JP4842251B2 - 下にあるバリア層への多孔性低誘電率膜の接着を促進する手法 - Google Patents
下にあるバリア層への多孔性低誘電率膜の接着を促進する手法 Download PDFInfo
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- JP4842251B2 JP4842251B2 JP2007506279A JP2007506279A JP4842251B2 JP 4842251 B2 JP4842251 B2 JP 4842251B2 JP 2007506279 A JP2007506279 A JP 2007506279A JP 2007506279 A JP2007506279 A JP 2007506279A JP 4842251 B2 JP4842251 B2 JP 4842251B2
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- barrier layer
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31633—Deposition of carbon doped silicon oxide, e.g. SiOC
-
- 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
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Description
メチルシラン CH3−SiH3
ジメチルシラン (CH3)2−SiH2
ジシラノメタン SiH3−CH2−SiH3
ビス(メチルシラノ)メタン CH3−SiH2−CH2−SiH2−CH3
2,4,6−トリシラオキサン −(−SiH2−CH2−SiH2−CH2−SiH2−O−)−(環状)
シクロ−1,3,5,7−テトラシラノ−2,6−ダイオキシ−4,8−ジメチレン (−SiH2−CH2−SiH2−O−)2−(環状)
1,3,5−トリシラシクロヘキサン −(−SiH2−CH2−)3−(環状)
1,3−ジメチルジシロキサン CH3−SiH2−O−SiH2−CH3
1,1,3,3−テトラメチルジシロキサン (CH3)2−SiH−O−SiH−(CH3)2
1,1,5,5−テトラメチルトリシロキサン (CH3)2−SiH−O−SiH2−O−SiH−(CH3)2
1,1,3,5,5−ペンタメチルトリシロキサン (CH3)2−SiH−O−SiH(CH3)−O−SiH−(CH3)2、
及び1,2−ジシラノテトラフルオロエタンなどのそのフッ化炭素誘導体を含む。有機シランと有機シロキサン内の炭化水素基は部分的に又は完全にフッ化されて、C−H結合をC−F結合に変換する。多くの好ましい有機シランと有機シロキサン化合物は、市販されている。有機シランや有機シロキサンは、誘電率、酸化物含量、疎水性、膜応力、及びプラズマエッチング特性などの望ましい性質の調和を提供するために二種以上を組み合わせて用いられる。
メチルシロキシ、及び (CH3−SiH2−O)
ジメチルシロキシ ((CH3)2−SiH−O−)
を含む。
1,3,5,7−テトラシラノ−2,6−ダイオキシ−4,8−ジメチレン、及び (−SiH2−CH2−SiH2−O−)2−(環状)
2,4,6−トリシラテトラハイドロピラン −SiH2−CH2−SiH2−CH2−SiH2−O−(環状)
[0032]熱的に不安定な有機基は、十分な酸素を含有し、シリコン酸化物層がアニールされる時、ガス状の生成物を形成する。
ダイオキシン、C4H4O2、 −(−CH=CH−O−CH=CH−O−)−、環状
フラン、C4H4O、 −(−CH=CH−CH=CH−O−)−、環状
フルベン、C6H6 −(−CH=CH−CH=CH−C(CH2)−)−、環状
を含む。
メチルシリル−1,4−ダイオキシニルエーテル CH3−SiH2−O−(C4H3O2)
2−メチルシロキサニルフラン −(−CH=CH−CH=C(O−SiH2−CH3)−O−)−、環状
3−メチルシロキサニルフラン −(−CH=CH−C(O−SiH2−CH3)=CH−O−)−、環状
2,5−ビス(メチルシロキシ)−1,4−ダイオキシン −(−CH=C(O−SiH2−CH3)−O−CH=C(O−SiH2−CH3)−O−)−、環状
3,4−ビス(メチルシロキサニル)フラン −(−CH=C(O−SiH2−CH3)−C(O−SiH2−CH3)=CH−O−)−、環状
2,3−ビス(メチルシロキサニル)フラン −(−CH=CH−C(O−SiH2−CH3)=C(O−SiH2−CH3)−O−)−、環状
2,4−ビス(メチルシロキサニル)フラン −(−CH=C(O−SiH2−CH3)−CH=C(O−SiH2−CH3)−O−)−、環状
2,5−ビス(メチルシロキサニル)フラン −(−C(O−SiH2−CH3)=CH−CH=C(O−SiH2−CH3)−O−)−、環状
1−メチルシロキサニルフルベン −(CH=CH−CH=CH−C(CH(O−SiH2−CH3))−)−、環状
2−メチルシロキサニルフルベン −(CH=CH−CH=CH−C(CH2)(O−SiH2−CH3)−)−、環状
6−メチルシロキサニルフルベン −(−C(O−SiH2−CH3)=CH−CH=CH−C=CH−)−、環状
ビス(メチルシロキサニル)フルベン (C6H4)(O−SiH2−CH3)2、環状
ジメチルシリル−1,4−ダイオキシニルエーテル (CH3)2−SiH−O−(C4H3O2)、環状
2−ジメチルシロキサニルフラン −(−CH=CH−CH=C(O−SiH−(CH3)2)−O−)−、環状
3−ジメチルシロキサニルフラン −(−CH=CH−C(O−SiH−(CH3)2)=CH−O−)−、環状
2,5−ビス(ジメチルシロキシ)−1,4−ダイオキシン −(−CH=C(O−SiH−(CH3)2)−O−CH=C(O−SiH−(CH3)2)−O−)−、環状
3,4−ビス(ジメチルシロキサニル)フラン −(−CH=C(O−SiH−(CH3)2)−C(O−SiH−CH3)2)=CH−O−)−環状
2,3−ビス(ジメチルシロキサニル)フラン −(−CH=CH−C(O−SiH−(CH3)2)=C(O−SiH−(CH3)2)−O−)−環状
2,4−ビス(ジメチルシロキサニル)フラン −(−CH=C(O−SiH−(CH3)2)−CH=C(O−SiH−(CH3)2)−O−)−環状
2,5−ビス(ジメチルシロキサニル)フラン −(−C(O−SiH−(CH3)2)=CH−CH=C(O−SiH−(CH3)2)−O−)−環状
1−ジメチルシロキサニルフルベン −(−CH=CH−CH=CH−C(CH(O−SiH−(CH3)2))−)−、環状
2−ジメチルシロキサニルフルベン −(−CH=CH−CH=CH−C(CH2)(O−SiH−(CH3)2)−)−、環状
6−ジメチルシロキサニルフルベン −(−C(O−SiH−(CH3)2)=CH−CH=CH−C=CH−)−、環状
ビス(ジメチルシロキサニル)フルベン −(C6H4)(O−SiH−(CH3)2)2、環状
及びその不和炭素誘導体を含む。好ましくは、上記化合物は、常温において液体であり、10トール近く又はそれ以上の圧力において揮発され得る。このような化合物は、酸化ガスと反応し、約50℃未満の温度において多くの不安定有機基を保有するゲル型シリコン/酸素含有材料を形成する。
ビニール−1,4−ダイオキシニルエーテル CH2=CH2−O−(C4H3O2)、環状
ビニールフリルエーテル CH2=CH2−O−(C4H3O)、環状
ビニール−1,4−ダイオキシン CH2=CH2−(C4H3O2)、環状
ビニールフラン CH2=CH2−O−(C4H3O)、環状
メチルフロエイト CH3C(O)−O−(C4H3O)、環状
フリルフォルメイト (C4H3O)−COOH、環状
フリルアセテート (C4H3O)−CH2COOH、環状
フルアルデヒド CH(O)−(C4H3O)K、環状
ジフリルケトン (C4H3O)2C(O)、環状
ジフリルエーテル (C4H3O)−O−(C4H3O)、環状
ジフルフリルエーテル (C4H3O)C(O)−O−C(O)(C4H3O)、環状
フラン C4H4O、(環状)
1,4−ダイオキシン C4H4O2、(環状)
及びその不和炭素誘導体を含む。
ジメチルシラン (CH3)2−SiH2
ジシラノメタン SiH3−CH2−SiH3
ビス(メチルシラノ)メタン CH3−SiH2−CH2−SiH2−CH3
2,4,6−トリシラオキサン −(−SiH2−CH2−SiH2−CH2−SiH2−O−)−(環状)
1,3,5−トリシラシクロヘキサン −(−SiH2−CH2−)3−(環状)
シクロ−1,3,5,7−テトラシラノ−2,6−ジオキシ−4,8−ジメチルレン −(−SiH2−CH2−SiH2−O−)2−(環状)
1,3−ジメチルジシロキサン CH3−SiH2−O−SiH2−CH3
1,1,3,3−テトラメチルジシロキサン (CH3)2−SiH−O−SiH−(CH3)2
1,1,5,5−テトラメチルトリシロキサン、及び (CH3)2−SiH−O−SiH2−O−SiH−(CH3)2
1,1,3,5,5−ペンタメチルトリシロキサン (CH3)2−SiH−O−SiH(CH3)−O−SiH−(CH3)2
及びその不和炭素誘導体。
[0044]本発明の方法を実施するのに適した一つのCVDプラズマ反応器としては、カリフォルニア州サンタクララにあるアプライドマテリアルズ社から入手できる「DLK」チャンバがあり、高真空領域115を有する平行板化学気相堆積反応器110の縦断面図である図2に示されている。反応器110は、プロセスガスをマニホールド内の穿孔を介して、基板又はリフトモータ114により昇降される基板支持板又はサセプタ112の上にある基板(図示せず)に分散させるためのガス分配マニホールド111を含有する。TEOSの液体噴射用として典型的に使用されるような、液体噴射システム(図示せず)が液体反応物質を噴射するために提供されてもよい。好ましい液体噴射システムは、アプライドマテリアルズ社から入手できる“AMAT Gas Precision Liquid Injection System(GPLIS)”及び“AMAT Extended Precision Liquid Injection System(EPLIS)”を含む。
[0066]本発明のナノ多孔性シリコン酸化物層は図2のPECVD又はマイクロ波チャンバを使用して、図5で示されているような、4層プロセスで堆積されてもよい。図5を参照すると、基板は反応器110に位置決めされ(ステップ300)、反応性シリコン含有化合物を備えるプラズマからPECVDプロセスによってライナ/バリア層が堆積される(ステップ305)。堆積ステップ305は、当分野において既知である方法によってプロセスチャンバ15内に容量結合プラズマ又は誘導及び容量結合プラズマの両方を含んでもよい。プラズマは、He、Ar、及びN2などの不活性ガスを使用することにより生成されてもよい。ヘリウムなどの非活性ガスは、PECVE堆積に広く使用されてプラズマ生成を助ける。
[0085]上述したように、低誘電率誘電体層を形成するプロセスは、熱的に不安定な基を除去して内部にナノ細孔を作り出すように後続してアニールされる材料の堆積を包含する。典型的に、このナノ多孔性低誘電率誘電体層は、炭素含量が10%未満のシリコン酸化物を含み、典型的に30%以上の高い炭素含量を有するシリコン炭化物を含むライナ/バリア層上に堆積される。ナノ多孔性低誘電率誘電層とその下にあるバリア/ライナ材料との間の組成及び構造の実質的な差は、これらの接着を妨害する。これらの層間の接着を向上するために、低誘電率堆積ステップの前に膜や基板を加熱するステップが別途実行されてもよい。
[0106]本発明の一実施形態に従って製造された好ましい二重ダマシン構造500が図7に示され、及びこの構造を作る方法が、本発明のステップが形成される基板の断面図である図8A〜8Hに順次概略的に描かれている。
(シリコン含有の熱的不安定性付与成分を有するシリコン化合物(仮定))
[0121]ナノ多孔性シリコン酸化物系膜は、次のような蒸発されて反応器に流入される反応ガスから1.0トールのチャンバ圧力と30℃の温度で堆積される。
150sccmにおけるメチルシリル−2−フリルエーテル
1000sccmにおける亜酸化窒素(N2O)
[0122]チャンバに入る前に、亜酸化窒素は、2000Wのマイクロ波エネルギーを提供するマイクロ波アプリケータで分離される。基板は、ガス分配シャワーヘッドから600ミルに位置決めされ、反応ガスは、2分間導入される。基板は次いで5分の期間に加熱され、50℃/分ずつ400℃の温度まで基板の温度を上昇させて、ナノ多孔性シリコン酸化物系膜を硬化してアニールする。
[0123]ナノ多孔性シリコン酸化物系膜は、次のような蒸発されて反応器に流入される反応ガスから1.0トールのチャンバ圧力と30℃の温度で堆積される。
100sccmでのシクロ−1,3,5,7−テトラシリレン−2,6−ダイオキシ−4,8ジメチレン
500sccmでのビニル−2−フリルエーテル
1000sccmでの亜酸化窒素(N2O)
[0124]チャンバに入る前に、亜酸化窒素は、2000Wのマイクロ波エネルギーを提供するマイクロ波アプリケータで分離される。基板は、ガス分配シャワーヘッドから600ミルに位置決めされ、反応ガスは、2分間導入される。基板は次いで5分の期間に加熱され、50℃/分ずつ400℃の温度まで基板の温度を上昇させて、ナノ多孔性シリコン酸化物系膜を硬化してアニールする。
(シリコン含有の熱的不安定性付与成分を有するシリコン化合物及び添加されたシリコン含有化合物(仮定))
[0125]ナノ多孔性シリコン酸化物系膜は、次のような蒸発されて反応器に流入される反応ガスから1.0トールのチャンバ圧力と0℃の温度で堆積される。
100sccmでのメチルシリル−2−フリルエーテル
50sccmでのシクロ−1,3,5,7−テトラシリレン−2,6−ダイオキシ−4,8ジメチレン
1000sccmでの亜酸化窒素(N2O)
[0126]チャンバに入る前に、亜酸化窒素は、2000Wのマイクロ波エネルギーを提供するマイクロ波アプリケータで分離される。基板は、ガス分配シャワーヘッドから600ミルに位置決めされ、反応ガスは、2分間導入される。基板は次いで5分の期間に加熱され、50℃/分ずつ400℃の温度まで基板の温度を上昇させて、ナノ多孔性シリコン酸化物系膜を硬化してアニールする。
Claims (15)
- ナノ多孔性低誘電率膜とその下にあるライナ/バリア層との間の接着を促進する方法であって、
シリコン及び炭素を含有するライナ/バリア層を支える基板を提供するステップと、
ライナ/バリア層の上面のSi前駆体を酸化させる濃酸化ガスにライナ/バリア層を曝すことにより、炭素含有量がライナ/バリア層よりも低い炭素含有シリコン酸化物接着層をライナ/バリア層上に形成するステップと、
前記炭素含有シリコン酸化物接着層上に低誘電率膜を堆積するステップと、
堆積された低誘電率膜を硬化させて内部にナノ細孔を形成するステップと、
を備え、
前記炭素含有シリコン酸化物接着層は、前記低誘電率膜よりも、炭素含有量が低く、シリコン酸化物が豊富である方法。 - 前記基板を提供するステップが、シリコン炭化物ライナ/バリア層を支える基板を提供する工程を備える、請求項1に記載の方法。
- 前記炭素含有シリコン酸化物接着層を形成するステップが、前記酸化ガスをシリコン含有ガスに曝す工程をさらに備える、請求項1又は2に記載の方法。
- 前記炭素含有シリコン酸化物接着層を形成するステップの前に、ライナ/バリア層をプラズマに曝す工程をさらに備える、請求項1〜3のいずれか一項に記載の方法。
- 前記プラズマが、前記バリア/ライナ層の堆積に引き続き、連続的に維持される、請求項4に記載の方法。
- 堆積された低誘電率膜が、電子ビーム放射線を印加することにより硬化される、請求項1〜5のいずれか一項に記載の方法。
- 前記電子ビーム放射線の印加が、ライナ/バリア層と低誘電率膜との間の界面に沿って炭素含量を減少させることにより、炭素含有シリコン酸化物接着層の形成に寄与する、請求項6に記載の方法。
- ナノ多孔性低誘電率膜とその下にあるライナ/バリア層との間の接着を促進する方法であって、
シリコン及び炭素を含有するライナ/バリア層を支える基板を提供するステップと、
ライナ/バリア層上に低誘電率膜を堆積するステップと、
前記低誘電率膜に電子ビーム放射線を印加して、内部に微細孔を作り出し、ライナ/バリア層と低誘電率膜との間の界面に沿って炭素含量を減少させることにより、ライナ/バリア層と低誘電率膜との間に炭素含有シリコン酸化物接着層を形成するステップと、
を備え、
前記炭素含有シリコン酸化物接着層は、前記低誘電率膜よりも炭素含有量が低く、シリコン酸化物が豊富であり、前記ライナ/バリア層よりも炭素含有量が低い、
方法。 - 前記基板を提供するステップが、シリコン炭化物ライナ/バリア層を支える基板を提供するステップを備える、請求項8に記載の方法。
- 低誘電率膜の堆積の前にライナ/バリア層を酸化ガスに曝すステップをさらに備える、請求項8又は9に記載の方法。
- 低誘電率膜の堆積の前に、前記酸化ガスをシリコン含有ガスに曝すステップをさらに備える、請求項10に記載の方法。
- 低誘電率膜の堆積の前に、ライナ/バリア層をプラズマに曝すステップをさらに備える、請求項8又は9に記載の方法。
- 前記プラズマが、前記バリア/ライナ層の堆積に引き続き、連続的に維持される、請求項12に記載の方法。
- 集積回路用の相互接続構造であって、
少なくとも30%の炭素含量を有するシリコン炭化物を備えるライナ/バリア層と、
前記ライナ/バリア層の上にあり、炭素含有量が前記ライナ/バリア層よりも低い炭素含有シリコン酸化物接着層と、
前記炭素含有シリコン酸化物接着層の上にあり、10%以下の炭素含量を有する炭素ドープされたシリコン酸化物を備えるナノ多孔性低誘電率層と、
を備え、
前記炭素含有シリコン酸化物接着層は、前記低誘電率膜よりも炭素含有量が低く、シリコン酸化物が豊富である、
相互接続構造。 - 前記ライナ/バリア層の下にある銅メタライズ層をさらに備える、請求項14に記載の相互接続構造。
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CN1938833B (zh) | 2010-12-22 |
JP2007531319A (ja) | 2007-11-01 |
US7547643B2 (en) | 2009-06-16 |
KR20070028361A (ko) | 2007-03-12 |
TWI275146B (en) | 2007-03-01 |
CN1938833A (zh) | 2007-03-28 |
KR101141459B1 (ko) | 2013-05-23 |
WO2005098925A1 (en) | 2005-10-20 |
US20050233591A1 (en) | 2005-10-20 |
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