JP5009993B2 - ナノワイヤの配列方法および堆積方法 - Google Patents
ナノワイヤの配列方法および堆積方法 Download PDFInfo
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- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/93—Batch processes
- H01L2224/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
- H01L2224/95053—Bonding environment
- H01L2224/95085—Bonding environment being a liquid, e.g. for fluidic self-assembly
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/882—Assembling of separate components, e.g. by attaching
- Y10S977/883—Fluidic self-assembly, FSA
Description
ここに示すと共に説明する特定の形態は、本発明の例であって、本発明の範囲を多少なりとも限定することを意図するものではないことは明らかであろう。簡潔にするために、実際には、従来の電子機器、製造方法、半導体デバイス、および、ナノワイヤ(NW)技術、ナノロッド技術、ナノチューブ技術、および、ナノリボン技術、および、このシステムの他の機能的な態様(および該システムの個々の操作部材である部材)については、ここでは詳細に説明していない。簡潔にするために、ここではさらに、本発明をナノワイヤに関連して記載している場合が多い。
[電場配列および堆積]
[概要]
一実施形態において、本発明は、電磁場の存在下において、ナノワイヤを、懸濁した状態から、電極がパターン加工された基板上に配列および堆積させる方法、並びに、このような配列および堆積を実行する装置およびシステム(図2参照)を提供する。基板およびナノワイヤの界面化学によって、基板およびナノワイヤの両方に正味電荷が提供される。電極パターンを適切に選択することによって、ナノワイヤには電磁場勾配が生じ、該電磁場勾配によって正味の力がナノワイヤ上に加えられる。この正味の力によって、(例えば懸濁液中の)ナノワイヤを基板上の特定の位置に制御しながら動かすことが可能になる。上記電極はまた、ナノワイヤを分極させる交流(AC)電場を生成し、結果的に正味双極子モーメントが生じる。続いて上記AC電場がこの双極子にトルクをかけ、上記電場の方向に対して平行な角度配列が可能となる。電気的パラメータ、例えば周波数および振幅を適切に選択することによって、ナノワイヤは配列および捕獲され、電極の上にナノワイヤ(NW)の「ピン止め」または「関連付け」が行われる。関連付けされた状態では、ナノワイヤは、好適には電場に平行に配列されているが、電極の縁に沿って十分に移動可能であり、ナノワイヤを凝集させることなく、配列および関連付け動作の時間シーケンスに対応可能である。本発明はまた、ナノワイヤを電極上に「固定」または「結合」させる方法を提供する。結合された状態では、ナノワイヤは、それ以前の関連付けされた状態と同様に、配列された状態に維持されるが、電極の縁に沿った横方向の移動性は失われる。本発明はまた、望ましくない/結合されていない/配列していないナノワイヤを電極から「洗い流す」ための流量の制御を適切に選択することを提供する。乾燥プロセスによって溶媒を除去して、表面のNW同士を静電気的に「粘着」させることが可能である。
[理論的考察]
電場配列の背後にある理論に関するさらなるいくつかの背景を提供するために、以下の章を記載する。当然ながら、本発明は、ここに記載する理論を抑制または制限するものではなく、当業者は、ここに記載する理論だけでなく他の理論も、本発明に適用可能であることを容易に認識するであろう。
[好適な実施形態]
一実施形態において、本発明は、1つまたは複数のナノワイヤを配置する方法を提供する。好適な実施形態では、これら方法は、1つまたは複数のナノワイヤを1つの電極対の近傍に供給する工程を含む。その後、この電極対に電圧を与え、これによってナノワイヤを該電極対に関連付ける。その後、電極対への電圧供給を調節し、これによって、ナノワイヤを電極対の上に結合させる。
多くの電子デバイスおよびシステムは、本発明の方法によって堆積したナノワイヤの薄膜を有する半導体あるいはその他の種類のデバイスを内蔵することができる。本発明のいくつかの応用例を以下あるいはその他の箇所にて説明するが、これに限定されるものではない。ここで説明する応用例には、ナノワイヤの配列あるいは非配列薄膜を含んでもよいし、ナノワイヤの複合あるいは非複合薄膜を含んでもよい。
図2および14aに示すように、流路206に、まず溶媒(IPA)1402を注入し、そして所望の濃度のナノワイヤ(NW)インク1404を注入する。NWインクの均一なフィルムをウェハ表面202上に導入した後、電極(204、205、207)パターンに、電場を印加した。E電場パラメータは、f=約500HzとV=1Vppであった。これらの状況下にあるナノワイヤは、その長軸が電場方向に平行に、懸濁液から電極に捕捉/関連付けされるのが確認される。この関連付けは、ナノワイヤが流体の流れにおいてあらかじめ配列されているか、あるいは静置した懸濁液から配列されずに抜き取られた状態で可能である。ナノワイヤは、互いに隣接して配列され、電極棒に沿って移動性を示すことが確認される。このナノワイヤの捕捉状態を、弱いナノワイヤの「ピン止め」あるいは関連付け1406と称し、図5および図8aに示す。この移動性は、電極幅毎におけるナノワイヤの均一且つ高いパッケージ密度を達成するのに用いられる。典型的なナノワイヤ堆積密度は、1ミクロンにつき、1ナノワイヤというオーダーである(距離は電極長さに沿う)。このナノワイヤピン止めは、引きつける誘電泳同力と、反発する電気浸透性力の間における均衡によってなされるものと思われる(図5参照)。当該プロセス(「ナノワイヤ配列」1408あるいは配列調節と称する)における次のステップには、同じAC振幅のままで、周波数をf=10kHzに増やすことが含まれる。このステップでは、おそらく高い誘電泳動力が、ナノワイヤの誘導された双極性モーメントに影響を及ぼすために、移動性の少ない状態(強いピン止め状態)でナノワイヤを互いに平行に配列する。当該プロセスにおける次のステップには、AC信号振幅を、f=10kHzにおいてV=4Vppに増やすことが含まれる。E電場におけるこの変化は、電極に対するナノワイヤの、いわゆる「固着」あるいは結合1410を示す。固着したナノワイヤの状態を、図11および図8bに示す。この状態において、ナノワイヤは、(おそらくナノワイヤと電極との間においてアクティブなファンデルワールス力により)電極棒に沿って、もしあったとしても、ごくわずかな移動性しか示さない。電極形状に適切に適合させたナノワイヤは、高い流体剪断力に対して強さを示すよう充分に固着される。しかしながら、電極形状に適合していないナノワイヤ(例えば、短いナノワイヤ)、ねじれたナノワイヤ、交差したナノワイヤ、あるいは枝分かれしたナノワイヤは、「ナノワイヤ分離」プロセスステップ1412において電極から分離されることが確認させる。所望のナノワイヤ堆積密度が達成できない場合(ステップ1414にて判断されるように)、「ナノワイヤピン止め」から「ナノワイヤ分離」までのプロセスステップを繰り返す(1406〜1412)。所望のナノワイヤ堆積密度が達成された場合(ステップ1414にて判断されるように)、E電場はオフに切り替え、流路は溶媒(EPA)1420で流す(好適には、数百マイクロリッターから数mLまでの流体が使用される)。最終的に、溶媒1422の揮発により、流路を乾燥することができる。電極パラメータのいくつかの変化により、ナノワイヤ堆積が行われることが確認された。具体的に、振幅調節を用いると、電極全体にわたって高い平衡配列を達成できることが分かった。「ナノワイヤピン止め」ステップにおいて、100%の調節指数(電場振幅比:キャリアの振幅)で、100Hzの調節周波数が用いられた。これらの状態で、ナノワイヤは主に、高ナノワイヤ堆積密度(1マイクロインチ毎に2つのナノワイヤ)までの平行配列で捕捉される傾向にある。さらに、交差ナノワイヤは、不安定であることが分かり、溶媒流速を上げることによって除去できる。典型的に生じるナノワイヤ堆積パターンを図9aおよび図9bに示す。
TaAl最外殻を有すCNOS組成(Si核)を含むナノワイヤは、標準成長・取り入れ技術(例えば、Gudiksen et al (2000) 「半導体ナノワイヤの直径選択的合成」J. Am. Chem. Soc. 122, 8801-8802; Cui et al. (2001)、「単結晶シリコンナノワイヤの直径制御合成」 Appl. Phys. Lett. 78, 2214-2216;Gudiksen et al. (2001)、および「単結晶半導体ナノワイの直径および長さの合成的制御」 J. Phys. Chem. B 105,4062-4064)を用いることにより生成された。ナノワイヤの長さは約22ミクロンで、直径は約100nm。 ナノワイヤの懸濁液は、中密度のものと、低密度のもの(中密度の懸濁液を10倍希釈したもの)を、イソプロパノール(IPA)中にて調整した。
TaAl最外殻を有すCNOS組成(Si核)を含むナノワイヤは、標準成長・取り入れ技術(例えば、Gudiksen et al (2000) 「半導体ナノワイヤの直径選択的合成」J. Am. Chem. Soc. 122, 8801-8802; Cui et al. (2001)、「単結晶シリコンナノワイヤの直径制御合成」 Appl. Phys. Lett. 78 2214-2216;Gudiksen et al. (2001)、および 「単結晶半導体ナノワイの直径および長さの合成的制御」 J. Phys. Chem. B 105,4062-4064)を用いることにより生成された。ナノワイヤの長さは約22ミクロンで、直径は約100nm。 ナノワイヤの懸濁液は、中密度のものと、低密度のもの(中密度の懸濁液を10倍希釈したもの)を、イソプロパノール(EPA)中にて調整した。
上記実施例1および2において説明したプロセスは、66マイクロメータのアレイにおいて配列される電極対に対して、ナノワイヤを生成、関連付け、結合するのに用いられた。初期の関連付けおよび結合段階に引き続き、5ミクロン毎に約1つのナノワイヤという密度が達成された(図9a参照)。
TaAlN最外殻を有するCNOS組成(Si核)を含むナノワイヤは、標準成長・取り入れ技術(例えば、Gudiksen et al (2000) 「半導体ナノワイヤの直径選択的合成」J. Am. Chem. Soc. 122, 8801-8802; Cui et al. (2001)、「単結晶シリコンナノワイヤの直径制御合成」 Appl. Phys. Lett. 78, 2214-2216;Gudiksen et al. (2001)、および 「単結晶半導体ナノワイの直径および長さの合成的制御」 J. Phys. Chem. B 105,4062-4064)を用いることにより生成された。ナノワイヤの長さは約20ミクロンで、直径は約100nm。 ナノワイヤの懸濁液は、高、中、低密度のもの(10倍希釈したもの)を、イソプロパノール(EPA)中にて調整した。
図22Aから図22Fは、明細書を通して説明する様々な方法を用いてナノワイヤを除去した後の、ナノワイヤの関連付けを示す一連の顕微鏡写真である。図22Aは、基板上に配置された一連の電極対207を示す。該顕微鏡写真は基板/電極対の上から撮られたものである。ナノワイヤが流路に導入され、電極対の上のぼやけた物体として確認できる。流路にはまた、電極対の上の除去電極が存在するが、ナノワイヤを可視化するために用いられている光学的画像システムの可視平面の上にあるときは、ナノワイヤは顕微鏡写真では見えない。図22Aによると、電極対の間、あるいは除去電極において電場は生成されなかった。
Claims (36)
- (a)1つまたは複数のナノワイヤを電極対の近傍に供給するナノワイヤ供給工程と
(b)上記電極対の間にAC電場を生成することにより、上記ナノワイヤを上記電極対に対して配列させる電圧供給工程と、
(c)上記電極対の間に印加されるAC電場の周波数または振幅、もしくはその両方を調節することにより、上記ナノワイヤを上記電極対上に結合させる調節工程とを含む、1つまたは複数のナノワイヤを配置する方法。 - 上記ナノワイヤ供給工程は、ナノワイヤの懸濁液を供給することを含む、請求項1に記載の方法。
- 上記AC電場を生成することは、直接電気的接続を用いて、上記電極対に信号を供給することを含む、請求項1に記載の方法。
- 上記AC電場を生成することは、上記電極対に電磁波を供給することを含む、請求項1に記載の方法。
- 上記電圧供給工程、および、上記調節工程は、上記電極対に電磁波を供給することを含む、請求項1に記載の方法。
- 上記電極対に電磁波を供給することは、上記電極対に約1GHzから約5GHzの電磁波を供給することを含む、請求項5に記載の方法。
- 上記AC電場を生成することは、約10Hzから約5kHzの周波数においてAC電場を生成することを含む、請求項1に記載の方法。
- 上記AC電場を生成することは、約0.5Vから約3Vの振幅においてAC電場を生成することを含む、請求項1に記載の方法。
- 上記調節工程は、上記AC電場の周波数を調節すること、上記AC電場の振幅を調節すること、または、これら両方を含む、請求項1に記載の方法。
- 上記調節工程は、上記AC電場の周波数を、約1kHzから約500kHzに増大させることを含む、請求項9に記載の方法。
- 上記調節工程は、上記AC電場の振幅を、約2Vから約20Vに増大させることを含む、請求項9に記載の方法。
- 上記調節工程は、上記AC電場の周波数を約500Hzから約100kHzまで増大させて、その後、上記AC電場の振幅を約1Vから約4Vまで増大させることを含む、請求項9に記載の方法。
- 上記電極対の電極の間に1つまたは複数の金属要素を配置する、請求項1に記載の方法。
- (d)上記電極対から、結合されていない1つまたは複数のナノワイヤを除去するナノワイヤ除去工程をさらに含む、請求項1に記載の方法。
- 上記除去工程は、結合されていないナノワイヤを洗い流すことを含む、請求項14に記載の方法。
- 結合された1つまたは複数のナノワイヤを乾燥させることをさらに含む、請求項14に記載の方法。
- 工程(b)〜(c)を繰り返すことをさらに含む、請求項14に記載の方法。
- (e)上記結合された1つまたは複数のナノワイヤを基板上に転写するナノワイヤ転写工程をさらに含む、請求項14または16に記載の方法。
- (e)上記電極対を除去する電極対除去工程をさらに含む、請求項14または16に記載の方法。
- 上記電極対の電極は、上記ナノワイヤの長軸の長さよりも短い間隔、または、上記長軸と同じ長さの間隔によって分離されている、請求項1に記載の方法。
- 上記1つまたは複数のナノワイヤは、1つの半導体核と上記核の周りに配置された1つまたは複数の殻層とを含む、請求項1に記載の方法。
- 上記半導体核はSiを含む、請求項21に記載の方法。
- 最外の殻層は金属または酸化物を含む、請求項21に記載の方法。
- 上記金属はTaAlNまたはWNである、請求項23に記載の方法。
- (a)懸濁液中の1つまたは複数のナノワイヤを、転写基板上の電極対の近傍に供給するナノワイヤ供給工程と、
(b)上記電極対の間にAC電場を生成することにより、上記ナノワイヤを上記電極対に対して配列させる電圧供給工程と、
(c)上記電極対の間に印加されるAC電場の周波数または振幅、もしくはその両方を調節することにより、上記ナノワイヤを上記電極対上に結合させる調節工程と、
(d)結合されていない1つまたは複数のナノワイヤを除去するナノワイヤ除去工程と、
(e)結合された1つまたは複数のナノワイヤを、上記転写基板から基板上に転写するナノワイヤ転写工程とを含む、1つまたは複数のナノワイヤを基板上に配置する方法。 - 上記ナノワイヤ転写工程の前に、上記結合された1つまたは複数のナノワイヤを乾燥させることをさらに含む、請求項25に記載の方法。
- 上記電極対の電極は、上記ナノワイヤの長軸の長さよりも短い間隔、または、上記長軸と同じ長さの間隔によって分離されている、請求項25に記載の方法。
- 上記AC電場を生成することは、直接電気的接続を用いて、上記電極対に信号を供給することを含む、請求項25に記載の方法。
- 上記AC電場を生成することは、上記電極対に電磁波を供給することを含む、請求項25に記載の方法。
- 上記AC電場を生成すること、および、上記調節工程は、上記電極対に電磁波を供給することを含む、請求項25に記載の方法。
- 上記電磁波を供給することは、上記電極対に、約1GHzから約5GHzの電磁波を供給することを含む、請求項29に記載の方法。
- 上記AC電場を生成することは、約10Hzから約5kHzのAC電場と、約0.5Vから約3Vの振幅とを生成することを含む、請求項25に記載の方法。
- 上記調節工程は、上記AC電場の周波数を調節すること、上記AC電場の振幅を調節すること、または、これら両方を含む、請求項25に記載の方法。
- 上記調節工程は、上記AC電場の周波数を、約1kHzから約500kHzまで増大することを含む、請求項25に記載の方法。
- 上記調節工程は、上記AC電場の振幅を、約2Vから約20Vまで増大させることを含む、請求項25に記載の方法。
- 上記調節工程は、上記AC電場の周波数を、約500Hzから約100kHzまで増大させて、その後、上記AC電場の振幅を、約1Vから約4Vまで増大させることを含む、請求項25に記載の方法。
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