1326247 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式 九、發明說明： 【發明所屬之技術領域】 本發明涉及-維奈;^材料，尤其涉及—辦Γ奈#線之結構及其合成方去 【先前技術】 一 ’° 半導體工業之發展主題係更小、更快'更低能耗。然而，從微米電子時代 入奈米電子時代之後，傳統半導體製造技術一光刻工藝（屬於所謂“自上而下” 技術）逐漸到達其所能企及之極限，顯得越來越難以滿足現在以及未來之要求。 因此’ “自下而上”之技術，或稱為自組裝技術被認為係未來發展趨勢。目前， 人們已經桐這種“自下而上”技術合成得各種奈米材料’包括奈米線、奈米 官，其潛在應用τ員域包括奈米電子、奈米光學、奈米感測器等。由於石夕係目前半 導體業界最常用之材料，故’相對而言，對矽奈米線之合成以及研究顯得較多。 早在1964年’ Wagner等人已經在矽基底上垂直合成微米級之矽須(SUic〇n Whisker) ’具體請參見Appl. Phys. Lett. 1964,4,89。發展到目前，石夕奈米線合成方 法包括催化劑化學氣相沈積(Catalytic Chemical Vapor Deposition，CCVD)，雷射蒸 發法(Laser Evaporation)，直接熱蒸發法(Direct Thermal Evaporation)，模板合成法 (Template Synthesis)等。惟，現有技術大多只能合成彎曲纏繞的、長度較小之奈 米線，並且夾雜許多雜質。 2001年11月6日公告之美國專利第6,313,015號揭示一種石夕奈米線與奈米 顆粒鏈(NanoparticleChains)之生長方法。該方法利用熱蒸發，雷舞燒触，電漿或 磁控濺射法將一氧4(^夕蒸發出來，在惰性氣體保護下，於800至1000度溫度條 件下，於基底上合成得矽奈米線及奈米顆粒鏈。矽奈米線沿<112>方向生長，而 無方向之奈米顆粒則形成奈米顆粒鏈。顯然，這種方法夹雜有奈米顆粒雜質，且 1326247 相對於基底’矽奈米線之形成方向並不確定，不利於其實際應用。1326247 VIII. If there is a chemical formula in this case, please disclose the chemical formula which best shows the characteristics of the invention. IX. Description of the invention: [Technical field of the invention] The present invention relates to -Vina; material, especially to the structure of the line And its synthesis side [previous technology] A '° semiconductor industry development theme is smaller, faster 'lower energy consumption. However, after entering the nanoelectronic era from the microelectronics era, traditional semiconductor manufacturing technology-lithography (which belongs to the so-called "top-down" technology) has gradually reached the limit that it can reach, and it is increasingly difficult to meet the present and the future. Requirements. Therefore, the technology of “bottom-up”, or self-assembly technology, is considered to be the future development trend. At present, people have already synthesized this kind of nano material from the "bottom-up" technology, including nanowires and nano-users. Its potential applications include nanoelectronics, nano-optics, and nanosensors. Wait. Since Shixia is currently the most commonly used material in the semiconductor industry, relatively speaking, the synthesis and research of the nanowires are more numerous. As early as 1964, Wagner et al. have vertically synthesized micron-sized whiskers (SUic〇n Whisker) on the substrate. See Appl. Phys. Lett. 1964, 4, 89. Up to now, the synthesis method of Shixi nanowire line includes Catalytic Chemical Vapor Deposition (CCVD), Laser Evaporation, Direct Thermal Evaporation, Template Synthesis (Template) Synthesis) and so on. However, most of the prior art can only synthesize a bend-wound, long-length nanowire and entrap many impurities. U.S. Patent No. 6,313,015, issued Nov. 6, 2001, discloses a method for the growth of a smectite nanowire and a nanoparticle chain. The method utilizes thermal evaporation, thunder dance, plasma or magnetron sputtering to evaporate an oxygen (meth), which is synthesized under the protection of an inert gas at a temperature of 800 to 1000 degrees. Nanowires and nanoparticle chains. The nanowires grow along the <112> direction, while the non-directional nanoparticles form nanoparticle chains. Obviously, this method is contaminated with nanoparticle impurities and 1326247 The direction of formation of the nanowires relative to the substrate is not determined, which is not conducive to its practical application.
Yiying Wu 等人在 2002 年發表於 ‘Hmo Lettere，2002, Vol. 2, No. 2, P83-86” —篇題為 “Block-by-Block Growth of Single-Crystalline Si/SiGe SuperlatticeYiying Wu et al., published in 2002, ‘Hmo Lettere, 2002, Vol. 2, No. 2, P83-86, entitled “Block-by-Block Growth of Single-Crystalline Si/SiGe Superlattice
Nanowires”之論文上描述一種單晶Si/SiGe超晶格奈米線之生長方法及其機理。 其係在(111)石夕晶片(Si Wafer)上塗覆一層厚度約20奈米之金薄膜置於石英爐内， 並通入氏及SiCU於高溫下發生反應，其中SiCU與氏之比值係_，同時利用 脈衝雷射間斷燒钱一 Ge靶，從而在矽晶片上垂直生長出矽奈米線，其中含有 Si/SiGe超晶格異質結構。惟，這種方法僅揭示出垂直生長之石夕奈米線，並未揭 露其他方向可控之石夕奈米線及其製備方法。 【内容】 為解決現有技術之奈米線方向單一、無法控制等技術問題，本發明之目的在 於k供一種石夕奈米線結構，其生長方向可控制，並可具有多個預定之生長方向。 為實現上述發明目的’本發明提供一種石夕奈米線結構，其包括：_石夕晶片基 底，其包括一任意晶向之晶面，複數根ε夕奈米線生長在所述晶面；其中，所述石夕 奈米線沿所述晶面之傾斜的外延<1Π>方向形成。 對應於本發明之一個方面，所述晶面包括(100)晶面，所述石夕奈米線與所述 (100)晶面成35.3~度夹角。這種石夕奈米線可以具有四個外延<;111>方向。 對應於本發明之另一個方面’所述晶面包括(11〇)晶面，所述石夕奈米線與所述 (110) 晶面成54.7度夾角。這種梦奈米線可以具有兩個外延<：111>方向。 對應於本發明之另一個方面’所述晶面包括(111)晶面，所述石夕奈米線可以沿 四個外延<111>方向，其卡一個方向與所述(m)晶面垂直，另外三個方向與所述 (111) 晶面成19.4度夾角。 上述石夕奈米線之直徑範圍為50奈米至250奈米。其長度寸達1〇微卡至數十 微米。 、 本發明之另一個目的係提供上述石夕奈米線結構之生長方法，其包括丁列步 驟.在石夕晶片之晶面上形成一層金属催化劑層；將含有金屬催化劑之石夕晶片置於 石英管内，在500至1000度反應溫度下、通入含石夕之反應氣及氫氣進^反應，' 並嫁保反應氣含石夕的量與氫氣之摩爾比值為0.05-0.4範圍内，在石英管内壁沈積 矽並逐漸達到平衡狀態；在碎晶片之晶面上生長出矽奈米線。 ' 1326247 其中，所述矽晶面包括(100)晶面，（i 1〇)晶面以及(i [ 〇晶面。 其中，金屬催化劑層係薄膜狀或顆粒狀，其厚度或粒徑為數奈米至數百夺 米’金屬催化劑包括金及鐵。 不 其中’含石夕之反應氣包括鹵化矽，矽烧及其衍生物以及鹵矽烷。 相較於先前技術’本發明方法具有如下優點:首先，本發明之石夕奈米線結構 具有確找肖，並且，這龄向可缺乡個方向；使得本發敗料米線結構可 以構築奈米結構，或直接應用於多個領域。通過本發明方法可得到具有確定 之石夕奈米線結構。 ° 【實施方式】 下面結合S兒明書附圖及具體實施例對本發明實施方式作詳細描述。 "本發明雜用晶體外延纟長方法在$體上外延生長奈米線。通過控制生長條 件攸而實現可控之晶體外延生長(Epitaxial Gr〇wth)，以實現大纖合成方向齡 構可控之奈米線。 本發明可以树⑼任意晶向之晶面上生長轉親，並構騎型之石夕奈米 線陣列結構。 、、 在實施例中’採用(1〇〇)、_及(11聊晶片為生長基底。所謂(1〇〇)石夕晶片、 ⑽冷晶片及(1Γ聊晶片是指含有⑽）、⑽)及㈣晶面之石夕晶片並以上述 三個晶面作為外延生長.將完整之#晶體沿預定方向蝴，即可制三種晶面 之^晶片。 在實施製備之前’首先要賴好上述^餅郎，並於抑^對應之晶面 表面沈積形成-層厚度為奈米級催化劑薄膜，催化劑可選用金，但不祕金例 如還可選用鐵金屬。催化劑薄膜之厚度對最終形成之奈米線直徑有直接影塑，催 化劑薄膜厚度鱗，触細得之絲線直鶴大，反之則越小。—般而二催 化劑厚度在數奈米到50奈米範圍内。可以選擇的，也可以直接在石夕晶片μ面 撒上粒徑小於300奈米之金屬催化劑顆粒。 又 為方便描述，本實施例係在三塊較大面積之_)、 曰^ ^ , lit 並分別編被’如表1所示： 1326247 表1三塊矽晶片之切片編號 (100)碎晶片 (110)^7 晶片 (m声夕晶片 1 11# 12# 13# 2 21# 22# 23# 3 31# 32# 33# 為便於比較，本實施例分為三輪次進行’每輪次分別有三塊不同晶面之石夕晶 片進行實驗’即每次分別將一塊(100)、（110)及(111)矽晶片同時置於反應爐中進 行生長矽奈米線。每輪次採用之矽晶片如表1所示。 在描述製備過程之前，先介紹製備裝置。首先請參見第四圖，係本發明實施 例採用之製備裝置示意圖。該製備裝置10包括：一加熱爐100 ; 一石英管110， 其兩端分別具有一入氣口 112及一出氣口 114，該石英管110，係可活動的置於 加熱爐100之内’且其長度較加熱爐100長，這樣使得在實驗中推、拉移動石英 管110時，總能保持石英管110有一部分可以置於加熱爐100内部；在靠近石英 管入氣口 112處，設置有一恒溫容器120，其内盛有SiCU液體，並設有一通氣 管122伸入SiCU液體内’本實施例中恒溫容器120保持在30度，其出口連接至 石英管110靠近八氣π 112之部位，當在通氣管112通入氣體，則沿〇4蒸氣可 以被帶入石英管no中進行反應。石英管no内部可放置一陶瓷反應舟116，該 陶瓷反應舟116上可放置待反應之石夕晶片118。需要注意的係，本發明不僅可採 用SiCU作為石夕源’還可採用其他含石夕之物質，例如石夕烧類之衍生物，齒化石夕， 鹵矽烷等。 製備時’預先將加熱爐100昇溫至反應溫度，其範圍為500至11〇〇度，本 實施例中昇溫至900度，此時，石英管11〇伸入加熱爐内之部分被加熱，而伸出 外面之部分仍處於較低溫度，即冷卻部。然後開始第一輪生長： 首先’將三塊石夕晶片：11#(1〇〇>ε夕晶片、12#(11〇>ε夕晶片及说讲聊晶片置 於陶瓷反應舟116上，然後將該陶瓷反應舟116置於石英管ι10之冷卻部。在入 氣口 112通入流里為350sccm之向純氬氣作為保護氣體流經石英管no;經過 分鐘後’石英管110内之空氣從出氣口 114排出完全被清除，將石英管11〇緩慢 推入加熱爐100内，使陶瓷反應舟116移至加熱爐1〇〇之中心加熱區。推動石英 管110之速度最好應該緩慢，最好確保加熱爐之溫度變化小於1〇度。在加熱爐 8 1326247 100之溫度穩定保持在900度時’將入氣口 U2通入之氬氣替代為流量為250sccm 之氫氣；並且由通氣管122通入流量為lOOsccm之氫氣，氫氣經過恒溫容器120 並將SiCU蒸氣帶入石英管110進行反應。當然，本發明不限於上述流量，只要 能夠確保帶入之SiCU與氫氣之摩爾比例保持在0.05-0.4範圍内即可，優選範圍 係0.05-0.2。本領域技術人員應當理解，進入反應區之SiCU的量可通過調節通 氣管122通入氫氣的量、SiCU之溫度來調節。反應持續時間為1〇分鐘，可以理 解’時間越久’石夕奈米線生長越長。在第一輪生長中，除在13#石夕晶片上生長石夕 奈米線之外，還在石英管110之内壁上沈積有石夕。然後，將入氣口 U2通入之氫 氣改為流量為350sccm之氬氣，並移動石英管11〇將陶瓷反應舟116及石夕晶片 118移出加熱爐100,以冷卻矽晶片118(包括ιι#(ι〇〇声夕晶片、夕晶片及 13#(111)«夕晶片）’而加熱爐100仍保持在9〇〇度高溫，並且石英管11〇之其他部 分仍處於加熱爐100内。當矽晶片118冷卻至室溫，取出矽晶片完成第一輪生長。 完成第一輪生長之後’無需清潔石英管110，即保留沈積在石英管11〇内壁 上之石夕，緊接著將三片新的21#(100>ε夕晶片、22#(110辦晶片及23#(ΐιΐ)ε夕晶片 置於陶瓷反應舟116上，按上述第一輪生長之步驟進行第二生長。 完成第二輪生長之後，同樣無需清潔石英管11〇，緊接著將三片新的31#(1〇〇) 石夕曰曰片、32#(110}s夕晶片及33#(111}ε夕晶片置於陶究反應舟U6上’按上述第一 輪生長的步驟進行第三輪生長。 在上述實施例中，在第一輪生長中，僅在1；3#(ιιι)石夕晶片上生長有矽奈米 線’而在編號為11#的(100)石夕晶片與編號為12#的(11〇)石夕晶片上並沒有奈米 線；在第二輪生長中’在編號為21#、22#和23#的三種石夕晶片上均生長有石夕 奈米線。在第三輪生長中，在編號為31# ’ 32#和33#的三種石夕晶片上均生長有石夕 奈米線。上述奈米線之長度可達10微米至數十微米，直徑為5〇奈米至20奈米。 完成上述實施例之後’對石英管110進行清潔，將管壁上沈積之碎去除重 復上述步驟’即重新製備石夕晶片 '沈積金催化劑層、切小片、編號並分三輪進行 生長，可得到同樣結果。 在上述所有矽晶片上生長的矽奈米線均係沿矽晶片之晶面外延<lu>方向生 長，不同晶面之碎晶片具有其各自不同的外延<lu>方向。例如：對於(1〇〇>6夕晶 片’其具有四個外延<m>方向，分別卿晶片之(100)晶面成353度爽角(如8第曰 9 1326247 D圖所不)’齡(1’晶片’其具有兩個外延仙〉方向，分別鱗晶片的(u〇) 晶面成517度靖如第二!）圖所示）；對邪聊晶片其具有四個外延<m> 方向’其中個方向垂直於石夕晶片的_晶面，另外三個分別與石夕晶片的⑽) 晶面成19.4度失角(如第二E圖所示)。本發明可在不同晶面之石夕晶片上得到沿各 個外延<111>方向线之石夕奈米線，從而可控制石夕奈米線之生長方向 ，得到不同 結構、不IS]方向之料米線’為特米線在各種倾的顧提供基礎。 下面對本發明實施例在具有不同晶面之石夕晶片上生長的石夕奈米線作詳細描 述。 ^參閱第-A圖、第-B圖，是從本發明_個實施例在(⑽淨晶片上第二 輪與第三輪生長得到的料米線之社方賴之掃描電子賴鏡 Electr〇nMicr_pe，SEM)照片。從圖中可看出，石夕奈米線似乎形成矩形網格狀， 實際上转米線係沿四财峡伸，分別财⑼職大約35度之夹角。從第 一 c圖之高解析度透射電子顯微鏡师动Resduti〇n TransmissiQn Hectrcn Microscope，ΗΚΙΈΜ)照片可確認，相鄰層間距為〇.314奈米，說明石夕奈米線係沿 矽晶面之四俯卜延<m>方向生長的。第__ D圖示出(1〇〇)晶面之四個外延<m> 方向’其巾’陰影面即(1〇〇)晶面，四條交又實断表示其外延·>方向分別 與(100)晶面成35.3度夹角。本實施例中石夕奈米線即沿此四個方向生長。 δ月參閱第一 A圖、第二B圖，係從本發明一個實施例在(11〇^g夕晶片上第二 輪與第二輪生長得到的矽奈米線之頂上方拍攝之SEM照片。從圖中看，大多數 矽奈米線係相互平等的，實際上矽奈米線係沿兩個方向延伸，分別與石夕晶片成大 約55度夾角。從第二C圖之hrjem照片可確認，其間距為〇314奈米石夕奈 米線係沿石夕晶面之兩個外延〈His方向生長。第二D圖示出(11〇)晶面的二個外延 <111>方向，其中，陰影面即(110)晶面，兩交又實線即表示其外延<m>方向， 分別與(110)晶面成54.7度夾角。本實施例中石夕奈米線即沿此兩個方向生長。 -用參見第二A圖、第二B圖及第二C圖’分別係本發明一個實施例在(in) 石夕aa片上弟一輪、第二輪及弟二輪生長得到的石夕奈米線之上方拍攝的照 片’其中第三A圖係將樣品傾斜大約60度拍攝得到，另外兩個係垂直拍攝得到。 從第三A圖可看出，第一輪生長之所有矽奈米線均係垂直於石夕晶片表面；在第 三B圖中，第二輪生長所得之石夕奈米線大多數形成三角形網格，還有一些亮點(圖 10 1326247 中圓圈處即為其中-個），仔細觀察可發現特米線有四個方向，其甲一個方向 係與第-輪生長之方向直神晶片表面(即圖t亮點），另外三個方向 辦夕晶片大約成19度夾角，·在第三c圖中，第三輪生長所得之料米線形成三 角形網格’並且沒有亮點存在，即，第三輪生長所得之石夕奈米線沿三個方向生長， 其分別财晶片大約成19度夹角，而沒有垂直生長之石夕奈米線。由第三〇圖之 HRTEM照片=確認，石夕奈米線係沿石夕晶片之外延<m>方向生長的其間距為 0.314奈米。第三E圖示出了(111沒晶片之四個外延<m>方向，其中一個盘 晶面垂直，另外三個與該晶面成19·4度夾角。其中，陰影面即(m)晶面，、四根 實線即外延<111>方向。 從上面多個實施例中可知，在第一輪次中生長所得之石夕奈米線之結敝後兩 輪次有所糊。其朗在於：雜外部餅綱，包括魏設備、聽溫度、通 入之疏氣體成份、流奴其濃度均未改變’但是在第一輪次中，實際聽區之 SiCU濃度有所區別，實際上，魏區石夕之濃度決定了石夕奈米線的生長係外延生 長與否，因此’含不同石夕原子之氣體分子可能由於原子比不同而使得需要通入之 氣體的量有所不同。在第-輪次生長過程中，由於石英管係清潔乾淨的有 -部分分織，矽雜在石英管110之内壁上，造成在實際砂區石夕濃度 下降，即矽的過屬和程度較低’使得矽僅僅沿石夕晶面之一個<m>方向，即垂直 晶面之方向生長；而在後續的第二、第三輪次生長過程中，由於石英管ιι〇内壁 在第一輪次生長過程已經沈積有矽，所以石夕在内壁上之沈積棘逐漸減少，直至 達到平衡’這樣使得貫際職區矽濃度逐漸上昇，即石夕的過飽和程度上昇，從而 造成矽奈親沿其他<111>獅生長。所以，雖穌實施娜通過三輪次生長石夕 奈米線結構的，但本發不祕這驟。只要制實跃躯卿的濃度 達到足夠高的過飽和程度即可生長出沿傾斜的外延<m>方向之石夕奈米線結構。 本發明·可控術奈親之生長方向，可4接朗於奈絲電神領域， 例如採用圖案化生長，可製得相應圖案形狀之奈米結構，直接用作光學器件。亦 可利用本發明形成之矩形、三角形以及交又立體網格結構，經過處理得到相應形 狀之平面器件，例如：可將這线立體網格結橼贿爲製成平面之矩形、三角形 及平行奈米線圖案’應用於奈米電子學領域等。 综上所述’本發明讀已符合發明專利之要件’遂依法提出專利申請。惟以Nanowires' paper describes a method for growing a single crystal Si/SiGe superlattice nanowire and its mechanism. It is coated on a (111) Si Wafer with a gold film thickness of about 20 nm. In the quartz furnace, and through the Si and SiCU at high temperatures, the ratio of SiCU to the ratio is _, while using a pulsed laser to interrupt the burning of a Ge target, thereby vertically growing the 矽 nanowire on the 矽 wafer It contains a Si/SiGe superlattice heterostructure. However, this method only reveals the vertical growth of the Shinai nanowire, and does not disclose the Shih Nylon line which is controllable in other directions and its preparation method. In order to solve the technical problems of single direction and uncontrollable nanowire direction in the prior art, the object of the present invention is to provide a structure for the growth of the stone, which has controllable growth direction and can have a plurality of predetermined growth directions. The object of the present invention is as follows: The present invention provides a structure of a stone nanowire, comprising: a stone substrate comprising an crystal plane of any crystal orientation, wherein a plurality of crystal lattices are grown on the crystal plane; The Shixi nanowire An oblique <1Π> direction along the inclined plane of the crystal plane is formed. Corresponding to an aspect of the invention, the crystal plane includes a (100) crystal plane, the sacrificial nanowire and the (100) crystal plane An angle of 35.3 deg. 3 degrees. This ray-n-ray nanowire may have four epitaxial <;111> directions. Corresponding to another aspect of the invention, the crystal plane includes (11 〇) crystal plane, the stone The midnight line is at an angle of 54.7 degrees to the (110) crystal plane. Such a nanowire may have two epitaxial <:111> directions. Corresponding to another aspect of the invention 'the crystal plane includes ( 111) a crystal face, wherein the stellite line may be along four epitaxial <111> directions, one direction of the card being perpendicular to the (m) crystal plane, and the other three directions being opposite to the (111) crystal plane The angle of 19.4 degrees. The diameter of the above-mentioned Shixi nanowire ranges from 50 nanometers to 250 nanometers, and the length thereof is from 1 microliter to several tens of micrometers. Another object of the present invention is to provide the above-mentioned Shixi nanowire. a method for growing a structure, comprising the step of forming a metal catalyst layer on a crystal face of a stone wafer; and containing a metal catalyst The wafer is placed in a quartz tube, and at a reaction temperature of 500 to 1000 degrees, a reaction gas containing sulfur and a hydrogen gas are introduced into the reaction, and the molar ratio of the amount of the reaction gas containing the gas to the hydrogen gas is 0.05-0.4. Within the range, germanium is deposited on the inner wall of the quartz tube and gradually reaches an equilibrium state; a germanium line is grown on the crystal face of the broken wafer. ' 1326247 wherein the twin plane includes (100) crystal plane, (i 1〇) The crystal face and (i [the twin face. Among them, the metal catalyst layer is film-like or granular, and its thickness or particle diameter is several nanometers to hundreds of meters of rice metal catalysts including gold and iron. The reaction gas includes antimony halide, antimony and its derivatives, and halodecane. Compared with the prior art, the method of the present invention has the following advantages: Firstly, the structure of the invention has the advantage of finding the right side, and the age of the line can be lacking in the direction of the home; Nano structure, or directly applied to multiple fields. A defined structure of the stone nanowires can be obtained by the method of the present invention. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail in conjunction with the drawings and specific embodiments of the drawings. " The hybrid crystal epitaxial growth method of the present invention epitaxially grows nanowires on the body. Controlled epitaxial growth (Epitaxial Gr〇wth) is achieved by controlling the growth conditions to achieve a nanowire with controllable age in the synthesis of large fibers. According to the invention, the tree (9) can be grown on the crystal plane of any crystal orientation, and the structure of the stone-shaped nanowire array can be constructed. In the embodiment, '(1〇〇), _, and (11 chat wafers are used as growth substrates. The so-called (1〇〇) Shixi wafer, (10) cold wafer and (1Γ wafer refers to contain (10)), (10)) And (4) the crystal face of the stone wafer and the above three crystal faces as the epitaxial growth. The complete # crystal is butterflyed in a predetermined direction, and the three crystal face wafers can be prepared. Before the preparation of the preparation, the first thing is to rely on the above-mentioned cakes, and deposit the surface layer on the surface of the corresponding crystal surface to form a nanometer-sized catalyst film. The catalyst may be gold, but the metal may be iron-free. . The thickness of the catalyst film directly affects the diameter of the finally formed nanowire. The thickness of the catalyst film is large, and the wire that is touched is straight and large, and vice versa. Typically, the thickness of the catalyst is in the range of a few nanometers to 50 nanometers. Alternatively, it is also possible to sprinkle metal catalyst particles having a particle diameter of less than 300 nm directly on the surface of the stone wafer. For convenience of description, the present embodiment is based on three large areas of _), 曰^^, lit and respectively edited as shown in Table 1: 1326247 Table 1 three 矽 wafer slice number (100) broken wafer (110)^7 wafer (m sound eve wafer 1 11# 12# 13# 2 21# 22# 23# 3 31# 32# 33# For the sake of comparison, this embodiment is divided into three rounds, 'three for each round Experiment with a different crystal face of the stone wafers, that is, each time a piece of (100), (110) and (111) 矽 wafers are simultaneously placed in a reaction furnace for growth of the nanowires. As shown in Table 1. Before describing the preparation process, the preparation device will be described first. First, please refer to the fourth figure, which is a schematic diagram of a preparation device used in the embodiment of the present invention. The preparation device 10 includes: a heating furnace 100; a quartz tube 110 Each of the two ends has an air inlet 112 and an air outlet 114. The quartz tube 110 is movable inside the heating furnace 100 and has a length longer than the heating furnace 100, so that the experiment is pushed and pulled. When the quartz tube 110 is moved, a part of the quartz tube 110 can always be placed inside the heating furnace 100; Near the inlet port 112 of the quartz tube, a thermostatic container 120 is disposed, which contains SiCU liquid, and is provided with a vent tube 122 extending into the SiCU liquid. In the present embodiment, the thermostatic container 120 is maintained at 30 degrees, and its outlet is connected to The quartz tube 110 is close to the portion of the eight gas π 112. When the gas is introduced into the vent pipe 112, the vapor along the 〇4 can be brought into the quartz tube no for reaction. A ceramic reaction boat 116 can be placed inside the quartz tube no. The reaction boat 116 can be placed on the stone wafer 118 to be reacted. It should be noted that the present invention can not only use SiCU as the stone source, but also other materials containing the stone, such as the derivative of the stone, the tooth Fossil eve, halodecane, etc. During preparation, the heating furnace 100 is heated up to the reaction temperature in the range of 500 to 11 Torr, and in this embodiment, the temperature is raised to 900 degrees. At this time, the quartz tube 11 〇 extends into the heating furnace. The inner part is heated, while the outer part is still at a lower temperature, ie the cooling part. Then the first round of growth begins: First, 'three pieces of stone wafer: 11# (1〇〇>12#(11〇> The wafer is placed on the ceramic reaction boat 116, and then the ceramic reaction boat 116 is placed in the cooling portion of the quartz tube ι10. 350 cc in the inlet port 112 into the flow of pure argon as a shielding gas flowing through the quartz tube no; After the minute, the air in the quartz tube 110 is completely removed from the air outlet 114, and the quartz tube 11 is slowly pushed into the heating furnace 100, and the ceramic reaction boat 116 is moved to the central heating zone of the heating furnace. The speed of the quartz tube 110 should preferably be slow, preferably to ensure that the temperature of the furnace changes by less than 1 degree. When the temperature of the heating furnace 8 1326247 100 is stably maintained at 900 degrees, the argon gas introduced into the gas inlet U2 is replaced by hydrogen gas having a flow rate of 250 sccm; and hydrogen gas having a flow rate of 100 sccm is introduced from the vent pipe 122, and the hydrogen gas passes through the constant temperature vessel 120. The SiCU vapor is brought into the quartz tube 110 for reaction. Of course, the present invention is not limited to the above flow rate as long as it can be ensured that the molar ratio of the brought SiCU to hydrogen is maintained in the range of 0.05 to 0.4, and the preferred range is 0.05 to 0.2. Those skilled in the art will appreciate that the amount of SiCU entering the reaction zone can be adjusted by adjusting the amount of hydrogen gas introduced into the gas pipe 122, the temperature of the SiCU. The duration of the reaction is 1 minute, and it can be understood that the longer the time is, the longer the growth of the Shiyin rice line is. In the first round of growth, in addition to the growth of the Shixia nanowire on the 13# Shi Xi wafer, a stone eve was deposited on the inner wall of the quartz tube 110. Then, the hydrogen gas introduced into the air inlet U2 is changed to argon gas having a flow rate of 350 sccm, and the quartz tube 11 is moved to remove the ceramic reaction boat 116 and the stone wafer 118 out of the heating furnace 100 to cool the crucible wafer 118 (including ιι# ( 〇〇 〇〇 晶片 wafer, 夕 wafer and 13 # (111) «夕 wafer) ' while the furnace 100 is still maintained at a high temperature of 9 ,, and the other part of the quartz tube 11 仍 is still in the heating furnace 100. The wafer 118 is cooled to room temperature, and the germanium wafer is taken out to complete the first round of growth. After the first round of growth is completed, the quartz tube 110 is not cleaned, that is, the stone deposited on the inner wall of the quartz tube 11 is retained, and then three new ones are 21#(100> Essence wafer, 22# (110 wafer and 23#(ΐιΐ) Essence wafer were placed on the ceramic reaction boat 116, and the second growth was carried out according to the above-mentioned first round growth step. The second round of growth was completed. After that, there is no need to clean the quartz tube 11〇, and then three new 31#(1〇〇) Shi Xiyi tablets, 32#(110}s 夕 wafers and 33#(111} 夕夕 wafers are placed in the pottery. In the reaction boat U6, the third round of growth is performed according to the above-mentioned first round growth step. In the above embodiment, in the first In the growth of the wheel, only the 矽 nanowire line is grown on the 1;3#(ιιι) Shixi wafer, and the (100) Shixi wafer numbered 11# and the (11〇) Shixi wafer numbered 12# There is no nanowire on the top; in the second round of growth, the Shixi nanowires are grown on the three types of stone wafers numbered 21#, 22# and 23#. In the third round of growth, the number is 31# '32# and 33# are grown on the three kinds of Shixi wafers. The length of the above nanowires can be from 10 micrometers to tens of micrometers and the diameter is from 5 nanometers to 20 nanometers. After the above embodiment, 'cleaning the quartz tube 110, removing the deposited material on the tube wall and repeating the above steps', re-preparing the Shihua wafer's deposited gold catalyst layer, cutting the small pieces, numbering and growing in three rounds, the same result can be obtained. The nanowires grown on all of the germanium wafers are grown along the crystallographic epitaxial <lu> direction of the germanium wafer, and the different wafers have their different epitaxial <lu> directions. For example: (1〇〇>6 夕片' has four epitaxial <m> directions, respectively (100) The surface is 353 degrees cool angle (such as 8 曰 9 1326247 D picture) 'age (1 'wafer' has two extensions of the direction of the direction, respectively, the scale of the (u〇) crystal plane into 517 degrees Jing Rudi 2))); for the sinister wafer, it has four epitaxial <m> directions, one of which is perpendicular to the _ crystal plane of the Shi Xi wafer, and the other three are respectively formed with the (10) crystal plane of the Shi Xi wafer. 19.4 degrees of out-of-angle (as shown in Figure 2E). The present invention can obtain the Shih Nylon line along the respective extension <111> direction lines on the different crystal face of the crystal wafer, thereby controlling the Shiyin nanometer. The direction of growth of the line, the rice noodle with different structure and not in the direction of IS] provides the basis for the various meters. Hereinafter, the Shih Nylon line grown on the Shihua wafer having different crystal faces will be described in detail in the examples of the present invention. ^See Figure-A, Figure-B, which is a scanning electron ray mirror from the invention of the second and third rounds of growth on the (10) net wafer. nMicr_pe, SEM) photo. As can be seen from the figure, the Shixi nano-line seems to form a rectangular grid shape. In fact, the rice noodle line is stretched along the Siguixia, and the angle of the financial (9) is about 35 degrees. From the high-resolution transmission electron microscopy of the first c-graph, Resduti〇n TransmissiQn Hectrcn Microscope, ΗΚΙΈΜ), it can be confirmed that the adjacent layer spacing is 314.314 nm, indicating that the Shixi nano-wire line is along the twin surface. Four prolonged <m> directions of growth. The __D diagram shows the four extensions of the (1 〇〇) crystal plane <m> the direction of the 'shadow' is the (1 〇〇) crystal plane, and the four intersections and the actual representation of the extension ·> direction They are respectively at an angle of 35.3 degrees with the (100) crystal plane. In this embodiment, the Shixi nanowire is grown in the four directions. δ month refers to the first A picture and the second B picture, which are SEM photos taken from the top of the 矽 nano line obtained by the second and second round growth on the wafer of one embodiment of the present invention. From the figure, most of the nanowires are equal to each other. In fact, the nanowires extend in two directions, respectively, at an angle of about 55 degrees with the Shixi wafer. The hrjem photo from the second C map can be It is confirmed that the pitch is 〇314 nm, and the Nishi-Nike line is grown along the two epitaxial <His directions of the Shi Xi crystal plane. The second D diagram shows the two epitaxial <111> directions of the (11〇) crystal plane Wherein, the shaded surface is the (110) crystal plane, and the two intersections and the solid line indicate the extension <m> direction, which is respectively at an angle of 54.7 degrees with the (110) crystal plane. In this embodiment, the Shi Xi nano line is along the line. Growth in two directions. - Referring to the second A diagram, the second B diagram, and the second C diagram, respectively, an embodiment of the present invention is obtained in (in) Shi Xia ai film on the second round, the second round and the second round. The photo taken above the Shixi nanometer line 'The third A picture is taken by tilting the sample about 60 degrees, and the other two are taken vertically. It can be seen from the third A map that all the nanowires in the first round of growth are perpendicular to the surface of the Shihua wafer; in the third B diagram, most of the Shihlin nanowires grown in the second round form a triangle. The grid, there are some bright spots (the circle in Figure 1 1326247 is one of them), a closer look reveals that there are four directions in the tem line, one direction of the arm and the direction of the first wheel growth straight to the surface of the wafer ( That is, the highlight of the figure t), in the other three directions, the wafer is about 19 degrees, and in the third c picture, the rice noodles grown in the third round form a triangular grid 'and no bright spots exist, that is, the third The Shixi nanowire obtained by the growth of the wheel grows in three directions, and the respective wafers are at an angle of about 19 degrees, and there is no vertical growth of the Shinai nanowire. The HRTEM photo of the third map confirms that Shi Xi The spacing of the nanowires along the extension of the Shixi wafer in the <m> direction is 0.314 nm. The third E diagram shows (the four epitaxial <m> directions of the 111 wafers, one of which is a crystal face) Vertical, the other three form an angle of 19.4 degrees with the crystal plane. Among them, the shadow surface is (m The crystal face, the four solid lines, that is, the extension <111> direction. It can be seen from the above various embodiments that the two rounds of the knot after the growth of the Shixi nanowire in the first round are confusing The lang is: miscellaneous external cakes, including Wei equipment, listening to temperature, the gas components of the pass, and the concentration of the slaves have not changed'. But in the first round, the concentration of SiCU in the actual listening area is different. In fact, the concentration of Shi Xi in the Wei area determines whether the growth system of the Shi Xi nano line is epitaxially grown or not. Therefore, the gas molecules containing different stone atoms may have a certain amount of gas that needs to be introduced due to different atomic ratios. Differently, during the first-round growth process, due to the clean and partial-weaving of the quartz tube system, it is doped on the inner wall of the quartz tube 110, resulting in a decrease in the concentration of the stone in the actual sand area, that is, the excessive The lower degree 'causes the 矽 to grow only in the direction of the <m> in the direction of the vertical crystal face; and in the subsequent second and third rounds of growth, due to the inner wall of the quartz tube The first round of growth has been deposited with sputum. Shi Tokyo inner deposition ratchet wall of gradually reduced until equilibrium is reached 'such that the through inter silicon concentration level region gradually increased, i.e. increased over the degree of saturation stone Xi, resulting silicon Nai affinity in other < 111 > lion growth. Therefore, although Shen Shina grew the structure of the Shi Xi nano line through three rounds, this issue is not secret. As long as the concentration of the solid thief reaches a sufficiently high degree of supersaturation, the structure of the slanting extension <m> The invention has the growth direction of the controllable na[iota], and can be used in the field of nanowires. For example, by pattern growth, a nanostructure of a corresponding pattern shape can be obtained and used directly as an optical device. The rectangular, triangular and intersecting three-dimensional grid structure formed by the invention can also be used to obtain a planar device of a corresponding shape, for example, the three-dimensional grid can be bribed to form a rectangular, triangular and parallel neat. The rice noodle pattern is applied to the field of nanoelectronics. In summary, the invention has been in compliance with the requirements of the invention patent. Only
II 1326247 2述者僅縣㈣之較佳實施例’自不能以此關本案之中請專利範圍。舉凡 ?本案技藝之人士援依本發曰月级神所作之等效修飾或變化，冑應涵蓋於 申請專利範圍内。 【圖式簡單說明】 第-A圖與第_ B圖係本發日月在(1零夕晶片基底外延生長的石夕奈米線結 結構之SEM圖； 第C圖係本發明在(100)矽晶片基底上外延生長之石夕奈米線結構結構之 HRTEM 圖； 第D圖係矽奈米線在(100)矽晶片基底上之四個〈in〉外延生長方向示音 第一 Α圖與第二8圖係本發明在(11〇声夕晶片基底外延生長之石夕奈米線結構 結構之SEM圖； 第二C圖係本發明在(110)矽晶片基底上外延生長之石夕奈米線結構結 ΗΚΓΕΜ 圖； 第二D圖係矽奈米線在(11〇)^夕晶片基底上之兩個<m>外延生長方向示意 圖； 第二A圖、飞三B圖及第三c圖係本發明在於晶片基底外延生長之石夕 不米線結才冓結才冓4LSEM圖； 第_ D圖係本發明在(m)石夕晶片基底上外延生長之石夕奈米線結構結構之 HRTEM 圖； 第—E圖係石夕奈米線在(111)石夕晶片基底上之四個<ιιι>外延生長方向示音 圖； 步糸本發明採用之製備裝置之示意圖。 【主要元件符 號說明】 製備裝置 10 加熱爐 100 石英管 110 入氣口 112. 出氣口 114 反應舟 116 碎晶片 118 恆溫容器 120 12 1326247 通氣管 122II 1326247 2 The preferred embodiment of the county (four) is not the scope of the patent. Anyone who has the skills of this case should be included in the scope of the patent application in accordance with the equivalent modification or change made by the moon-level god. [Simple description of the drawings] The first-A and the _B-pictures are the SEM images of the Shih-Nylon line junction structure of the epitaxial growth of the wafer substrate; the C-picture is the present invention (100) HRTEM image of the structure of the epitaxial growth of the 夕 奈 nanowire line on the wafer substrate; the first picture of the four <in> epitaxial growth direction of the 矽 nanowire on the (100) 矽 wafer substrate And the second 8 figure is an SEM image of the structure of the invention of the invention, wherein the second C picture is the epitaxial growth of the invention on the (110) germanium wafer substrate. The structure of the nanowire structure is shown in Fig.; the second D diagram is a schematic diagram of the two <m> epitaxial growth directions on the wafer substrate of the (11〇) 夕 ; line; the second A picture, the fly three B picture and the The present invention is based on the epitaxial growth of the wafer substrate, and the 4LSEM image is formed by the epitaxial growth of the wafer on the (m) stone substrate. HRTEM image of the structure structure; the first-E diagram is the four-thickness growth direction of the Shih-Nylon line on the (111) Shixi wafer substrate. ;. A schematic view showing the apparatus using the present invention The main steps Ito element symbols DESCRIPTION 10 Preparation furnace apparatus 100 silica tube 112. The air inlet 110 into the reaction gas outlet 114 of the wafer boat 116 118 broken 12 is a constant temperature vessel 1,326,247 snorkel 122 120