1274736 五、發明說明（1) 【發明所屬之技術領域】 本發明關於一種奈米碳管陣列結構及其製備方法。 【先前技術】 因奈米碳管具獨特之電學性質，其在奈米積體電路、 單分子電子器件等領域之應用具不可估量之前景。目前人 們已經能夠在實驗室少量製造基於奈米碳管之場效應管、 邏輯器件及記憶體件等，並研究其性質，具體請參閱1274736 V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) Technical Field of the Invention The present invention relates to a carbon nanotube array structure and a preparation method thereof. [Prior Art] Due to its unique electrical properties, the carbon nanotubes have an inestimable prospect in applications such as nano-integrated circuits and single-molecule electronic devices. At present, people have been able to manufacture a small number of FET-based FETs, logic devices and memory devices in the laboratory and study their properties.
Sander J Tans 專人 1998 年發表在Nature 393-49，’’Room- temperature transistor based on a single carbon nanotube” 一文。但大規模之製備及具實際意義之應用則 必須借助於由下而上（Bottom Up )之生製備工藝。 由下而上之製備工藝要求能夠對奈米碳管之生長位 置、方向、尺度、甚至奈米碳管之螺旋度進行必要之控 制，通過少量而經濟之步驟直接生長出所需之器件結構。 范守善等人在Sc i ence 283， 5 1 2-5 1 4 ( 1 999)，” se 1 f-oriented reguiar arrays of carbon nanotubes and their field emission propert i e s ” 一文中，以及Z. F. Ren 等人在文獻Science 282，Π05-1107(Νον 6， 1 998 )，丨丨 Synthes is of large arrays of well-aligned carbon nano tubes on glass” 一文中均揭露一種通過催匕 劑圖形（Patterned Catalyst)來控制奈米碳管之生長位置 及使其垂直於基底之製備方法。 另外，B. Q· Wei 等人在文獻Nature 416，495-496 (Apr 4， 2 0 02 )，丨丨 Organized assembly of carbonSander J Tans was published in Nature 393-49, ''Room-temperature transistor based on a single carbon nanotube' in 1998. But large-scale preparation and practical applications must rely on bottom-up (Bottom Up) The preparation process of the bottom. The bottom-up preparation process requires the necessary control of the growth position, direction, scale, and even the helicity of the carbon nanotubes, and grows directly through a small number of economic steps. The required device structure. Fan Shoushan et al. in Sc ence 283, 5 1 2-5 1 4 (1 999), "se 1 f-oriented reguiar arrays of carbon nanotubes and their field emission proper ies", and ZF Ren et al., in the literature Science 282, Π05-1107 (Νον 6, 1 998), 丨丨Synthes is of large arrays of well-aligned carbon nano tubes on glass, discloses a pattern of passing Catalyst. The method for preparing the growth position of the carbon nanotubes and making them perpendicular to the substrate. In addition, B. Q. Wei et al., in Nature 416, 495-496 (Apr 4, 2 0 02), 丨丨 Organized assembly of carbon
第6頁 1274736 五、發明說明（2) nanotubes” 一文中揭露了—種可通過對基底形狀之設計以 實現於三維基底上生長出垂直於各表面之奈米碳管。 Yuegang Zhang 等人在Applied physics Letters，v〇1. 79, Number 19, Nov 5, 2001, "E1ectric-fie1d- directed growth of aligned sing1e-wa11ed carbon nanotubes” 一文中揭示一種通過電場控制奈米碳管生長方 向之方法。 惟’利用上述各種方法所獲得之奈米碳管陣列之生長 方向均為線性，且均垂直於生長基底之表面，從而限制奈 米器件之多樣化設計。 有鑒於此，提供一種生長方向可控之奈米碳管陣列結 構尤為必要。 【發明内容】 本發明目的之一係提供—種適用於奈米碳管器件多樣 化設計之奈米碳管陣列結構。 列結：：：：另一個目的係提供一種製造上述奈米破管陣 為解決上述技術問題，本發明揭示一奈米碳管陣列社 構，包括一基底、形成於基底之催化劑層及於催化劑声^ 長之奈米碳管陣列，其中催化劑層包括複數奈米級催二 該催化劑顆粒之尺寸沿—預定方向漸變，該奈米： 官陣列向催化劑顆粒尺寸較小方向彎曲。 本發明還揭示一種製造上述奈米碳管陣列結構之 法，其步驟包括：Page 6 1274736 V. Inventions (2) nanotubes” It is disclosed that the carbon nanotubes perpendicular to the surfaces can be grown on a three-dimensional substrate by designing the shape of the substrate. Yuegang Zhang et al. Applied physics Letters, v. 1. 79, Number 19, Nov 5, 2001, "E1ectric-fie1d-directed growth of aligned sing1e-wa11ed carbon nanotubes" discloses a method for controlling the growth direction of carbon nanotubes by an electric field. However, the growth directions of the nanotube arrays obtained by the above various methods are linear and perpendicular to the surface of the growth substrate, thereby limiting the diversified design of the nanodevice. In view of this, it is particularly necessary to provide a carbon nanotube array structure with a controllable growth direction. SUMMARY OF THE INVENTION One object of the present invention is to provide a carbon nanotube array structure suitable for a diverse design of carbon nanotube devices. Alignment:::: Another object is to provide a nano tube array to solve the above technical problems. The present invention discloses a carbon nanotube array structure comprising a substrate, a catalyst layer formed on the substrate, and a catalyst. The nanometer carbon nanotube array, wherein the catalyst layer comprises a plurality of nanometers, and the size of the catalyst particles is gradually changed along a predetermined direction, and the nanometer array is bent in a direction smaller than the size of the catalyst particles. The present invention also discloses a method of fabricating the above-described carbon nanotube array structure, the steps of which include:
五、發明說明（3) (1 )提供一基底； (2) ，積:催化劑層於該基底之表面，該催化劑層之 =度〜預定方向漸變，形成一較厚端及一較薄 (3) 2 ί保護了退火，使催化劑層收縮成為奈米級 催化劑顆粒； (4) ί f f化劑顆粒於碳源氣中，奈米碳管從該催化 劑顆粒上長出。 關，^ Ϊ ί ^之生長速度與催化劑顆粒之尺寸大小相 ^ ^ 将疋之尺寸範圍内，於較小尺寸催化南j 米碳管生長速ΐΪί 於較大尺寸催化劑顆粒上之奈 膜之厚度由」=^另故，在沈積催化劑圖形時，控制薄 度比較厚-端i :斜或彎曲。叫^ 制奈米碳管陣列之生長方向。1催仆二方向，即可控、 ,制係決定圖形上所生長之奈；碳管 狀況之主要因素。 单歹η員斜角度或彎曲 與先前技術相比，本發明方法:太〃 ，之方向灣曲，所得之奈米碳管陣二=二米碳管陣列向預 盗件設計之多樣性需求。 $可丰富奈米碳管 【貫施方式】 請參閱第一圖，首先提供— 底10，基底10選用多孔 1274736 五、發明說明（4) 石夕，亦可選擇拋光硅片、祐摘 一光阻層u。通過光刻之屬等。於該基底10形成 圖案。在需要生長奈米碳管之固安：：11上形成-預定之 劑薄膜，催化劑薄膜13之厚】；處=奈"之催化 或增厚，催化劑薄膜13較厚：-端逐漸減薄 端約為1〜5nm，催化劑薄膜13之^+1 為太5〜〗0nm，較薄之— 或彎曲方向之需要，將碳夺乎乂車§十:奈米石炭管陣列傾斜 端設計較薄。 陣相向灣曲或傾斜之- 催化劑沈積之方法可選用熱蒸發法，亦可選 積方法配合光刻工藝或帶通孔之掩 板：成，或者利用溶液噴塗配合甩膜、光刻等 成。催化劑之材料可選用鐵、鈷、鎳或其合金， 式選用鐵質之直線型蒸發源12沈積催北劑薄膜13。^線 型％發源12置於光阻圖案之斜上方，以使沈催卜^為 2度形成一漸變梯度。上述直線型蒸發源以亦可用二丨= 移動之點蒸發源代替，或將點蒸發源固定，亦可^ U 型蒸發源1 2 ,而沿直鍊移動待鍍基片代替。。 、、泉 膜”請第二圖，除去光阻層U，將帶有催化劑薄 膜13之基底10置於空氣中，在3〇〇。c下退 μ 薄膜1 3氧化、收縮成為奈米級之催化劑顆粒〗31。催^ 劑薄膜13之兩端所沉積之厚度不等，呈一漸變分佈， 退火過程中形成的催化劑顆粒131大小不等。催化 1 3較薄之一端形成之催化劑顆粒】3 i較小，較厚一^ _忐 催化劑顆粒131較大。待退火完畢，再將分佈有催化= 第9頁 1274736 五、發明說明（5) 粒131之基底置於反應室内（圖未示），通入碳源氣乙炔， 利用熱化學氣相沈積法，於上述催化劑顆粒1 3 1上生長奈 米石厌管’碳源氣亦可選用其他含碳之氣體，如乙稀等。 — 其中薄膜厚度的調節控制及生長奈米碳管之時間係決 疋圖形上所生長奈米碳管陣列〗4生長長度及傾斜角度 曲狀況之主要因素。 A弓 請參閱第三圖’利用上述方法獲得之奈米碳管陣列結 構2 0包括一基底1 〇、形成於基底丨〇之複數催化劑顆粒1 3 1 及從複數催化劑顆粒131生長之奈米碳管陣列14，其中 ，：顆粒⑶之尺寸沿一預定方向漸變，形成一較：顆粒 而 小顆粒端，該奈米碳管陣列14向催化劑ΐ3ι之 小顆粒端方向彎曲。 ^ 與、ΐ ΐ奈t碳管陣列結構20可用於平面顯示、奈米電子 予 电流％發射電子搶等器件的陰極製造工蓺。 專利ΐΐ所ί 修傅或變化，皆應包含於=明精神所作之等效 1274736 圖式簡單說明 【圖式簡單說明】 第一圖係本發明中催化劑薄膜沈積過程之示意圖。 第二圖係本發明退火後基底與催化劑顆粒示意圖。 第三圖係本發明中奈米碳管陣列結構之示意圖。 【主要元件符號說明】V. Description of the invention (3) (1) providing a substrate; (2), product: the catalyst layer on the surface of the substrate, the catalyst layer = degree ~ predetermined direction gradient, forming a thicker end and a thinner (3 2 ί protects the annealing, shrinking the catalyst layer into nano-sized catalyst particles; (4) ί ff granules in the carbon source gas, the carbon nanotubes grow from the catalyst particles. The growth rate of Guan, ^ Ϊ ί ^ is the same as the size of the catalyst particles. In the size range of the crucible, the growth rate of the carbon nanotubes in the smaller size is catalyzed by the thickness of the naphthalene film on the larger catalyst particles. By "=^", when the catalyst pattern is deposited, the control thinness is thicker - end i: oblique or curved. Called the growth direction of the carbon nanotube array. 1 urging the two directions, you can control, and the system determines the growth of the graph; the main factor of the carbon tube condition. Single-angle slant angle or bending Compared with the prior art, the method of the present invention: the ambiguity, the direction of the Bayer, and the resulting nanocarbon tube array 2 = two-meter carbon tube array to the pirate design of the diversity requirements. $Enrichable carbon nanotubes [common method] Please refer to the first figure, first provide - bottom 10, base 10 is porous 1274736 V. Invention description (4) Shi Xi, you can also choose polished silicon, you can pick a light Resistance layer u. By lithography, etc. The substrate 10 is patterned. On the solid::11 which needs to grow the carbon nanotubes, a predetermined film is formed, the thickness of the catalyst film 13 is thick; the catalysis or thickening of the catalyst is thickened, and the catalyst film 13 is thicker: the end is gradually thinned The end of the catalyst film is about 1~5nm, and the +1 of the catalyst film 13 is too 5~0nm, which is thinner or the direction of the bend, and the carbon is ridiculously §10: the inclined end of the nano-carbon tube array is thinner. . The phase of the array is curved or tilted. The method of catalyst deposition can be carried out by thermal evaporation or by a combination of photolithography or a mask with through holes: or by solution coating with ruthenium film or photolithography. The catalyst material may be selected from iron, cobalt, nickel or an alloy thereof, and a linear linear evaporation source 12 is used to deposit the northmost film 13 . The line type % source 12 is placed obliquely above the photoresist pattern so that the sinker is 2 degrees to form a gradient gradient. The above-mentioned linear evaporation source may be replaced by a point evaporation source which may also be moved by two dots, or a point evaporation source may be fixed, or a U-type evaporation source 1 2 may be used, and the substrate to be plated may be moved along the linear chain instead. . The second film is removed. The photoresist layer U is removed, and the substrate 10 with the catalyst film 13 is placed in the air, and the film is lowered at 3 〇〇 c. The film 13 is oxidized and shrunk to a nanometer level. Catalyst particles 31. The thickness of the catalyst film 13 deposited at both ends is unequal, showing a gradual distribution, and the catalyst particles 131 formed during the annealing process are unequal in size. Catalyst catalyst particles formed at one end of the thinner layer 3 3 i is smaller, thicker than ^ _ 忐 catalyst particles 131 is larger. After annealing is completed, there will be distribution of catalysis = page 9 1274736 V. Description of the invention (5) The substrate of the granule 131 is placed in the reaction chamber (not shown) The carbon source gas acetylene is introduced, and the carbon nanotube gas is grown on the catalyst particle 13 by using a thermal chemical vapor deposition method. Other carbon-containing gases such as ethylene may be used. The adjustment of film thickness and the time of growth of carbon nanotubes are the main factors for the growth length and tilt angle of the carbon nanotube arrays grown on the graph. A bow is referred to the third figure. Nano carbon tube array structure 20 packages a substrate 1 〇, a plurality of catalyst particles 133 formed on the substrate 及 and a carbon nanotube array 14 grown from the plurality of catalyst particles 131, wherein: the size of the particles (3) is gradually changed along a predetermined direction to form a granule At the small particle end, the carbon nanotube array 14 is bent toward the small particle end of the catalyst ΐ3ι. ^ and ΐ ΐ t t carbon tube array structure 20 can be used for planar display, nanoelectronics, pre-current, electron emission, etc. The cathode manufacturing process. The patented ί 修 修 修 修 修 修 12 12 12 12 12 12 12 12 12 12 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 747 The second figure is a schematic diagram of the substrate and catalyst particles after annealing in the present invention. The third figure is a schematic diagram of the structure of the carbon nanotube array in the present invention.
基底 10 光阻層 11 線性蒸發源 12 催化劑薄膜 13 催化劑顆粒 131 奈米碳管陣列 14Substrate 10 photoresist layer 11 linear evaporation source 12 catalyst film 13 catalyst particles 131 carbon nanotube array 14