JP2021520640A - 原子層堆積で使用するための重合性自己組織化単分子層 - Google Patents
原子層堆積で使用するための重合性自己組織化単分子層 Download PDFInfo
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Images
Classifications
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Abstract
Description
SAMと呼ばれる自己組織化単分子層を、基板の表面の一部分上に配置し、それによって、表面の一部分がマスクされないまま、表面のマスクされた部分を形成することであって、SAMが、式(1):
aは、1または2であり、
H’は、静電相互作用または共有結合あるいはその両方によって、表面の前記部分に結合することができる官能基を含む頭部基であり、
T’は、頭部基に共有結合的に連結した尾部基であり、尾部基は、水素結合形成官能基、重合性基、および無極性周辺末端基(peripheral end group)を含む]
の化合物の結合形態を含む、形成すること;
SAMを放射に露光し、それによって重合したSAMを形成すること;および
原子層堆積のプロセスを使用して、表面のマスクされていない部分上に材料を選択的に堆積させ、それによって層状構造を形成すること
を含む。
SAMと呼ばれる自己組織化単分子層を、基板の表面上に配置することであって、SAMが、式(1):
aは、1または2であり、
H’は、静電相互作用または共有結合あるいはその両方によって、表面の部分に結合することができる官能基を含む頭部基であり、
T’は、頭部基に共有結合的に連結した尾部基であり、尾部基は、水素結合形成官能基、重合性基、および無極性周辺末端基を含む]
の化合物の結合形態を含む、配置すること;
SAMを放射にパターン的に露光し、それによって、露光SAMおよび非露光SAMを含むパターン化されたSAMを形成することであって、露光SAMは化合物の重合した形態を含む、形成すること;
非露光SAMを選択的に除去し、それによって基板の表面のマスクされない領域を形成すること;および
原子層堆積のプロセスを使用して、基板のマスクされない領域上に材料を選択的に堆積させること
を含む。
自己組織化単分子層を基板の一部分上に配置し、それによって、基板の一部分がマスクされないまま、基板のマスクされた部分を形成することであって、自己組織化単分子層は、光重合性部分、水素結合形成部分、およびこれらの組合せからなる群から選択される部分を含む、形成すること;および
原子層堆積のプロセスを使用して、基板のマスクされていない部分上に材料を選択的に堆積させること
を含む。
[式中、
aは、1または2であり、
H’は、静電相互作用または共有結合あるいはその両方によって、基板の所与の選択された上面に結合することができる官能基を含むは頭部基であり、
T’は頭部基に共有結合的に連結した尾部基であり、尾部基は、水素結合形成官能基、重合性基、および無極性周辺末端基を含む]
による構造を有する。
[式中、
H’は、静電相互作用または共有結合あるいはその両方によって、基板の所与の選択された上面に結合することができる官能基を含む頭部基であり、
S’−B’−S’’−P’−E’は、H’に共有結合的に連結した尾部基であり、
S’は、少なくとも1個の炭素を含む第1のスペーサー基であり、
B’は、水素結合形成官能基を含む部分であり、
S’’は、少なくとも1個の炭素を含む第2のスペーサー基であり、
P’は重合性基を含む部分であり、
E’は1〜20個の炭素を含む無極性周辺末端基である]
による構造を有する。
[式中、
mは、4〜20の値を有する正の整数であり、
nは、0〜19の値を有する正の整数であり、
H’は、静電相互作用または共有結合あるいはその両方によって、基板の所与の選択された上面に結合することができる官能基を含む頭部基であり、
S’は、少なくとも1個の炭素を含むスペーサー基であり、
B’は、水素結合形成基を含む部分であり、
各Xは、水素およびフッ素からなる群から選択される独立した置換基である]
による構造を有する。
[式中、
kは、1〜10の値を有する正の整数であり、
mは、4〜20の値を有する正の整数であり、
nは、4〜20の値を有する正の整数であり、
H’は、静電相互作用または共有結合あるいはその両方によって、基板の所与の選択された上面に結合することができる官能基を含む頭部基であり、
B’は、アミド、尿素、およびウレタンからなる群から選択される一員を含む部分であり、各Xは、水素およびフッ素からなる群から選択される独立した置換基である]
による構造を有する。
ALDによって層状構造を形成する第1の方法を、図1の(A)〜(F)の断面層の略図で説明する。この方法は、原子層堆積中に表面をマスクするためのレジストとして、重合性SAMを利用する。図1の(A)の基板110は、1つまたは複数の層を含むことができる。簡単にするため、基板110は、1つの層である層112(例えば、銅箔)を有して示される。層112は、SAM形成化合物の頭部基とイオン的または共有結合的に結びつくことができる、上面114を有する。
この方法では、SAM形成化合物の頭部基は、異なる化学組成の2つまたはそれ以上の領域を含む基板の上面の部分への優先的親和性を有し、そこへ選択的に吸着する。
基板は、1つまたは複数の層を含む層状構造であり、上面を有する。基板、より具体的には基板の表面は、無機または有機材料、例えば、金属、炭素、またはポリマーあるいはその組合せを含むことができる。より具体的には、基板は、例えば、Si、SiGe、SiGeC、SiC、Ge合金、GaAs、InAs、InP、窒化ケイ素、窒化チタン、酸化ハフニウム、および他のIII〜V族またはII〜VI族化合物半導体を含む、半導体材料を含むことができる。基板は、誘電材料、例えば、SiO2、TiO2、Al2O3、Ta2O5およびポリマー(例えば、ポリイミド、ポリアミド、ポリエチレン)などを含むことができる。基板は、層状半導体、例えば、Si/SiGe、またはセミコンダクター・オン・インシュレータ(SOI)も含むことができる。特に、基板は、Si含有半導体材料(すなわち、Siを含む半導体材料)を含有することができる。半導体材料は、ドープされ得、非ドープされ得、またはその中にドープ領域および非ドープ領域を含有することができる。
SAM層を調製するための組成物も開示される。組成物は、溶媒および溶媒に接する0.1〜5wt%のSAM形成化合物を含み、wt%は組成物の全重量に対するものである。SAM形成化合物は、溶媒中に溶解または分散することができる。組成物は、SAM形成化合物を含むSAM層を形成するのに好適である。例示的な溶媒としては、限定されるものではないが、トルエン、キシレン、ジクロロメタン(DCM)、クロロホルム、四塩化炭素、酢酸エチル、酢酸ブチル、酢酸アミル、プロピレングリコールモノメチルエーテルアセテート(PGMEA)、プロピレングリコールモノメチルエーテル(PGME)、エトキシエチルプロピオナート、アニソール、乳酸エチル、ジエチルエーテル、ジオキサン、テトラヒドロフラン(THF)、アセトニトリル、酢酸、酢酸アミル、酢酸n−ブチル、γ−ブチロラクトン(GBL)、アセトン、メチルイソブチルケトン、2−ヘプタノン、シクロヘキサノン、メタノール、エタノール、2−エトキシエタノール、2−ブトキシエタノール、イソ−プロピルアルコール、n−ブタノール、N,N−ジメチルホルムアミド(DMF)、N,N−ジメチルアセトアミド、ピリジン、およびジメチルスルホキシド(DMSO)が挙げられる。溶媒は、単独でまたは組合せて使用され得る。
ALD堆積に対して所与の基板表面を非活性化するSAMの選択性の程度は、SAM形成化合物の尾部の化学構造、頭部基が基板表面へ結合する性質(イオン性または共有結合性)、SAM層中の任意の溶媒の存在、最密充填を達成するために使用されるアニーリング条件(例えば、温度、環境、およびアニーリング時間)、達成された重合度、およびSAM界面(例えば、SAM−空気界面)の特性の関数である。これらのパラメータは、所与のALD前駆体の堆積に対してSAMの抵抗性を最適化するために、調整され得る。
SAMフィーチャーの選択的除去は、任意の好適なプロセス(例えば、熱分解性材料の熱ベーキング、反応性イオンエッチングプロセス、選択的溶媒中での溶解、紫外線露光、または前述の組合せ)によって実施することができる。選択的除去としては、プラズマエッチングなどのドライエッチング、または選択溶媒もしくは蒸気またはその両方を使用するウェットエッチング、あるいはその両方が挙げられる。典型的には、好適なガス(O2)を使用するドライエッチングプロセスが、50nm以下の寸法でのエッチングに用いられる。選択的にSAMフィーチャーを除去することによって、下にある基板へ転写され得るレリーフパターンが作り出される。
金属、金属酸化物、窒化物またはポリシリコンのパターン化された層を含む層状構造を形成するために、上記方法を使用することができる。この方法は、低減されたフィーチャーの大きさおよび良好な均一性を有する、構造的フィーチャーを有利に提供する。
(3−(ペンタコサ−10,12−ジインアミド)プロピル)ホスホン酸(DA)を、市販のジエチル(2−シアノエチル)ホスホネートおよび10,12−ペンタコサジイン酸から3ステップで合成した。
様々なSAMの接触角を、浸漬時間の関数として、金属表面(Cu、Sn、Zn、V)およびシリコン表面(本来のSiO2、SiN)を含む様々な表面上で測定した。すべてのSAM溶液を、溶媒4−メチル−2−ペンタノール中の0.1wt%溶液として調製し、次に、0.2マイクロメートルのPTFEシリンジフィルターを通してろ過した。被覆直前に、表面を酸素プラズマによって浄化した。この方法で浄化した場合、金属表面は金属酸化物を含有することを理解すべきである。特に明記しない限り、被覆はすべて室温で行った。
本来のSiO2表面の一部分をCuの堆積から保護する円形のシャドウマスクを使用して、4インチ(10.16cm)の再生シリコンウエハ上に、厚さ50nmのCu膜を蒸着した。真空を破った後、Cu層は、表面上に本来の酸化物層(すなわち、CuOまたはCu2Oあるいはその両方)を成長させた。次に、ウエハを、ジメチルスルホキシド(0.5mg/mL、試薬用)中の(3−(ペンタコサ−10,12−ジインアミド)プロピル)ホスホン酸(DA)溶液に65℃で24時間浸漬し、次に、イソプロパノールですすぎ、定流量の窒素を使用して乾燥した。SAMに対する接触角は104°であり、Cu表面上に良好に組織化されたSAMの形成を表している。ウエハを窒素雰囲気下で120℃に加熱し、金属酸化物によるホスホン酸のエステル化を促進した。次に、SAMに対する接触角は104°であると測定され、SAMがCu膜から脱着されなかったことを表している。
SAMを形成するために使用されるこの基板を、図5に示す。基板300は、上面314を有するCuラインパターン312を含む。Cuラインパターン312は誘電体層316に埋め込まれており、誘電体層はオクタメチルシクロテトラシロキサン(OMCTS)から調製され、SiO2を含む上面318を有する。Cuラインパターン312の上面314は、銅の酸化物を含有する。Cuラインパターン312の上面314は、誘電体層316の上面318と同一平面上でもある。基板300の底層310は、シリコンウエハであった。
ZnO堆積の手順は、上に記載されている。
Claims (20)
- SAMと呼ばれる自己組織化単分子層を、基板の表面の一部分上に配置し、それによって、前記表面の一部分がマスクされないまま、前記表面のマスクされた部分を形成することであって、前記SAMが、式(1):
aは、1または2であり、
H’は、静電相互作用または共有結合あるいはその両方によって、前記表面の前記部分に結合することができる官能基を含む頭部基であり、
T’は、前記頭部基に共有結合的に連結した尾部基であり、前記尾部基は、水素結合形成官能基、重合性基、および無極性周辺末端基を含む]
の化合物の結合形態を含む、前記形成すること;
前記SAMを放射に露光し、それによって重合したSAMを形成すること;および
原子層堆積のプロセスを使用して、前記表面のマスクされていない部分上に材料を選択的に堆積させ、それによって層状構造を形成すること
を含む、方法。 - aが1である、請求項1に記載の方法。
- 前記頭部基H’が、ホスホン酸基(*−P(=O)(−OH)2およびその塩、カルボン酸基(*−C(=O)OH)およびその塩、スルホン酸基(*−S(=O)2OH)およびその塩、スルフィン酸基(*−S(=O)OH)およびその塩、アルコール(*−OH)、チオール(*−SH)、アルケン(*−C=C−*)、アルキン(*−C≡C−*)、シラン、ならびにこれらの組合せからなる群の一員を含む、請求項1に記載の方法。
- 前記水素結合形成官能基が、アミド、ウレタン、尿素、およびこれらの組合せからなる群から選択される官能基を含む、請求項1に記載の方法。
- 前記尾部基の前記重合性基が、1,3−ブタジエン−1,4−ジイル基(*−C=C(H)−C(H)=C−*)、ブタジイン−1,4−ジイル基(*−C≡C−C≡C−*)、およびこれらの組合せからなる群の一員を含む、請求項1に記載の方法。
- 前記重合性基が、ブタジイン−1,4−ジイル基(*−C≡C−C≡C−*)を含む、請求項1に記載の方法。
- 前記化合物が、環を含まない、請求項1に記載の方法。
- 前記SAMが、無極性上面を有する、請求項1に記載の方法。
- 前記基板の前記表面の前記マスクされた部分が、銅の酸化物を含有する、請求項1に記載の方法。
- 前記基板の前記表面の前記マスクされていない部分が、SiO2を含有する、請求項1に記載の方法。
- 前記無極性周辺末端基が、炭素ならびに、水素、フッ素、およびこれらの組合せからなる群から選択される一員を含む、請求項1に記載の方法。
- 前記SAMが、溶媒に溶解した前記化合物を含む溶液と前記基板を接触させることによって形成され、前記化合物が前記基板の前記部分に選択的に吸着する、請求項1に記載の方法。
- B’が、アミド基、ウレタン基、および尿素基からなる群から選択される、請求項13に記載の方法。
- 請求項1に記載の方法によって形成された、層状構造。
- SAMと呼ばれる自己組織化単分子層を、基板の表面に配置することであって、前記SAMが、式(1):
aは、1または2であり、
H’は、静電相互作用または共有結合あるいはその両方によって、前記表面の前記部分に結合することができる官能基を含む頭部基であり、
T’は、前記頭部基に共有結合的に連結した尾部基であり、前記尾部基は、水素結合形成官能基、重合性基、および無極性周辺末端基を含む]
の化合物の結合形態を含む、前記配置すること;
前記SAMを放射にパターン露光し、それによって、露光SAMおよび非露光SAMを含むパターン化されたSAMを形成することであって、前記露光SAMは前記化合物の重合した形態を含む、前記形成すること;
前記非露光SAMを選択的に除去し、それによって前記基板の前記表面のマスクされていない領域を形成すること;および
原子層堆積のプロセスを使用して、前記基板の前記マスクされていない領域上に材料を選択的に堆積させること
を含む、方法。 - 前記SAMを露光することが、紫外光を使用して行われる、請求項16に記載の方法。
- 自己組織化単分子層を基板の一部分上に配置し、それによって、前記基板の一部分がマスクされないまま、前記基板のマスクされた部分を形成することであって、前記自己組織化単分子層が、光重合性部分、水素結合形成部分、およびこれらの組合せからなる群から選択される部分を含む、前記形成すること;および、
原子層堆積のプロセスを使用して、前記基板のマスクされていない部分上に材料を選択的に堆積させること
を含む、方法。 - 前記単分子層が光重合性部分を含み、前記方法が、前記自己組織化単分子層を光重合し、それによって原子層堆積中の前記マスクされた部分の選択性を強化することを含む、請求項18に記載の方法。
- 前記単分子層が、原子層堆積中の前記マスクされた部分の選択性を強化する水素結合形成部分を含む、請求項18に記載の方法。
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GB2591002A (en) | 2021-07-14 |
JP7189963B2 (ja) | 2022-12-14 |
GB202016154D0 (en) | 2020-11-25 |
GB2591002B (en) | 2022-05-04 |
DE112019002026T5 (de) | 2021-01-07 |
US20190322812A1 (en) | 2019-10-24 |
US10782613B2 (en) | 2020-09-22 |
CN111971803A (zh) | 2020-11-20 |
WO2019202418A1 (en) | 2019-10-24 |
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