JP5560147B2 - 成膜方法及び半導体装置の製造方法 - Google Patents
成膜方法及び半導体装置の製造方法 Download PDFInfo
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- JP5560147B2 JP5560147B2 JP2010203923A JP2010203923A JP5560147B2 JP 5560147 B2 JP5560147 B2 JP 5560147B2 JP 2010203923 A JP2010203923 A JP 2010203923A JP 2010203923 A JP2010203923 A JP 2010203923A JP 5560147 B2 JP5560147 B2 JP 5560147B2
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Images
Classifications
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
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Description
前記半導体材料層が表面に露出した基板にポリシラン溶液を塗布し、前記半導体材料層上にポリシラン膜を形成する工程と、
前記ポリシラン膜上に、金属塩溶液を塗布して金属イオン含有膜を形成することにより、前記ポリシラン膜をポリシロキサン膜へ、前記金属イオン含有膜を金属微粒子含有膜へ、それぞれ改質してMOS構造の積層膜を形成する工程と、
を備えている。
前記半導体材料層上に前記第1の絶縁膜を形成する工程と、
前記第1の絶縁膜が表面に露出した基板にポリシラン溶液を塗布し、前記第1の絶縁膜上にポリシラン膜を形成する工程と、
前記ポリシラン膜上に、金属塩溶液を塗布して金属イオン含有膜を形成することにより、前記ポリシラン膜を前記第2の絶縁膜としてのポリシロキサン膜へ、前記金属イオン含有膜を金属微粒子含有膜へ、それぞれ改質してMOS構造の積層膜を形成する工程と、
を備えている。
前記半導体材料層が表面に露出した基板に、ポリシラン溶液を塗布し、前記半導体材料層上に第1のポリシラン膜を形成する工程と、
前記第1のポリシラン膜の上に、単分子膜を所定のパターンで形成する工程と、
前記第1のポリシラン膜及び前記単分子膜の上から金属塩溶液を塗布して金属イオン含有膜を形成することにより、前記金属イオン含有膜に接している部分の前記第1のポリシラン膜を第1のポリシロキサン膜へ、前記金属イオン含有膜を金属微粒子含有膜へ、それぞれ改質してMOS構造の積層膜を形成する工程と、
未改質の前記金属イオン含有膜と前記単分子膜と未改質の前記第1のポリシラン膜をエッチングによって除去する工程と、
を備えている。
前記第2のポリシラン膜に部分的に紫外線を照射し、第2のポリシロキサン膜に改質する工程と、
未改質の前記第2のポリシラン膜をエッチングによって除去することにより、前記第2のポリシロキサン膜に前記半導体材料層または前記金属膜に達する開口を形成する工程と、
をさらに備えていてもよい。
前記ポリシラン膜上に、金属塩溶液を塗布し、金属イオン含有膜を形成する第2の塗布ユニットと、
を備え、
前記ポリシラン膜をポリシロキサン膜へ、前記金属イオン含有膜を金属微粒子含有膜へ、それぞれ改質してMOS構造の積層膜を形成するものである。
未改質の前記金属イオン含有膜と前記単分子膜と未改質の前記ポリシラン膜をエッチングによって除去するエッチングユニットとを、さらに備えていてもよい。
図1から図5を参照しながら、本発明の第1の実施の形態に係る成膜方法について説明する。図1は、第1の実施の形態にかかる成膜方法の主な工程を示すフローチャートである。また、図2〜図5は、本実施の形態の成膜方法の工程図である。本実施の形態では、例えばトランジスタに利用可能なMOS(Metal-Oxide-Semiconductor)構造の積層体を製造する。
STEP1では、図2に示す基板の半導体膜3上にポリシラン溶液を塗布し、図3に示すようにポリシラン膜5を形成する。ここで、ポリシラン溶液は、ポリシランを溶媒に溶かした溶液である。ポリシランとしては、有機溶媒に可溶なものを使用することができる。好ましくは下記式(1)
(R1 m1R2 m2R3 m3Si)n … (1)
で示されるポリシランが用いられる。
次に、STEP2では、ポリシラン膜5の上に、金属塩溶液を塗布し、図4に示すように、金属イオン含有膜7を形成する。そして、図5に示すように、ポリシラン膜5中のポリシランが酸化されてポリシロキサンとなり、ポリシロキサン膜5Aに改質される。これに伴い、金属イオン含有膜7中の金属イオンが還元されて金属微粒子となり、金属微粒子どうしが凝集して導電性を有する金属微粒子含有膜7Aに改質される。このように、本実施の形態の成膜方法は、ポリシランからポリシロキサンへの酸化に伴う強い還元力を利用して金属イオン含有膜7中の金属イオンを還元し、導電性の金属に転換させるものである。
次に、STEP3では、STEP2で形成された2層の膜、つまり、ポリシロキサン膜5A及び金属微粒子含有膜7Aを加熱(アニール)する。アニールによって、ポリシランからポリシロキサンへの酸化反応と、金属イオンから金属への還元反応とを完結させることができる。また、金属微粒子含有膜7A中の金属微粒子の凝集を促すことができる。従って、アニールによってポリシロキサン膜5Aの絶縁性と、金属微粒子含有膜7Aの導電性を向上させて、それぞれを良質な絶縁膜と導電性膜に改質することができる。
次に、図6及び図7を参照しながら、本発明の第2の実施の形態に係る成膜方法について説明する。図6は、第2の実施の形態にかかる成膜方法の主な工程を示すフローチャートである。また、図7は、本実施の形態の成膜方法の主要工程を示す工程図である。本実施の形態でも、例えばトランジスタに利用可能なMOS構造の積層体を製造する。
本実施の形態のSTEP11及びSTEP12は、第1の実施の形態のSTEP1及びSTEP2と同様に実施できる。従って、第1の実施の形態における図2から図5の工程図を本実施の形態でも援用し、重複する説明を省略する。
次に、STEP13では、図5に示す状態から、金属微粒子含有膜7Aをめっき触媒(めっき核)として無電解めっきを行い、図7に示すように金属膜9を成膜する。
次に、図8から図13を参照しながら、本発明の第3の実施の形態に係る半導体装置の製造方法について説明する。図8は、第3の実施の形態にかかる半導体装置の製造方法の主な工程を示すフローチャートである。また、図9〜図13は、本実施の形態の半導体装置の製造方法の主要工程を示す工程図である。本実施の形態では、例えばトランジスタに利用可能なMOS構造の積層体を製造する。
本実施の形態のSTEP21は、第1の実施の形態のSTEP1と同様に実施できる。従って、第1の実施の形態における図2及び図3の工程図を本実施の形態でも援用し、重複する説明を省略する。
次に、STEP22では、図3に示す状態から、図9に示すように、ポリシラン膜5の上に、単分子膜11を形成する。単分子膜11は、例えば末端官能性長鎖アルキル化合物がSAM(自己組織化膜)と呼ばれる単分子膜を形成する能力を利用して形成できる薄膜である。ここで、末端官能性長鎖アルキル化合物としては、例えばアルカンチオール類、ジアルキドジスルフィドのような有機イオウ化合物、有機シラン化合物、アルコール、アミン化合物等を用いることができる。これらの末端官能性長鎖アルキル化合物のなかで、ポリシラン膜5上に好適に単分子膜を形成できる化合物の例としては、R−Si(OR’)3[ここで、R,R’は、アルキル基等の炭化水素基を意味する]で表される有機シラン化合物が挙げられる。
次に、STEP23では、ポリシラン膜5の上に、金属塩溶液を塗布し、図10に示すように、金属イオン含有膜7を形成する。本実施の形態における金属イオン含有膜7の形成は、第1の実施の形態のSTEP2と同様に実施できるが、第1の実施の形態と異なる点として、本実施の形態では、ポリシラン膜5上にパターン状の単分子膜11が存在しているため、金属イオン含有膜7は、単分子膜11上、及びポリシラン膜5上にそれぞれ形成される。そして、図11に示すように、ポリシラン膜5は部分的に酸化されてポリシロキサン膜5Aに改質される。これに伴い、金属イオン含有膜7中の金属イオンは部分的に還元されて金属微粒子となり、金属微粒子含有膜7Aに改質される。ここで、ポリシラン膜5と金属イオン含有膜7が積層されている部位のみ、ポリシラン膜5が酸化されてポリシロキサン膜5Aとなり、金属イオン含有膜7が還元されて金属微粒子含有膜7Aに改質される。金属イオン含有膜7とポリシラン膜5との間に単分子膜11がある部位は、金属イオン含有膜7が改質されずにそのまま残存する。従って、図11に示すように、ポリシロキサン膜5Aと金属微粒子含有膜7Aは同一のパターンに形成される。
次に、STEP24では、図11に示す状態から、金属微粒子含有膜7Aをめっき触媒(めっき核)として無電解めっきを行い、図12に示すように金属微粒子含有膜7A上に金属膜9を積層形成する。本実施の形態では、金属イオン含有膜7が残存している部位にはめっき触媒(めっき核)が無いため、金属イオン含有膜7上に金属膜9は析出しない。従って、金属膜9を金属微粒子含有膜7A上にパターン状に析出させることができる。
次に、金属微粒子含有膜7Aに改質されなかった金属イオン含有膜7と、単分子膜11と、ポリシロキサンに改質されなかったポリシラン膜5を除去する。これらの3種類の膜の除去は、例えば、溶媒を用いるウエットエッチングによって行うことができる。金属イオン含有膜7の除去に用いる溶媒としては、金属イオン含有膜7の形成に用いた金属塩溶液で使用した溶媒と同様の溶媒を好適に用いることができる。単分子膜11の除去に用いる溶媒としては、単分子膜11の形成に用いた末端官能性長鎖アルキル化合物を含む溶液で使用した溶媒と同様の溶媒を好適に用いることができる。ポリシラン膜5の除去に用いる溶媒としては、ポリシラン膜5の形成に用いたポリシラン溶液で使用した溶媒と同様の溶媒を好適に用いることができる。各膜除去用の溶媒を混合した液体を使用すれば、一度のウエットエッチングで3種類の膜を除去することもできる。ウエットエッチングは、例えばスピンコーターを利用して溶媒を基板の表面に適用する現像法や、浸漬法などによって行うことができる。
次に図14から図17を参照しながら、本発明の第4の実施の形態に係る半導体装置の製造方法について説明する。図14は、第4の実施の形態にかかる半導体装置の製造方法の主な工程を示すフローチャートである。また、図15〜図17は、本実施の形態の半導体装置の製造方法の主要工程を示す工程図である。本実施の形態では、トランジスタに利用可能なMOS構造の積層体と多層配線用の層間絶縁膜を製造する。
本実施の形態におけるSTEP31から35の各工程は、第3の実施の形態のSTEP21から25の各工程と同様に実施できるので、重複した内容の説明を省略する。STEP31〜STEP35を行うことによって、第3の実施の形態と同様に、半導体膜3上に、絶縁性のポリシロキサン膜5Aと金属微粒子含有膜7A及び金属膜9が所定のパターンで形成されたMOS構造の積層体101が得られる(図13参照)。
STEP36では、図13に示す状態から、半導体膜3上にポリシラン溶液を塗布し、図15に示すように金属微粒子含有膜7A、金属膜9を覆うように、ポリシラン膜21を形成する。ここで、STEP36は、ポリシラン膜21の膜厚を厚く形成する点以外は、第1の実施の形態のSTEP1と同様に実施できる。このポリシラン膜21は、後の工程で改質されて層間絶縁膜となるものであるため、乾燥後の膜厚として、例えば50nm〜10000nmとなるように形成することが好ましく、500nm〜3000nmがより好ましい。膜厚が50nmより小さいと、ポリシロキサン膜5Aと金属微粒子含有膜7A及び金属膜9を覆うためには不充分な膜厚となり、10000nmより大きいと、ポリシラン膜21にクラックが入りやすく、また次の工程での紫外線照射による改質が困難となる。
次に、STEP37では、図16に示すように、所定パターンの開口を有する遮蔽部材30を用い、ポリシラン膜21に部分的に紫外線31を照射する。照射する紫外線としては、ポリシランの光吸収体の波長光、すなわち波長180nm〜400nmの紫外線を照射することが必要である。紫外線照射された部位では、ポリシラン膜21が酸化されてポリシロキサン膜23となる。一方、遮蔽部材30によって紫外線31の照射を受けなかった部位では、ポリシラン膜21がそのまま残存する。紫外線31の照射量は、吸収光に換算して0.1J/cm2〜100J/cm2が好ましく、1J/cm2〜10J/cm2がより好ましい。紫外線31の光源としては、例えば、水銀灯、ハロゲンランプ、水素放電管、希ガス放電管、タングステンランプ、各種レーザーなどを用いることができる。紫外線照射は、空気雰囲気下もしくは酸素ガス雰囲気下で行うことが望ましい。
次に、STEP38では、ポリシロキサンに改質されなかったポリシラン膜21を除去する。ポリシラン膜21の除去は、ウエットエッチングによって行うことができる。その結果、図17に示すように、絶縁性のポリシロキサン膜23に、所定のパターンで半導体膜3又は金属膜9に達する開口21aが形成される。なお、ウエットエッチングは、第3の実施の形態のSTEP25と同様に実施できるので、重複する説明を省略する。
次に、図18を参照しながら、第1及び第2の実施の形態にかかる成膜方法、並びに第3及び第4の実施の形態にかかる半導体装置の製造方法に利用可能な基板処理装置について説明する。図18は、基板処理装置200の概要を示す平面図である。基板処理装置200は、インターフェィス部201、処理ステーション203及び制御部205を備えている。
インターフェイス部201は、図示しない外部の処理装置と処理ステーション203との間で被処理体としての基板の受け渡しを行う。インターフェイス部201によって、他のシステムから基板処理装置200へ基板を搬入したり、基板処理装置200から他のシステムへ基板を搬出したりすることができる。インターフェイス部201は、搬送路211と、この搬送路211を図18中に示されるX方向に往復移動可能な第1の搬送装置RBT1を有している。第1の搬送装置RBT1は、θ方向に回転可能な図示しない搬送用アームを備えている。このような構成により、第1の搬送装置RBT1は、後述する処理ステーション203のエクステンションユニットEXTにアクセスできるようになっている。
処理ステーション203は、基板へ対して、ポリシラン溶液や金属塩溶液の塗布処理、アニール処理、冷却処理、無電解めっき処理、ポリシラン膜等のウエットエッチング処理、及び紫外線照射処理を行う際の一連の工程を実施するための複数の処理ユニットを備えている。
基板処理装置200を構成する各構成部は、制御部(CTL)205に接続されて制御される構成となっている。コンピュータ機能を有する制御部205は、図示は省略するが、CPUを備えたコントローラと、このコントローラに接続されたユーザーインターフェースと記憶部を備えている。記憶部には、基板処理装置200で実行される各種処理をコントローラの制御にて実現するための制御プログラム(ソフトウェア)や処理条件データ等が記録されたレシピが保存されている。そして、必要に応じて、ユーザーインターフェースからの指示等にて任意の制御プログラムやレシピを記憶部から呼び出してコントローラに実行させることで、制御部205の制御下で、基板処理装置200において所望の処理が行われる。なお、前記制御プログラムや処理条件データ等のレシピは、コンピュータ読み取り可能な記録媒体に格納された状態のものを記憶部にインストールすることによっても利用できる。コンピュータ読み取り可能な記録媒体としては、特に制限はないが、例えばCD−ROM、ハードディスク、フレキシブルディスク、フラッシュメモリ、DVDなどを使用できる。また、前記レシピは、他の装置から、例えば専用回線を介して随時伝送させてオンラインで利用したりすることも可能である。
Claims (8)
- 膜状または基板状の半導体材料層上に設けられた第1の絶縁膜及び第2の絶縁膜からなるゲート絶縁膜と、該ゲート絶縁膜上に設けられたゲート電極としての導体膜と、を有するMOS構造の積層膜を形成する成膜方法であって、
前記半導体材料層上に前記第1の絶縁膜を形成する工程と、
前記第1の絶縁膜が表面に露出した基板にポリシラン溶液を塗布し、前記第1の絶縁膜上にポリシラン膜を形成する工程と、
前記ポリシラン膜上に、金属塩溶液を塗布して金属イオン含有膜を形成することにより、前記ポリシラン膜を前記第2の絶縁膜としてのポリシロキサン膜へ、前記金属イオン含有膜を金属微粒子含有膜へ、それぞれ改質してMOS構造の積層膜を形成する工程と、
を備えた成膜方法。 - 前記金属微粒子含有膜をめっき触媒としてめっき法により金属膜を積層形成する工程をさらに備えた請求項1に記載の成膜方法。
- 前記基板を加熱処理する工程をさらに備えた請求項1又は2に記載の成膜方法。
- 膜状または基板状の半導体材料層上に設けられたゲート絶縁膜としての酸化物膜と、該酸化物膜上に設けられたゲート電極としての導体膜と、を有するMOS構造の半導体装置の製造方法であって、
前記半導体材料層が表面に露出した基板に、ポリシラン溶液を塗布し、前記半導体材料層上に第1のポリシラン膜を形成する工程と、
前記第1のポリシラン膜の上に、単分子膜を所定のパターンで形成する工程と、
前記第1のポリシラン膜及び前記単分子膜の上から金属塩溶液を塗布して金属イオン含有膜を形成することにより、前記金属イオン含有膜に接している部分の前記第1のポリシラン膜を第1のポリシロキサン膜へ、前記金属イオン含有膜を金属微粒子含有膜へ、それぞれ改質してMOS構造の積層膜を形成する工程と、
未改質の前記金属イオン含有膜と前記単分子膜と未改質の前記第1のポリシラン膜をエッチングによって除去する工程と、
前記金属微粒子含有膜をめっき触媒としてめっき法により金属膜を積層形成する工程と、
前記第1のポリシロキサン膜と前記金属微粒子含有膜の上に、さらに、ポリシラン溶液を塗布し、前記金属微粒子含有膜と前記第1のポリシロキサン膜を覆うように第2のポリシラン膜を形成する工程と、
前記第2のポリシラン膜に部分的に紫外線を照射し、第2のポリシロキサン膜に改質する工程と、
未改質の前記第2のポリシラン膜をエッチングによって除去することにより、前記第2のポリシロキサン膜に前記半導体材料層または前記金属膜に達する開口を形成する工程と、
を備えた半導体装置の製造方法。 - 前記基板を加熱処理する工程をさらに備えた請求項4に記載の半導体装置の製造方法。
- 前記開口の内部に露出した状態の前記半導体材料層又は前記金属膜の表面に形成された酸化膜を除去する工程をさらに備えた請求項4又は5に記載の半導体装置の製造方法。
- 前記第2のポリシラン膜のエッチングをウエットエッチングにより行う請求項4から6のいずれか1項に記載の半導体装置の製造方法。
- 前記単分子膜と前記第1のポリシラン膜のエッチングをウエットエッチングにより行う請求項4から7のいずれか1項に記載の半導体装置の製造方法。
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US8785311B2 (en) | 2014-07-22 |
KR101267165B1 (ko) | 2013-05-23 |
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US20140290857A1 (en) | 2014-10-02 |
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