200523976 玖、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與探針接合之製作方法和 結構，尤其是指一種藉由電泳或介電泳原理，使奈米碳管 可受電場驅使而自組接合於探針上之方法及結構、厌s 【先前技術】 奈米碳管（CarbonNanotubes)是由碳原子所組成的一 種單層或多層壁之管狀結構，管徑約為數奈米，長度可達 數微米。由於奈米碳管的特殊結構與特性，使其具備良好 的機械特性、高深寬比、曲饒性等優勢，而可廣泛應^在 光電元件、電子it件、生化醫療、能源材料··等各種不同 領域。此外，更可利用奈米碳管細長金屬與半導電特性及 曲饒性之優點，更可應用於奈米級微探針或微電極。但是， 由於奈米碳管為奈米級之尺寸，當奈米碳管欲與一探針接 合時，將因奈米碳管之尺寸太小而不易處理。 當欲進行奈米碳管與探針接合之製程時，目前習知之 技術都是採用配合觸媒之塗佈及化學氣相沉積法進行，使 奈米被管沿者沾有觸媒的地方成長，例如··電聚強化化學 氣相>儿積法、常溫化學氣相沉積法、電弧放電等。伸是， 上述之製程條件需要真空環境(50〜400T〇rr)或在高溫下進 行’即便是低溫製程也要450〜500t，且低溫製程僅限於 MWNTs ’對於SWNTs仍需要1000〜12〇〇°c高溫製程。此 類習用技術對於大尺寸與低溫平台材料上沉積奈米碳管均 200523976 有很大的限制。此外，由於觸媒通常是由鐵、鎳、鈷 屬研磨至奈米等級’不僅價格昂貴’且在沉積碳管的過程 中，常附帶產生不純物，如結晶或非結晶性的碳化物及未 反應元之催化劑等，因此會增加純化之額外製程，且技術 亦相對較—。有鑒於習知之制配合觸媒之塗佈及化^ 7儿積法之缺失及限制，因此本發明其係提供一種奈米礙管 與探針自組裝接合技術，以克服奈米尺寸之材料 件接合所面臨之困難。 、 【發明内容】 本發明之主要目的係提供一種奈米碳管與探針接合之 製作方法，可在常溫常壓下進行奈米碳管與探針接合製程。 本發明之另-目的係提供一種奈米碳管與探針自組接 合之製作方法，藉由電泳或介電泳原理，使奈米碳管可在 高壓電場驅使下^接合於探針尖端之上。 本發明之再一目的係提供一種奈米碳管與探針接合之 結構，其奈米碳管係平行於電場方向制並附著於探針尖 端之上。 本發明之更-目的係提供—種奈米碳管與探針接合之 j架構’可進行使奈米碳管受高麼電場驅使而自組接合 於探針尖端的製程。 牛為達上述之目的，本發明之製作方法，至少包含下列 形成—微米探針’於探針表面並覆蓋有—導電層； “探針暴路於-含有分散奈米碳管之溶液環境中，於該 200523976 設有一電極;並對該導電層及電極之間施加 虛Γ ’使至少—奈米碳f因電泳效應或是介電泳效 Μ而朝向探針之尖端泳動、並藉由凡得瓦耳力畴於其上。 、為使貴審查委員能對本發明之特徵、目的及功能有 更進-步的認知與瞭解，魏合圖式詳細說明如後： 【實施方式】 本發明之奈米碳管與探針接合之製作方法係使用簡單 之電泳或介電泳技術。在常溫常壓的狀態下，即可以進行 奈巧管與微米探針的接合，且製程技術及製程條件均相 對簡单，以下將舉若干實施例詳細_本㈣之技術特徵 及功效。 、請參閱圖一，為本發明藉由電泳（或介電泳）原理來 進行奈米碳管與探針自組裝接合之系統架構與方法示意 圖。 如圖一所示，該方法主要是先提供一矽材質之基底 11於基底11上並藉由半導體製程而製作至少一微米探針 12(，中係以四隻探針12為例）。於基底η及探針12表 面覆蓋有-導電層I3，例如金、銅、㉝或其他金屬或合金 等，其可藉由電鍍或是薄膜沈積方式形成為較佳。於導電 層13上更覆蓋有一非導電物質層14以作為遮蔽層，於本 較佳實施例中係以光阻作為非導電物質層14但亦可選用其 他非導電材質。該非導電物質層14係覆蓋於導電層13上 預定區域處，並使探針12尖端121處之導電層131不被非 200523976 導電物質層14所覆蓋而係暴露於外界。 該基底11連同其上之探針12、導電層13及非導電物 質層14 一起被置入一溶液環境20中，例如置入—反應槽 等。於該溶液環境20中分散有懸浮之多數奈米碳管21。於 溶液環境20中與基底11相隔一預定距離處並設置有另一 電極31。藉由導電膠41、42與連接線43、44將基底u 上之導電層13與電極31分別連接到一直流電源45的正負 兩極。該直流電源45可在導電層13與電極31之間提供二 預定強度的直流電壓。由於導電層13僅有探針12尖端\21 處係暴露於溶液環境20中、其暴露於溶液環境2〇之表面 積遠小於電極31。所以，在靠近探針12尖端121處將會有 電場集中強化之效應。在此情形之下，溶液環境2G中之多 數奈米碳管21將會g為電制或是介電減應而朝向探 針12尖端121處泳動，並在探針12尖端121時會被電場 所導引而使奈米碳管21的長度方向與探針12延伸方向呈 現平行於電場整齊制，並進_步藉由凡得瓦耳力而附著 固定於探針12尖端121。 於一較佳實施例中，該溶液環境20係包括有陰離子界 面/舌f生劑，例如十二烧基硫酸納(substantiaiiy decreased， fDS)、或是其他種類之界面活性劑等，其可在原本不帶電 荷之奈米碳管21表面附著一層負電荷。並且，該導電層13 係為連接直流電源45的正極、而電極31則是連接直流電 源45之負極（如圖一所示）。如此一來，帶著負電荷之奈 米碳管21將會受到電場影響而朝向相反電性(也就是正極） 200523976 ’最後則因凡得瓦耳力而附著固定 :這種現象便稱作電泳(Ele_h〇resis， ί中，奈米碳管21 #泳鱗將取決於其 之探針12尖端121泳動， 於探針12尖端121。這種 EP )。於此電泳技術中，$ 分子量，而與原來分子所帶的電荷無關。 、、/、 而在另-較佳實施射，該溶液環境2G係為不帶電之 溶劑，例如異丙醇或其他有機溶劑等。由於奈米碳管2丨本 身亦不帶電荷，所以不會主動朝某—電極泳動。铁而，由 於導電層13僅有在探針12尖端121處係暴露於溶液環境 20中、其暴露於溶液環境2〇之表面積遠小於電極μ。所 以，在罪近探針12尖端121處將會有電場集申強化之效應 並產生不一致的電場強度。在其影響下，未帶電之奈米碳 g 21由於極化之誘導，造成側向移動。其原理是在每場影 響下’誘發粒予'表面受到極化的效應，而產生一耦極距。 如此’即使異丙醇與奈米碳管21兩者都不帶電荷，也將因 不一致之電場環境而仍將奈米碳管21引導朝向電場流密度 大之探針12尖端121泳動，最後則因凡得瓦耳力而附著固 定於探針12尖端121。這種現象便稱作介電泳動 (Dielectrophoresis ) 〇 於本較佳實施例中，更可設置包括一超音波裝置46， 其可對該溶液環境20提供超音波震盪，不僅避免溶液環境 20中之複數個奈米碳管21凝聚成團、也可使奈米碳管21 均勻分散懸浮於溶液環境20中。 請參閱圖二A至圖二E所示，為如圖一所示之該含有探 針12之基底11的製程步驟的較佳實施例，其包括有下列步 200523976 驟： 首先，如圖二A所示，於矽材質之基底51上（例如矽晶 圓）依序形成一敗化石夕層52及一阻障層53 (例如光阻）。 利用黃光微影蝕刻等半導體製程技術於該阻障層53預定位 置處開設有若干開口 53卜而使開口531部分之氤化韻52 可暴露於外界。 接著，如圖二B所示，對如圖二A所示之裝置進行反 應性離子侧機（RIE)侧，並利用基底51作為侧終 點，使開口 531部分之氮化矽層52因蝕刻而遭侵蝕，之後 再去除阻障層53，而在基底上留下若干柱狀之氮化矽柱 521 〇 然後，如圖一 C所示，對氮化石夕柱521進行非等向性 濕姓刻，而於基底51上形成若干氮化石夕材質之圓錐狀探針 522結構。 再來，如圖二D所示，藉由電鍍、濺鍍、物理氣相沈積、 化學氣相沈積、或是其他方式在基底51及探針522上形成一 金屬導電層54，例如金、銅、鋁、鎳或其他金屬或合金等。 於本較佳實施例中，該導電層54係廣泛覆蓋整個基底51與 探針522。然而，於其他實施例中，該導電層54至少需覆蓋 有探針522之尖端。 最後，如圖二E所示，形成一非導電物質層55覆蓋於導 電層54上之預定區域處而僅暴露出探針522尖端處之導電 層541。於本實施例中，該非導電物質55可為光阻或其他不 導電薄膜或南分子材料等。其先將光阻廣泛覆蓋於整個導 200523976 電層54上後、再藉由反應性離子蝕刻掉預定厚度的光阻， 而使除了探針522尖端處之外的其他部分導電層54均被非 導電物質55所遮蔽。如此，便完成圖一所示之具有探針之 基板結構的製作。 值仔一長:的疋，於圖一A至圖二E所示之本發明之該含 有探針12之基底11的製程步驟的實施例中，雖然是以氮化 矽（SiNJ作為製作微米探針的材料，然而，吾人亦可選 用其他氮切、氧切、金屬、或高分子聚合物等來在基 底上形成探針者。 如上述之電泳系統/介電泳系統係可在常溫常壓下進行 奈米碳管與探針接合之製作，可㈣免習知技術需要在高 溫高壓下進行奈米碳管與探針接合之缺失。並且，本發明 於申請前從未曾見於#何刊物及公開場合中，確實具有新 穎性及高度進步性。 唯以上所述者’僅為本㈣之較佳實闕，#不能以之 限制本發明的範圍。即大驗本刺_請專纖圍所做之 均等變化及修飾’仍料失本發明之要義所在亦不脫離 =發明之騎和範圍’故都應視為本發明的進—步實施狀 【圖式簡單說明】 由電泳（或介電泳）絲來進行奈米碳管 二探針自組装接合之系統架構與方法示意圖。 圖- A至圖二E係為本發明之具有探針之基底的製程步驟 12 200523976 流程圖。 圖示之圖號說明： 11基底 12探針 121尖端 13導電層 131尖端處導電層 14非導電物質層 20溶液環境 21奈米碳管 31電極 41、42導電膠 43、44連接線 45直流電源 46超音波裝置 51基底 52氮化矽層 521氮化矽柱 522探針 53阻障層 531 開口 54導電層 55非導電物質 13200523976 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method and structure for manufacturing a nanometer carbon tube and a probe, and particularly refers to a method for making a nanometer carbon tube through electrophoresis or dielectrophoresis. Method and structure of self-organized bonding to a probe driven by an electric field [Previous technology] Carbon nanotubes (carbon nanotubes) are a single-layer or multi-layered tubular structure composed of carbon atoms, the diameter of which is about several Nanometers can reach several microns in length. Due to the special structure and characteristics of carbon nanotubes, they have advantages such as good mechanical properties, high aspect ratio, and flexibility, and can be widely used in optoelectronic components, electronic it parts, biochemical medical, energy materials, etc. Various fields. In addition, it can take advantage of the advantages of the slender metal and semi-conducting properties and flexibility of the carbon nanotube, and it can also be applied to nano-level microprobes or microelectrodes. However, because the carbon nanotubes are nano-sized, when the carbon nanotubes are to be connected to a probe, the size of the carbon nanotubes is too small to handle. When the process of joining carbon nanotubes and probes is to be carried out, currently known technologies are carried out by coating with a catalyst and chemical vapor deposition, so that the place where the nanometer tube is exposed to the catalyst grows. For example, ... Electrochemical Polymerization Enhanced Chemical Vapor > Child Product, Normal Temperature Chemical Vapor Deposition, Arc Discharge, etc. The extension is that the above process conditions require a vacuum environment (50 ~ 400T〇rr) or under high temperature. 'Even low-temperature processes need to be 450 ~ 500t, and low-temperature processes are limited to MWNTs.' For SWNTs, it still needs 1000 ~ 1200 ° c. High temperature process. This type of conventional technology has significant limitations on the deposition of nanometer carbon nanotubes on large-scale and low-temperature platform materials. In addition, because the catalyst is usually ground from iron, nickel, and cobalt to nanometer grades, it is not only expensive, and in the process of depositing carbon tubes, impurities are often incidentally generated, such as crystalline or amorphous carbides and unreacted. Yuan catalysts, etc., will therefore increase the additional purification process, and the technology is relatively relatively-. In view of the lack and limitation of the conventional coating system and catalyst coating and chemical method, the present invention provides a technology for self-assembly of nanometer obstruction tube and probe to overcome nanometer-sized materials. Difficulties in joining. [Summary of the Invention] The main purpose of the present invention is to provide a method for manufacturing a nano carbon tube and a probe, which can perform a process of bonding a carbon nano tube and a probe under normal temperature and pressure. Another object of the present invention is to provide a method for manufacturing a self-assembled nanometer carbon tube and a probe. By using electrophoresis or dielectrophoresis, a nanometer carbon tube can be connected to a probe tip under a high voltage electric field. . Another object of the present invention is to provide a structure in which a nano carbon tube is bonded to a probe, and the nano carbon tube is parallel to the direction of the electric field and is attached to the tip of the probe. A further object of the present invention is to provide a j-frame structure for bonding a carbon nanotube to a probe, which can perform a process in which the carbon nanotube is driven by a high electric field and is self-assembled to the probe tip. In order to achieve the above-mentioned object, the manufacturing method of the present invention includes at least the following formation-a micron probe 'on the surface of the probe and covered with a conductive layer; "the probe explodes in a solution environment containing dispersed carbon nanotubes" An electrode is provided in the 200523976; and a virtual Γ 'is applied between the conductive layer and the electrode to cause at least the nano-carbon f to swim toward the tip of the probe due to the electrophoretic effect or the dielectrophoretic effect M, and by using Watt's force is on it. In order to allow your reviewers to have a further understanding and understanding of the features, purposes and functions of the present invention, the Wei He diagram is detailed as follows: [Embodiment] The nano carbon tube of the present invention The method of bonding with the probe uses simple electrophoresis or dielectrophoresis technology. Under normal temperature and pressure conditions, the junction of the nano tube and the micro probe can be performed, and the process technology and process conditions are relatively simple, as follows: Several examples will be given in detail _ the technical features and effects of the present invention. Please refer to FIG. 1, which is a system frame for self-assembly and bonding of a carbon nanotube and a probe by electrophoresis (or dielectrophoresis) according to the present invention. Schematic diagram of the method. As shown in Figure 1, the method is mainly to first provide a silicon substrate 11 on the substrate 11 and make at least one micron probe 12 (in the system, four probes 12 are used as the semiconductor). Example). The surface of the substrate η and the probe 12 is covered with a conductive layer I3, such as gold, copper, rhenium, or other metals or alloys, which can be preferably formed by electroplating or thin film deposition. On the conductive layer 13 It is further covered with a non-conductive material layer 14 as a shielding layer. In the preferred embodiment, a photoresist is used as the non-conductive material layer 14 but other non-conductive materials may be used. The non-conductive material layer 14 is covered on the conductive layer. 13 on a predetermined area, and the conductive layer 131 at the tip 121 of the probe 12 is not covered by the non-200523976 conductive material layer 14 and is exposed to the outside. The substrate 11 together with the probe 12, the conductive layer 13 and the non- The conductive material layer 14 is placed together in a solution environment 20, such as a reaction tank, etc. Most of the suspended carbon nanotubes 21 are dispersed in the solution environment 20. The solution environment 20 is separated from the substrate 11 by a predetermined distance. Distance and set An electrode 31. The conductive layer 13 and the electrode 31 on the substrate u are respectively connected to the positive and negative poles of a DC power supply 45 through conductive glues 41, 42 and connecting wires 43, 44. The DC power supply 45 can be provided on the conductive layer 13 and the electrodes. A DC voltage of two predetermined strengths is provided between 31. Since the conductive layer 13 has only the tip of the probe 12 \ 21, it is exposed to the solution environment 20, and its surface area exposed to the solution environment 20 is much smaller than the electrode 31. Therefore, near At the tip 121 of the probe 12, there will be an effect of concentration enhancement of the electric field. In this case, most of the carbon nanotubes 21 in the solution environment 2G will be oriented towards the tip of the probe 12 for electrical or dielectric subtraction. 121 swims, and will be guided by the electric field when the tip 121 of the probe 12 makes the length direction of the nano carbon tube 21 and the extension direction of the probe 12 appear to be parallel to the electric field. And attached to and fixed to the tip 121 of the probe 12. In a preferred embodiment, the solution environment 20 includes an anionic interface / tongue agent, such as sodium dodecyl sulfate (fDS), or other types of surfactants. A layer of negative charge was attached to the surface of the carbon nanotube 21 that was originally uncharged. In addition, the conductive layer 13 is a positive electrode connected to the DC power source 45, and the electrode 31 is a negative electrode connected to the DC power source 45 (as shown in Fig. 1). In this way, the negatively charged nano carbon tube 21 will be affected by the electric field and will face the opposite electrical property (that is, the positive electrode) 200523976 'Finally, it will be fixed due to Van der Waals force: this phenomenon is called electrophoresis ( Ele_horesis, ί, nano carbon tube 21 # swimming scale will depend on its probe 12 tip 121 swimming, on the probe 12 tip 121. This EP). In this electrophoresis technique, the molecular weight is independent of the charge carried by the original molecule. ,, /, and in another preferred embodiment, the solution environment 2G is an uncharged solvent, such as isopropyl alcohol or other organic solvents. Since the carbon nanotube 2 itself is not charged, it will not actively swim towards an electrode. Since the conductive layer 13 is exposed to the solution environment 20 only at the tip 121 of the probe 12, the surface area of the conductive layer 13 exposed to the solution environment 20 is much smaller than that of the electrode µ. Therefore, there will be an electric field concentration enhancement effect at the tip 121 of the sin near probe 12, and an inconsistent electric field strength will be generated. Under its influence, the uncharged nano-carbon g 21 causes lateral movement due to polarization induction. The principle is that under the influence of each field, the surface of the 'induced particle' is subject to polarization effect, and a pole pitch is generated. In this way, even if both isopropanol and the carbon nanotube 21 are not charged, the carbon nanotube 21 will still be guided toward the tip 121 of the probe 12 with high electric field current density due to the inconsistent electric field environment. Finally, It is attached and fixed to the tip 121 of the probe 12 by Van der Waals force. This phenomenon is called Dielectrophoresis. In the preferred embodiment, an ultrasonic device 46 may be further provided, which can provide ultrasonic oscillation to the solution environment 20, which not only avoids the The plurality of carbon nanotubes 21 can be aggregated into clusters, and the carbon nanotubes 21 can be dispersed and suspended in the solution environment 20 uniformly. Please refer to FIG. 2A to FIG. 2E for a preferred embodiment of the process steps of the substrate 11 containing the probe 12 as shown in FIG. 1, which includes the following steps 200523976: First, as shown in FIG. 2A As shown, a fossil layer 52 and a barrier layer 53 (such as a photoresist) are sequentially formed on a silicon substrate 51 (such as a silicon wafer). A plurality of openings 53 are formed at predetermined positions of the barrier layer 53 by using a semiconductor process technology such as yellow light lithography etc., so that the opening 52 of the opening 531 can be exposed to the outside. Next, as shown in FIG. 2B, the device shown in FIG. 2A is subjected to a reactive ion side (RIE) side, and the substrate 51 is used as a side end point, so that the silicon nitride layer 52 in the opening 531 is caused by etching. After being eroded, the barrier layer 53 is removed, and a number of pillar-shaped silicon nitride pillars 521 are left on the substrate. Then, as shown in FIG. 1C, the nitride pillars 521 are anisotropically wet-etched. A plurality of cone-shaped probes 522 made of nitride stone are formed on the substrate 51. Further, as shown in FIG. 2D, a metal conductive layer 54 such as gold or copper is formed on the substrate 51 and the probe 522 by electroplating, sputtering, physical vapor deposition, chemical vapor deposition, or other methods. , Aluminum, nickel, or other metals or alloys. In the preferred embodiment, the conductive layer 54 covers the entire substrate 51 and the probe 522 widely. However, in other embodiments, the conductive layer 54 needs to cover at least the tip of the probe 522. Finally, as shown in FIG. 2E, a non-conductive material layer 55 is formed to cover a predetermined area on the conductive layer 54 and only the conductive layer 541 at the tip of the probe 522 is exposed. In this embodiment, the non-conductive material 55 may be a photoresist or other non-conductive film or a molecular material. It covers the entire conductive layer 54 with the photoresist 200523976, and then etches out the photoresist with a predetermined thickness by reactive ions, so that the conductive layer 54 other than the tip of the probe 522 is non-conductive. Covered by the conductive substance 55. In this way, the fabrication of the substrate structure with the probe shown in Fig. 1 is completed. One of the most valuable ones: in the embodiment of the process steps of the substrate 11 containing the probe 12 of the present invention shown in FIGS. 1A to 2E, although silicon nitride (SiNJ is used as a micron probe) Needle materials, however, we can also use other nitrogen cutting, oxygen cutting, metal, or high molecular polymers to form probes on the substrate. As mentioned above, the electrophoresis system / dielectrophoresis system can be used at room temperature and pressure. The jointing of the nano carbon tube and the probe can avoid the lack of the conventional technology that requires the joining of the nano carbon tube and the probe under high temperature and pressure. Moreover, the present invention has never been seen in # 何 刊物 and before the application. In the public places, it is indeed novel and highly progressive. The only ones mentioned above are only the best practices of this book, and # cannot be used to limit the scope of the invention. Equivalent changes and modifications 'are still missing the essence of the present invention and do not depart from = the scope and scope of the invention', so they should be regarded as a step-by-step implementation of the present invention. [Schematic description] Electrophoresis (or dielectrophoresis) ) Silk to perform nano carbon tube two probe self-assembly Schematic diagram of the system architecture and method of the combination. Figure-A to Figure E are the process steps of the substrate with a probe 12 200523976 flow chart of the present invention. The figure number shown in the figure illustrates: 11 substrate 12 probe 121 tip 13 conductive layer 131 Conductive layer at the tip 14 Non-conductive material layer 20 Solution environment 21 Nano carbon tube 31 Electrode 41, 42 Conductive glue 43, 44 Connecting line 45 DC power source 46 Ultrasonic device 51 Substrate 52 Silicon nitride layer 521 Silicon nitride pillar 522 Probe 53 barrier layer 531 opening 54 conductive layer 55 non-conductive substance 13