TW554388B - Methods of fabricating nanostructures and nanowires and devices fabricated therefrom - Google Patents

Methods of fabricating nanostructures and nanowires and devices fabricated therefrom Download PDF

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TW554388B
TW554388B TW91106432A TW91106432A TW554388B TW 554388 B TW554388 B TW 554388B TW 91106432 A TW91106432 A TW 91106432A TW 91106432 A TW91106432 A TW 91106432A TW 554388 B TW554388 B TW 554388B
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TW91106432A
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Arun Majumdar
Samuel S Mao
Eicke R Weber
Ali Shakouri
Richard E Russo
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Univ California
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Description

乃4388 五、發明說^7 【發明領域】 結晶ί ϊ:係ΐ關於—種奈米結才冓’特別有關於〆種實質 之最夫二只ί、"構，其包含有一沿著線軸之直徑，其直徑 可以制匕量小於10%，且其直徑約為2〇〇nm。此奈米結構 組合纟I構、種同質結構'一種異質結構或是上述兩種之 【發明背景】 第1圖顯示有政轉換不同型式能量（例如：熱力、電 Y機械與光學）的技術，其乃現代經濟之創造基礎，且 二，學與工程之發展最被認可的象徵。舉例而言，光電子 二是用來處理光學與電子之間的轉換，其展現出現代資訊 、'技方面之基礎。熱能與電能之間的轉換是能量經濟之一 種特徵’即使效率與轉換方法僅獲得微小的改善，亦會對 金融儲蓄、能量儲存量以及環境造成巨大的影響。相同 地’電子機械之能量轉換成已經成為現代機械與感應器之 核心技術’可使其廣泛地應用於工業技術上。基於其重要 十生’很自然的會聯想到奈米等級之科技與工程是否能夠在 月匕量轉換中扮演一個角色。無疑的，對元件之小型化以及 高效率的持續要求情況下，奈米等級之元件可以在能量轉 換中發揮作用。因此，以一維無機奈米結構或奈米線為基 礎之高品質的能量轉換元件，確實有其大幅度開發之必要 性。有鑑於此，本發明之技術會滿足上述需求，並克服習 知技術之缺點。
l〇12-4754-PF(N).ptd 第8頁 554388 -------- 五、f明說明（3) •播材料組成。例如有一種縱向的異質社 ,鄰之線段是由Si與SiGe這兩種不同=奈米線，其中兩 、 本發明之奈米線異質結構中，在〜1料所構成的。 一接合面具有相當明顯的輪摩。舉$ ^，晶材料之間產 遞變帶（transition zone)，其輪廊與歹一來Ί才料之間的 子層相當。對L0HN而言，其遞變帶合q厚度20nm之原 的-個端點朝向相鄰之第二材口：著第：材料之二 一材料成分會降低，且約為第一材料^立於這個端點的第 99%。特別是，異質結構之成分變化距離由，向9中心處成分的 至第二材料之間1 // m距離内。對c〇HN而古，疋並在1 一材料 端點處是以放射狀方式量測。對任一 -巧/。成分之 帶會自一實質結晶或實質單晶材料變化：：：；同巧= 料。不過，由於本發明之異質結構可包 ^刀 故後不7 Μ 4梦貝避變現豕 。 使用前述之本發明結構可以獲得各種表面配置型態， 分已經在先前描述。其他的例子為··單個或多個接合 JHN、單個或多個接合面之c〇HN、LOHN斑ΓΟΗΝ之組 軸向之夕重線段，因此基於特殊應用與需求，显質社構之 二部份的接合面會顯示出非常明顯的輪廓’其他部^則不 s 。，且，不但相鄰線段之材料成分可為急遽或緩和的變 化藉由控制異質結構之線段材料的摻雜，亦可在線段之 間形成急遽或緩和的摻質遞變現象。 7土 CD 、产 . « 一 " 部 面之L0HN、單個或多個接合面之c〇HN、L0HN與COHN之組 合、兩端子配置、N > 2端子配置、異質結構與同質結構之 組合、具有一個或多個電極（可為異質結構）之同質結構、 具有一個或多個電極之異質結構、具有絕緣體之同質結
1012-4754-PF(N).ptd 第10頁 554388 五、發明說明（4) 構、具有絕緣體之異質結構。在一 =面係構成一異質接合面。使用這些^構與配^之間的 束制電子的量子點、熱電寺殊區域中 2元件(如•奈米雷射)、奈米心 制動器與感應器）、纟種形式之能量轉換元牛(如·電機 至機械能、熱能轉換至光）以及其他元件。 如·光轉換 【發明之詳細說明】 為讓本發明之上述和其他目的、特徵 員易懂，下文特舉出較佳實施例，並配 明 細說明如下： 口式’作詳 1·介紹 本發明提供一系列奈米結構（nanostructure)， t之為奈米線（nanowires)。本發明之奈米線包含 = 、·口構（heter〇structure)，其乃由至少一種實質姓日絲， =另種不相同的材料所構成，則可於這兩種材曰:: 形成一"面（interface)或接合面（juncti〇n)。而且間 發明之奈米線所使用的異質結構，亦可採用材質 晶方向不同的兩種材料。此外，本發明之奈米線（一、、，。 夤結構或異質結構）的表面具有捕獲特殊的化學戋生^ 5 類的功能。實際上，實質結晶材料是用來製作異質結種， 可以使異質結構具有相同的實質結晶效果。在較佳 中，在異質結構中至少包含有一種材料具有實質結晶^例
554388 五、發明說明（5) 就這一點而言，如果材料表現出 r則最佳的選擇為使用實二律=一 直徑線= = 於2°-，… L ^ 不木線之直徑變化量小於1 〇%。因 :’本么明之奈米線具有各種剖面形狀’包含有圓形、方 ，、矩u邊形等，但是不限定為哪—種形狀。舉例來 祝’ ZnO奈米線具有六邊形剖面輪廓，Sn〇2奈米線具有方 形剖面輪廓，Si或Ge奈米線具有圓形剖面輪廓。 、本發明之奈米線異質結構的表面配置中，包含有兩個 或多個實質單晶材肖，其於空間中的排列方式可以開發出 新穎且獨特的量子限制效應。此種方式係期望開啟一條科 學發現之道路，並提供一種能量轉換技術之戲劇性變化的 期望。 本發明係借助熟知之氣—液一固 (vapor - liquid-solid，VLS)化學合成製程，本文中將會 描述此製程，且此製程已詳述於下列之參考刊物中： Wagner, R. S. , UVLS Mechanical of Crystal Growth"；
Whisker Technology， ρρ·47-119(1970) ; Wagner， et al·， Vapor-Liquid-Solid Mechanism of Single Crystal Growth’1，Applied Physical Letters，Vol 4·，
No. 5，pp· 89-90(1964) ;Givargizov，E·，n Fundamental
Aspect of VLS Growth", Journal of Crystal Growth, Vol.31, ρρ·2 0-30 ( 1 975 )。在VLS製程中，若是採用廣泛 變化之半導體材料（如：Si、Ge、ZnO等）可以長出單晶奈
1012-4754-PF(N).ptd 第12頁 554388 五、發明說明（6) ' 米，’且其直經可控制在2〇〇nm以下，且最佳情況下可將 直徑控制於5〜5〇nm範圍内，而其長度範圍可為卜2〇 “瓜。 此外，也可利用III-V族、n-IV族、Π—¥1族等材料，以 VLS製程進行單晶奈米線之製作。 除此之外，若是半導體奈米線的直徑縮短至5~50nm， 則電子之量子束制效應會允許更改電子帶結構。此種束制 亦會強烈地影響奈米線之聲子傳送’纟乃因為顯著地修改 聲譜以及使用壽命。在VLS奈米線合成中，其表面能與成 長方向的重要性，乃在於奈米線的合成相（synthesizing phases)可呈現穩定狀態’至於在一個主體或薄膜中的合 成相則會呈現準安定狀態。也因此，具有獨特相態與性1 之材料可以創造出此種作用。 ' 2. 奈米線異質結構 請參閱第2與3圖，其顯示本發明之兩種奈米線異質結 構，.包含有（1)軸向的異質結構奈米線（簡稱為⑶腳）1〇以 及（i i)縱向的異質結構奈米線（簡稱為Lqhn) 1 2，其可用 作其他異質結構與元件之基礎材料。如第2圖所示^樣 品，軸向的異質結構奈米線10包含有一實質結晶之軸心 14，其乃被一不同成分材料之護套16所圍繞，且軸心“與 護套1 6之間形成有一接合面丨8。護套丨6之材質可為實質姓 晶或非晶質、高分子、+導體、氧化物或是其他類似的$ 料。如第3圖所不之樣品，縱向的異質結構奈米線12至少 包含有-實質結晶材料的線段20，其乃與一不同成分 之線段22相鄰，且這兩線段20、22之間會形成一接合面
554388 五、發明說明（7) 24 〇 ： 本發明之異質結構可由任一個數 種配置之線段所構成，其乃如下所述 輛向、縱向或各 舉例來說，如第3圖所示之額外添。 (superlattice)線段26、28、30，這-的超晶袼 限定只包含兩個相鄰的線段。不過乂 ^不一個異質結構不 構，至少兩個線段是由不同成分Ϊ料所為—種異質結 成分材料是指（i )材料具有不同的化與、八成。所謂的不同 的或是添加過的材料），或是指（丨丨）=义（不論是本質上 方向（例如：相同的材料但具有不 =具有不同的晶格 向觀察時，奈米線異質結構可包含 θ9袼排列）。當以縱 間隔的或週期的線段是由不同材问f分材料，亦即 多重線段的奈米線，其中至少兩個線i ^者可視為一種 成。例如有一種縱向的異質結構奈米^疋发不同材料組 段是由Si與SiGe這兩種不同的材料^斤構成^ ^兩相鄰之線 第4〜7圖顯不之多種樣品，係為具有添加 的異質結構奈米線。如第4圖所#，一軸显：，軸向 米線32包含有一軸心34、一第一段護套36 '”負 '、、吉構奈 一第一奴軸心42、第二段軸心44以及一護套46。 〇匕各有 所示，一軸向的異質結構奈米線48包含有— =第6圖 50、第二段軸心52、一第〆段護套54以及—心 56。如第7圖所示，一軸向的異質結構奈米線^又^蔓套> 數個超晶格線段6 0、6 2、6 4、6 6、6 8、7 0，甘、έ有複 /、乃被一^護套
1012-4754-PF(N).ptd
第14頁 554388 五、發明說明（11) 度的關注且具有科技上的重要性。可是，因為一維控制的 困難性，使得奈米線合成在材料科學上仍然遇到巨大的挑 戰。碳奈米管（carbon nanotube)之合成中，雖然實際之 成長機制可避免掉’但是於氣相中進行之電弧放電、雷射 剝落（laser ablation)或是化學氣相沉積等卻遭遇到巨大 的挑戰。碳奈米管也可以製作成為模板，用以預製具有不 同成分之奈米棒（nanorod)。目前亦致力於使用薄膜板來 製作金屬奈米棒或半導體奈米棒。然而，大部分的奈米棒 是多晶質，其部份之使用性會受到限制。為了在一維系統 中獲得定義，確之結構性質，則需開發出普遍且可預測之 方法來合成單晶奈米線，以使其尺寸與長寬比達到一致 性。 3. 1 VLS 機^ 相較於上述之合成技術，氣-液—固 (vapor·-liQuid-solid，簡稱VLS)製程是一種更有效的方 ^1 ΐ化予口成單晶—維之奈米材料。VLS製程已廣用 始1 =早期t微米〖寸鬚狀物與近年來之各種成分奈米 方法乃先於奈米尺寸之催化液體中溶解氣體反應 圖之八It 一 ΐ成長方式形成單晶奈米鬚狀物。依據相平衡 圖之/刀析’可以選擇出適當的催化劑。 例一 太平圖，其顯示於一"夕(1 ")基底100上進行石夕 ;=此例中採用Μ氣體物的氣相 源並知用W米團㈣4作^_
554388 五、發明說明（13) 寶石）也可用來製作基底。金屬催化劑亦可使用Au之外的 材質。例如：GaN奈米線之製作，係於藍寶石基底上 使用Ni催化劑以及Ga、NHs氣體，其中最佳之成長^向為 ( 002 )。而且，可使用.〇2與(：的混合物，以於此奈米線中 摻雜Μη。相同地，Ga(c〇)N奈米線之成長，可使用下 ^a+NH3»Co ^Go3 04 +C^ Π =们？雜。GaN奈米線之成長，可使用下列條件： 1 ^ —藍寶石基底、Ga2 03 + C的混合物。 a至G a Ν Ζ η 〇奈米線之成長，可使用 劑、C-藍寶石基底、Ga+NH3 —、211〇+(：的混合物:催化 例二 J用高溫TEM觀察Ge奈米線於同一環境下的成長，會 曰 > 里的Ge粒子以及Au奈米團簇散佈在TEM格子上，此乃 提供作為於真空腔體中進行加熱步驟的Ge氣相源。而且發 ==，當，成Ge〜Au合金之後，Au奈米團簇會開始熔解。 /二^Ge乳相攱結製程中，會使液滴之尺寸增加。當含有
Ge成分之液滴達到過飽和時，^奈米線便會自液滴中喷出 ^開始成長。在第丨2圖顯示中，實際觀察奈米線成長 間可反映出VLS機制。 ^ 依據追些觀察，可明顯得知以下有關於奈米 觀點： 、 (1)具有不同成分（如·· Si、Ge、GaAs、CdSe、GaN、 AIN Bi2Te3 Zn〇等）之無機奈米線的合成，可使用適合之 金屬催化劑、t體預製體與反應溫度。後續則可由檢查二
554388 五、發明說明（14) 元相圖或三元相圖以決定。 (2) 可使用傳統之摻質，如：b、Ph、As、In與A1。 (3) 材料可選擇自二族、三族、四族、五族與六族等 元素，且可包含有quaternaries以及teriaries以及氧化 物。實質上而言，任何一種半導體材料及其合金皆可用來 製作本發明之奈米線異質結構中的相鄰材料。 (4) to the first order approximation，催化劑係 定義奈米線之直徑。較小的奈米團簇會形成較薄的奈米 線。此亦成功地證明於GaP、Si奈米線系統中。 以VLS機制進行合成，其特徵為居間的表面活化劑會 造成蟲晶成長，其中藉由防止半導體成長表面之復原，居 間材料（如：熔解金屬之奈米粒子或單層）會催化磊晶成 長。由於沒有穩定的復原（因為復原需要持續的拆解與再 建^因此相較於傳統了磊晶成長技術，VLS成長技術可以 f t:=以及低溫的條件下進行。在低溫下，▼以提供較 二i ^達新的相態中’可製造明顯的界面輪廓，可 /V 中的奈米線材料產生形態演化（例如··瑞利 分解（Rayleigh breakup))。 3·2,基复平衡 成
二：ΐ::學可使大塊或薄膜中的不穩定相有機會合 性，尤豆:ί ί !一體積比可提高自由能之表面能的重要 三五族7 =二t两度異向表面能的結晶相。舉例而言，在 衡邊界，閃：t之半導體的多型體中，相較於-整塊之平 、 ^ (立方晶系）與纖鋅礦（六方晶系）之間的平
554388 五、發明說明（15) 衡相界會因壓力與溫度而產生偏移。例如，具有相同成分 之奈米線，比較<111>配置之閃鋅礦奈米線以及<〇〇〇1>配 置之纖鋅礦奈米線’圓柱狀的纖鋅礦奈米線會比較相似於 伍耳夫（Wullf)平衡形狀，其暴露出低表面能的菱柱切 面。在先前之奈米線研究中，以OMCVD可觀察到纖鋅礦相 態確實為GaAs之較佳相態。而且，基底與奈米線之間的磊 晶關係可用來捕捉奈米線型式之準穩定相。此種策略已經 成功地運用在薄膜成長中。 3· 3查米線内的異質磊总 半導體異質結構可以限制電子與電洞，可以引導光 線，且可進行選擇性的摻雜，但是如果異質結構是存在於 2 2 ί Ϊ Ϊ區域内’則在介面處不可以產生差排現象。材 二$丨β ^靶圍為，須在基板上長成相干（coherent)磊晶， 達H夠厚度，且會高度受限於晶格錯合（1州— 7差1排之妨對於一個晶格錯合而言，藉由薄膜之彈性、錯 之，能與晶體發生學（如：柏格向量之平面端點 干異&磊曰°镇以眩估汁出相干磊晶之平衡臨界厚度。雖然相 是;專膜會』忐進可2 f虽成長且超越過平衡臨界厚度，但 態。VU太文t峻穩疋恶，則差排機制會使之變成鬆弛狀 ΐ衡臨面產生變化，進而顯著擴增 兩個主要的效應如下所述。 長方向之遝料八 4 第一個效應為，垂直於成 態變成鬆弛。理想的薄膜形態中，應 在於母早位面積之相干薄膜中，且此應變能會隨
554388 五、發明說明（17) "" " 言，此製程允許一維之帶隙工程“⑽仏邛 engineering)，則可製作一系列多樣的量子點（quantuffl d = 1：S)。在薄膜成長中，量子點通常是在溶液中成長或是 藉由形成島狀物而成長。由於無法事先知道這些量子點的 =置，所以非常不容易聯繫個別的量子點。藉由準確地在 一奈米線中整合量子點，可以避免聯繫上的困難。這就 是所稱之’’奈米線系統（system 〇n an nan〇wire)n。此種 ^ f之一維奈米結構提供較多的機會去探究低維系統之新 的物理現象。此極有可能應用於主動性奈米電子、奈米光 學之奈米熱電子以及奈米電子機械等等。而且，這可以用 m具有r不同晶格結構之奈米線，如：閃鋅礦、纖鋅 ί;之^等奈米線。其製作方式可於遙晶成長之基 材與奈米線關係中，俊用石^装 土 相 1史用不同的基材來網羅某些準穩定 3·5 米線（簡稱為 使，It作之奈米線作為物理樣板以 於Ge太+ # ΐ 冓。例如：分解線表面之有機分子，可 伸以形成具有強列雷：==的石厌塗佈，如此可立即延 涂佑一麻往不米線，其後續可以低溫化學氣相沉積方弋 成县=/的八^^^層，可有效防止VLS晶格沿著、後^ 成長，且可促佶A〗r〇 Λ 阳物〜者線軸 I，甘#太使八層之表面過度成長。但要、、主立沾 疋，其護套可為晶質或兆θ所 ^ 1罟，主思的 體、氧4卜你+ ' 日日負，且可包含有高分子、丰導 體氧化物或類似的材質。為了形成_，須以此述= 554388 五、發明說明（18) 何一種方式先製作一個單段的奈米線或是一個L〇HN。單段 的奈米線或是一個LOHN將會成為COHN的軸心，然後會被用 作為一個製作護套的樣板。例如··護套的製造，可於單段 的奈米線或是一個L0HN的表面上進行單體聚合。或者是， 以任何的物理氣相沉積（PVD)或化學氣相沉積（CVD)製程於 奈米線或是L0HN表面上進行塗佈。軸心/護套之材質不限 制，可為下列之組合，如：Si/ZnO、Ge/C、Si/Si02、 Sn02/Ti02、GaN/ZnO、GaAlN/GaN 等等。重要的是，軸心/ 護套材質之配置數目亦不受限。即使是氧化物，如：
ZnO，亦可用作為軸心材料。下列為軸心/護套之材質組 合，且軸心與護套之材質均為單晶，例如：Ti〇2/Sn〇2、 M :Ti02/Sn02(M:Mn、Fe、Co、Cr 等）、PbTi03/Sn02、 BaTi03/Sn〇2、LaMn03/Sn02、HTSC(高溫半導體）/Sn02。 此種方式也可用來合成一奈米管。例如：可於一以奈 米線軸心塗佈一層有機分子材料。其後於真空下進行熱 解’此有機材料表面會被碳化。然後，於8 〇 〇〜1 〇 〇 〇它溫度 下，此Ga奈米線軸心會被熔解或蒸發，而成為一碳奈米 管。 為了了解這些奈米線之結構特徵，須倚重TEM以及 XRD。TEM與XRD均可決定出奈米線之結構與相態。而且，籲 TEM更可提供個別奈米線内之缺陷結構、介面處之區域微 結構、成長方向、整體結晶性等等。 4· 奈米線性曾 4· 1 |子結槿斑性皙
1012-4754-PF(N).ptd
554388 五、發明說明（19) 4.1.1 奈米線内的介面粗超度與位 泛地研究於量子線令，此量 ^刼演的角色已經被廣 f是分離式閘極之電子靜態束制方：義：使用電子束黃光 出從彈道傳送至漫射傳送的變，。在低溫下已經關查 :量子化與一般波動。使用 的或負的磁電阻、傳 且，摻雜太半L，准電子材料中電子傳送之變化性。而 機會去研究在各種電子密卢的故可提供額外的 2圖與第15圖，中，X ·政·射機制。請參閱第 雜可以使離子化掺 :^寬廣页隙之材料調整摻 而達到較高之遷移；:與自自由由//^2在 千 將自由載子侷限在本丰始雄太# 土丄 心區域内會降低表面散射 。佔^ '、二 奈米線之異質結構介面子：據了鄰近於 ^^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 心4 k二狀怨會明顯地影響奈米線之電子性質。其中 之叮舍現如同一維共振穿遂效應之庫倫閉鎖現象。 較佳之模型建立於下述之兩階段。首先，使用簡單的 一維帶結構模型以及鬆弛時間近似值，於高溫下沿著奈米 線來ΐ測電子遷移率。然後，使用精製的模型（如：變量 範圍Α跳模型），來說明表面/介面之散射，並計算溫度與 導電性之依存關係。其他的應用，例如：聲子光譜以及散 射時間之修改、電子聲子反應等，可使用波茲曼
第26頁 554388 五、發明說明（20) (B〇ltZmann)方程式之蒙特卡羅（Monte Carl0)模擬。注音 到，異質結構奈米線可包含數種束制之介面聲子模型，= 可自整體半導體中之任一個以不同的方式散射電子。、 4.1.2 為了要描繪塊體的異質結構奈米線的電子特性，量 之摻雜濃度輪廓、電子遷移率、異f介面處之電壓 能障是相當重要的。在提供奈米線材料之前，必、須藉 統之塊體或薄膜的特性描繪方法進行仔細的檢查 米，之電子導電性是一個重要的係數，且須於一個大的^ 度範圍内定義其特性。&外，電磁阻之量測可以提供較； f關於表面散射如何影響電子輸送的訊息。熱電性質之 1測如·賽貝克係數（Seebeck coefficient)，可以提 供較多有關於靠近費米表面（Fermi surface)之電子密产 狀態以及散射機制的訊息。&離子發射電流之量測可以又 來決定沿著奈米線方向之異質結構能障。 彈道電子發射顯微鏡（ballistic elec讨⑽emissi⑽ m1Cr〇scopy，BEEM)是一種較理想的技術，可以量測奈米 線結構之區域電子性質，且可描繪出軸向異質結構之特 徵。BEEM是一種有效的低能量之側面影像以及光譜的電子 由其對於埋置於表面3〇nm以下之基材可提供⑽等級 的解析度。BEEM已經應用在成長於GaAs上之自動聚集量子 點結構的研究。 成長於GaAs上之GaSb量子點可藉由STM與⑽]^影像來
1012-4754-PF(N).ptd 第27頁 554388 五、發明說明（21) 觀察。在STM影像中，一個粗糙的圓形外貌（直徑約5〇nm且 高度約5nm)標示出一個埋置點的側面位置。在BEEM影像 中’與STM影像之此點輪廓對齊的區域較周邊暗，這暗示 著由於電子反射偏離此點之電壓能障，因此通過此點之 BEEM電流降低。能障之高度（如：區域帶偏移量）可以自開 啟與關閉之間的BEEM光譜變化中取得。在光譜之許多 點中，開啟點與關閉點是由一修正之貝爾-凱瑟平面穿遂 模型（Bell-Kaiser planar tunneling model)所配置，其 可提供GaAs上之GaSb點一個區域導電帶偏移量約〇· 〇8 土 0.02eV。第17與18圖顯示GaSb/GaAs自動聚合之個別量子 # 點的BEEM光譜特性。 、除了 s測液直接合面帶偏移量的性質之外，此技術亦 已用來研究GaAs^Nx合金材料的電子帶結構、Galnp之帶結 構上的序列效應、以及束制於A丨丨nP能障之間的丨np量子點 的共振穿遂。 由上述可知，BEEM不但可以用來描繪個別奈米線之電 子性質’還可以縱向異質結構之變化性，如第1 9圖所示之 結構1 50。限制效應會使得在BEEM電流所示之結構可藉由 第二推導（second-derivative，SD)之BEEM光譜進行分 析0 4. 2 光學性質 由於表面狀態所扮演的角色以及在表面狀態上的非放 射再結合，因此從奈米線中觀察光放射現象遭遇相當大的 挑戰。在COHN使用中，電子會被束制於奈米線内部之中心
第28頁 554388
奈米線異質結構中的聲子傳輸，會隨著整個半導體中 的聲子傳輸而產生巨大變化，其主要原因為兩個方向上的 強加限制會使分佈關係產生明顯 ，里
之^面存在會誘發多種聲子型式，且這些聲子形 於；I面上。如此一來，除了兩個橫向的聲部分枝與一個直 向的聲部分枝之外，還會在整個半導體中產生多種不同的 耷子極化。聲子溫度之變化源自以下兩個原因：第一，聲 子-聲子之介面會變化，此乃因基於能量不滅以及隨著分 佈關係而變化的波向量關係的選擇規則；第二，相較於整 體半導體而言，5〜50nm直徑之奈米線的邊界散射會變得更 強。最後，由於奈米線束制允許我們進入新的結晶相，所 以能夠徹底地修改聲子散佈關係。
本發明之奈米線的熱與熱電性質，可採用一種微製作 結構來量測，其具有兩個懸掛的加熱器，且此加熱器^含 有電子束微影系統所製作之線圈。在測試中，係將一個多 重牆壁之碳奈米管束橫跨放置於這兩個加熱器上，用以架 出兩個加熱器的橋樑。藉由監控一個加熱器之熱輸入以及 兩個加熱器之溫度，可以獲得奈米管的熱導電值。第2〇圖 顯示於10 κ - 350 κ範圍内，此多重牆壁之碳奈米管的 熱導電性與溫度的函數，其中T2代表在二維材料中聲子束 制之聯想變化。熱導性之單調增加係顯示聲子-聲子散射 的抑制以及非常長的平均自由路徑（約i 。此研究亦可 用於量測本發明之C0HN與⑶㈣的熱導電性。而且，採用分 批製作之原子力顯微鏡（atomic force microscope，
554388 五、發明說明（24) AFM)、頂端設置有溫度感應器的散射熱顯微鏡（scanning thermal microscope，SThM)，可以獲得 COHN 與 LOHN 之區 域性的熱性質與熱導特徵。 奈米線的特性計算係集中在以下三個觀點：（丨）聲子 月欠佈關係之计算，（i i)以摻質散射、奈米線尺寸與邊界散 射為基礎之聲子壽命的計算；（iii)聲子輸送之計算。因 為波效應（聲子帶隙）已經考慮在散佈關係中，所以可以用 豕特卡羅模擬（Monte-Carlo simulation)來解出波茲曼輸 送方程式（Boltzmann transport equation)，其可簡單算 出奈米線之不同極化分枝的密度狀態、頻率相依群組 以及聲子壽命。 4· 4 i電性質 半導體的熱功率係與以下三種性質產生相依關係： (曰1)罪 費米能階的電子狀態密度；（i i)電子有效質 ΐ走^ 載子散射速率/因為在奈米線中的電子經由量 速率），因可此以：顯地改變電子帶結構(狀態密度以及散射 ί:用以Λ 建造出帶狀結構以及費米能階的位置， > ?熱功率。前述之懸掛的力献 個奈米線，以量測豆、、w碎盥你兰叼力…、兀件可以検越一 。K〜35〇。K ，皿度與位差。例如：第21圖顯示在10 值，豆中顯-视内，多重牆壁之碳奈米管的熱功率量測 支配載正數熱功率係表示在奈米線中以電洞作為 熱電性質，：十兀件可以用來量測奈米線異質結構的 电『玍 > 如·前述之COHN與L0HN。 4.5墨j；性質
554388 五、發明說明（25) 纖鋅礦型結構提供一種自發電偶極矩（sp〇ntane〇us electric dipole moment)，因此具有此種結構的材料會 產生熱電性與壓電性，這些性質可容許強大的線性耦合形 成於機械應力與極化之間（直接壓電效應）以及一個溫度變 化與極化變化之間（熱電效應）。纖鋅礦型奈米線（如： GaAs、InAs、GaN、A1N、ZnO等等）以及奈米線異質結構會 因此而可應用在奈米規格之感應器與操縱器上。有潛力之 應用包括冑··、整合原子力顯微鏡探針、具有單分子感應性 之共振負里感應器、奈米規格之熱感應器、可調整電場 GHz之濾波裔、大位移之奈米束操縱器以及奈米規格之流 、>，鋅礦型奈米線中，自發極化的方位係沿 f軸’因此沿著線軸所提供之電場與金屬機械應力會產 t的壓電響應。最簡單的電極配置係 =點上，而經由直接壓電效應 與頂】 = 生大的應力。對於應用在共振感應ί
:線之一端必須不受機械性控制，而且 查接近之導電表面來偵測奈米線頂端之電荷， 穿逐的方式來移除或增加電荷。 二 第22圖顯不一個管输祐很 4+ m來量測放置於—導貫電驗基用，懸… 160的機械運動，而且同日^可之壓電或熱電奈米 橫跨奈米、線之靜電位* J利用—電壓感應器166來量 ^位此。為了達成電性與機械性之量測
554388 五、發明說明（26) AFM懸臂探針164之端點係接觸奈米線上的一個金蓋 168 〇 5· i Ge之區堍掊區塊的成長 對於多種有潛力的半導體奈米線應用，奈米規格光電 子學之異質接合以及超晶袼的形成是相當重要的。有鑑於 此，已經發展出一混成脈衝雷射/化學氣相沉積（hybrid pulsed lased-chemical vapor deposition ， HPL-CVD)製 程，用以合成一具有軸向序列異質結構之半導體奈米線。 雷射移蝕製程會產生一可程式化脈衝氣相源，則奈米線成 長可在線軸上以明確的合成物輪廓進行區塊接區塊方式成 型。具有軸向Si/SiGe超晶格結構的單晶奈米線已經被成 功合成，此種獨特的異質一維奈米結構極 光元件與熱電學中。 ^用在^ =導體積體電路之成功大數取決於仔細控制摻 …負、、口構的月匕力。貫際上，二維半導體介面 存在於光電元件中，如 《弁— ， τ 戈 心九一極體、雷射二極體、吾； 串集雷射以及電晶體。一飧太半 里子 製作亦對於潛Λ甚I,、准/未、、、。構（奈米線）之異質結構 差器)相告重I二1°. ΐ效光發射源以及較佳之熱溫 ;)可用靖薄膜異質結構以及超晶格乂\刀= 乏一個普遍的合成方案，用以製作具有明確相疋干先心乃缺 維異夤結構的異質接合面盥超曰。 "面之一 或奈米管之研究她e ; p ^ 。早期對半導體奈米線 之異質結構=ί統，其形成有少量例外 包3有·形成於碳奈米管與矽/碳奈米線之
554388 五、發明說明（28) 中’利用二雙頻的Nd-YAG雷射（波長532nm，6Hz，功密度 l〇J/cm2.單位脈衝）可使純Ge靶材182產生脈衝剝蝕，進而 產生一脈衝型式的Ge氣相。H2的流速約為1〇〇sccm，Sicl4 與&的比例約為0.02，系統壓力約為一大氣壓’反應溫度 約為8j0 C〜95(TC。在這個溫度下，Au薄膜186形成一含“ 的液態合金，且自發性地崩離成為奈米尺寸液滴型式的 Si合金188。然後，持續將y種沉積至“_以合金液滴 如^中Si奈米線！ 90會開始成長至接近過飽和。當關掉 J射時，只有Sl種會沉積至合金液滴中以及成長一純^區 而丄rU是在成長製程中開啟雷射，會產生Ge氣相， s H 均會沉積至合金液滴中。當開啟雷射時， β二：“ 2會自固/液介面中析出。藉由週期性的開啟盥 :閉【(：順序很容易程式化)，便可在各個奈米匕 $ £，接區塊型式的以“丨以超晶格194。 耘類似成塊共聚物的活性聚合合成。 成長t 與乾ί他ίΞΠ的4米：結構成長可以使用不同的氣體 # ^ # . ° PbSe成長可於Ar氣體中對PbSe/Au靶 受= = 的… ;電腦操縱雷射以選擇乾材。因此二個挺材且利 或化學氣相沉積製程均可;供乳相之物理 MBE。例如：ϋ -担^M用且不限制於PLD、CVD、 預定氣體之流動。〃源可裝配有電腦控制閥，用以脈衝
1012-4754-PF(N).ptd 第35頁 554388 發明說明（29) 第25圖顯示一個使用例四描述之製程所合成的奈 陣列200，且可獲得此合成奈米線陣列的掃描式電子「、顯^/線 鏡（scanning electron microscopy，SEM)影像 〇 在例 中，係將厚度為20nm的Au薄膜置於Si(lll)基底2〇2上，、 以黃光製程將A u薄膜的圖案定義成為四個區域，而 ^ > — 叫便母個
薄膜區域係被嫁成四個液滴’每個液滴係用以作為一相 奈米線之觸媒。在成長過程中，係週期性地開啟雷射5§秒_ 鐘、關閉雷射25秒鐘，且此循環須重複進行達丨5 $鐘。^則 如同先前所示，Si奈米線會沿著[：[丨丨]方向成長，進而在 S i (1 11)基底上完成定性磊晶奈米線陣列之成長。當合金 液滴固化之後，在每條奈米線2〇6之頂端204上會顯胃現"成為 :個亮點。對奈米線的嚴密檢查中顯示，頂端係呈現類似 花的形狀，其乃於形成於液態合金液滴的固化過程甲。奈 米線的直徑範圍約為5〇nm〜3〇〇nm。於2〇〇KeV下操作Phi 1 ip CM20 0 TEM，可獲得兩條奈米線的STEM影像，其亮域模式 中可看到沿著線軸且週期性出現的暗條，其乃由s丨Ge合金 與si等線段所週期積疊而成。Ge原子的剖面電子掃描係大 於S 1的剖面電子掃描，因此顯現出的s丨以合金塊體會比純 ~塊體還要暗—些。使用能散χ射線光譜儀
(energy-dispersive X-ray spectroscopy，EDS)可以檢 f出較暗$域内的化學成分，結果如第26圖所示，發現有 、，的Sl大峰以及明顯的以摻雜（〜12%重量百分比的Ge)。 進步對Ge摻雜進行的週期性調整，係沿著奈米線成長軸 以掃描一聚焦的電子束，並追蹤此線中X射線訊號自Si與
554388
Ge原子中的變化，如第27圖所示與以的乂射線訊號顯 示出週期性的調整以及非相關聯的強度。㈣話說，當Ge m ^達到-最大值時’則Si則射線訊號會達到一 最小值，如此證實si/siGe超晶格係沿著線軸而形成。我 們注意到的是，此階段中，奈米線之si/siGe介面的陡峭 性並不理想、’但相信這可藉由準確且快速的氣相配料/開 關系統（如··分子束製程）獲得改善。 必須強調的是，VLS奈米線異質磊晶成長的彈性邊界 狀態，藉著在平坦基底上進行磊晶薄膜成長，可供予超晶 格奈米線創造無差排介面的可能性，此種無差排介面在習 知的二維配置中是不穩定的。雖然相干性異質蟲晶薄膜成 長良好，可超越平衡臨界厚度，但是差排機制會使薄膜由 準穩態變成鬆弛態。VLS奈米線的型態提供顯著延伸平衡 與動力臨界厚度的機會，或相當於，在一個厚度條件下使 邊界條件改變，則可使晶袼不匹配變成互相適應。 利用一選擇面積電子繞射儀（selected area electron diffraction，SAED)以及一高解析度穿透電子 顯微鏡（hig-resolution transmission electron microscopy，HRTEM)可以定義出此超晶格奈米線的高度結 晶性質。將垂直於奈米線軸的^⑽圖索紀錄下來，再^二 圖案編成索引以作為沿結晶Si之[110]區域軸的繞射，、並 建議奈米線成長確實沿著[Π1]方向發生。在HRTEM影像中 可進一步證實，其清楚顯示（111)原子平面（間隔〇.3、u^) 垂直於奈米線軸。若STEM影像中無法馬上看出介面對比，
554388 五、發明說明（32) 同的反應條件下，成 示，由實驗觀察之ώ、具^二與直徑有相關性。如第28圖所 較小的奈米線直徑，^厂與奈米線直徑的關係圖可知， 應（Gibbs-Th〇ms(J 較小。吉布斯-湯瑪斯效 增加Si氣相壓力，則告太：化解釋此種趨勢’例如： 超飽和之降低值與奈；：直徑⑷=時為可降低超飽和。 其中，△ 系為營養（氣或 差分；△…平坦介面上的V同;二位能，間的有效 表面之特別自*能；Ω係為s Γ的；1子差體刀積，V:為奈米線 ΊΓ r Αμ ^ j ^ y 其中’ b為不相關於超飽和车 ι/d之線性相關函數““之係數。可推導成V-正比於 *令夸巧 Φ △凡二丄 打 ~lcr~Tc 其中’dc代表臨界直徑。 在GiVargiZ0v對典型CVD晶格成長研究微 觀察，其同意Si/SiGe奈米線成長資料可符合^η = 2。1 、
第39頁 554388 五、發明說明（34) — __ (或加熱）的現象。相反的，當一、、w疮兰 會產生一電流以通過一電位；，=電材料時， 流氣相壓縮致冷器以及氣基引擎件 ^ =於電 原因為：⑴包含任何移動零件；(二二 允許縮小化。此固態元件現今不被廣泛應用的V因為2 表現（弓丨擎效率以及致冷器的表現係數（coefficient /、 performance ’COP))遠低於運用氣體/氣相的系統。= 而’若：可以改善其表現以比得上或優於氣相系· '、、: 以想像得到，如何使用或轉換 =，·、，、彳可 Γ:ΐΓ不的理由可促使運:電變：， 件。=下述可知’近有使用本發明奈米線可1^成、電兀 應用於固態的熱電致冷器與發電器 ： :列之優'點：叫〜^，其中s代表熱功率，km 性，σ代表電導性，τ代表絕對溫 ^表熱導 前最廣為使用的材料，其ζτ=1。理論上。及為當 =致：器與引擎的表現便可以比得上氣相壓二】：二 矛、，右熱電材料為奈米結構，電子與聲子@ # ^由貫 :劇烈地提高其ΖΤ值，如第29圖所示： = : = : 線，如果線的直徑為5〜10nm，則ζτ = 2〜5。 、1丁、米 6· 1 · 1查」Ui設計 佳的Ξ以值：具備高的電子遷移率，所以較 選擇的材料性會反比於原子質量(。，所以 員，、有向Γ值，這就是為什麼Bi或奈米
554388 五、發明說明（35) 線ί是熱電應用之良好候選者。藉由減少奈米線直徑合進 ==其熱導性胃，這是因為可預期地在= 2 仫小於2〇nm之奈米線的邊界散射。除了Bi2Te之 =，亦可使用其他材料’如：SiGe、InGaAs，/ 3 可以降低光子輸送。 。至政射 6· 1 · 2 計 械強产於：f線:艮脆弱’所以須嵌埋至一母體中以提供機 二，或^隨奈米線陣列可以埋入— 電元件2一 10勺a古4中，#第3°圖所示之熱電元件210。熱 牛10匕3有一對上、下絕緣基板212、214，苴内設 224 雜之/求線陣列216以及一“參雜之奈米線陣列 1、中，η払雜之奈米線陣列216係成長於一基底218 不米線220係埋入一聚合物母體222中；ρ摻雜之奈 二聚^i224J系成長於一基底226上，其奈米線228係埋人 妖查:母體230中。利用串聯的電連接方式以及並聯的 Γ式將η摻雜以及13摻雜之奈米線陣列晶圓接合在一 ^，以成為一熱電冷卻器與發電器， 人物母俨η $合物洛液’以使奈米線陣列埋入-聚 觸塾、24〇(位於奈米線之頂端卜應優先將聚 X至暴路出奈米線，然後才沉積該金屬接觸墊。 成物的設計參數為：（a)奈米線的表面密度；（b) 件厗度。這個構想是為了開發出具有超低熱導性之聚合 第42頁 1012-4754-PF(N),ptd 554388 五、發明說明（36) 物（k = 0· lW/m-k)以及高功率因子 高ZT值。元件表現之特徵可經 σ)的奈米線，以達成 的有效電導性元件的有效埶"列量測獲得：（a)元件 (Seebeck)係數；（d)反映出通過、、一性，（c)有效賽貝克 (e)反映出溫度差與熱流率的電功&件。之電流的溫度差； 6. 2 元件設3 ,、 奈米線合成材料具有兩個不 光元件上。一方面，電子之低因；、〖生質’可以應用在發 用來調整吸收與發射波長，沿著=束制與能階之量化可以 許不同材料間之晶格不匹配性具=米，之一維晶格成長允 收與發射光譜的範圍變寬廣。^ 較高的彈性，進而使吸 導體的折射係數(3 4)遠高廣於空^ 創造出-種尺时不匹配性，成為石纖維（1〜1.5)，這 連結的其中-個主要難題。這也Ip心t導體之間的光線 量子效率，因為大不分的發射光；：二=2體的外部 收。 丁㈢於材枓中破再度吸 以各種II I-V族與IIVI族奈米線之雷w έ 如第31圖所示，-奈米線聚合物U二 之1作係依照前述方式，將複數條奈米線252整人 合物母體中254，以提供作為-具有低有效係數二有 效材枓。聚合物折射係數之變化高於傳統半導體一子旦 級]結合大的熱-光係數以及半導體奈米線之光電性里， 可以提供一個新的能量轉化元件。 、 554388 5·、發明說明（38) 性質可經修改而超越現八 法所獲得的結果。 本發明之奈米線可以 外，尚包含有但並不限^來製作各種元件，除了前述之 “…子遷下元件： ⑻高電子遷移率線(使用c_); 提供外赠以耗盡/V加 (C)用於紅外線偵測器之奈米線（使用LOHN以及嵌埋 的量子點）； (d) 用於1D共鳴穿遂二極體之奈米線（使用L〇HN以及 嵌埋的量子點）； (e) 用於單電子電晶體之奈米線（使用L〇HN以及嵌埋 的量子點，亦可以結合COHN); (f) 用於紅外線偵測器之奈米線（使用C0HN以及量子 化耳語廊（quantized whispering gallery)的電子模 式）； (g) 用於磁偵測器之奈米線（使用COHN以及一會受磁 場影響的量子化耳s吾廊（Quantized whispering gallery) 電子模式）； (h) 聚合物-奈米線合成物之發光元件（高的外加量子 效率、寬廣的光譜、與纖維具有良好的耦合）； (i )聚合物-奈米線合成物之光學調節器（由於電子訊 號與光學訊號速度匹配，故可以成為具有非常高速傳導波 的調節器）；
1012-4754-PF(N).ptd 第45頁 554388 五、發明說明（40) (d).余米^級61^ :較小的直徑可允許壓電或埶電 =:吏用於原子力或分子力、奈米等級溫度等情二；的 & =針。而且’奈米束單位模型之彎曲物，其具有以投 =^鍍方式製造的縱向電極與彈性層，可提供非常大的撓 二^ ’因為長度與厚度的比例為1〇〇〇 : i，以及具有適度 2 =橫切面電場（對1V而言，有觸仏通過_厚度 <录木束）。 配署參Γi3i〜39圖’其顯示電機轉換器之奈米線元件的 - "中第3 6、3 7圖顯示其縱向配置，第3 8、3 - 其橫向配置。 直弟Μ、39圖顯不 在縱5第3』:丄7圖所示，在〈0 0 0 1 >纖鋅礦中，其自發極化 ϊπ產列。0此，沿著線轴之電場與機械 麴置I带f 的自發極化現象。在軸向配置31〇甲，最 3曰14，而裎^丘配置係在底部與頂部分別使用接觸電極312、 二而二=^ 力即可產生大應力。舉例jn j=小，所以施加小外 言，單軸拉伸應力為對=二:=;:2:“ 此壓電係數5nC/N可產^^ ςΡ/ 26Ar_軸應力 ，因 以债測出纟。用: 的壓電變化’此值通常可 端必須是無機械力：鳴：應=;米線而，，奈米線之-偵測奈米線之端點卢w 而要提供一個導電表面，用來 除或增加電荷。處附近的電荷，並可藉由穿遂方式來移 如第38、39岡01^- 圖所不，由纖辞礦奈米線之<hki〇>排列中
554388 五、發明說明（41) 也就是，自發極化會垂 其成長方式可選用單晶 藍寶石基材之（ 00 0 1 )、 可將電極設置於線端 可以獲得完全分隔的感應與致動， 直於線成長方向。如此的奈米線： 基材之適當表面排列處進行，如： (hki〇)排列處。在橫向配置32〇中 ______^ ^ 處以，舌化壓電切變模式dls，或是沿著線長度設置以使用 w。第38圖顯示‘模式，其電極322、324係沿著線長度方 =，置，可以提供大的電崩潰強度（>3〇〇MV/m)以及高破壞 矣f給無缺陷之A1N奈米線，進而用來製作高位移的奈米 ，單位模彎曲物以及外力感應器。假設一個合適的彈性層 疋以投影沉積方式形成於奈米線之一側，相對於另一側i 電巧長條，則奈米線之端點位移占會近似於‘L2V/t2。 :=向電壓IV、厚度10nm、長度5 以及‘為3pm/v，則 ‘點位移約為0 · 7 5 // m。 、 橫向配置之合成與製程所遭遇的挑戰遠超過縱向配 *曰：：垆ί :線必須在橫向排列上成核，其成核需要在 二 ，、有矩形剖面之奈米線，對投影沉積而言是相當理 沉ϋΪίί大幅超越縱向奈米線。一旦合成，利用投影 曲物，工^製作複數個金屬層，以成為奈米束單位模之彎 其中一缚的順應金屬層（如Cr/Au)可作為電極，一 可^應質金屬層（如Ti/Pt)可以用作為電極或彈性層， 以利用Ϊ制彎曲模式致動之中心軸的最適位置。或者曰，可 /合液製裎，以兩個表面之不同表面性質來遷擇性地
l〇12-4754-PF(N).ptd 第48頁 554388
沉積金屬。 6· 5复J最紫外線奈米線之争土___ 短波長之半導體雷射的開發是 a 題’已經開發室溫綠-藍二極體雷射 的課 及Ιηχ、Ν為活化層。Zn〇是另—種射寬:構’其使用—以 物半導體，適合於藍色光電的應用種；、(上3.3=化合 丰導辦奸粗二一 Λ ^ , 對於見V隙的 種=: 達到足以產生雷射作用的光線。此
?的二灭於早期的雷射二極體中，基本上需要 = = 界值。對EHP之另一方面而言，半導體中的激 = =、，、„ & ，則玻子性質可以提供低臨界值的激發射。為了 j::下達成有效的激子雷射作用，激子連接能(Ebex)必 ϋ 溫下的熱能（26meV)。此種考量下，Zn〇成為很好 的k擇，這是因為其Ebex相當於6〇meV，明顯大於
ZnSe(22meV)以及GaN(25meV)。
_為了進一步降低臨界值，係製作出低維的化合物半導 體2米結構’其量子尺寸效應可於帶端點處提供實質密度 狀怨’且其載子束制可增加放射的再結合性。使用半導體 里子井結構作為低臨界光學的獲得媒介物，可以在半導體 雷射技術中顯現出明顯的進步性。激發放射以及光學獲取 的現象已經可以由Si與CdSe奈米團及其整體結構中證實。 本發明之另一個觀點，在臨界值4〇kW/cm2之光學激發 下’證實ZnO奈米線中產生第一激子雷射作用。奈米線之
554388 五、發明說明（43) 化學彈性如同其一維特性，可使其雷射光源達到理想的微 小化。這些小波長奈米雷射可以大量地應用在光學計算、 資料儲存以及奈米分析上。 例六
ZnO奈米線之合成係使用氣相傳輸製程，以於一藍寶 石（110)基材上進行催化磊晶成長，其乃使用具有圖案之 A1薄膜作為奈米線成長之催化物。在奈米線成長中，先於 乾淨的藍寶石（Π 〇 )基材上塗佈一層丨〇〜3 5 a厚度之金薄 其可採用或不採用TEM格子作為陰影罩幕（此au圖案的 製作方式也可先用微米接觸列印方式再進行選擇性蝕 刻）。然後將等量的ZnO粉與石墨粉傳送至一鋁船中，再將 塗佈有A u圖案之藍寶石基材放置於距離銘船中心之〇 · $〜〇. 25c=處。接著將其於Ar氣氛中加熱至88〇〜95〇，則會Zn〇 之石厌熱還原會產生Zn氣相並傳送至基材上，便可進行Zn〇 奈米線成長。這成長通常需花費2—丨〇分鐘。 於基材上進行磊晶式成長後，可形成高度陣列之奈米 線。當使用Au圖案薄膜時，可以馬上進行選擇性的奈米線 成長，則ZnO奈米線僅成長於^塗佈的面積丨，這是因為 Au薄膜之催化性質可提供極佳之選擇性，^且奈米線陣列 可以延伸至cm2。一般而言，奈米線的直徑範圍為 八土责扪直仏靶圍為70〜lOOnm，其影響直徑 因子f於成長之退火過程[Au奈米束催化物之尺 寸不均-。糟由調整成長時間，可將奈米線長 2~1〇"m °此種可圖案化的奈米線成長技術可應用於奈米
554388 五、發明說明（45) '~' 奈米線之光學發光的光譜，其發現靠近帶隙端可產生強烈 發光約377nm。為了要知道從排列之奈米線中激發光線的 可能性，對能量依附之發射性做了測試，樣品係採用一在 室溫下為第四諧波的Nd-YAG雷射（ 2 66nm，3ns脈衝寬度）。 聚焦於奈米線索吸取的光束，相對於奈米線之對稱軸的入 射角為1 0 ’並於以垂直於奈米線之端面的方向收集發射 的光線（沿著對稱軸），並可使用單色器（ISA)與珀耳冷卻 CCD(EG&G)來收集自奈米線激發的光線。所有的實驗均於 至/孤下元成’可以發現Zn〇奈米線中的雷射反應。 第4 1圖顯示在增加幫浦功率的情況下之發射光譜進 展。在低激發密度下（低於雷射臨界值），光譜包含有單一 且主要的自發射峰（曲線a)，其FWHM為17·，其自發性發 射為140meV乃低於帶隙337eV，一般歸因於激子撞擊過x程 =的f，合而產生光子。隨著幫浦功率增加會使發射峰變 窄，這是因為振幅接近光譜之最大值。當激子密度超過雷 射臨界值UOkW/cm2)，光譜中會出現尖銳峰（曲線b以及^ 入圖）。這些光谱之幫浦功率分別為2〇、、15〇 kW/cm2。在低於臨界值的情況下，這些峰的線寬均小於 3nm，乃小於自一發射峰之線寬的5〇倍以上。在高於臨界值 的情況下，隨著幫浦功率的增加，整合的發射強度也會快 速增加，如第42圖所示。於此，窄的線寬與快速增加的 射強^意味著，在奈米線中會產生激發發射現象。所觀^ 到的單一或多條尖銳峰（第41圖之曲線1)與插入圖），顯示^ 在370〜40 Onm波長内會顯現不同的雷射模式。而且，相較 I·» 1012-4754-PF(N).ptd 第52頁
554388 ―、發明說明（46) 於先前報導之散I於無序粒子或薄膜的雷射臨 OOOkW/cm2) ’其雷射臨界值相當低。明顯可知i 米線的奈米雷射可於室溫下操作， 可達l.lxl〇iQCm-2。 且/、實際奈未雷射密度 實際上，不需藉由製作鏡子，益山抱由I 作用便可聯想到使用單晶、1有切：由=察奈米線之雷射 第43圖顯示-奈米雷射二V: 豹之Ζη〇奈米線332，注音的ΐΐ:具有多個切邊（如：六 而是同質結構。奈米線適用來作 =^:’ 個六邊形切面3 3 6、3 3 8，適用*二八”、、歼 八g s兩 大的震盈強度效應，此乃發工：：=鏡…利用巨 大於激子波耳尺寸但小於光^ : °σ ^米線晶格的尺寸 陣列中產生激發發射現象。波長的情況下’可使奈米線 裂邊緣可用來作為對於U—VI族半導體而言，劈 材334與Zn0之間的一=一對奈米線而言，在藍寶石基 奈米晶格之尖銳面( 0 0 0 1、、)U介面336，❿另-端為“〇 子，此乃有鑒於K寶石 兩者均可用來作為雷射開口鏡 1. δ、2. 45、1 n風ί Zn〇、空氣之反射係數分別為 是，因為非常六二Ϊ對於奈米線的性質非常重要，也就 口 /波導管製作仏#接於一波導管。在奈米線中的天然開 使用裂解與餘則柄使人聯想到一種簡單的化學方法，不需 如第41圖所示Χ，:以形成一奈米線雷射開口。事實上， 約5 // m長户:在這些奈米線中發現到的多種雷射模式， 又、、、、之間距為5nm，其數量相當符合於相鄰共
554388 五、發明說明（48) 另一種製作光學開口的方法為，在線的一端製作介電質。 而且’在奈米線的一部分區域中可包含有一種能量轉換形 式，另一部分可包含有不同的能量轉換形式，如同在一'分 配回饋雷射中。也可以不蓋住光學開口的一端，如同雷射 或光放大器。此外，此開口也可為前述奈米線的一部分， 此開口也可為外加至奈米線的。在本質上，雷射或光放大 器之製作可採用奈米線、幫浦源以及開口，而此開口可為 奈米線之一部分或是與奈米線分離。甚至於，若是使用傳 統的激發發光技術，並不需要此開口。
本發明之奈米線可以用作為的一個量子點雷射的功能 元件’如參考資料中所提及之美國專利第5, 26〇, 957號，
其中里子點可被整合至奈米線中’而幫浦源可被安裝以用 來激發4子點中的居量反轉（population inversi〇n)。不 過’為了產生雷射，奈米線可推拉其自身，以處使奈米線 中的居量反轉。可如同前述方式，將奈米線整合至一聚合 物母體中’而成為一個母體（如：雷射元件）中的一個單 元。幫浦源可為一光學幫浦源（如：幫浦雷射），或是一電 子幫浦源’其陰極與陽極以直接接觸方式或歐姆接觸方式 而與奈米線連接。如果使用幫浦雷射，幫浦的波長最好要 比奈米線的波長多1 eV以上。奈米線可放置於一開口内， 或是其端點處可製作成反射面，以使奈米線用作為一開 口 〇 6·6 由前述可知，使用奈米線及其合成方式可製作出大量
i 554388 五、發明說明（54) — 力，可戲劇性地改變其埶柹晳。& β ^ ^ ，有希望mi:? 奈米線異質結構提 中，進而用以製作奈米電機轉換器。而且， (量子井與異質結構)或薄膜形式下呈現不穩定在 使在塊體或薄膜形式下呈現準穩定的相變成為—穩定 C:HN與LOHN亦提供其自身於能量轉換元件之 包含有熱電致冷氣或發電器、發光元件以及奈米電機轉換 器。在些το件中的有效材料包含有由VLS合成單方向太、 米線陣列的合成物，且埋入一聚合物母不 案定義與整合方式成為奈米系統。 了左由圖 μ i，5^〇17的半導體奈米線可提供獨特的機會，以開 ‘ ^ ί ί電器’其表現優於以氣相為基礎的元 以對環境上之能量使用科技產生巨大 調整尺寸的光電轉㈣。 應 1為有效率且可 甚至於，將奈米線埋入聚合物母體 彈性媒介物’其有效指數低於半導體，可心开纖== 效率的耦合，進而大幅地改善外加的量子效2 土有 電子之後，此量子點奈米線可提供作為單：二、、，。：早 具可成為一高品質因子以及高共振；；矣器 在分子感應/奈米致動器與高頻信號處’可以&供 &王p之間的應用範
554388 五、發明說明（56) 不可少的，因 轉換方式。這 礎。 使用前述 一部分已經在 面之LOHN、單 合、兩端子配 組合、具有一 具有一個或多 構、具 介面係 製作出 束制電 光子元 制動器 至機械 雖 以限定 神和範 護範圍 有絕緣 構成一 各種元 子的量 件（如： 與感應 能、熱 然本發 本發明 圍内， 當視後 為其可以大幅地改善轉換效率或是開啟新的 些簡單的元件也可作為其他更複雜元件的基 之f發明結構可以獲得各種表面配置型態， 先前描述。其他的例子為：單個或多個&合 個或多個接合面之COHN、LOHN與COHN之組 置、N>2端子配置、異質結構與同質結構之 個或多個電極（可為異質結構）之同質結構、 個電極之異質結構、具有絕緣體之同質結 體t異質結構。在一奈米線與一端子之間的 異質接合面。使用這些結構與配 :’包含有：聲子帶隙元件、在特殊以 點…熱電元件（如：固態致冷氣與引擎）、 奈米雷射）、奈米電機（MEM)元件（如：電 器Λ、各種形式之能量轉換元件（如：光轉換 月匕轉換至光）以及其他元件。 、 明已以一較佳實施例揭露如，然其並非用 ，任何熟習此技藝者’在不脫離 二 當可作些許之更動與潤飾，因此本發明之^ 附之申請專利範圍所界定者為準。
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Claims (1)

  1. 554388 六、申請專利範圍 1. 一種奈米結構，包括有： 一第一段，由一實質結晶材料所構'成；α及 一第二段，係與該第一段連接，且由不同於該第一段 材質之材料所構成； 其中，該第一段以及該第二段之中至少一個包含有一 實質均勻的直徑，且該直徑小於2 0 0 n m。 2. 如申請專利範圍第1項所述之奈米結構，其中該奈 米結構變遷自該第一段至該第二段之距離範圍為一原子層 〜2Onm 〇 3. 如申請專利範圍第2項所述之奈米結構，其中自該4 第一段至該第二段之變遷係起始於一朝向該第二段之端 點，該第一段之該端點成份降低成為該第一段中心處成份 的 99%。 4. 如申請專利範圍第1項所述之奈米結構，其中該第 二段包含有一實質結晶材料。 5. 如申請專利範圍第1.項所述之奈米結構，其中該第 一段與該第二段之中至少一個包含有一半導體材料。 6. 如申請專利範圍第1項所述之奈米結構，其中該第 一段與該第二段之中至少一個包含有一摻雜之半導體材 料。 7. 如申請專利範圍第1項所述之奈米結構，其中該第 一段與該第二段之中至少一個表現出一塊體摻雜之半導體 的電性特徵。 8. —種奈米結構，包括有：
    1012-4754-PF(N).ptd 第70頁 554388 六、申請專利範園 由實質結晶材料所構成； ，該第-段連接…〜實ΐ結晶材料 一第—段 一第二段 所構成； 實質均!的ΐ ί 一段以及該第二段之甲至少一個包含有 ”的直徑，且該直徑小於20 0nm。 個㈠有— 米結構變^自請//^/8項所述之奈米結構，其中該奈 〜。…弟-段至該第二段之距離範圍為一原子; 該第二段第9項所述之奈米結構 點，該第一^ 又爻遷係起始於朝向該第二段之端 的9 9 %。 端點成份降低成為該第-段中心處成份 第一 i·盥ί :請：利範圍第8項所述之奈米結構，其中該 12 、Γί 一之中至少—個包含有—半導體材料。 第-段血專利範圍第8項所述之奈求結構，其中該 一 Μ第一段包含有一半導體材料。 第鱼^ ί請專利範圍第8項所述之奈米結構，其中該 料。^ Μ第一段之中至少一個包含有一摻雜之半導體材 14.如申请專利範圍第8項所述之奈米結構，其中該 第一段與該第二段包含有一摻雜之爭導體材料。、 15·如申請專利範圍第8項所述之奈米結構，其中該 第一段與該第二段之中至少一個表現出一塊體摻雜之半導 體的電性特徵。 ΙΗ 1012-4754-PF(N).ptd 第71買 554388
    16·如申請專利範圍第8項所述之奈米結構，其中該 :段與該第二段表現出一塊體摻雜之半導體的電性特/ 構成 一檀奈米結構 _…y 第一段，由一半導體材牲所構成；以及 第二段，係與該第一段連接，且由一半導體材料所 6 其中，該第一段以及該第二段之中至少一個包含右一 貫質均勻的直徑，且該直徑小於2 〇〇 nm。 18.如申請專利範圍第丨7項所述之奈米結構，兑 ^米結構變遷自該第一段至該第二段之距離範圍為二= 層〜20nm。 τ 結構，其中自 該第二段之端 段中心處成份 ^ 1 9 ·如申請專利範圍第1 8項所述之奈米 違第一段至該第二段之變遷係起始於一朝向 點’該第一段之該端點成份降低成為該第一 的 99°/〇。 21·如申請專利範圍第17項所述之奈米結構，其中該船 第一段與该第二段包含有一摻雜之半導體材料。 22· 一種奈米結構，包括有： 一第一段，由一摻雜之半導體材料所構成；以及 第一奴，係與該第一段連接，且由一摻雜之半導體
    1012-4754-PF(N).ptd 第72頁 554388 六、申請專利範圍 材料所構成； 其中，該第一段以及該第二段之中至少一個包含有一 實質均勻的直徑，且該直徑小於2 0 0nm。 23. 如申請專利範圍第22項所述之奈米結構，其中該 奈米結構變遷自該第一段至該第二段之距離範圍為一原子 層〜20nm 〇 24. 如申請專利範圍第23項所述之奈米結構，其中自 該第一段至該第二段之變遷係起始於一朝向該第二段之端 點，該第一段之該端點成份降低成為該第一段中心處成份 的 99%。 2 5. —種奈米結構，包括有： 一第一段，由一實質結晶材料所構成；以及 一第二段，係與該第一段連接，且由不同於該第一段 材質之材料所構成； 其中，該奈米結構變遷自該第一段至該第二段之距離 範圍為一原子層〜20nm ;以及 其中，該第一段以及該第二段之中至少一個包含有一 實質均勻的直徑，且該直徑小於2 0 0 n m。 26. 如申請專利範圍第25項所述之奈米結構，其中自 該第一段至該第二段之變遷係起始於一朝向該第二段之端 點，該第一段之該端點成份降低成為該第一段中心處成份 的 99%。 27. 如申請專利範圍第25項所述之奈米結構，其中該 第二段包含有一實質結晶材料。
    1012-4754-PF(N).ptd 第73頁 第 554388 六、申請專利範圍 28·如申請專利範圍第25項所述之奈 段與該第二段之中至少一個包含有一 2 9 ·如申請專利範圍第2 5項所述之奈 第一段與該第二段之中至少一個包含有— 料。 3 〇 ·如申請專利範圍第2 5項所述之奈 第一段與該第二段之中至少一個表現出一 體的電性特徵。 3 1 · —種奈米結構，包括有： —第一段，由一實質結晶材料所構成 —第二段，係與該第一段連接，且由 所構成； ^ 其中’該奈米結構變遷自該第一段至 範圍為一原子層〜20nm ;以及 — 其中’該第一段以及該第二段之中至 實質均勻的直徑，且該直徑小於2 0 0nm。 3 2.如申請專利範圍第3 1項所述之奈 该第一段至該第二段之變遷係起始於一朝 點’該第一段之該端點成份降低成為該第 的 99〇/〇 〇 33·如申請專利範圍第31項所述之奈 第一段與該第二段之中至少一個包含有一 34·如申請專利範圍第31項所述之奈 第 ^又與該第二段包含有一半導體材料。 米結構，其中該 半導體材料。 米結構，其中該 摻雜之半導體材 米結構，其中該 塊體摻雜之半導 ;以及 一實質結晶材料 該第二段之距離 ^ 一個包含有一 米結構，其中自 向該第二段之端 一段中心處成份 米結構，其中該 半導體材料。 米結構，其中該
    1012-4754-PF(N).ptd 第74頁 554388 申請專利範圍 ___ 35. 如申請專利範圍第31項所述之奈 段與該第二段之中至少一個包含有一摻=本J中該 枓。 滩之半導體材 36. 如申請專利範圍第31項所述之奈米結構， 第一段與該第二段包含有—捧雜之半導體材〃中该 37·如申請專利範圍第31項所述之奈米結構，立 體：Ϊ ΐ:第二段之中至少一個表現出一塊體摻雜：半ΐ 體的電性特徵。 '^干V 38·如申請專利範圍第31項所述之奈米結構，其中該 y 一段與該第二段表現出一塊體摻雜之半導體的電性特 徵0 、 3 9 · —種奈米結構，包括有： 一第一段’由一半導體材料所構成；以及 第一 ，係與該第一段連接，且由一半導體材料所 構成； ^ 其中’該奈米結構變遷自該第一段至該第二段之距離 範圍為一原子層〜2〇ηηι ;以及 — 其中’該第一段以及該第二段之中至少一個包含有一 實質均勻的直徑，且該直徑小於2〇〇nm。 4 0·如申請專利範圍第3 9項所述之奈米結構，其中自你 該第一段至該第二段之變遷係起始於一朝向該第二段之端 點’該第一段之該端點成份降低成為該第一段中心處成份 的 99°/〇。 41.如申請專利範圍第4 〇項所述之奈米結構，其中該
    1012-4754-PF(N).ptd 第75頁 ^4388 六、申請專利範圍 個包含有一摻雜之半導體材 其中該 段與該第二段之中至少 第一 如申請專利範圍第39項所述之奈米結構 該第二段包含有一摻雜之半導體材料。 ·»種奈米結構，包括有： =一段，由一摻雜之半導體材料所 材料段’係與該第-段連接，且由1雜=導體 範圍：構變以遷及自該第-段至該第二段之距離 實皙it，該第一段以及該第二段之中至少一 貫\句的直徑，且該直徑小於2〇_。⑯包含有— 該第—段ΐ43項所述之奈米結構，其中自 點’該第-段之該端點該第二段之端 的99%。 降低成為该第-段中心處成份 4一5.—種严米結構，包括有： 又由貫為結晶材料戶斤構成.以另 材質之材料所構成； 又逑接’且由不同於該第—段 —其申，該奈米結構變遷自該第一段至 範圍為一原子層〜20nm。 第—段之距離 其中，自該第一段至該第二段之 該第二段之端點，該第一段 ’、起始於一朝向 之6亥知點成份降低成為該第— ^_ 第76頁 1012-4754-PF(N).ptd 554388 六、申請專利範圍 段中心處成份的9 9% ;以及 其中，該第一段以及該第二段之中至少一個包含有一 實質均勻的直徑，且該直徑小於2〇〇nm ° 46.如申請專利範圍第45項所述之奈米結構，其中該 第一段包含有一實質結晶材料。 47·如申請專利範圍第45項所述之奈米結構，其中該 第一段與該第二段之中至少一個包含有—半導體材料。 48·如申請專利範圍第45項所述之奈米結構，其中該 第一段與該第二段之中至少一個包含有一摻雜之半導體材 料。 ❿ 4 9·如申請專利範圍第4 5項所述之奈米結構，其中該 第一段與該第二段之中至少一個表現出一塊體摻雜之半導 體的電性特徵。 5 〇 · —種奈米結構，包括有： 一第一段，由一實質結晶材料所構成；以及 一第二段，係與該第一段連接，且由一實質結晶材料 所構成； 7 其中，該奈米結構變遷自該第一段至該第二段之距離 範圍為一原子層〜2〇nm ; 其中’自該第一段至該第二段之變遷係起始於一朝向j 該第二段之端點，該第一段之該端點成份降低成為該第一 段中心處成份的99% ; 其中，該第一段以及該第二段之中至少一個包含有_ 貫負均勻的直徑，且該直徑小於2 〇 〇nm ;以及
    554388 六、申請專利範圍 其中，該直徑小於200nm之線段的直徑變化不會大於 該線段之長度的10°/〇。 51·如申請專利範圍第5 0項所述之奈米結構，其中該 第一段與該第二段之中至少一個包含有一半導體材料。 52·如申請專利範圍第50項所述之奈米結構，其中該 第一段與該第二段包含有一半導體材料。 53·如申請專利範圍第50項所述之奈米結構，其中該 第一段與該第二段之中至少一個包含有一摻雜之半導體材 料0 54·如申請專利範圍第5〇項所述之奈米結構，i 第一段與該第二段包含有一摻雜之半導體材料。 / 55·如申請專利範圍第5〇項所述之 第-段與該第二段之中至少一個表現=雜ί:该 體的電性特徵。 鬼體4雜之半導 56·如申請專利範圍第50項所述之夺乎έ 第-段與該第二段表現出-塊體摻雜之半中該 徵。 〜千導體的電性特 57· —種奈米結構，包括有·· 以及 一半導體材料所儀[ 一第一段，由一半導體材料所構成； 一第二段，係與該第一段連接，且士 構成； φ 其中，忒奈米結構變遷自該第一一 範圍為一原子層〜2〇nm ; 主4第二段之距離 其中。自該第一段至該第 丰又之變遷係起始於一朝向
    1012-4754-PF(N).ptd 第78頁 554388 六、申請專利範圍 該第二段之端點，該第一段之該端點成份降低成為該第一 段中心處成份的99% ; ^ 其中，該第一段以及該第二段之中至少一個包含有一 實質均勻的直徑，且該直徑小於20 Onm ;以及 其中，該直徑小於2〇〇nm之線段的直徑變化不會大於 該線段之長度的10%。 《 ' 58·如申請專利範圍第57項所述之奈米結構，其中該 第一段與該第二段之中至少一個包含有一摻雜之半導體材 59·如申請專利範圍第57項所述之奈米結構，其中該 第一段與該第二段包含有一摻雜之半導體材料。 Λ 6 0. —種奈米結構，包括有：
    一第一段，由一摻雜之半導體材料所 一第二段，係與該第一段連接，且由 材料所構成； 其中，該奈米結構變遷自該第一段至 範圍為一原子層〜2〇nm ; 構成；以及 一摻雜之半導體 該第二段之距離 其中 該第一段至該第二段之變遷係起始於 該第二段之端點，該第一段之該端點成份降低成為該 段中心處成份的99% ; — 其中，該第一段以及該第二段之中至少一個包含 實質均勻的直徑，且該直徑小於20 Onm ;以及 朝向 其中，該直徑小於20 Onm之線段的 該線段之長度的10%。 直變化不會大於
    l〇12.4754-PF(N).ptd 第79頁
    554388 六、申請專利範圍 遵套包含有一非晶質材料。 ^ 78·如申請專利範圍第76項所述 濩套包含有一實質結晶材料。 —☆ 79·如申請專利範圍第78項所述之不/ 實質結晶材料為實質單結晶。 8〇·如申請專利範圍第1、8、17… 該 43、45、50、57或60項所述之奈沭1谈广 〇ι > 39 、22^該奈米1 下列元件的-個功能部件，包含有：聲，水電 點疋件、熱電元件、光子元件、奈米電機 f遂；椏 機感應器、場效電晶體、紅外線偵測器、/、學調整器 體、單電子電晶體、磁感應器、#光元件學開關以及雷 光學偵測器、光學導波管、光學耦合器、尤 射。 25 、 31 、 39 破 22:中该条米结構 4 3、4 5、5 0、5 7 々 β α 4 ，处構’，、 81·如申請專利範圍第i、8、1 7 45、50、57或60項所述之奈米結 是一奈米結構陣列的一個單元。 8 2 · —種奈米結構，包括有： 一第一段，由一材料所構成； 一第二段，係與該第一段連接， 以及 一第三段，係與該第一段與該第 接，且由一材料所構成； 的 其中，至少一個線段包含有〆實質均勾、 直徑小於200nm ; 由 段 之 材料所 中秦少 構成； /個$ 該 Η
    1012-4754-PF(N).ptd 第82頁 554388 六、申請專利範圍 其中，至少兩個線段是由不同材料所構成；以及 其中，至少兩個線段是相鄰的。 83. 如申請專利範圍第82項所述之奈米結構，其中該 直徑小於200nm之線段的直徑變化不會大於該線段之長度 的 10%。 84. 如申請專利範圍第82項所述之奈米結構，其中該 奈米結構變遷自至少一線段至相鄰之線段之距離範圍為一 原子層〜20nm。 8 5·如申請專利範圍第8 2項所述之奈米結構，其中自 至少一線段至一相鄰線段之變遷係起始於一朝向該相鄰線儀| 段之端點，該線段之該端點成份降低成為該線段中心處成 份的99%。 8 6·如申請專利範圍第8 2項所述之奈米結構，其中至 少兩個線段是縱向相鄰的。 8 7·如申請專利範圍第8 2項所述之奈米結構，其中該 第二段係軸向縱向相鄰於該第一段，且該第三段係縱向相 鄰於該第二段。 8 8·如申請專利範圍第8 2項所述之奈米結構，其中至 少兩個線段是軸向相鄰的。 8 9 ·如申請專利範圍第8 2項所述之奈米結構，其中至· 少一線段的材料包含有一實質、结晶材料。 9 0·如申請專利範圍第8 9所述之奈米結構，其中該實 質結晶材料為實質單結晶。 9 1 ·如申請專利範圍第8 2項所述之奈米結構，其中至
    1012-4754-PF(N).ptd 第83頁 554388 六、申請專利範圍 103·如申請專利範圍第82項所述之奈米結構，更包 含有一電極，係與至少一個線段形成電連接。 104·如申請專利範圍第82項所述之奈米結構，其中 至少一個線段的材料是選自於I I族、I Π族、I V族、V族或 V I族元素。 10 5·如申請專利範圍第g 2項戶斤述之奈米結構’其中 至少一個線段係埋入一聚合物母體中。 10 6.如申請專利範圍第§ 2項戶斤述之奈米結構，其中 至少一個線段的至少一部分係被一護套所覆蓋。
    10 7·如申請專利範圍第丨〇 6項所述之奈米結構，其中 該護套包含有一非晶質材料。 )1 0 8 ·如申請專利範圍第1 0 6項所述之奈米結構，其中 该濩套包含有一實質結晶材料。 109·如申請專利範圍第1〇8項所述之奈米結構，豆中 該實質結晶材料為實質單結晶。 〃 110·如申請專利範圍第8 2項所述之奈米結構，豆中 該奈米線是下列元件的-個功能部件，包含有··聲子帶丨 ;件夺= = 熱電元件、光子元件、奈米電機致]
    穿遂二極體^ :裔、场效電晶體、紅外線偵測11、共; ^ 7 早電子電晶體、磁感應器、發光元件、光： 調！ 、光學偵測器、光學導波管 1 關以及雷射。 ％予祸口态、先學1
    1012-4754-PF(N).ptd 第85頁 554388 六 申請專利範圍 分解媒介一二？:―構巧 段；以及 第一軋體反應物，然後成長一第一 第二段，，亥^ 1 ^ : : : - 2 :氣體反應物，然後成長一 材質之材料所構成’;、/、"第一段連接且由不同於該第一段 實質Ϊ:的該第二段之中至少-個包含有-113 二且違直徑小於20 0nm。 方法’其中V」:專氣利體範/第112項所述之奈米結構的製作 同組成之液體合金：且5應=;:介液體係形成-相 和處。 母—線段係形成自該液體合金之飽 方法，其申二專利乾圍第112項所述之奈米結構的製作 物種成長：應物包含有-氣體…運“ 氣體反應物 ，供的，^該第二段包含有該第— "5.種太/;播氧… 分解—媒/液米體。 段；以及、/ _的—氣體反應物，然後成長一第— 段广该第-段上塗佈—不同成份材料，以形成一第二 八T ，緣乐一杈以及贫繁—i；L +丄 實質均勻的直彳/第一奴之中至少一個包含有 J妁直瓜，且忒直徑小於2〇〇nm。 •如申請專利範圍第11 5項所计、 . 禾 貝所述之奈米結構的製
    554388 六、申請專利範圍 方法’其中該氣體反應物以及該媒介液體係形成一液體合 金，且該第一段係形成自該液體合金之飽和處。 117· 一種奈米結構的製作方法，包含有下列步驟： 長 (a) 分解—媒介液體中的—帛—氣體反應物，然後成 第一材料，以形成一第一段； 長 (b) 分解該媒介液體中的一第二氣體反應物，然後成 第二材料，以形成一與該一段相連接之第二段； 金 處 (c I該氣體反應物以及該媒介液體係形成一液體合 且忒第一&與a亥第一段均形成自一液態合金的飽和 以 形成(一％ = 一線段之至少一部份塗佈-第三材料 (e) 該第一材料、該第二材料與該第三材料之中至少 兩個為不同成份；以及 (f) 該第一段、該第二段以及該第三段之中至少一個 包含有一實質均勻的直徑，且該直徑小於2 0 0nm。 118· —種奈米結構的製作方法，包含有下列步驟： 分解一媒介液體中的一第一氣體反應物，然後成長一 第一材料，以形成一第一段； 分解該媒介液體中的一第二氣體反應物，然後成長一❿ 第一材料，以形成一與該第一段相連接之第二段；以及 分解該媒介液體中的一第三氣體反應物，然後成長一 第三材料，以形成一與該第二段相連接之第三段； 其中，該第一段、該第二段以及該第三段係為縱向相
    1012-4754-PF(N).ptd 第87頁 六、申請專利範圍 鄰； 其中， 及 其中， 個包含有一 119. 方法，其 者為相同 少兩者由 120. 方法，其 金，且該 121. 方法，其 用於物種 段包含有 的組合。 122. 步驟： 該第 段位於該第一段以及該第三段之間；以 一‘ =M t、"亥第二段以及該第三段之中至少一 如申貝^直二的直#，且該直#小於2〇〇nm。 0利範圍第118項所述之奈米結構 的了ί;第第；與第三氣體反應物之中至少有兩 相同材質所構成。 又n亥第二奴之中至 中今申/專利犯圍第11 8項所述之奈米結構的製作 夺應物以及該媒介液體係形成-液體合 ^水、二構線段係形成自該液體合金之飽和處。 中;空凊丨專利範®第1 1 8項所述之奈米結構的製作 . ^種氣體反應物包含有一氣體，是由道 =,射移姓所提供的，1至少一奈米結構： 〇Λ 礼體反應物以及該第二氣體反應物之種類 種奈米線異質結構的製作方法，包含有下列 媒介液體中的一第一氣體反應物，然 ^以形成一第一段；以及 交成長〜 :媒介液體中的一第二氣體反應物 材料不同的第二材#，以形成一與該 之第二段； 布仅呈現 分解 第一材料 分解 與該第一 縱向連接
    554388 六、申請專利範圍 其中該第一、第二氣體反應物以及該媒介液體係形 成兩種不同成份的液體合金； ^ ，該第一段與該第二段係分別形成自相關氣體反 應物成伤之該液體合金之飽和處；以及 其中’該第一段與該第二段之中至少一個包含右一 質均勾的直經，且該直徑小於20 0nm。 ^3·—種奈米結構的製作方法，包含有下列步驟： 分解一媒介液體中的一第一氣體反應物， 第-材料，以形成一第一段；以纟 ’，、、後成長- 、 依序雷射移蝕該第一氣體反應物中的成長物種，以 成一=二氣體反應物；以及 乂 >分解該媒介液體中的一第二氣體反應物，然後成長一 與讀第一材料不同的第二材料，以形成一與該第一 縱向相連接之第二段； 兄 其中’該第二段包含有該第一氣體反應物以及該第二 氣體=應物之種類的組合；以及 其中’該第一段與該第二段之中至少一個包含有一實 質均勻的直么； 息k ’且該直徑小於2〇〇nm。 1 2 4 ·如申請專利範圍第1 2 3項所述之奈米結構的製作 方法，其中該第一、第二氣體反應物以及該媒介液體係形 成兩種不同成份的液體合金，且該第一段與該第二段係分 別形j自相關氣體反應物成份之該液體合金之飽和處。 、去，勺八t種摻雜半導體超晶格之奈米結構的製作方 / ，0 3有下列步驟：
    554388 六、申請專利範圍 將一氣體反應物通入一反應爐的 反應搶體包含有一塗佈有反應金屬的 將該反應艙體加熱至一溫度，其 成為至少一個液滴； 將該反應氣體分解至該液滴中直 一段成核與成長；以及 將一摻質與該氣體反應物分解至 其可使一摻雜之第二段在該第一段上 其中’該第一段與該第二段之中 質均勻的直徑，且該直徑小於20Onm ( 1 2 6 ·如申請專利範圍第1 2 5項所 格之奈米結構的製作方法，其中該基 族以及I V族元素。 12 7·如申請專利範圍第丨2 5項所 格之奈米結構的製作方法，其中該金 12 8·如申請專利範圍第丨2 7項所 格之奈米結構的製作方法，其中該金 (colloidal gold) 〇 12 9·如申請專利範圍第丨2 5項所 格之奈米結構的製作方法，其中該基 屬包含有金。 13 0·如申請專利範圍第丨2 5項所 格之奈米結構的製作方法，其中該反 應爐管。 反應搶體中，其中該 基板； 可使該反應金屬液化 至飽和，其可使一第 該液滴中直至飽和， 進形成核與成長； 至少一個包含有一實 述之摻雜半導體超 板中主要包含有111 B曰 述之摻雜半導體超晶 屬包含有金。 述之摻雜半導體超晶 包含有膠態金 述之摻雜半導體超晶 板包含有矽，且該金❿ 述之摻雜半導體超晶 應爐包含有一石英反
    554388 六、申請專利範圍 1 3 1 ·如申請專利範圍第丨2 5項所述之掺雜半導體超晶 格之奈米結構的製作方法，其中該氣體反應物包含有H2與 的混合物。 、132· —種Si/si Ge超晶格之奈米線異質結構的製作方 法’包含有下列步驟： 於一基板上沉積一 Au層； 將該基板放置於一石英反應爐管中； 將一包含有H2與3 i C 14的混合氣體反應物通入該反應爐 管中； 將該反應爐管加熱至一溫度，其可使該Au層液化成為船 至少一個奈米規格的A u - s i合金液滴； 將β亥反應氣體分解至該液滴中直至飽和，其可成核與 成長出一 S i線段； 、 在成長該S i線段的過程中，雷射移蝕一 G e靶材以產生 一 G e氣相；以及 沉積Ge與Si物種於該Au-Si合金液滴中直至飽和，其 可於該Si線段上成核與成長出—SiGe線段； — 其中，忒S丨線段與該s i G e線段之中至少一個包含有， 實質均勻的直徑，且該直徑小於2〇〇nm。 其中該氣體反應物包含有
    格之奈米結構的製作方法， H2與S i C 14的混合物。 133.如申請專利範圍第132項所述之一種s 晶格之奈米線*質結構的製作方*，另&含有一步驟.。 啟關閉該雷射之脈衝’可使該^⑽超晶格形成塊體/
    1012-4754-PF(N).ptd 第91頁 554388 六、申請專利範圍 連接。 134·如申請專利範圍第Η?項所述之一種Si/SiGe超 晶格之奈米線異質結構的製作方法，其中該基板中主要包 含有I I I族以及I V族元素。 13 5·如申請專利範圍第1 3 2項所述之一種S i / S i G e超 晶格之奈米線異質結構的製作方法，其中該A u層包含有膠 態金（colloidal gold)。 136·如申請專利範圍第132項所述之一種Si/Si Ge超 晶格之奈米線異質結構的製作方法，其中該基板金包含有 石夕。 1 3 7 ·如申請專利範圍第11 2、11 5、11 7、11 8、1 2 2、 123、125或132項所述之製作方法，其中直徑小於200nm之 線段的直徑變化不會大於該線段之長度的1 〇 %。 1 3 8 ·如申請專利範圍第11 2、11 5、11 7、11 8、1 2 2、 1 2 3、1 2 5或1 3 2項所述之製作方法，其中該奈米結構變遷 自該第一段至該第二段之距離範圍為一原子層〜20nm。 139.如申請專利範圍第138項所述之製作方法，其中 自該第一段至該第二段之變遷係起始於一朝向該第二段之 端點，該第一段之該端點成份降低成為該線段中心處成份 的 99%。 140·如申請專利範圍第112、115、117、118、122、 123、125或132項所述之製作方法，其中至少一線段包含 有一實質結晶材質。 1 4 1 ·如申請專利範圍第11 2、11 5、11 7、1 1 8、1 2 2、
    l〇12-4754-PF(N).ptd 第92頁 554388 六、申請專利範圍 158·如申請專利範圍第156項所述之製作方法，豆 I護套包含有一實質結晶材料。 ’、 ^159·如申請專利範圍第158項所述之製作方法，其中 这實質結晶材料為實質單結晶。 1 6 0 ·如申請專利範圍第！ ！ 2、11 5、11 7、1 i 8、！ 2 2、 1 2 3、1 2 5或1 3 2項所述之製作方法，其中該奈米線是下列 元件的一個功能部件，包含有：聲子帶隙元件、量子點元 件、熱電元件、光子元件、奈米電機致動器、奈米電機感 應器、場效電晶體、紅外線偵測器、共振穿遂二極體、單 電子電晶體、磁感應器、發光元件、光學調整器、光學偵 測器、光學導波管、光學耦合器、光學開關以及雷射。 161.如申請專利範圍第112， 1 2 3、1 2 5或1 3 2項所述之製作方法 個單元。 雷射，包含有 115 '117 >118 >122 ，其中該奈米結構是一 奈米結構陣列的 162 —種奈# ，其包含有一實質均勻的直徑，且該直徑 一奈米結構 小於2 0 0nm ;以及 一幫浦源。 163.如申請專利範圍第162項 該奈米結構係由不同成伤"且成之複之太乎雷身十士 a I利範圍第1 62項所述之不木雷射， =4.如明發該結構中的居量反轉 該幫浦源之配置是用 ^ Α _ . 所述之奈米雷射 同成份組成之複數個線段所構成 其中 其中 灰木雷射’包含有· 16 5· 種不"皮乃由不同成份組成之複數個縱向相鄰 一奈米結構’ #
    第95頁 l〇12-4754-PF(N).ptd 554388
    六、申請專利範圍 的線段所構成，其中至少一個線段包含有一實質均勻的直 徑’且該直徑小於2〇〇nm ;以及 一幫浦源。 16 6·如申請專利範圍第1 6 5項所述之奈米雷射，其中 該幫浦源之配置是用來激發該奈米結構中的居量反轉。 167· —種奈米雷射，包含有： 一奈米結構，其乃由不同成份組成之複數個縱向相鄰 的線段所構成，其中至少一個線段包含有一貫質岣勻的直 # ’且該直徑小於200nm ;以及 一幫浦源，其配置是用來激發該奈米結構中的居量反‘ 轉。 168. 一種奈米雷射 包含有： 且該直徑 一奈米結構，其包含有一實質均勻的直徑 小於20 0nm ; 複數個量子點，係置於該奈米結構中；以及 一幫浦源。 1 6 9 ·如申請專利範圍第1 6 8項所述之奈米雷射，其中 該奈米結構係由不同成份組成之複數個線段所構成。 17 0.如申請專利範圍第1 6 9項所述之奈米雷射，其中 該幫浦源之配置是用來激發該量子點中的居量反轉。 171·—種奈米雷射，包含有： 一奈米結構，其乃由不同成份組成之複數個縱向相鄰 的線段所構成，其中至少一個線段包含有一實質 徑’且該直徑小於2〇〇nm; 勾的直
    1012-4754-PF(N).ptd 第96頁 554388 六、申請專利範圍 複數個量子點，係置於該奈米結構中；以及 一幫浦源。 二 172·如申請專利範圍第171項所述之奈米雷射，其中 "亥幫浦源之配置是用來激發該量子點中的居量反轉。 173· 一種奈米雷射，包含有： 一奈米結構，其乃由不同成份組成之複數個縱向相鄰 的線段所構成，其中至少一個線段包含有一實質均勻的直 徑’且該直徑小於2〇〇nm ;
    複數個量子點，係置於該奈米結構中；以及 一幫浦源，其配置是用來激發該量子點中的居量反 轉0 174·如申請專利範圍第162、us、167、171或173項 所述之奈米雷射，其中該奈米結構包含有一實質結晶材 質。 175·如申請專利範圍第162、165、167、171或173項 所述之奈米雷射，其中該實質結晶材質為一實質單結晶材 質。 176·如申請專利範圍第162、165、167、171或173項
    所述之奈米雷射，其中該奈米結構之直徑範圍為5〜5〇nm。 177. 如申請專利範圍第162、165、167、171或173項 所述之奈米雷射’其中該奈米結構的直徑變化不會大於該 線段之長度的1 0 %。 178. 如申請專利範圍第162、165、167、171或173項 所述之奈米雷射，其中該奈米結構的材料是選自於丨丨族、
    1012-4754-PF(N).ptd 第97頁 554388 六、申請專利範圍 III族、IV族、v族或^族元素。 17 9·如申請專利範圍第1 6 2 所述之奈米雷射，其中該奈米結 中。 18 0·如申請專利範圍第1 6 2 所述之奈米雷射，其中該奈米結 個單元。 181.如申請專利範圍第1 6 2 所述之奈米雷射，其中該幫浦源 1 8 2 ·如申請專利範圍第1 8 1 忒光學脈衝源包含有一脈衝雷射 1 8 3 ·如申請專利範圍第1 6 2 所述之奈米雷射，其中該幫浦源 1 8 4 ·如申請專利範圍第1 8 3 該導電脈衝源包含有一陰極與一 185·如申請專利範圍第184 該陽極與該奈米結構形成一電連 1 8 6 ·如申請專利範圍第1 8 5 該電連接係為一歐姆接觸。 1 8 7 ·如申請專利範圍第1 8 5 該電連接係為一直接接觸。 188·如申請專利範圍第184 該陰極與該奈米結構形成一電連 18 9·如申請專利範圍第1 8 8 、165 、 167 構係埋入一 、165 、 167 構是一奈米 、165 、 167 包含有一光 項所述之奈 〇 〜165 > 167 包含有一導 項所述之奈 陽極。 項所述之奈 接。 項所述之奈 、171 或173 項 聚合物母體 、171 或173 項 結構陣列的一 、171 或17 3 項 學脈衝源。 米雷射，其中· 、171 或173 項 電脈衝源。 米雷射，其中 米雷射，其中 米雷射，其中 項所述之奈米雷射，其中 米雷射，其中 米雷射，其中 項所述之奈 接。 項所述之奈
    l〇12-4754-PF(N).ptd
    554388 六、申請專利範圍 ' -- 該電連接係為一歐姆接觸。 —兩190·如申請專利範圍第188項所述之奈米雷射，其中 该電連接係為一直接接觸。 1 9 1 ·如申請專利範圍第1 84項所述之奈米雷射，其中 μ陽極與遠陰極皆與該奈米結構形成一電連接。 19 2·如申請專利範圍第丨9 1項所述之奈米雷射，其中 該電連接係為一歐姆接觸。 1 9 3 ·如申請專利範圍第1 9 1項所述之奈米雷射，其中 4電連接係為一直接接觸。 194·如申請專利範圍第162、165、167、168、171或Φ 1^3項所述之奈米雷射，其中該奈米結構包含有一第一端 以及一第二端’且該第一端以及該第二端均包含有反射表 面。 19 5.如申請專利範圍第1 9 4項所述之奈米雷射，其中 該奈米結構包含有一開口。 196· —種奈米雷射，包含有： —一具有多個切面、單結晶之Ζη〇奈米結構，其包含有 一實質均句的直徑，且該直徑小於2〇〇ηπι ; 遠奈米結構包含有一第一端以及一第二端； ^该第一端包含有一磊晶介面，係自該奈米結構延伸而 形成於該奈米結構與一藍寶石基材之間；以及 該第一端與該第二端包含有相對應之反射表面； 其中’該奈米結構之功能是用作為該端點面之間的一 個共振開口。
    554388 六、申請專利範圍 197·如申請專利範圍第196項所述之奈米雷射 該奈米結構係埋入一聚合物母體中。 ^ 198·如申請專利範圍第196項所述之奈米雷射 該奈米結構是一奈米結構陣列的一個單元。 19 9·如申請專利範圍第丨9 6項所述之奈米雷射 含有一幫浦源。 2 0 0 ·如申請專利範圍第1 9 9項所述之奈米雷射 該幫浦源包含有一光學脈衝源。 2 〇 1 ·如申請專利範圍第2 0 0項所述之奈米雷射 該光學脈衝源包含有一脈衝雷射。 202·如申請專利範圍第199項所述之奈米雷射 忒幫浦源包含有一導電脈衝源。 2 0 3 ·如申請專利範圍第2 0 2項所述之奈米雷射 其中該導電脈衝源包含有一陰極與一陽極。 2 0 4 ·如申請專利範圍第2 0 3項所述之奈米雷射 該陽極與該奈米結構形成一電連接。 2 0 5 ·如申請專利範圍第2 0 3項所述之奈米雷射 孩陰極與該奈米結構形成一電連接。 > θ 2 〇 6 ·如申請專利範圍第2 0 3項所述之奈米雷射 S陽極與陰極均與該奈米結構形成一電連接。 2〇7·如申請專利範圍第204、205或20 6項所述 雷射，其中該電連接係為一歐姆接觸。 208.如申請專利範圍第2〇4、205或206項所述 雷射，其中該電連接係為一直接接觸。 ，其中 ，其中 ，另包 ，其中 ，其中 ，其中 ，其中 ，其中 ，其中 ，其中 之奈米 之奈米
    l〇12-4754-PF(N).ptd 第100頁
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