1302904 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種奈米碳管陣列結構及其製備方法。 【先前技術】 由於奈米碳管獨特之電學性質，其在奈米積體電路、 單分子器件等領域的應用有著不可估量之前景。目前人們 已能在實驗室少量製造基於奈米碳管之場效應管、邏輯器 件及記憶體等，並研究其性質，具體請參閱Sander J Tans 等人 1998年發表在Nature 393-49，Room-temperature transistor based on a single carbon nanotube 一文。 但大規模製備與具實際意義之應用則須求助於由下而上 (Bottom Up)之製備工藝。 由下而上之製備工藝要求能對奈米碳管之生長位置、 方向、大小、長短、甚至奈米碳管之螺旋度進行必要控制， 藉由少量且經濟之步驟直接生長出所需之器件結構。範守 善等人在Science 283，512-514(1999)，Self-oriented regular arrays of carbon nanotubes and their field emission properties—文中，以及Z. F. Ren等人在Science 282, 1 105-1 107(Nov 6, 1998) 5 Synthesis of large arrays of well-aligned carbon nanotubes on glass—文中均揭 露一種藉由催化劑圖形（Patterned Catalyst)來控制奈米 碳管之生長位置及使其垂直於基底之生長方法。 另，B. Q· Wei 等人在 Nature 416，495-496(Apr 4， 2002)，Organized assembly of carbon nanotubes—文中 1302904 揭露一種可藉由對基底形狀之設計實現奈米碳管於三維基 底上生長出垂直於各處表面之奈米碳管生長方法。 准，上述方法獲付之奈米碳管陣列均垂直於生長基 底’無法對陣列之生長方向做出控制與改變。1302904 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a carbon nanotube array structure and a preparation method thereof. [Prior Art] Due to the unique electrical properties of nanocarbon tubes, their applications in fields such as nano-integrated circuits and single-molecule devices are invaluable. At present, it is possible to manufacture a small number of FET-based FETs, logic devices, and memories in the laboratory, and to study their properties. For details, see Sander J Tans et al., 1998, Nature 393-49, Room- Temperature transistor based on a single carbon nanotube However, for large-scale preparation and practical applications, it is necessary to resort to the Bottom Up preparation process. The bottom-up preparation process requires the necessary control of the growth position, orientation, size, length, and even the helicity of the carbon nanotubes, and directly grows the required devices by a small number of economic steps. structure. Fan Shoushan et al., Science 283, 512-514 (1999), Self-oriented regular arrays of carbon nanotubes and their field emission properties, and ZF Ren et al., Science 282, 1 105-1 107 (Nov 6, 1998) 5 Synthesis of large arrays of well-aligned carbon nanotubes on glass - A method for controlling the growth position of a carbon nanotube and making it perpendicular to the substrate by a Catalyst pattern is disclosed. In addition, B. Q. Wei et al., Nature 416, 495-496 (Apr 4, 2002), Organized assembly of carbon nanotubes - 1302904 discloses that a carbon nanotube can be realized on a three-dimensional substrate by designing the shape of the substrate. A method of growing carbon nanotubes perpendicular to the surface is developed. Precisely, the carbon nanotube arrays obtained by the above methods are perpendicular to the growth substrate' and cannot control and change the growth direction of the array.
Yuegang Zhang等人在Applied Physics Leners ν〇ι 79, Number 19, Nov 5, 2001, Electric-field-directed growth of aligned single-walled carbon nanotubes-文中揭露一種藉由電場控制奈米碳管生長方向之方法，在 電場作用下，奈米碳管沿電場方向生長。 惟，上述方法中，用電場控制奈米碳管生長方向之方 法會加重器件設計之複雜程度，且由^電場本身之廣域 ⑽種生長方向控制。該等因素均限制 奈未奴官益件設計之多樣化及實用性。 有鑒於此，提供一種不需外場之控制局部奈米碳管生 長方向之方法實為必要。 【發明内容】 碳管目的係提供—種向—特定方向彎曲之奈米 結構之目的係提供一種製備上述奈米碳管陣列 本發明所揭示之奈米碳管陣列結構， 形成於基底之俏各如入A ”匕括基底、 夺米碳管陣列Γ 顆粒及從催化劑合金顆粒生長之 車歹1，该催化劑合金顆粒包括 速度之材料，崎料之 ;u 長 里。方向漸變，該奈米碳管陣 1302904 列向一特定方向彎曲。 管陣列結構之方 本發明還揭示一種製備上述奈米碳 法，其步驟包括： (1)提供一基底； (2) 於基底之表面形成催化劑層； (3) 於催化劑層沈積-層影響奈米 料，該材料之厚錢變分佈； 材 ㈣=含氧氣氛中退火，㈣化劑層氧化成為奈米級催 (5)通入碳源氣，生長奈米碳管。 先前技射奈米碳管陣列均是垂直於基底，本發明提 供之奈米碳管陣列向―肢方向彎曲，豐富奈米碳管器件 设計之多樣性，為奈米碳管器件之設計提供更多選擇空間 〗與先前奈米碳管陣列之生長方法相比，本發明提供之 製備方法於催化劑圖形沈積一層影響奈米碳管生長速度之 材料’藉由控制材料厚度之變化與分佈，使得於基底ς不 !!位置奈米石炭管有不同之生長速度，因奈米碳管之間有范 德瓦爾力（van der waal)之影響，使得奈米碳管陣列在 生長過程中向一特定方向彎曲。其中影響奈米碳管生長速 度材料之厚度調製係決定奈米碳管陣列彎曲形狀之主要因 素0 【實施方式】 凊參閱第一圖，首先提供一基底10，該基底10可選用 矽，於該基底10形成一光阻層11，藉由光刻使光阻層1 ^形 1302904 成預定之圖案。於需要生長奈米碳管之位 催化劑13 ’催化劑13之厚度至少2〜3奈米，至多7〜9=厚 且厚度均句一致，催化劑13之沈積方法可選用熱;ίΜΊ、奸 法、亦可選用電子束加熱蒸發法等方法配合光刻;;藝2 形掩H催化賴之材料可選用鐵、銘、麵其入一: 本實施例選用鐵作催化劑13之材料，其沈積厚度係^半。。 請參閱第二Κ ’於催化船3沈積-層影響奈米碳不管生 速度之材料12卜該材料121之厚度由一端向另— 遞減，本實施方式係藉由於光阻層⑽上方放置一銅 直線型蒸發源12,通過熱蒸發沈積法，於催化劑13上二 :層材料12卜該材料121厚度漸變分佈，一般要求較厚二 端之厚度不超出10奈米，較薄一端之厚度接近零夺米，本 實太施例中，其較厚-端之厚度係8奈米，較薄一端之厚度係 不米，上述直線型蒸發源12亦可用沿直線移動之點 影響奈米碳管生長速度之材料121之沈積也可以選用 :束蒸發等有方向性之沈積方法配合光刻工藝或圖形掩 杲凡j，或者利用溶液喷塗配合甩膜、光刻等工藝完成。 °月併參閱第二圖與第四圖，洗除光阻層11，將帶有 催化船3及影響奈米碳管生長速度之材料121之基底㈣ 2氣中，於20(TC〜40(rc下退火，使催化劑13氧化，收縮 1不米、’及之催化劑顆粒（圖未示），退火時間與溫度有關， 6回，則退火時間相對越短，原則上，只要催化劑1 3 氧化即可。再將基底10置於反應爐（圖未示）中，於保 氣體氬氣中，通入碳源氣乙炔，利用熱化學氣相沈積法， 1302904 在600〜7G(TC下生長，此時催化劑鐵與材料銅形成合金顆粒 131，於材料121較厚之一端合金顆粒131所含銅較多，材料 121較薄一端合金顆粒131銅含量相對較少，而銅材料i2i具 j緩奈米碳管生長速度之特性，因材料121較厚一端奈米碳 官生長文銅之影響較大，生長較慢，相反，材料Μ〗較薄一 端奈米碳管生長相對較快，故，於上述合金顆粒131上生長 之奈米碳管陣列15向材料121較厚一側彎曲。碳源氣亦可選 用^碳之其他氣體，如乙烯等，保護氣體亦可為其他氣體， 如氮氣、氫氣、氨氣等。控制生長時間與生長溫度則可控 制奈米碳管陣列15之生長高度。 請參閱第四圖，利用上述方法所獲得之奈米碳管陣列 結構40包括-基底1G、形成於基底1()之奈米級合金顆粒⑶ 及從合金顆粒131上長出之奈米碳管陣列15，其中合金 131尺寸大小沿一方向線性變化，且其銅的含量沿同一方向 亦線性變化，該奈米碳料列15向—特定方向彎曲。 本實施例巾，材料121係減緩奈米碳管生長速度之銅， 惟’該材料121亦可為加快奈米碳管生長速度之材料，如 翻。如材料121係加快奈米碳管生長速度之材料，則夺米石户 官向材料121較薄一側彎曲’如材料121係減緩奈米碳管生火 長速度之材料’則奈米碳管向材料121較厚-側彎曲。 既ϋ劑13之沈積與材料m之沈積順序可相互交換，即 可先沈積催化劑13後沈積材料⑵，亦可先沈積材料⑵ j沈積催化劑13’因沈積材料121對催化_之覆蓋不會影 曰催化劑13之氧化’因而該沈積順序之交換對奈米碳管陣 11 1302904 t 列15之生長方向控制沒有影響。 上述奈㈣管陣列結構亦可用於平面顯示、奈米電子風 大電流場發射電子㈣n件之陰極製造工藝。 =所述，本創作符合發明專利之要件，爰依法 專利以。m料者僅為本㈣之㈣實施例，兴 凡熟悉本案技藝之人士，在援依本案創作精神所作之等二 修飾或變化，皆應包含於以τ之申請專利範圍内。" 【圖式簡單說明】 第一圖係本發明中沈積有催化劑薄臈之基底示意圖。# 第二圖係第一圖所示基底沈積影響奈米碳管生長速度 之材料過程示意圖。 第三圖係第二圖催化劑薄膜與影響奈米碳管生長速度 之材料形成合金顆粒示意圖。 第四圖係本發明奈米碳管陣列結構之示意圖。 要元件符號說明】 1 基底 10 光阻層 11 催化劑 13 蒸發源 12 材料 121 合金顆粒 131 奈米碳管陣列 15 12Yuegang Zhang et al., Applied Physics Leners ν〇ι 79, Number 19, Nov 5, 2001, Electric-field-directed growth of aligned single-walled carbon nanotubes - A method for controlling the growth direction of carbon nanotubes by electric field is disclosed Under the action of an electric field, the carbon nanotubes grow in the direction of the electric field. However, in the above method, the method of controlling the growth direction of the carbon nanotube by the electric field increases the complexity of the device design and is controlled by the wide field (10) growth direction of the electric field itself. These factors all limit the diversification and practicality of the design of the Nai Nu Nuo. In view of this, it is necessary to provide a method of controlling the growth direction of a local carbon nanotube without an external field. SUMMARY OF THE INVENTION The purpose of the carbon tube is to provide a nano-structure that is bent in a specific direction. The purpose of the carbon nanotube array is to provide a carbon nanotube array structure disclosed in the present invention, which is formed on the substrate. For example, into the A" matrix, the carbon nanotube array Γ particles and the rut 1 grown from the catalyst alloy particles, the catalyst alloy particles include the material of the velocity, the material of the material; u long, the direction gradient, the nano carbon The array of tubes 1302904 is bent in a specific direction. The invention also discloses a method for preparing the above nanocarbon, the steps of which include: (1) providing a substrate; (2) forming a catalyst layer on the surface of the substrate; 3) In the deposition of the catalyst layer - the layer affects the nanomaterial, the material is thick and variable; the material (4) = annealing in an oxygen-containing atmosphere, (4) the oxidation of the chemical layer into a nano-grade (5) into the carbon source gas, growth The carbon nanotube arrays of the prior art are perpendicular to the substrate, and the carbon nanotube array provided by the invention bends toward the limbs, enriching the diversity of the carbon nanotube device design, and is a nano carbon. Tube device design Providing more choice space The present invention provides a preparation method for depositing a layer of material affecting the growth rate of the carbon nanotubes in the catalyst pattern by controlling the change and distribution of the thickness of the material, compared to the growth method of the prior carbon nanotube array. So that the carbon nanotubes have different growth rates, because of the van der waal between the carbon nanotubes, the carbon nanotube array is in the process of growth. Bending in a specific direction. The thickness modulation of the material affecting the growth rate of the carbon nanotubes determines the main factor of the curved shape of the carbon nanotube array. [Embodiment] Referring to the first figure, a substrate 10 is first provided, and the substrate 10 can be selected.形成, a photoresist layer 11 is formed on the substrate 10, and the photoresist layer is patterned into a predetermined pattern by photolithography. The catalyst 13' of the catalyst 13 is required to grow at least 2 to 3 thick. Nano, at most 7~9=thick and uniform thickness, the deposition method of catalyst 13 can be selected with heat; ΜΊ, rape, or electron beam heating evaporation method can be used together with lithography; The material of H catalyzed can be selected from iron, inscription and surface. In this embodiment, iron is used as the material of catalyst 13 and its deposition thickness is half. Please refer to the second Κ 'in the catalytic ship 3 deposition-layer influence The thickness of the material 12 is reduced from one end to the other, and the present embodiment is formed by a thermal evaporation deposition method on the catalyst 13 by placing a copper linear evaporation source 12 above the photoresist layer (10). The second layer: the layer material 12, the thickness of the material 121 is gradually distributed, generally the thickness of the thicker end is not more than 10 nm, and the thickness of the thinner end is close to zero, which is thicker-end. The thickness is 8 nm, and the thickness of the thinner end is not. The linear evaporation source 12 can also be used to deposit the material 121 which affects the growth rate of the carbon nanotubes by the point of linear movement: the beam evaporation and the like are also available. The deposition method of the nature is combined with the lithography process or the pattern masking, or by the solution spraying with the ruthenium film, photolithography and the like. ° ° and refer to the second and fourth figures, the photoresist layer 11 is removed, and the substrate (4) 2 with the catalytic vessel 3 and the material 121 affecting the growth rate of the carbon nanotubes is at 20 (TC~40 ( Annealing under rc, the catalyst 13 is oxidized, shrinking 1 meter, and the catalyst particles (not shown), the annealing time is related to temperature, 6 times, the annealing time is relatively shorter, in principle, as long as the catalyst 13 is oxidized Then, the substrate 10 is placed in a reaction furnace (not shown), and a carbon source gas acetylene is introduced into the gas-preserving argon gas by a thermal chemical vapor deposition method, and 1302904 is grown at 600 to 7 G (TC). The catalyst iron forms a alloy particle 131 with the material copper. The alloy particle 131 contains more copper at the one end of the thicker material 121, and the copper content of the alloy material 131 is relatively less at the thinner end of the material 121, and the copper material i2i has a j-nano carbon. The characteristics of the growth rate of the tube are mainly due to the influence of the thicker end of the material 121, and the growth of the copper is relatively slow. On the contrary, the thinner end of the material is relatively faster, so the alloy is relatively fast. The carbon nanotube array 15 grown on the particles 131 is compared to the material 121 One side is bent. The carbon source gas can also be selected from other gases such as ethylene, and the protective gas can also be other gases such as nitrogen, hydrogen, ammonia, etc. Controlling the growth time and growth temperature can control the carbon nanotubes. The growth height of the array 15. Referring to the fourth figure, the carbon nanotube array structure 40 obtained by the above method includes a substrate 1G, a nano-sized alloy particle (3) formed on the substrate 1 (), and a long length from the alloy particle 131. The carbon nanotube array 15 is obtained, wherein the size of the alloy 131 varies linearly in one direction, and the copper content thereof also varies linearly in the same direction, and the nano carbon row 15 is bent in a specific direction. Material 121 is a copper that slows down the growth rate of carbon nanotubes, but 'this material 121 can also be a material that accelerates the growth rate of carbon nanotubes, such as turning over. If material 121 is a material that accelerates the growth rate of carbon nanotubes, then it takes Mishito officially bends the material 121 toward the thinner side. If the material 121 is a material that slows down the length of the carbon nanotubes, the carbon nanotubes are thicker-side curved toward the material 121. The deposition and materials of the tantalum agent 13 The deposition order of m can be phased For the exchange, the catalyst 13 may be deposited first, then the material (2) may be deposited, or the material may be deposited first (2) j. The catalyst 13' is deposited because the deposition of the catalyst 121 does not affect the oxidation of the catalyst 13 and thus the exchange order is exchanged. The carbon nanotube array 11 1302904 t column 15 has no effect on the growth direction control. The above nematic (four) tube array structure can also be used for the cathode display manufacturing process of the flat display, nanoelectronic wind and large current field emission electrons (4) n pieces. In accordance with the requirements of the invention patent, the patent is based on the law. The material is only the (4) (4) embodiment. Anyone who is familiar with the skill of the case should be included in the creative spirit of the case. τ is within the scope of the patent application. "Simplified illustration of the drawings] The first figure is a schematic diagram of a substrate on which a catalyst thin layer is deposited in the present invention. # 第二图 The schematic diagram of the material process of the basement deposition affecting the growth rate of the carbon nanotubes in the first figure. The third figure is a schematic diagram of the formation of alloy particles of the catalyst film of the second figure and the material affecting the growth rate of the carbon nanotubes. The fourth figure is a schematic diagram of the structure of the carbon nanotube array of the present invention. Element symbol description] 1 Substrate 10 Photoresist layer 11 Catalyst 13 Evaporation source 12 Material 121 Alloy particles 131 Carbon nanotube array 15 12