TWI750352B - 鍍膜處理方法，鍍膜處理系統及記憶媒體 - Google Patents

鍍膜處理方法，鍍膜處理系統及記憶媒體 Download PDF

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TWI750352B
TWI750352B TW107109208A TW107109208A TWI750352B TW I750352 B TWI750352 B TW I750352B TW 107109208 A TW107109208 A TW 107109208A TW 107109208 A TW107109208 A TW 107109208A TW I750352 B TWI750352 B TW I750352B
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sam
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水谷信崇
岩井和俊
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日商東京威力科創股份有限公司
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Abstract

[課題] 在於表面具有由包含氮的矽化合物所構成的第1部分(5)、及由與前述第1部分不同的材料所構成的第2部分(4)的基板上，至少不在第1部分形成鍍膜。 　　[解決手段] 鍍膜處理方法具有：在基板(2)的表面形成SAM(6)(自組織化單分子膜)的SAM形成工程、對形成SAM的基板供應觸媒含有液，並對基板賦予觸媒(7)的觸媒賦予工程、對賦予觸媒的基板施予鍍膜(8)的鍍膜工程。SAM形成工程，藉由將未具有含有氮的官能基的SAM形成用的藥劑供應至基板來進行。

Description

鍍膜處理方法，鍍膜處理系統及記憶媒體
本發明係有關於用以對半導體晶圓等的基板表面施予選擇鍍膜的技術。
在製造途中的半導體晶圓等基板的表面，會露出金屬、氮化矽(本說明書中也會略稱為「SiN」)、氧化矽(本說明書中也會略稱為「SiO」)等各種材料。僅對這些材料之中的一部分藉由無電解鍍膜來形成鍍膜的選擇鍍膜技術，從半導體裝置的生產性提升的觀點來看，近年越來越受到注目。藉由選擇鍍膜技術，期待有製造工序數的刪減、圖案形狀的加工精度提升(將鍍膜作為硬遮罩使用時)等各種效果。
進行無電解鍍膜時，為了使成為鍍膜的析出核的觸媒例如鈀(Pd)良好地附著於基板的表面，常會對基板表面賦予矽烷偶合劑等耦合劑而在基板表面形成自組織化單分子膜(SAM)。在半導體裝置製造的領域中，作為矽烷偶合劑，其作為官能基有使用具有氨基(-NH2 )者的例子(例如參照專利文獻1)。與基板表面的相反側具有氨基(-NH2 )的自組織化單分子膜，良好地吸附Pd觸媒。
有要求不在SiN的表面形成鍍膜，而僅在SiN以外的部分例如由導電性材料所構成的部分的表面形成鍍膜的選擇鍍膜的情形。但是因為SiN中含有的N原子，SiN容易吸附於Pd觸媒。又，在Pd觸媒的賦予之前，即便在從前一般使用的末端以具有氨基(-NH2 )的矽烷偶合劑來覆蓋SiN的表面，由該矽烷偶合劑所形成的層的表面也會強固地附著Pd觸媒。因此，使SiN的表面不形成鍍膜是非常困難的。 [先前技術文獻] [專利文獻]
[專利文獻1] 特開2012-216732號公報
[發明所欲解決的問題]
本發明的目的為提供一種鍍膜處理方法，在於表面具有由包含氮的矽化合物所構成的第1部分、及由與前述第1部分不同的材料所構成的第2部分的基板上，能夠至少不在第1部分形成鍍膜。 [解決問題的手段]
根據本發明適合的一實施形態，提供一種鍍膜處理方法，具有：準備於表面具有由包含氮的矽化合物所構成的第1部分、及由與前述第1部分不同的材料所構成的第2部分的基板之工程；在前述基板的表面形成SAM(自組織化單分子膜)的SAM形成工程；對形成前述SAM的前述基板供應觸媒含有液，而對前述基板賦予觸媒的觸媒賦予工程；對賦予前述觸媒的前述基板施以鍍膜的鍍膜工程；前述SAM形成工程，藉由將未具有含有氮的官能基的SAM形成用的藥劑供應至前述基板來進行。 [發明的效果]
根據本發明，在由包含氮的矽化合物所構成的第1部分的表面強固地附著不具有包含氮的官能基的SAM，該SAM會妨害矽化合物中的氮所具有的觸媒吸附能力。因此，在包含氮的矽化合物表面完全不會附著觸媒，能夠使在鍍膜工程中至少在第1部分不成長鍍膜。作為構成第2部分的材料，藉由選擇難以附著SAM且具有觸媒吸附性的材料，能夠進行選擇鍍膜。
參照以下圖式說明有關鍍膜處理方法。
首先，說明有關成為本實施形態的鍍膜處理的對象的基板1的構造。如圖1A所示，基板2具有：形成凹槽(凹部或溝)的矽(以下，記為「Si」)層3、在形成Si層3的凹槽的內壁面之表面形成的鈦矽化物(以下，記為「TiSi」)層4、形成於Si層3的凹槽間的柱狀體上面的氮化矽層(以下，記為「SiN」)5。以下說明的鍍膜處理方法，為不在SiN層5的表面形成鍍膜，而是在TiSi層4的表面形成鍍膜層8(參照圖1D)者。以下具體說明有關鍍膜處理方法。
[前洗淨處理] 　　首先，作為前洗淨處理，進行SC1洗淨處理，接著進行沖洗處理，藉此除去基板表面的粒子、有機系汙染物質等。前洗淨處理，可以用圖2所概略表示的構成的旋塗機(旋轉式液處理裝置)40來進行。具體來說，前洗淨處理，如圖2所示，藉由轉盤41使基板2保持水平姿態而繞鉛直軸線旋轉，朝向該旋轉的基板2的表面中央部從噴嘴42將SC1液以預定時間供應，之後，從噴嘴42將沖洗液例如DIW以預定時間供應來進行。
[SAM形成處理] 　　接著，進行將未具有含有N的官能基的矽烷系的自組織化單分子膜(SAM)的層6(以下，記為「SAM層」)形成於基板2的表面的SAM形成處理。在SAM層6的形成中，SAM層形成用的藥劑被供應至基板2的表面。作為SAM層形成用的藥劑，可以使用稱為矽烷偶合劑的藥劑或具有類似於其的分子構造的藥劑。在這裡，作為SAM層形成用的藥劑，可以使用能從信越化學工業株式會社商業得到的烷氧矽烷系藥劑即商品名「KBE-3033」。KBE-3033的化學名為n-丙基三乙氧基矽烷，構造式為(C2 H5 O)3 Si(CH2 )2 CH3 。該藥劑未包含具有N的官能基，在3個O-乙氧基(與向基板2的表面的結合有關的基)的相反側，具有以一般式CX HY (具體為(CH2 )2 -CH3 )表示的官能基。
SAM層6的形成能夠藉由液處理或蒸鍍處理來進行。
藉由液處理形成SAM層6時，使用作為具有圖2所概略表示的構成的SAM形成部的旋塗機40。此時，首先，藉由圖2所示的旋塗機40的轉盤41使基板2保持水平姿態而繞鉛直軸線旋轉，朝向該旋轉的基板2的表面中央部從噴嘴42供應SAM層形成用的藥劑，將藥劑的薄膜形成於基板2的表面。之後，進行藥劑的薄膜的燒結處理。該燒結處理，能夠藉由在低氧環境例如氮氣環境下將基板加熱而進行。具體來說，例如，使用具有圖4所概略表示的構成的加熱裝置(烘烤裝置)50，在設於處於氮氣環境下的處理室51內的載置台(熱板)52之上將基板2載置，藉由設於載置台52內部的加熱器53將基板2加熱至例如100℃左右。藉由該燒結(烘烤)處理，形成SAM層6。
藉由蒸鍍處理形成SAM層6時，能夠使用作為具有圖3所概略表示的構成的真空蒸鍍裝置30。此時，在設於處於低氧環境下(例如氮環境或減壓環境)的處理室31內的載置台32之上將基板2載置，藉由設於載置台32內部的加熱器33將基板2加熱至例如100℃左右。在該狀態下，使儲留於槽34內的液體狀態的SAM層形成用藥劑藉由加熱器35來加熱而使其氣化，乘著從載體氣體供應源36供應的載體氣體(例如氮氣)而供應至處理室31內。利用蒸鍍處理時不需要燒結處理。
[觸媒賦予處理] 　　接著，將使作為金屬觸媒粒子的Pd奈米粒子(Pd-NPs)、及作為被覆Pd奈米粒子的分散劑的聚乙烯吡咯啶酮(PVP)在溶劑中分散而成的Pd奈米膠體溶液，亦即觸媒粒子溶液供應至基板2，進行觸媒賦予處理。
觸媒賦予處理，例如，能夠利用作為具有如圖2所概略表示的構成的觸媒賦予部的旋塗機40，藉由轉盤41使基板2保持水平姿態而繞鉛直軸線旋轉，朝向該旋轉的基板2的表面中央部從噴嘴將觸媒含有液吐出來進行。又，觸媒含有液調整成酸性較佳。
結束觸媒賦予處理後，觸媒粒子含有層7附著於TiSi層4的表面(在這裡幾乎沒有附著SAM層6)，另一方面，在SiN層5的表面所具有的SAM層6上幾乎沒有附著觸媒(其理由將於後述)。此外，觸媒含有液為酸性較佳，這樣的話觸媒的附著程度差會變得顯著，而能夠使鍍膜的選擇性提升。
[沖洗處理] 　　接著，進行沖洗處理。該沖洗處理，可以藉由在觸媒賦予處理之後，接著藉由轉盤41將基板2保持而使其旋轉，朝向該旋轉的基板2的表面中央部從噴嘴將作為沖洗液的純水(DIW)吐出來進行。沖洗處理後進行烘烤處理也可以。
[鍍膜處理] 　　接著，藉由無電解鍍膜，形成由銅(Cu)、鎢(W)、鈷(Co)、鎳(Ni)或其合金所形成的鍍膜層8。該鍍膜處理，例如，能夠利用作為具有如圖2所概略表示的構成的鍍膜處理部的旋塗機40，藉由轉盤41使基板2保持水平姿態而繞鉛直軸線旋轉，朝向該旋轉的基板2的表面中央部從噴嘴將鍍膜液吐出來進行。
藉由鍍膜處理，如圖1D所示，鍍膜層8僅在附著有觸媒粒子含有層7的TiSi層4的表面選擇地形成，而在沒有附著觸媒粒子含有層7的SiN層5上的SAM層6的表面未形成。鍍膜層8在凹槽(凹部)內由下而上形成。也就是說，僅在欲填埋鍍膜層8的凹槽內部形成，在不想要形成鍍膜層的部分(SiN層4的表面)未形成。因此，在鍍膜處理後變得沒有必要除去剩餘的鍍膜層、或者能夠大幅地降低用來除去剩餘的鍍膜層的工序數。以不能進行選擇性成長的CVD(Chemical Vapor Deposition)或ALD(Atomic Layer Deposition)來進行凹部內的填埋時，為了在基板2的全面完全形成鍍膜層而有在凹部內產生間隙的問題，相對於此，根據上述實施形態的方法，能夠進行無間隙的凹部內填埋。
實際依照上述順序執行鍍膜處理時，鍍膜層8僅在TiSi層4上選擇地形成，而未在SiN層5上形成。
雖然關於藉由上述方法能夠進行選擇鍍膜的理由還未能完全被解析，但發明者的想法如下。
SAM材(形成SAM層6的材料)暫時附著於TiSi層4及SiN層5的表面。不過，根據下記(1)及(2)之中的至少一個理由，最遲到沖洗處理結束的時點，於TiSi層4上存在的SAM材被除去，僅留下SiN層5上存在的SAM材。 　　(1) 向金屬層即TiSi層4的表面，比向SiN層5的SAM材的結合力還弱。因此，將觸媒含有液或沖洗液供應至基板2時，因為液的流動所造成的物理力而容易將TiSi層4上的SAM材除去。 　　(2) 金屬層即TiSi層4的表面，被調整成酸性或鹼性的觸媒含有液所侵入，隨此，在TiSi層4的表面暫時附著的SAM材被從TiSi層4上除去。另一方面，因為SiN層5的表面沒有被調整成酸性或鹼性的觸媒含有液所侵入，SiN層5上的SAM材在將觸媒含有液供應至基板2之後仍殘留在SiN層5上。
未具有包含N(氮)原子的官能基的SAM材，幾乎未吸附觸媒金屬(在此為Pd粒子)。再來，SAM層6的基底的SiN層5所具有的Pd粒子的吸附性，因為表面被未具有包含N(氮)原子的官能基的SAM材所包覆，實質地喪失了。因此，即便假若Pd粒子附著於SAM層6，該Pd粒子最遲會在沖洗處理結束時，從SAM層6被除去。
另一方面，在TiSi層4上有Pd粒子直接附著。發明者認為附著的機制應如以下所述。觸媒含有液的pH，藉由將基板表面的電位與Pd粒子的電位調整成異號，觸媒含有液中的Pd粒子被吸引至基板的表面而附著。附著的Pd粒子相對於基板表面因凡得瓦力而持續地強力附著。
本發明雖並不侷限於上述原理，但不管如何，藉由上述的順序，能夠進行選擇鍍膜是清楚的。
在上述實施形態中，觸媒含有液中包含的金屬觸媒雖然是鈀(Pd)，但並不限於此，例如是金(Au)、鉑(Pt)、釕(Ru)也可以。
在上述實施形態中，觸媒粒子溶液中包含的分散劑雖然是聚乙烯吡咯啶酮(PVP)，但並不限於此，例如是聚丙烯酸(PAA)、聚乙烯亞胺(PEI)、四甲基銨(TMA)、檸檬酸也可以。
作為具有上述一般式CX HY (具體以(CH2 )2 -CH3 )來表示)官能基的稱為矽烷偶合劑的藥劑或具有與其類似的分子構造的藥劑(詳細為在一端側作為與基板結合有關的基而具有O-甲氧基或O-乙氧基，在另一端側具有CX HY 基者)，除了上述n-丙基三乙氧基矽烷(KBE-3033)以外，例如可以使用以下所示者。乙烯基三甲氧基矽烷(KBM-1003)、乙烯基三乙氧基矽烷(KBE-1003)、2-(3,4-環氧環己烷基)乙基三甲氧基矽烷(KBM-303)、3-縮水甘油醚氧基丙基甲基二甲氧基矽烷(KBM-402)、3-縮水甘油醚氧基丙基三甲氧基矽烷(KBM-403)、3-縮水甘油醚氧基丙基甲基二乙氧基矽烷(KBE-402)及3-縮水甘油醚氧丙基三乙氧基矽烷(KBE-403)。該等藥劑，可以以括號中的製品名來從信越化學工業株式會社商業地得到。
此外，作為不適合在上述實施形態中使用的具有氨基的稱為矽烷偶合劑的藥劑或具有與其類似的分子構造的藥劑(詳細為在一端側作為與基板結合有關的基而具有O-甲氧基或O-乙氧基，在另一端側具有氨基者)，例示如下。N-2-(氨乙基)-3-氨丙基甲基二甲氧基矽烷(KBM-602)、N-2-(氨乙基)-3-氨丙基三甲氧基矽烷(KBM-603)、3-氨丙基三甲氧基矽烷(KBM-903)及3-氨丙基三乙氧基矽烷(KBE-903)。該等藥劑，可以以括號中的製品名來從信越化學工業株式會社商業地得到。
在上述鍍膜處理方法中作為不希望附有鍍膜層的層，除了SiN以外，例示有由SiCN(碳氮化矽)、SiON(氮氧化矽)、SiOCN(碳氮氧化矽)等的含N的膜所形成的層。
此外，雖在基板的表面TEOS也時常露出，但藉由適用上述鍍膜處理方法，確認到在TEOS上也能防止鍍膜層的形成。
在上述鍍膜處理方法中作為不希望附有鍍膜層的層，除了TiSi以外，例示有由以TiN、Si、或者B或P等來摻雜的含Si等的導電性材料所形成的層。作為構成附有鍍膜層的材料，若是未具有包含上述氮的官能基的SAM難以附著且具有觸媒吸附性的話，可以使用任意的材料。
鍍膜處理方法在圖1A所示的凹槽構造填埋鍍膜金屬者則沒有限定。上述鍍膜處理方法，在不同材料露出的平坦基板的表面選擇地設置鍍膜層時也能使用。此時，例如，鍍膜層也能作為乾蝕刻用的硬遮罩使用。
上述一連的處理，亦即前洗淨處理、SAM形成處理、燒結(烘烤)處理、觸媒賦予處理、沖洗處理、鍍膜處理，例如能夠由圖4所概略表示的鍍膜處理系統來執行。
在如圖5所示的鍍膜處理系統100中，設於搬入搬出平台200的基板搬送裝置13，從載置於載體載置部11的載體C將基板2取出，將取出的基板2載置於收授部14。設於處理平台的處理單元16，以能夠執行處理一連的處理中的至少任一者的方式構成。亦即，處理單元16的任一為圖2A～圖2C所示的裝置30、40、50。載置於收授部14的基板2，藉由處理平台300的基板搬送裝置17而從收授部14取出，向對應上述處理的處理單元16依序搬入，在各處理單元16施予預定的處理。在一連的處理結束後，基板2被從處理單元16搬出，並載置於收授部14。接著，載置於收授部14的處理完的基板2，藉由基板搬送裝置13來返向載體載置部11的載體C。
鍍膜處理系統100具備控制裝置400。控制裝置400例如是電腦，具備控制部401及記憶部402。在記憶部402中，儲存有控制鍍膜處理系統100中執行的各種處理的程式。控制部401藉由將記憶於記憶部402中的程式讀出並執行，來控制鍍膜處理系統100的動作。亦即，控制裝置400為了實施與鍍膜有關的上述一連的處理，控制各處理單元16的動作、基板搬送裝置13、17所致的基板2的搬送動作。
此外，相關的程式可以是記錄於由電腦可讀取的記憶媒體中，也可以是從該記憶媒體安裝於控制裝置400的記憶部19者。作為由電腦可讀取的記憶媒體，例如有硬碟(HD)、可撓性磁碟(FD)、光碟(CD)、磁光碟(MO)、記憶卡等。
2‧‧‧基板4‧‧‧第2部分(TiSi層)5‧‧‧由包含氮的矽化合物所構成的第1部分(SiN層)6‧‧‧自組織化單分子膜(SAM層)7‧‧‧觸媒(觸媒粒子含有層)8‧‧‧鍍膜(鍍膜層)
[圖1A] 表示鍍膜對象基板的構成之概略縱剖面圖。 　　[圖1B] 表示SAM形成處理後的基板的狀態之概略縱剖面圖。 　　[圖1C] 表示觸媒賦予處理及沖洗處理之後的基板的狀態之概略縱剖面圖。 　　[圖1D] 表示鍍膜處理後的基板的狀態之概略縱剖面圖。 　　[圖2] 概略地表示用於鍍膜處理方法的實施的裝置(旋塗機)的構成的圖。 　　[圖3] 概略地表示用於鍍膜處理方法的實施的裝置(蒸鍍裝置)的構成的圖。 　　[圖4] 概略地表示用於鍍膜處理方法的實施的裝置(烘烤裝置)的構成的圖。 　　[圖5] 表示包含用於鍍膜處理方法的實施的圖2~圖4所示的裝置的鍍膜處理系統的一例的概略平面圖。
2‧‧‧基板
3‧‧‧Si層
4‧‧‧第2部分(TiSi層)
5‧‧‧由包含氮的矽化合物所構成的第1部分(SiN層)
6‧‧‧自組織化單分子膜(SAM層)
7‧‧‧觸媒(觸媒粒子含有層)
8‧‧‧鍍膜(鍍膜層)

Claims (5)

  1. 一種鍍膜處理方法，具有：準備於表面具有由包含氮的矽化合物所構成的第1部分、及由與前述第1部分不同的材料所構成的第2部分的基板之工程；在前述基板的表面形成自組織化單分子膜(SAM)的SAM形成工程；對形成前述SAM的前述基板供應觸媒含有液，而對前述基板賦予觸媒的觸媒賦予工程；對賦予前述觸媒的前述基板施以鍍膜的鍍膜工程；前述SAM形成工程，藉由將未具有含有氮的官能基的SAM形成用的藥劑供應至前述基板來進行；其中，前述SAM形成用的藥劑為矽烷偶合劑；前述第2部分由導電性材料所構成；前述包含氮的矽化合物為SiN、SiCN、SiON或SiOCN，前述導電性材料為TiSi、TiN、Si、或者以B或P進行摻雜的Si；前述觸媒含有液為酸性。
  2. 如請求項1所記載的鍍膜處理方法，更具有：在前述觸媒賦予工程之後前述鍍膜工程之前，對前述基板的表面供應沖洗液的沖洗工程。
  3. 如請求項1所記載的鍍膜處理方法，其中，前述SAM 形成工程，藉由將藥液作為前述SAM形成用的藥劑供應至前述基板後，在非氧化性環境下烘烤前述基板而進行。
  4. 一種記憶媒體，係記錄程式，該程式在藉由用以控制鍍膜處理系統的動作的電腦來執行時，讓前述電腦控制前述鍍膜處理系統，執行如請求項1至3中任1項所記載的鍍膜處理方法。
  5. 一種鍍膜處理系統，具備：藉由將未具有含有氮的官能基的SAM形成用的藥劑供應至於表面具有由包含氮的矽化合物所構成的第1部分、及由與前述第1部分不同的材料所構成的第2部分的基板，在前述基板的表面形成自組織化單分子膜(SAM)的SAM形成部；對形成前述SAM的前述基板供應觸媒液，而對前述基板賦予觸媒的觸媒賦予部；對賦予前述觸媒的前述基板施以鍍膜的鍍膜處理部；其中，前述SAM形成用的藥劑為矽烷偶合劑；前述第2部分由導電性材料所構成；前述包含氮的矽化合物為SiN、SiCN、SiON或SiOCN，前述導電性材料為TiSi、TiN、Si、或者以B或P進行摻雜的Si；前述觸媒液為酸性。
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