於牆壁外面供服務技師使用。該二個監視器可同時顯示相同的資訊,在任一情況中在同一時間只有一個監視器接受輸入。為了要選擇特殊的畫面或功能,操作員使用手指或滑鼠觸碰顯示螢幕上的指定區域。經觸碰的區域會改變其彰顯的顏色,或者會顯示出新的選單或畫面,以確認操作員的選擇。
本文中使用的「基板」可為支撐基板,該支撐基板上可有或無層形成。圖案化基板可以是絕緣體或具有各種摻雜濃度與分佈的半導體,而且例如該圖案化基板可以是半導體基板,該半導體基板的類型與製造積體電路中所使用的半導體基板類型相同。該圖案化基板的曝露「氧化矽」主要是SiO2,但可以包括其他元素組分的濃度,例如氮、氫、碳及類似者。在一些實施例中,使用本文所述方法蝕刻的氧化矽薄膜主要由矽和氧組成。用語「前驅物」係用以指稱任何製程氣體,該製程氣體參與反應,以從表面去除材料或沉積材
料於基板上。「電漿流出物」描述從腔室電漿區域離開並進入基板處理區域的氣體。電漿流出物係處於「激發態」,其中至少某些氣體分子處於振動激發、離解及/或離子化狀態。「自由基前驅物」係用於描述電漿流出物(處於激發態且激發電漿的氣體),該電漿流出物參與反應,以從表面去除材料或沉積材料於基板上。「自由基氧前驅物」為含有氧但還可以含有其他元素組份的自由基前驅物。「自由基氟前驅物」為含有氟但還可以含有其他元素組份的自由基前驅物。「自由基氧前驅物」和「自由基氟前驅物」分別等同於「含氧電漿流出物」和「含氟電漿流出物」。片語「惰性氣體」係指任何當蝕刻或被併入薄膜中時不會形成化學鍵結的氣體。示例性的惰性氣體包括鈍氣,但也可以包括其他氣體,只要當微量(典型上)陷入薄膜中時無化學鍵結形成即可。
貫穿全文使用用語「縫隙」和「溝槽」,但並非暗示蝕刻出的幾何形狀具有大的水平深寬比。從表面上方觀看,溝槽可能會呈現圓形、橢圓形、多邊形、矩形或各式各樣的其他形狀。溝槽可以處於圍繞材料島嶼的護城河形狀。用語「通孔」是用來指稱低深寬比的溝槽(從上方觀看),該溝槽可能會或可能不會被填充金屬來形成垂直的電連線。如本文中所使用的,保角蝕刻製程係指表面上以與該表面相同的形狀大致均勻地去除材料,亦即被蝕刻層的表面與預先蝕刻的表面大體上是平行的。在本技術領域中具有通常知識之人士將理解到,所蝕刻的界面可能無法100%保角,因此,用語「大體上」容許可接受的誤差。
有了揭示的幾個實施例,在本技術領域中具有通常知識者將理解到,可以在不偏離本發明之精神下使用各種修改、替代結構以及均等物。此外,並未描述數個習知的製程及元件,以避免不必要地混淆本發明。因此,不應將以上描述視為限制本發明之範圍。
當提供數值的範圍時,應瞭解到,除非內文以其他方式清楚指明,否則在該範圍的上限與下限之間、每個到下限單位的十分之一之中間值亦為具體揭示的。在陳述範圍中的任何陳述值或中間值與該陳述範圍中的任何其他陳述值或中間值之間的每個較小範圍亦被涵括。該等較小範圍的上限與下限可獨立地被包括或排除於該範圍中,而且不論是該等較小範圍包括任一限值、不包括二限值或是包括二限值,該等較小範圍中的每個範圍亦被涵括於本發明中,取決於該陳述範圍中任何經具體排除的限值。當該陳述範圍包括該等限值中之一者或二者時,排除該等包括的限值中之任一者或二者的範圍亦被包括。
除非內文以其他方式清楚指明,否則本文中與所附申請專利範圍中使用的單數形「一」及「該」包括複數的指示對象。因此,舉例來說,提及「一製程」係包括複數個該種製程,而提及「該介電質材料」係包括提及一或多個介電質材料及其為本技術領域中具有通常知識者所習知的均等物,以此類推。
同樣地,當用於本說明書中及以下申請專利範圍中時,字眼「包含」與「包括」意欲指明陳述的特徵、整數、
成分或步驟之存在,但該等字眼並不排除一或多個其他的特徵、整數、成分、步驟、動作或基團的存在或加入。
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Claims (20)
- 一種在一基板處理腔室之一基板處理區域中蝕刻一圖案化基板的方法,其中該圖案化基板具有一曝露的含-矽-氮-和-碳區域,該方法包含以下步驟:使一含氟前驅物和一含氧前驅物中之每一者流入流體耦接至該基板處理區域的一遠端電漿區域,同時在該電漿區域中形成一電漿,以產生電漿流出物;以及藉由使該電漿流出物經由一噴灑頭中的通孔流入該基板處理區域而蝕刻該曝露的含-矽-氮-和-碳區域。
- 如請求項1所述之方法,其中該曝露的含-矽-氮-和-碳區域為矽碳氮化物。
- 如請求項1所述之方法,其中該曝露的含-矽-氮-和-碳區域基本上係由矽、氮和碳所組成。
- 如請求項1所述之方法,其中以原子百分比量測,該曝露的含-矽-氮-和-碳區域包含約10%或更多的氮。
- 如請求項1所述之方法,其中以原子百分比量測,該曝露的含-矽-氮-和-碳區域包含約15%或更多的氮。
- 如請求項1所述之方法,其中以原子百分比量測,該曝露的含-矽-氮-和-碳區域包含約20%或更多的氮。
- 如請求項1所述之方法,其中該圖案化基板之一溫度係大於或約0℃並小於或約50℃。
- 如請求項1所述之方法,其中該基板處理區域內之一壓力係低於或約50托並高於或約0.1托。
- 如請求項1所述之方法,其中在該電漿區域中形成一電漿以產生電漿流出物包含施加約10瓦和約2000瓦之間的RF功率至該電漿區域。
- 如請求項1所述之方法,其中該電漿為一電容耦合電漿。
- 如請求項1所述之方法,其中該含氧前驅物包含O2、O3、N2O或NO2中之至少一者。
- 如請求項1所述之方法,其中在該蝕刻操作過程中該基板處理區域係無電漿。
- 如請求項1所述之方法,其中該圖案化基板進一步包含一曝露的氧化矽區域,並且該蝕刻操作之選擇性(曝露的含-矽-氮-和-碳區域:曝露的氧化矽區域)係大於或約50:1。
- 如請求項1所述之方法,其中該圖案化基板進一步包含 一曝露的氮化矽區域,並且該蝕刻操作之選擇性(曝露的含-矽-氮-和-碳區域:曝露的氮化矽區域)係大於或約2:1。
- 如請求項1所述之方法,其中該含氟前驅物包含NF3。
- 如請求項1所述之方法,其中該含氟前驅物包含一選自於由原子氟、雙原子氟、三氟化溴、三氟化氯、三氟化氮、氟化氫、六氟化硫、二氟化氙、四氟化碳、三氟甲烷、二氟甲烷或氟甲烷所組成之群組的前驅物。
- 如請求項1所述之方法,其中該含氟前驅物和該電漿流出物基本上係無氫。
- 如請求項1所述之方法,其中該基板處理區域內基本上係無離子化物種和自由電子濃度。
- 如請求項1所述之方法,其中該噴灑頭中的該通孔之最小內徑係介於約0.2mm和約5mm之間。
- 如請求項1所述之方法,其中使該含氟前驅物和該含氧前驅物中之每一者流入該遠端電漿區域包含將一O:F原子流量比保持在高於或約0.5:1並低於或約10:1。
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- 2013-03-15 US US13/833,033 patent/US9390937B2/en active Active
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- 2013-08-29 JP JP2015533083A patent/JP6272873B2/ja not_active Expired - Fee Related
- 2013-08-29 KR KR1020157010015A patent/KR102159750B1/ko active IP Right Grant
- 2013-08-29 CN CN201380048686.5A patent/CN104838479B/zh not_active Expired - Fee Related
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US11335565B2 (en) | 2018-02-28 | 2022-05-17 | Applied Materials, Inc. | Systems and methods to form airgaps |
TWI766433B (zh) * | 2018-02-28 | 2022-06-01 | 美商應用材料股份有限公司 | 形成氣隙的系統及方法 |
Also Published As
Publication number | Publication date |
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JP6272873B2 (ja) | 2018-01-31 |
CN104838479B (zh) | 2019-01-18 |
TWI618139B (zh) | 2018-03-11 |
KR102159750B1 (ko) | 2020-09-24 |
US9390937B2 (en) | 2016-07-12 |
CN104838479A (zh) | 2015-08-12 |
JP2015529405A (ja) | 2015-10-05 |
WO2014046858A1 (en) | 2014-03-27 |
KR20150056639A (ko) | 2015-05-26 |
US20140080310A1 (en) | 2014-03-20 |
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