TW201031586A - Carbon nanotube array sensor and method for making the same - Google Patents
Carbon nanotube array sensor and method for making the same Download PDFInfo
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201031586 , 六、發明說明： _ 【發明所屬之技術領域】 . 本發明涉及H雜感器及錄備方法，尤其涉及一種奈 . 米碳管陣列傳感器及其製備方法。 【先前技術】 自九十年代初以來，以奈米碳管為代表之奈米材料以其獨特 之結構和性質引起了人們極大之關注，請參見“Η_ microtubules of graphitic carbon^ , Sumio Iijima, Nature, vol. 354, ❹p56(1991)近歲年來’隨著奈米碳管及奈米材料研究之不斷深 入’其廣闊之應时來。如，由於其具有較大之比 表面積使其具有較好之吸附能力；由於奈米碳管之電子特性主 要係由其原子排狀結構決定的，故其受力之變化和化學吸附之 變化都會對電導率產生巨大之影響，其變化值可由電流訊號來檢 測。這些性質使得奈米碳管可作為微型傳感器，如，奈米生物傳 感斋、化學傳感器或奈米氣敏傳感器等。 2008年8月27日公開之一件中國專利申請第1〇1252145號 ⑩提供-種奈米碳管佩^，該奈米碳管傳感魏括奈米碳管和與 該奈米碳管連接之兩個電極。該奈米碳管傳感器之製備方法具體 為：首先，於奈米碳管之兩端塗上光刻膠；之後，通過光刻（電 子束或光學光刻）技術於奈米碳管兩端形成電極之形狀；最後， 再於奈米碳管上蒸鍍一層金屬層以形成電極，然後剝離去除多餘 之金屬層，於金屬電極與奈米碳管之間建立電連接。另，請參閱 Recent progress in carbon nanotube-based gas sensors^ , Ting201031586, VI. Description of the invention: _ [Technical field to which the invention pertains] The present invention relates to a H sensor and a recording method, and more particularly to a carbon nanotube array sensor and a method of fabricating the same. [Prior Art] Since the early 1990s, nanomaterials represented by carbon nanotubes have attracted great attention due to their unique structure and properties. See "Η_ microtubules of graphitic carbon^ , Sumio Iijima, Nature , vol. 354, ❹p56 (1991) in recent years, 'with the deepening of research on carbon nanotubes and nanomaterials', its broad response time. For example, it has better surface area due to its larger specific surface area. The adsorption capacity; because the electronic properties of the carbon nanotubes are mainly determined by their atomic row structure, the change of the force and the change of the chemical adsorption will have a huge impact on the conductivity, and the change value can be obtained by the current signal. These properties make the carbon nanotubes useful as micro-sensors, such as nano biosensing, chemical sensors or nano gas sensors. One of the Chinese patent applications published on August 27, 2008 is 1252452. No. 10 provides a kind of nano carbon tube, which is a carbon nanotube and a two electrode connected to the carbon nanotube. The preparation method of the carbon nanotube sensor is specifically First, a photoresist is applied to both ends of the carbon nanotube; after that, the shape of the electrode is formed at both ends of the carbon nanotube by photolithography (electron beam or optical lithography); finally, the carbon nanotube is further A metal layer is vapor-deposited to form an electrode, and then the excess metal layer is peeled off to establish an electrical connection between the metal electrode and the carbon nanotube. For further, please refer to Recent progress in carbon nanotube-based gas sensors^ , Ting
Zhang et al，Nanotechnology，Vol.19, p332001，（2008)，該文獻揭示 4 201031586 ’ 了另—種製作奈祕管傳感器之方法’具體為：首錢光刻技術 ，於第-電極表面上做出—層特定分佈之催化_膜，制化學氣 ， 相沈積或其他方法於催化劑圖形表面生長奈米碳管，所生長之奈 • 米碳管和第二電極電接觸即可。然，上述兩種方法中之光刻膠二 難以徹底清除，同時金屬電極與奈米碳管之間之結合性不好。 ^故，為解決上述問題，習知技術中揭露了另一種採用奈米碳 管陣列之傳感器結構，請參閱2008年1〇月8日公開之第 101281154號中國專利申請，該專利申請提供之奈米碳管陣列傳 ，器之、、’!〇構包括上下兩個電極及設置於上下兩個電極之間之奈 米石反管陣列。製作該奈米碳管陣列傳感器之方法為直接採用金衆 將奈米碳管陣雜合於電極之表面。該方法採用黏結劑黏結之方 法於奈米碳管兩端形成了金屬電極，從而克服了上述採用光刻技 術而引起之光刻雜以徹底清除之缺點，同時，也改善 官^極之間之結合力。然金漿與奈米碳管之浸潤性較差，使奈 米碳管與金電極之結合健不物，影響了 ^之靈敏度和精 度。Zhang et al, Nanotechnology, Vol. 19, p. 332001, (2008), which discloses 4 201031586 'Another method for making a Nei tube sensor' is specifically: First Money Lithography, on the surface of the first electrode The layer-specific distribution of catalysis _ membrane, chemical gas, phase deposition or other methods on the surface of the catalyst pattern growth of carbon nanotubes, the growth of the carbon nanotubes and the second electrode can be electrically contacted. However, in the above two methods, the photoresist 2 is difficult to be completely removed, and the bonding between the metal electrode and the carbon nanotube is not good. Therefore, in order to solve the above problems, another sensor structure using a carbon nanotube array is disclosed in the prior art. Please refer to the Chinese Patent Application No. 101281154 published on January 8th, 2008, which is provided by the patent application. The carbon nanotube array is transmitted, and the '! structure includes two upper and lower electrodes and a nanometer anti-tube array disposed between the upper and lower electrodes. The method of fabricating the carbon nanotube array sensor is to directly hybridize the carbon nanotube array to the surface of the electrode. The method uses a binder bonding method to form a metal electrode at both ends of the carbon nanotube, thereby overcoming the shortcomings of the above-mentioned lithography caused by the lithography technique, and simultaneously improving the relationship between the electrodes Binding force. However, the wettability of the gold paste and the carbon nanotubes is poor, so that the combination of the carbon nanotubes and the gold electrodes is not good, which affects the sensitivity and precision.
® 【發明内容J 有鑒於此，提供-種奈来碳管_佩狀其製備方法實為 必要’通麟製備方法峨狀奈米碳f_傳感^具有較高之 靈敏度和精度，且穩定性好。 -種奈米碳管陣列傳感器，其包括：—第—電極丨一第二電 極，》又置於帛|極舆第二電極之間的奈米碳管陣列，所述奈 米碳管陣列包括多個奈米礙管，且所述奈米礙管陣列包括一第一 端和與該第-端相背的—第二端；至少—第—導電金屬層，所述 201031586 ，第^電極與奈米碳管_的第1通過該第—導電金屬層電連 :接’至夕一第一導電金屬層，所述第二電極與奈来碳管陣列的第 • 1通第二導電金屬層電連接；其中，該奈米碳管陣列傳感 •器進步包括在奈米碳管陣列的第-端沈積形成的-第-親金 屬層，和在該奈来碳管陣列的第二端沈積形成的一第二親金屬 層該第-親金屬層與上述第一導電金屬層接觸並電連接該第 二親金屬層與上述第二導電金屬層接觸並電連接。 —種奈料管_傳感n的製備方法，包括：提供一包括多 個奈米碳管的奈米碳管_，所述奈米碳管陣航括-第-端和 ，第端相#的-第二端；在所述奈米碳管陣觸第—端形成一 弟-親金屬層；提供一第一電極；形成至少一第一導電金屬層， 以使該第-導電金屬層與所述第一親金屬層接觸並電連接，從而 將奈米碳管陣列第一端通過該第一導電金屬層與第一電極電連 接4所述奈米碳管降列的第二端形成一第二親金屬層；提供一 第4極；形成至少-第二導電金屬層，使該第二導電金屬層與 ❷所述第二親金屬層接觸並電連接，從而將奈米碳管陣列的第二端 通過該第二導電金屬層與帛二電㈣連接。 種奈米碳管陣列傳感器，其包括：-第-電極；—第二電 極1一設置於第—電極與第二電極之間的奈米碳f陣列，所述奈 t碳管陣列包括多個奈米碳管且所述奈米碳管陣列包括一第一 的—第二端；其中’該奈米碳管陣列傳感器 V 〇括，一與第一電極電連接的第一導電金屬層，—與 電極電連接的第二導電金屬層，所述第—導電金屬層和第二導 金屬層的材料的溶點分別低於第一電極和第二電極材料的溶 6 201031586 ‘’在不米石厌答ρ車列的第一端沈積开》成的一第一親金屬層，及在 :該奈米碳管陣列的第二端沈積形成的第二親金屬層，該第一親金 .屬層與上述第一導電金屬層接觸並電連接，該第二親金屬層與上 •述第二導電金朗_並電連接，所述第-親金屬層和第二親金 . 屬層的材料域、把、鉻、鎳及鈦中的-種或幾種的組合。 • —種奈米碳管_傳感器的製備方法，包括：提供一包括多 個奈米碳管的奈米碳管_，所述奈米碳管_包括—第一端和 /、第端相♦的—第二端；在所述奈米碳管陣列的第—端形成一 第一親金屬層，該第一親金屬層的材料為鎂、把、鉻、錄及鈦中 的一種或幾種的組合；提供—第—電極；在第—電極的表面形成 一第一導電金屬層，該第—導電金屬層的材料的熔點低於第一電 極的材料的熔點；加熱該第一導電金屬層使其姐融狀態下分別 與奈米碳管陣列的第一端和第一電極相結合；在所述奈来碳管陣 列的第二端形成—第二親金屬層；提供—第二電極·在第二電極 的表面形成-第二導電金屬層，該第二導電金屬層的材料的炼點 ❹低料二電㈣觀點；及加触第二導電金屬層使1在炫 融狀態下分別與奈米碳管陣列的第二端和第二電極相结合。 一種奈米碳管_傳感騎製備方法，包括：提供一包 =米碳管的奈米碳管_，所述奈米碳管陣航括—第一端和 二-端相背m在所述奈米碳料觸第—端形 第一親金制，該第-驗朗騎料祕， 的_種或幾種敝合；提供-第―電極；在奈米碳管陣列的2 一第—導電金屬層，該第—導電金屬層的材料的溶點低於 第電極的材料的熔點；加熱該第一導電金屬層使其麵融狀態 7 201031586 =別與第-電極和奈米碳管陣列的第—端相結合；在所述奈米 碳管陣列的第二端形成—第二親金屬層；提供—第二電極；在奈 米碳管陣列的第二端形成-第二導電金屬層，該第二導電金屬層 的材料的熔點低於第二電___點；及加熱該第二導電金 屬層使其在熔融狀態下與第二電極和奈米碳管陣列的第二端相 結合。 Ο -種奈米碳管_傳感n的製備方法，包括：提供一包括多 個奈米碳管的奈米碳管陣列，所述奈米碳管陣列包括—第一端和 與第-端相背m在所述奈米碳管_的第—端形成一 第-親金屬層，該第-親金屬相材料域，、鉻、錦及欽中 的-種或幾種的組合；提供—第—電極；在第—電極的表面形成 -第-導電金屬層，該第-導電金屬層的材料的熔點低於第一電 極的材料的賴；加_第—導電金屬層使其麵綠態下分別 與奈来碳管_的第-端和第1極城合；在所述奈米碳管陣 列的第二端形成-第二親金屬層；提供一第二電極；在奈米碳管 陣列的第二端形成-第二導電金屬層，該第二導電金屬層的材料 的溶點低於第二電極的材料的溶點；及加熱該第二導電金屬層使 其在溶融狀態下與第二電極和奈米碳管陣列的第二端相結合曰。 相較於先前技術’本發明提供之奈米碳管陣列 備方法具扣下伽：紗錢管㈣傳絲之 需^ 用導電祕使奈料管料—_和第二電極實現電連接:2 製備之奈轉管_傳❹之奈轉管之第1和第二端分別 沈積有第-親金顧和第二親金屬層，且該第-親金屬層和 親金屬層補與奈米碳管具雜好之浸雜，且鄕—導電材料 8 201031586 ，層和第二導電材料也有良好之浸潤性’故，該奈米碳管陣列與第 :一電極和第二電極結合物’保證了奈米碳管陣列傳感器工作之 •可靠性和穩定性’提咼了該跋置之靈敏度。 【實施方式】 以下將結合附圖詳細說明本發明實施例提供之奈米碳管陣 列傳感器及其製備方法。 請參閱圖1 ’本發明第-實施例提供—種奈米碳管陣列傳感 器10’該奈米碳管陣列傳感器10包括第一電極η、第二電極 ❹12、設置於第一電極η和第二電極12之間之奈米碳管陣列13， 一第一導電金屬層14及一第二導電金屬層15。 該第一電極11和第二電極12通過奈米碳管陣列13間隔設 置’該第一電極11和第二電極12為導電性材料，如銅、鋁、金、 鐵及銀等中之一種或者幾種之合金，本實施例為銅。該第一電極 11和第·一電極12之厚度為1微米〜20微米。 所述的奈米碳管陣列13包括多個沿相同方向排列的奈米碳 ❹管130 ’每一奈米碳管130包括一第一端132和與第一端132相 背的一第二端134且該第一端132和第二端134的表面分別沈積 有第一親金屬層136和第二親金屬層138。該奈米碳管13〇的第 一端132通過第一導電金屬層14與第一電極u電連接，該奈米 碳管130的第二端134通過第二導電金屬層15與第二電極12電 連接。該各個奈米碳管13〇的第一端132位於奈米碳管陣列13 的同一端，該所有奈米碳管130的第一端132可以理解為奈米碳 管陣列13的第一端（圖未示），該各個奈米碳管13〇的第二端 134位於奈米碳管陣列13的同一端，該所有奈米碳管13〇的第 9 201031586 , 二端134可理解為奈米碳管陣列13的第二端（圖未示）。 :曰該奈米碳管陣列13通過化學氣相沈積法或其他方法生長獲 .得。該奈米碳管陣列13包括複數彼此基本平行之奈米碳管13〇。 .該奈米碳管130包括單壁奈米碳管、雙壁奈米碳管或多壁夺米礙 管中之-種或者多種。該單壁奈米碳管之直徑為〇5奈米〜5〇奈 米，該雙壁奈米碳管之直徑為L〇奈米〜5〇奈米，該多壁奈米碳 管之直徑為1.5奈来〜50奈求。本實施例選用多壁奈米碳管。該 鲁奈米碳管陣列I3之高度為1〜8〇〇微米。 該第親金屬層136和第二親金屬層138可通過電鍍、化學 鍍或磁控機鏡之方法分別沈積於奈米碳管陣列I3中奈来碳管 山之第4 132和第二端134 〇具體地，該第一端13之和第二 端134 ^奈米碳管陣列13中奈米碳管130之端面及從端面至距 離=米碳管13〇之端面〇〇1微米〜5〇微米之間之奈米碳管咖 之目壁表面’該第一親金屬層⑽和第二親金屬層⑽分別部分 或王她覆該第-端132和第二端说。該第一親金屬層攻和 ❷第一親金屬層I38之材料分別與奈米碳管時第一導電金屬層 ^及第—導電金屬層15之材料具有良好之浸潤性，使該奈米碳 I⑽與第—導電金屬層14和第二導電金屬層15可更好地結 :從而保持良好之電連接。該第一親金屬層ι3ό和第二親金屬 =38之材料可選用把、鉻、錄、欽及鎂中之一種或其合金。該 ，親金屬層136和第二親金屬層138之厚度為〇5奈米〜5〇奈 米。 該第一導電金屬層14設置於第一電極^鄰近於奈米琰管陣 歹J 13之第一端132之表面，該第二導電金屬層15設置於第二電 201031586 極12鄰近於奈米碳管陣列13之第二端134之表面。進一步地， 帶有第一親金屬層136之奈米碳管13〇之第一端132可部分或全 部极入該第-導電金屬層14中，帶有第二親金屬層138之奈米 碳管130之第二端134可部分或全部嵌入該第二導電金屬層15 中’從而使該第一親金屬層136及第二親金屬層138分別與該第 -導電金屬層14及該第二導電金屬層15接觸並電連接，進而使 該奈米碳管陣列13與該第一電極11及第二電極12電連接。 該第-導電金屬層14和第二導電金屬層15之材料於溶融態 時分別與第—電極11和第二電極12之材料具有很好之浸潤性， 該材料可選用熔點較低之金屬，如銦、錫、銅、銦、鉛、銻、金、 銀和錢中之一種或者幾種之組合。同時該材料之溶點需低於第一 電極11或第二電極12之溶點，因於製備過程中該第一導電金屬 層14和第二導電金屬層15會被熔融並於此熔融狀態下分別與第 1極11和第二電極12黏結，若該材料溶點高於第一電極u 或第二電極12之材料之魅，則於雜之過程中該第—電極u 籲 或第二電極12也會被溶融，故第一導電金屬層14和第二導電金 屬層15分別選用溶點低於第一電極11和第二電極12之祕合 確保於黏結之過程中第一電極u和第二電極玉 融 另’該第—導電金屬層14和第二導電金屬層15之厚 奈米:由輯第-導電金衫14和第二料金^f5^900 僅與第-電極U和第二電極12之浸潤 ’ 金屬層136釦笙如入痛 阳且也與第一親 坧t ^ 屬層138之浸潤性較好，從而可使第-電 與第一親金屬層136更好地結合，第二電極12鱼 屬層138更好地結合。 ，、第一親金 11 201031586 本實施例之奈米碳官陣列傳感器10進一步包括·支擇體 16’該支撐體16設置於第一電極11和第二電極12之間，該支 禮體16之高度等於第一電極11和苐二電極12之間奈米碳管陣 列13之高度，該支撐體16用於支撐第一電極u和第二電極12, 可確保奈米碳管陣列13不致被損壞或者彎曲，從而提高該奈米 碳管陣列13之使用壽命。該支撐體16之材料為一絕緣材料，如 玻璃、陶瓷等。 進一步地，本實施例中之奈米碳管陣列傳感器1〇中之奈米® [Inventive content J In view of this, it is necessary to provide a kind of Nailai carbon tube_Pei-like preparation method.] The general preparation method of Tonglin has a high sensitivity and precision, and is stable. Good sex. a carbon nanotube array sensor comprising: a first electrode, a second electrode, and an array of carbon nanotubes disposed between the second electrode of the crucible, the carbon nanotube array comprising a plurality of nanoparticles obstructing the tube, and the nano-tube array includes a first end and a second end opposite the first end; at least a first conductive metal layer, the 201031586, the second electrode The first portion of the carbon nanotube _ is electrically connected through the first conductive metal layer: a first conductive metal layer, and a second conductive metal layer of the second electrode and the carbon nanotube array Electrical connection; wherein the carbon nanotube array sensor advancement comprises a -first-electrophilic layer deposited at the first end of the carbon nanotube array, and deposited at the second end of the carbon nanotube array Forming a second metal-philic layer, the first-electrophilic layer is in contact with the first conductive metal layer and electrically connected to the second metal-friendly layer and in contact with the second conductive metal layer and electrically connected. - a method for preparing a raw material tube - sensing n, comprising: providing a carbon nanotube comprising a plurality of carbon nanotubes, the carbon nanotube array comprising - the first end and the first end phase Forming a second-electrophilic layer at the first end of the carbon nanotube array; providing a first electrode; forming at least one first conductive metal layer to enable the first conductive metal layer The first metal-philic layer is in contact with and electrically connected, so that the first end of the carbon nanotube array is electrically connected to the first electrode through the first conductive metal layer, and the second end of the carbon nanotube is delimited. a second metal-philic layer; providing a fourth electrode; forming at least a second conductive metal layer, contacting the second conductive metal layer with the second metal-philic layer and electrically connecting, thereby arranging the carbon nanotube array The second end is connected to the second electric (four) through the second conductive metal layer. a carbon nanotube array sensor comprising: - a first electrode; - a second electrode 1 - a nano carbon f array disposed between the first electrode and the second electrode, the nano carbon nanotube array comprising a plurality of a carbon nanotube and the carbon nanotube array includes a first-second end; wherein the carbon nanotube array sensor V includes a first conductive metal layer electrically connected to the first electrode, a second conductive metal layer electrically connected to the electrode, wherein a melting point of the material of the first conductive metal layer and the second conductive metal layer is lower than that of the first electrode and the second electrode material respectively a first metal layer deposited on the first end of the ρ 车 train, and a second metal layer formed on the second end of the carbon nanotube array, the first nucleophile The layer is in contact with and electrically connected to the first conductive metal layer, and the second metalophilic layer is electrically connected to the second conductive metal galvanic layer, and the material of the first metal-philic layer and the second nucleophilic layer a combination of a species, a combination of a chromium, a nickel, and a titanium. • A method for preparing a carbon nanotube sensor, comprising: providing a carbon nanotube comprising a plurality of carbon nanotubes, the carbon nanotube _ comprising - a first end and/or a first end phase ♦ a second end; forming a first metalophilic layer at the first end of the carbon nanotube array, the first metal layer is made of one or more of magnesium, palladium, chromium, and titanium a combination of a first electrode; a first conductive metal layer formed on a surface of the first electrode, the material of the first conductive metal layer having a lower melting point than a material of the first electrode; heating the first conductive metal layer Combining with the first end of the carbon nanotube array and the first electrode respectively; forming a second metal-philic layer at the second end of the carbon nanotube array; providing a second electrode Forming a second conductive metal layer on the surface of the second electrode, the material of the second conductive metal layer is lower than the second electric (four) point of view; and the second conductive metal layer is touched to make 1 in the state of being fused The second end of the carbon nanotube array is combined with the second electrode. A carbon nanotube_sensing riding preparation method comprises: providing a carbon nanotube tube of a package=m carbon tube, wherein the first carbon nanotube array comprises a first end and a second end end The nano carbon material touches the first end of the first pro-gold system, the first - chronograph riding secret, the _ species or several combinations; the supply - the first electrode; the second in the carbon nanotube array a conductive metal layer, the material of the first conductive metal layer having a melting point lower than a melting point of the material of the first electrode; heating the first conductive metal layer to be in a surface-melting state 7 201031586 = other than the first electrode and the carbon nanotube The first end of the array is combined; a second metal-philic layer is formed at the second end of the carbon nanotube array; a second electrode is provided; and a second conductive metal is formed at the second end of the carbon nanotube array a layer, the material of the second conductive metal layer has a melting point lower than a second electric ___ point; and heating the second conductive metal layer to be in a molten state with the second electrode and the second end of the carbon nanotube array Combine. A method for preparing a nanocarbon tube_sensing n, comprising: providing a carbon nanotube array comprising a plurality of carbon nanotubes, the carbon nanotube array comprising - a first end and a first end Forming a first-electrophilic layer at the first end of the carbon nanotube _, the first-philophilic phase material domain, a combination of chrome, brocade, and chin; or a combination of several; a first electrode; a first conductive metal layer formed on the surface of the first electrode, the material of the first conductive metal layer having a lower melting point than the material of the first electrode; and the first conductive metal layer to be green Lower with the first end and the first pole of the carbon nanotubes respectively; forming a second second metal layer at the second end of the carbon nanotube array; providing a second electrode; in the carbon nanotube Forming a second conductive metal layer on the second end of the array, the material of the second conductive metal layer having a melting point lower than a melting point of the material of the second electrode; and heating the second conductive metal layer to be in a molten state The second electrode and the second end of the carbon nanotube array are combined. Compared with the prior art, the method for preparing a carbon nanotube array provided by the present invention has the function of deducting the gamma: the yarn tube (four), and the electrical connection is made by using the conductive material to make the electrical connection: 2 and the second electrode: 2 The first and second ends of the prepared nematic tube, the first and second ends, respectively, are deposited with a first-parent and a second metal-philic layer, and the first-electrophilic layer and the metal-friendly layer complement the nanocarbon The tube is miscellaneous, and the crucible-conductive material 8 201031586, the layer and the second conductive material also have good wettability, so the carbon nanotube array and the first electrode and the second electrode combination ensure The reliability and stability of the operation of the carbon nanotube array sensor improves the sensitivity of the device. [Embodiment] Hereinafter, a carbon nanotube array sensor and a method for fabricating the same according to embodiments of the present invention will be described in detail with reference to the accompanying drawings. Referring to FIG. 1 , a carbon nanotube array sensor 10 is provided in a first embodiment of the present invention. The carbon nanotube array sensor 10 includes a first electrode η, a second electrode ❹12, and is disposed on the first electrode η and the second. A carbon nanotube array 13 between the electrodes 12, a first conductive metal layer 14 and a second conductive metal layer 15. The first electrode 11 and the second electrode 12 are spaced apart by the carbon nanotube array 13. The first electrode 11 and the second electrode 12 are electrically conductive materials, such as one of copper, aluminum, gold, iron, and silver. Several alloys, this embodiment is copper. The first electrode 11 and the first electrode 12 have a thickness of 1 μm to 20 μm. The carbon nanotube array 13 includes a plurality of carbon nanotube tubes 130 arranged in the same direction. Each of the carbon nanotube tubes 130 includes a first end 132 and a second end opposite the first end 132. 134 and the surfaces of the first end 132 and the second end 134 are respectively deposited with a first metal-friendly layer 136 and a second metal-friendly layer 138. The first end 132 of the carbon nanotube 13 is electrically connected to the first electrode u through the first conductive metal layer 14. The second end 134 of the carbon nanotube 130 passes through the second conductive metal layer 15 and the second electrode 12. Electrical connection. The first end 132 of each of the carbon nanotubes 13A is located at the same end of the carbon nanotube array 13, and the first end 132 of all the carbon nanotubes 130 can be understood as the first end of the carbon nanotube array 13 ( The second end 134 of each of the carbon nanotubes 13A is located at the same end of the carbon nanotube array 13, and the 9th 201031586 of the all carbon nanotubes 13〇, the two ends 134 can be understood as nanometers. The second end of the carbon tube array 13 (not shown). : The carbon nanotube array 13 is obtained by chemical vapor deposition or other methods. The carbon nanotube array 13 includes a plurality of carbon nanotubes 13 that are substantially parallel to each other. The carbon nanotube 130 includes one or more of a single-walled carbon nanotube, a double-walled carbon nanotube, or a multi-walled nanotube. The diameter of the single-walled carbon nanotube is 〇5 nm to 5 〇 nanometer, and the diameter of the double-walled carbon nanotube is L 〇 nanometer ~ 5 〇 nanometer, and the diameter of the multi-walled carbon nanotube is 1.5 Nai ~ 50 Naiqiu. In this embodiment, a multi-walled carbon nanotube is used. The Lunene carbon nanotube array I3 has a height of 1 to 8 Å. The first affinity metal layer 136 and the second metalophilic layer 138 may be deposited on the 4132 and the second end 134 of the carbon nanotube array I3 in the carbon nanotube array I3 by electroplating, electroless plating or magnetron mirroring, respectively. Specifically, the first end 13 and the second end 134 of the carbon nanotube array 13 have an end face of the carbon nanotube 130 and an end face from the end face to the distance = m carbon tube 13 〇〇 1 μm to 5 〇 The first pro-metal layer (10) and the second metal-friendly layer (10) are partially or partially covered by the first end 132 and the second end, respectively. The materials of the first metal-philic layer and the first metal-philic layer I38 have good wettability with the materials of the first conductive metal layer and the first conductive metal layer 15 respectively, so that the nano carbon I(10) and the first conductive metal layer 14 and the second conductive metal layer 15 can be better bonded: thereby maintaining a good electrical connection. The material of the first metal-compatible layer ι3 ό and the second affinic metal = 38 may be selected from the group consisting of chrome, chrome, chrome, and magnesium or an alloy thereof. The thickness of the metal-philic layer 136 and the second metal-philic layer 138 is 〇5 nm to 5 〇N. The first conductive metal layer 14 is disposed on a surface of the first electrode ^ adjacent to the first end 132 of the nano tube array J 13 , and the second conductive metal layer 15 is disposed on the second electrode 201031586 12 adjacent to the nano pole The surface of the second end 134 of the carbon tube array 13. Further, the first end 132 of the carbon nanotube 13 having the first metal-friendly layer 136 may partially or completely enter the first conductive metal layer 14 and the nano-carbon with the second metal-friendly layer 138. The second end 134 of the tube 130 may be partially or completely embedded in the second conductive metal layer 15 such that the first metal-friendly layer 136 and the second metal-friendly layer 138 are respectively associated with the first conductive metal layer 14 and the second The conductive metal layer 15 is in contact with and electrically connected, and the carbon nanotube array 13 is electrically connected to the first electrode 11 and the second electrode 12. The materials of the first conductive metal layer 14 and the second conductive metal layer 15 have good wettability with the materials of the first electrode 11 and the second electrode 12 respectively in the molten state, and the material may be a metal having a lower melting point. Such as one or a combination of indium, tin, copper, indium, lead, antimony, gold, silver and money. At the same time, the melting point of the material needs to be lower than the melting point of the first electrode 11 or the second electrode 12, because the first conductive metal layer 14 and the second conductive metal layer 15 are melted and melted in the molten state during the preparation process. Bonding to the first pole 11 and the second electrode 12 respectively, if the melting point of the material is higher than the material of the first electrode u or the second electrode 12, the first electrode or the second electrode is in the process of mixing 12 will also be melted, so that the first conductive metal layer 14 and the second conductive metal layer 15 respectively have a melting point lower than that of the first electrode 11 and the second electrode 12 to ensure the first electrode u and the first in the process of bonding The two-electrode jade melts the thickness of the first conductive metal layer 14 and the second conductive metal layer 15: the first-conducting gold-plated 14 and the second-material gold-f5^900 are only connected to the first electrode U and the second The infiltration of the electrode 12 'the metal layer 136 is as good as the pain and is also better in wettability with the first relative t ^ genus layer 138, so that the first electric and the first electrophilic layer 136 can be better combined. The second electrode 12 fish layer 138 is better bonded. , the first parent gold 11 201031586 The nano carbon official array sensor 10 of the present embodiment further includes a support body 16 ′. The support body 16 is disposed between the first electrode 11 and the second electrode 12 , the support body 16 The height is equal to the height of the carbon nanotube array 13 between the first electrode 11 and the second electrode 12. The support 16 is used to support the first electrode u and the second electrode 12, thereby ensuring that the carbon nanotube array 13 is not blocked. Damage or bending, thereby increasing the useful life of the carbon nanotube array 13. The material of the support body 16 is an insulating material such as glass, ceramics or the like. Further, the nano tube in the carbon nanotube array sensor 1 in this embodiment
碳管130表面可包括一修飾層（圖未標），該修飾層可提高該奈 米碳管陣列傳感器10探測之準確性和靈敏度。該修飾層之材料 可為鈀、銘或金等，不同材料之修飾層可分別準確探測不同氣體 之含量’如表面修財—独可提高探職氣和找之含量準確 度。 以下將結合附圖詳細說明本發明第一實施例提供之奈米碳 管陣列傳感器K)之製備方法。請參_ 2及圖3，且體包括以 下步驟： 步驟一：提供一奈米碳管陣歹13，該奈米碳管陣列13中奈 米碳管130包括第1 132和第二端134。 太虫^實⑯例提供之奈米碳管_ 13中之奈米碳管⑽為單壁 為，H碳管或多壁奈米碳管。優選地，該奈米碳管 陣列13讀=奈米。本實施财’超順排奈米碳管 触-基底=27_她料，細鱗包括：⑷ 成有氧化層之獅Ρ^Ν轉基底，或選用形 -本實施例優選為採用4英寸之矽基底；（b) 12 201031586 :於基底17表面均勻地形成—催化㈣，該催化劑層材料可選用 *鐵（F〇、鈷（Co)、鎳⑽）或其任意組合之合金之一；（c)將 ， 上述形成有催化劑層之基底Π於700~900〇C之空氣中退火約30 .分鐘〜90分鐘；⑷將處理過之基底17置於反應爐中，於保護 .M環境下加細〜74Gt：，然後通人碳職體反應約5〜3〇 賴，生長制超禱奈来碳管_ 13，其高度為i〜腦微米。 該超順排奈米碳管陣列13為由複數彼此平行且垂直於基底17生 長之奈米碳管130形成。通過控制超麵絲碳管陣列13之生 ❹長條件，該超順排奈米碳管陣列13中基本不含有雜質，如無定 型碳或殘留之催化劑金屬顆粒等。該超順排奈米碳管陣列13中 之奈米碳管ISO彼此通過凡德瓦爾力吸引。且所述奈米碳管陣列 13包括第一端（圖未示）和與第一端相背的第二端（圖未示），所 述奈米碳管陣列13的第一端包括多個奈米碳管13〇的第—端 132 ’其為遠離生長基底π的一端。所述奈米碳管陣列13的第二 端包括多個奈米壤管D0的第二端m，其為靠近生長基底17的 ©一端。 本實施例中碳源氣可選用乙块、乙烯、甲烧等化學性質較活 潑之碳氫化合物，本實施例優選之碳源氣為乙炔；保護氣體為氮 氣或惰性氣體’本實施例優選之保護氣體為氬氣。 可理解地，本實施例提供之奈米碳管陣列13不限於上述製 備方法。也可為石墨電極恒流電弧放電沈積法、鐳射蒸發沈積法 等。 步驟二··於該奈米碳管陣列13中奈米碳管13〇之第一端132 之表面形成一第一親金屬層136。 13 201031586 魯 該步驟為_雜、化學骸者雜雜法於奈米碳管陣列 13中奈米奸130之第一端132之表面製備一第一親金屬層 =6。本實施例制驗之方法，具體包括以下步驟：將奈米碳 管陣列13中奈米碳管130之第一端132浸入一酸溶液中進行酸 化處理以去除奈米碳管13〇之第一端132表面之殘留物，如催化 劑等。該酸溶液可為硫酸、硝酸和鹽酸中之一種或者幾種，本實 施例選用硫酸和硝酸之混合溶液，其f量比為3:1 ;提供一電二 液，該電舰包括-金屬鹽，該金屬鹽可為硫魏、氯化把或硫 酸鉻等，本實崎為氣她；將經過纟4化之奈米碳管P車列13中 奈米故官130之第一端132浸入上述電鑛液中作為陰極，再將一 陽極浸入電鑛液中，通入一定大小之電流使奈米碳管13q反應— 段時間’從而於奈米碳管13〇浸入端，即第一端132之表面形成 一層第-親金屬層136 ;取出奈米碳管陣列m並將其供乾，該 洪乾方式可採用低溫加熱等方法。 上述步驟中陽極之材料可選用化學活潑性較第一親金屬層 Ο I36差之材料或者與第一親金屬層136相同之材料，如金、石墨、 铑把H、鈦或鉻等。本實施例優選為與第一親金屬層 同之材料，如t。因於施加電流且電鑛液之金屬開始於奈 米碳管130之表面沈積時，電錢液中之金屬離子會被消耗且數目 下降’此時同樣數目之陽極金屬離子便溶解於溶液中，從而 電鍍液中金屬離子之短缺。 本實施例中該氣化鈀於電鍍液中之質量百分含量為 2〇^〜35% ’電鍍液之溶劑為水，該電鍍液之PH值為3.5〜6。該 電I·為直机電，電流密度為毫安培/平方厘米，通電時 201031586 間為5〜10分鐘。 本實施中之電鍍液可進一步包括一導電鹽溶液，可選用氣化 銨，其質量百分含量為3%，該導電鹽之存在可進一步提高電鍍 液之電導率。The surface of the carbon tube 130 may include a finishing layer (not shown) which enhances the accuracy and sensitivity of the carbon nanotube array sensor 10 detection. The material of the modifying layer can be palladium, inscription or gold, etc., and the modifying layers of different materials can accurately detect the content of different gases respectively, such as surface repairing, which can improve the accuracy of the exploration gas and the content of the content. Hereinafter, a method of preparing the carbon nanotube array sensor K) according to the first embodiment of the present invention will be described in detail with reference to the accompanying drawings. Referring to _ 2 and FIG. 3, the body comprises the following steps: Step 1: A carbon nanotube array 13 is provided. The carbon nanotube 130 in the array of carbon nanotubes 13 includes a first 132 and a second end 134. The carbon nanotubes (10) provided by the 16 cases of the nano-tubes of the worms are single-walled, H-carbon tubes or multi-walled carbon tubes. Preferably, the carbon nanotube array 13 reads = nano. The implementation of the 'super-semi-nano carbon nanotube touch-substrate=27_ her material, fine scales include: (4) oxidized layer of the lion's Ν Ν 基底, or optional shape - this embodiment is preferably 4 inches矽 substrate; (b) 12 201031586: uniformly formed on the surface of the substrate 17 - catalysis (4), the catalyst layer material may be selected from * iron (F 〇, cobalt (Co), nickel (10)) or any combination of alloys; c) annealing the substrate on which the catalyst layer is formed in an air of 700 to 900 〇C for about 30 minutes to 90 minutes; (4) placing the treated substrate 17 in a reaction furnace and adding it under the protection of the .M environment. Fine ~ 74Gt:, then pass the carbon body reaction about 5 ~ 3 〇, the growth system of super prayer Nai carbon tube _ 13, its height is i ~ brain micron. The super-sequential carbon nanotube array 13 is formed of a plurality of carbon nanotubes 130 which are parallel to each other and which grow perpendicular to the substrate 17. The super-sequential carbon nanotube array 13 contains substantially no impurities, such as amorphous carbon or residual catalyst metal particles, by controlling the growth conditions of the ultra-finished carbon nanotube array 13. The carbon nanotubes ISO in the super-sequential carbon nanotube array 13 are attracted to each other by Van der Waals force. The carbon nanotube array 13 includes a first end (not shown) and a second end opposite the first end (not shown), and the first end of the carbon nanotube array 13 includes a plurality of The first end 132' of the carbon nanotube 13 is the end away from the growth substrate π. The second end of the array of carbon nanotubes 13 includes a second end m of a plurality of nano-tubes D0 which is adjacent to the © end of the growth substrate 17. In the present embodiment, the carbon source gas may be a chemically active hydrocarbon such as an ethylene block, an ethylene or a methyl bromide. The preferred carbon source gas in this embodiment is acetylene; the protective gas is nitrogen or an inert gas. The shielding gas is argon. It is to be understood that the carbon nanotube array 13 provided in the present embodiment is not limited to the above-described preparation method. It can also be a graphite electrode constant current arc discharge deposition method, a laser evaporation deposition method, or the like. Step 2: A first metal-friendly layer 136 is formed on the surface of the first end 132 of the carbon nanotube 13 in the carbon nanotube array 13. 13 201031586 Lu This step is to prepare a first metal layer = 6 on the surface of the first end 132 of the nanoparticle 130 in the carbon nanotube array 13 . The method for testing in this embodiment specifically includes the following steps: immersing the first end 132 of the carbon nanotube 130 in the carbon nanotube array 13 in an acid solution for acidification to remove the first carbon nanotube 13 A residue on the surface of the end 132, such as a catalyst or the like. The acid solution may be one or more of sulfuric acid, nitric acid and hydrochloric acid. In this embodiment, a mixed solution of sulfuric acid and nitric acid is used, and the ratio of f is 3:1; and an electric two liquid is provided, the electric ship includes -metal salt The metal salt may be sulphur, chlorinated or chromic sulphate, etc., and Saki is mad at her; the immersed first end 132 of the nanometer 130 in the 奈4 carbon nanotube P train 13 In the above electric ore liquid as a cathode, an anode is immersed in the electric ore liquid, and a current of a certain size is passed to cause the carbon nanotube 13q to react for a period of time, thereby immersing the carbon nanotube 13 in the end, that is, the first end A surface of the first metal-philic layer 136 is formed on the surface of 132; the carbon nanotube array m is taken out and dried, and the flooding method may be a method such as low-temperature heating. In the above step, the material of the anode may be selected from materials having a chemical reactivity lower than that of the first metal layer Ο I36 or the same material as the first metal layer 136, such as gold, graphite, ruthenium H, titanium or chromium. This embodiment is preferably a material such as t that is the same as the first metalophilic layer. When a current is applied and the metal of the electro-mineral liquid begins to deposit on the surface of the carbon nanotube 130, the metal ions in the electro-money liquid are consumed and the number is decreased. At this time, the same number of anode metal ions are dissolved in the solution. Thus, there is a shortage of metal ions in the plating solution. In this embodiment, the mass percentage of the vaporized palladium in the plating solution is 2 〇 3 to 35% Å. The solvent of the plating solution is water, and the pH of the plating solution is 3.5 to 6. The electric current is direct electromechanical, the current density is mA/cm 2 , and the power is between 10 and 10 minutes during 201031586. The plating solution in the present embodiment may further comprise a conductive salt solution, optionally using ammonium sulfate, the mass percentage of which is 3%, and the presence of the conductive salt further increases the conductivity of the plating solution.
進一步地，本實施例之電鍛液可包括一緩衝劑，該緩衝劑可 選用硫酸鋁和硼酸之混合溶液，該硫酸鋁之質量百分含量為 3% ’硼酸之質量百分含量為1% ’該緩衝劑可用來穩定電鍍液之 PH值，特別係可減緩陰極表面因析氮而引起之電链液pH值升 高’也有利於提高電鍍液之分散能力和鍍層之穩定性。 步驟三：提供一第一電極11，於第一電極u與奈米碳管陣 列13中奈米碳管130之第一端132之間形成一第一導電金屬層 14，將奈米碳管陣列13中奈米碳管13〇之第一端132通過該第 一導電金屬層14與第一電極連接。 該電連接方法可為於第一電極U之表面形成一第一導電金 屬層14，通過該第一導電金屬層14使第一電極u與奈米碳管 130之第一端；|32電連接，具體包括以下步驛： 11 11 百先，提供一第一電極u，該第一電極u之厚度為玉微米 〜2〇微米’該第—電極之面積大於等於奈米碳管陣列13之端部 ^積。於該第—電極11之表面形成-第-導電金屬層14,具體 ^通過磁控濺_、物理_法或化學氣減積法於第一電極 之表面鍍覆一層第一導電金屬層I4，本實施例為於第-電極 11 2面通细控峨魏上第—導電金屬層14。該第一電極 之材料可為鋼、 導電金屬層Um 鐵、金或銀等’本實施例為銅’該第， 才料之炫融態與第一電極11之材料具有很好之 15 201031586 :浸潤性，該金屬可選用熔點較低之金屬，如銦、錫、銅、鋼、仏、 :銻、金、銀和財之-種或料種德合，同時該金屬材料之^ 點需低於第一電極11之溶點。 •、 其次，加熱上述表面鍍有第一導電金屬層14之第一 11 ’使第一導電金屬層η熔融。 最後，將上述有第-親金屬層136之奈米碳管陣列13中太 米碳管m之第-端m與上述已熔融之第一導電金屬層w ^ •表面相接觸。進-步地，可使奈米碳管陣列13中奈米碳管咖 之第-端m全部插入該溶融之第一導電金屬層w巾。將該溶 融之第一導電金屬層14快速冷卻，從而使奈米碳管130牢固地 固定於第一導電金屬層14之上。由於奈米碳管130與第-親金 屬層136具有較好浸潤性，同時該第-親金屬層136與第-導電 金屬層I4也具有較好之浸潤性，故將第一導電金屬層^作為奈 米碳管130與第-電極u之間之過渡層可保證奈米碳管13〇 ^ 第-電極11之間電連接牢固，避免第一電極u與奈米碳管13〇 鲁之間之電接觸不良，或者奈求碳管咖從第一電極u中被剝離， 保持了整個傳感器性能之穩定性和靈敏性。 步驟四：於奈来碳管陣列13中奈米碳管13〇之第二端132 之表面形成一第二親金屬層138。 首先’將步驟二中之奈米碳管陣列13從基底17中剝離，由 於該不米碳管陣列13中奈米碳管13〇之第一端已經固定於 第一電極11上，而奈米碳管陣列13與基底17之結合力較弱， 故只需很小的力即可把奈米碳管陣列ls從基底1?上剝離下來， 而且不致損壞奈米碳管陣列13之形態，從而使奈米碳管陣列13 16 201031586 中奈米被管130之第一端134成為一自由端。其次，於談太、， 管陣列13中奈米碳管130之第二端134之表面形成一第 屬層138 ’該步驟同步驟二基本相同。 —親主 該步驟可進-步包括於軸第二親金屬層之前 電極11上形成-支撐體I6之過程，具體為通過普通黏 樓體黏結於第-電極u上。該支撐體16可為任何:j將支 m 鲁 實施例為猶面為㈣之條雜構，該支魏1ό緣祖本 如陶瓷、玻璃等。 緣材枓’ 步驟五：提供-第二電極12，於第二電極12 歹us中奈米碳㈣之第二細之間形成一第二導電= 車Further, the electric forging liquid of the embodiment may include a buffering agent, and the buffering agent may be selected from a mixed solution of aluminum sulfate and boric acid, and the mass percentage of the aluminum sulfate is 3% 'the mass percentage of boric acid is 1%. 'The buffer can be used to stabilize the pH value of the plating solution, especially to slow down the pH of the electro-chain liquid caused by nitrogen evolution on the cathode surface'. It is also beneficial to improve the dispersion ability of the plating solution and the stability of the plating layer. Step 3: providing a first electrode 11 and forming a first conductive metal layer 14 between the first electrode u and the first end 132 of the carbon nanotube 130 in the carbon nanotube array 13 The first end 132 of the 13-nanocarbon tube 13 is connected to the first electrode through the first conductive metal layer 14. The electrical connection method may be such that a first conductive metal layer 14 is formed on the surface of the first electrode U, and the first electrode u is electrically connected to the first end of the carbon nanotube 130 through the first conductive metal layer 14; Specifically, the method includes the following steps: 11 11 first, providing a first electrode u, the thickness of the first electrode u is jade micron ~ 2 〇 micron 'the area of the first electrode is greater than or equal to the end of the carbon nanotube array 13 Department ^ product. Forming a first-conductive metal layer 14 on the surface of the first electrode 11, specifically plating a first conductive metal layer I4 on the surface of the first electrode by magnetron sputtering, physical_method or chemical gas subtraction method, In this embodiment, the first-electrode conductive layer 14 is finely controlled on the first electrode 11 2 . The material of the first electrode may be steel, a conductive metal layer Um iron, gold or silver, etc. 'This embodiment is copper', and the material of the first electrode 11 has a good 15 201031586: Invasive, the metal can be selected from metals with lower melting points, such as indium, tin, copper, steel, niobium, tantalum, gold, silver, and the kind of seed or material, and the metal material needs to be low. The melting point of the first electrode 11. • Next, heating the first surface 11 on which the surface is plated with the first conductive metal layer 14 melts the first conductive metal layer η. Finally, the first end m of the carbon nanotube m in the carbon nanotube array 13 having the first-electrophilic layer 136 is brought into contact with the surface of the molten first conductive metal layer w ^ . Further, the first end m of the carbon nanotubes in the carbon nanotube array 13 can be inserted into the molten first conductive metal layer w. The molten first conductive metal layer 14 is rapidly cooled, whereby the carbon nanotubes 130 are firmly fixed on the first conductive metal layer 14. Since the carbon nanotubes 130 and the first-electrophilic layer 136 have better wettability, and the first-electrophilic layer 136 and the first conductive metal layer I4 also have better wettability, the first conductive metal layer is As a transition layer between the carbon nanotube 130 and the first electrode u, the electrical connection between the first carbon electrode 13 and the first electrode 11 is ensured, and the first electrode u and the carbon nanotube 13 are avoided. The electrical contact is poor, or the carbon tube is stripped from the first electrode u, maintaining the stability and sensitivity of the entire sensor performance. Step 4: Form a second metalophilic layer 138 on the surface of the second end 132 of the carbon nanotube 13 in the carbon nanotube array 13. First, the carbon nanotube array 13 in the second step is stripped from the substrate 17, since the first end of the carbon nanotube 13 in the array of carbon nanotubes 13 has been fixed to the first electrode 11, and the nanometer The carbon tube array 13 has a weak bonding force with the substrate 17, so that the carbon nanotube array ls can be peeled off from the substrate 1 without a small force, and the shape of the carbon nanotube array 13 is not damaged. The first end 134 of the nanotube tube 130 in the carbon nanotube array 13 16 201031586 is made a free end. Next, in the discussion, the surface of the second end 134 of the carbon nanotube 130 in the tube array 13 forms a first layer 138'. This step is substantially the same as in the second step. - Pro-master This step can be carried out in a step comprising the formation of a support I6 on the electrode 11 before the second electrophilic layer of the shaft, in particular by bonding to the first electrode u through a common adhesive body. The support body 16 can be any of the following: a sub-structure of the sub-surface is (4), and the progenitor is a ceramic, glass, or the like. The edge material 枓' step 5: providing - the second electrode 12, forming a second conductivity between the second thinner of the carbon (4) in the second electrode 12 歹us = car
…將奈米碳管陣列13中奈米碳管13W 二導電金屬層15與第二電極12電連接，從而形成 列傳感器10。 & ^ 奈米碳管陣列13中奈米碳管130之第二端m 12電連接之方村為於第二電極12表崎成_第二=^^ =，通過该第二導電金屬心使第二電極12與奈求碳管⑽ 第二端134電連接，具體為： ’提供—第二電極12並通綱㈣鍍法、物理沉積法 $予軋相沈積法於第二電極12之表面鑛覆 =本實施例為於第二電極126之表面通過磁控雜法鑛上第: ，電金屬層15。料極材料可為銅、紹、鐵、金或銀等，本實 属列為銅，該第二導電金屬層15之材料可選用熔點較低之金 屬’如銦、錫、鋼、銦、鉛、銻、金、銀和鉍中之一種或者幾種， 同時該金騎料之熔點需低於第二雜12之魅㈣ 17 201031586 : 其次，加熱上述表面錢有第二導電金屬層15 m :12，使第二導電金屬層15熔融。 一電極 i碳管^之屬心之奈米碳管陣列13令奈米 相接觸谁〃、八已嫁融之第二導電金屬層15表面 相接觸。進-步地，可使奈米碳管陣列13 部分或全部插入贿融之第二導電金屬層^中，2 熔融之第二導電金屬層15快速冷 e 定於第二導電金屬層15之上，從而料㈣牛固地固 器10。 從而开v成了—奈米碳管陣列傳感The carbon nanotube 13W secondary conductive metal layer 15 in the carbon nanotube array 13 is electrically connected to the second electrode 12, thereby forming the column sensor 10. & ^ The square end of the carbon nanotube array 13 in which the second end m 12 of the carbon nanotubes 130 is electrically connected is formed by the second electrode 12 _ second = ^ ^ =, through the second conductive metal core The second electrode 12 is electrically connected to the second end 134 of the carbon tube (10), specifically: 'providing - the second electrode 12 and the general (four) plating method, physical deposition method, and the pre-rolling phase deposition method on the second electrode 12 Surface mineralization = in this embodiment, the surface of the second electrode 126 is passed through a magnetron hybrid ore: an electric metal layer 15. The material of the material can be copper, sho, iron, gold or silver, etc., which is actually listed as copper. The material of the second conductive metal layer 15 can be selected from metals with lower melting points such as indium, tin, steel, indium and lead. One or more of 锑, 金, gold, silver and ,, at the same time the melting point of the gold riding material needs to be lower than the charm of the second miscellaneous 12 (4) 17 201031586 : Secondly, heating the surface of the surface has a second conductive metal layer 15 m : 12. The second conductive metal layer 15 is melted. An electrode i carbon tube ^ the core of the carbon nanotube array 13 allows the nano-contact with the surface of the second conductive metal layer 15 which is in contact with the occupant. Further, the carbon nanotube array 13 may be partially or completely inserted into the bridging second conductive metal layer, and the second molten conductive metal layer 15 is rapidly cooled to the second conductive metal layer 15. And thus the material (four) cattle solid grounding device 10. Thus open v becomes - carbon nanotube array sensing
該步驟進-步包括將上職定於第—_ U 過普通黏結劑黏結於第二電極12 通 第-電極11和第1極12 π 使其更好地固定於 吊电蚀弟一電極12之間，該支撐體16之 電極11和第二電極12之間之距離。 又； 本實施例中，該支樓體也可於上述步驟 並與熔融之第-導電金屬層14黏結 :程中形成 接通過普通黏結劑將該支撐體16f於* S中形成亚直 12之間。 謂16黏結於第一電極11和第二電極 本實施例奈米碳管傳感器10之槊 米碳管130之表面通過電锻、化學Μ者_ 二’該修飾層可提高該奈米碳管陣列傳感心二 準確探測不同氣體之含量，如表面二之修飾層可分別 和甲燒之含量準確度。表面修飾有一層把可提高探測氫氣 本實施例中該第-導電金屬層14和第二導電金屬層Μ也可 18 201031586 : 通過電錄、化學鑛或磁控賤鍍法分別形成於奈米碳管陣列13之 . 兩個端部。 . 該奈米碳管陣列傳感器10中之奈米碳管陣列13可作為電子 . 導線，當通入電流後，第一電極11和第二電極12之間之電導率 可被測出。因為奈米碳管130之電子特性主要係由其原子結構決 定之’故奈米碳管130受力後原子結構之形變或化學吸附都會對 其電導率產生影響，其變化值可由電流訊號來檢測，故該奈米碳 管陣列傳感器10可用於檢測氣體分子。具體原理為氣體分子被 瘳奈米碳管130吸附，導致了奈米碳管130電荷之遷移，從而引起 了電導率之變化。吸附於奈米碳管13〇上之氣體分子之量不同， 不米碳管130電導率變化量也不同，故於通入電流後，通過測量 該奈米碳管13〇電導率之變化，該奈米碳管陣列傳感_ 1〇便可 檢測氣體分子之含量。同時，不同氣體分子吸附到奈米碳管上 時，由於氣體分子之分子量和分子結構之差異，其對奈米碳管之 作用力也會有差異，導致所引起奈米碳管之電導率變化亦各不相 〇 同，故於通入電流後，通過測量該奈米碳管130電導率之變化便 可檢測氣體分子之種類。 。明參閱圖4,本發明第二實施例提供一種奈米碳管陣列傳感 器20，該奈米碳管陣列傳感胃2〇包括—第一電極21，一第二電 極22 ’ -設置於第一電極21與第二電極22之間之奈米礙管陣 列23’複數第一導電金屬層24、複數第二導電金屬層％及一支 撐體26。 ”本實施例與第-實施例基本相同，其區別在於本實施例之奈 米碳管陣列傳感器20包括複數第一導電金屬層24和複數第二導 19 201031586 電金屬層25。 該奈米碳管陣列23包括複數奈米碳管23〇，每一奈米礙管 230包括第-端232和與第一端232相背之第二端234，該第一 端232和第二端234為從奈米碳管陣列23中奈米碳管23〇之端 面及從該，面至距離奈米碳管23〇之端飢〇1微米〜5〇微米之間 之奈米碳官230之側壁表面。該第一端232和第二端234之表面 分別>儿積有第一親金屬層236和第二親金屬層238。該奈米碳管The step further comprises: bonding the upper member to the first -_ U bonding adhesive to the second electrode 12 through the first electrode 11 and the first pole 12 π to better fix the electrode 12 The distance between the electrode 11 of the support 16 and the second electrode 12 is between. In this embodiment, the support body may also be adhered to the molten first conductive metal layer 14 in the above step: forming a joint in the process to form the support body 16f in the * S by the ordinary bonding agent. between. The surface of the first electrode 11 and the second electrode is bonded to the first electrode 11 and the second electrode. The surface of the carbon nanotube 130 of the carbon nanotube sensor 10 of the present embodiment can be improved by electroforging, and the chemical layer can improve the carbon nanotube array. Sensing heart 2 accurately detects the content of different gases, such as the surface layer of the modified layer can be separately and the content of the burnt content. The surface modification has a layer to enhance the detection of hydrogen. The first conductive metal layer 14 and the second conductive metal layer in the embodiment can also be formed on the nanocarbon by electro-recording, chemical ore or magnetron plating. Tube array 13. Two ends. The carbon nanotube array 13 in the carbon nanotube array sensor 10 can function as an electron. The electrical conductivity between the first electrode 11 and the second electrode 12 can be measured when an electric current is applied. Because the electronic properties of the carbon nanotubes 130 are mainly determined by their atomic structure, the deformation or chemical adsorption of the atomic structure will affect the conductivity of the carbon nanotubes 130. The change value can be detected by the current signal. Therefore, the carbon nanotube array sensor 10 can be used to detect gas molecules. The specific principle is that gas molecules are adsorbed by the nanotube carbon nanotubes 130, resulting in the migration of the charge of the carbon nanotubes 130, thereby causing a change in conductivity. The amount of gas molecules adsorbed on the carbon nanotubes 13 is different, and the conductivity change of the carbon nanotubes 130 is also different. Therefore, after the current is supplied, the conductivity of the carbon nanotubes 13 is measured. The carbon nanotube array sensing _ 1〇 can detect the content of gas molecules. At the same time, when different gas molecules are adsorbed onto the carbon nanotubes, due to the difference in molecular weight and molecular structure of the gas molecules, the force on the carbon nanotubes will also be different, resulting in the change of the conductivity of the carbon nanotubes. Different from each other, the type of gas molecules can be detected by measuring the change in the conductivity of the carbon nanotubes 130 after the current is applied. . Referring to FIG. 4, a second embodiment of the present invention provides a carbon nanotube array sensor 20, wherein the carbon nanotube array sensing stomach 2 includes a first electrode 21 and a second electrode 22' - disposed at the first The nano tube array 23' between the electrode 21 and the second electrode 22 is a plurality of first conductive metal layers 24, a plurality of second conductive metal layers, and a support 26. The present embodiment is substantially the same as the first embodiment except that the carbon nanotube array sensor 20 of the present embodiment includes a plurality of first conductive metal layers 24 and a plurality of second conductive layers 19 201031586. The tube array 23 includes a plurality of carbon nanotubes 23, each of which includes a first end 232 and a second end 234 opposite the first end 232, the first end 232 and the second end 234 being The end face of the carbon nanotube 23 in the carbon nanotube array 23 and the side surface of the nanocarbon official 230 between the surface and the end of the carbon nanotube 23 from the end of the nanometer to 5 micron. The surfaces of the first end 232 and the second end 234 respectively have a first metal-friendly layer 236 and a second metal-friendly layer 238. The carbon nanotubes
陣列23中之每個奈米碳管230之第一端232通過第一導電金屬 層24與第一電極21電連接，該奈米碳管陣列幻中每個奈米碳 管230之第二端234通過第二導電金屬層25與第二電極22電連 接。該每個第-導電金顧24形成於一奈米碳管23〇之第一端 232’且每個第二導電金屬層2S形成於一奈米碳管挪之第二端 234。 一 請參閱圖5 ’本發明第二實施例提供之奈米破管陣列傳感器 20之製備方法，具體包括以下步驟： 步驟一：提供一奈米碳管陣列23，該奈米碳管陣列幻包括 第一端232和第二端234。 本實施例奈米碳管陣列23之製備方法具體為，提供一基底 27並於該基底27上_鱗氣相沈積法製備該絲礙管^列 232之表面形成一第 步驟二··於該奈米碳管陣列23第一端 一親金屬層236。 屬 步驟三：提供—第1極21，於第-電極21與奈米 列23中奈米破管230之第一端a2之間形成複數第一 ^電金 201031586 碳管陣列23中奈米碳管23〇之第一 第-導電金屬層24與第-電極21電連接。 、過該 該電連接之方法可為於奈米碳管_ 2 ^之/—鎌輸秦輸如4,^ 金屬層24與第一電極21電連接。具體為 電 紐或磁_舰於絲碳_ 23 _奈米^ =第 ❿ 成-第-導電金屬層24。本實施例選用魏之方= 人，加熱上述奈米碳管_ 23中奈米碳f 230之第一端改 上之第—導電金4層24，使第—導電金屬層24縣。最後，將 上述有第-親金屬層236和炼融之第—導電金 =2”奈米伽之第一職與上述第一電極= 觸待其黏結牛固之後，將該熔融之第一導電金屬層％快 撕物_-咖1結合並保 步驟四：於奈米碳管陣列23 _奈米碳管23〇之第二端^ 之表面形成一第二親金屬層238。 首先’將步驟二中之奈来碳管陣列23從基底27中剝離，由 於該奈米碳管陣列23中奈米碳管23()之第一端232已經固定於 第一電極21上，而奈米碳管陣列23與基底巧之結合力較弱， 故只需很小之力即可把奈求碳管陣列23從基底27上剝離下來， 而且不致娜奈料管_ 23之雜，獅使奈米碳f陣列23 中奈米奴管230之第二端234成為一自由端。其次，於該奈米碳 管陣列23巾奈米碳管23〇之第二端234之表面形成一第二親金 屬層238。該步驟同步驟二基本相同。 21 201031586 ::::::::二 乂驟五m電極a，料二_ a與奈絲管陣 列23中^卡碳管230之第二端234之間形成複數第二導電金屬 層25:將奈米碳管陣列23中奈米碳管23〇之第二端说通過該 弟-導電金屬層25與第：電極22電連接，從而 陣列傳感器20。The first end 232 of each of the carbon nanotubes 230 in the array 23 is electrically connected to the first electrode 21 through the first conductive metal layer 24, the second end of each of the carbon nanotubes 230 234 is electrically connected to the second electrode 22 through the second conductive metal layer 25. Each of the first conductive particles 24 is formed at a first end 232' of a carbon nanotube 23's and each second conductive metal layer 2S is formed at a second end 234 of the carbon nanotube. Referring to FIG. 5, a method for preparing a nano tube-breaking array sensor 20 according to a second embodiment of the present invention includes the following steps: Step 1: providing a carbon nanotube array 23, the carbon nanotube array includes First end 232 and second end 234. The method for preparing the carbon nanotube array 23 of the present embodiment is specifically to provide a substrate 27 and to form a surface of the wire barrier tube 232 on the substrate 27 to form a second step. The first end of the carbon nanotube array 23 is a metal-philic layer 236. Step 3: Providing - the first pole 21, forming a plurality of first electric gold 201031586 between the first electrode 21 and the first end a2 of the nano tube 230 in the nano column 23 The first first conductive metal layer 24 of the tube 23 is electrically connected to the first electrode 21. The method of electrically connecting may be to electrically connect the first layer 21 to the metal layer 24 at the carbon nanotubes. Specifically, it is an electric or magnetic _ ship on the wire carbon _ 23 _ nanometer ^ = ❿ into a - conductive metal layer 24. In this embodiment, Wei Zhifang = person is selected, and the first end of the nano carbon tube 230 in the above carbon nanotube _ 23 is heated to the fourth layer of the conductive gold layer 24, so that the first conductive metal layer is 24 counties. Finally, after the first-electrophilic layer 236 having the first-electrophilic layer 236 and the fused first-conducting gold=2" nanogae and the first electrode = resisting the bonding of the bovine solid, the molten first conductive The metal layer % fast tearing material - the coffee 1 is combined and secured. Step 4: forming a second metal-friendly layer 238 on the surface of the second end ^ of the carbon nanotube array 23 _ carbon nanotube 23 。. First, the steps will be The second carbon nanotube array 23 is stripped from the substrate 27, since the first end 232 of the carbon nanotube 23 () in the carbon nanotube array 23 has been fixed to the first electrode 21, and the carbon nanotube The combination of the array 23 and the substrate is weak, so that the carbon tube array 23 can be peeled off from the substrate 27 with a small force, and the nano tube is not mixed, and the lion is made of nano carbon. The second end 234 of the melon tube 230 in the f array 23 becomes a free end. Secondly, a second metalophilic layer is formed on the surface of the second end 234 of the carbon nanotube array 23 238. This step is basically the same as step 2. 21 201031586 :::::::: Two steps of five m electrode a, material two _ a and the tube array 23 in the ^ card carbon tube 230 A plurality of second conductive metal layers 25 are formed between the ends 234: the second ends of the carbon nanotubes 23 in the carbon nanotube array 23 are electrically connected to the electrode 22 through the second conductive metal layer 25, thereby forming an array Sensor 20.
該電連接方法可為於奈米碳管陣列23中奈采碳管23〇 二端234形成複數第二導電金騎25，通職第二導電金 25與第二電極電連接。具體為：首先，通過化學鑛、電鍵或磁 控舰法於奈米碳管陣列23中奈米碳管23()之第二端234形成 -第二導電金屬層25’本實施例選用紐之方法。其次，加熱 上述奈米礙管陣列23中奈米碳管23〇之第二端234上之第二導 電金属層25 ’使第二導電金屬層25溶融。最後，將上述有第二 親金屬層238㈣融之第二導電金屬層25之奈来碳管陣列幻^ 奈米碳管230之第二端234與上述第二電極22之一表面接觸， 待其黏結牢@之後’將融之第二導電金㈣％快速冷卻， 從而使奈米碳管陣列23牢固地與第二電極Μ結合並保持良好之 電連接。 該步驟進一步包括將上述形成於第一電極21上之支撐體％ 通過普通黏結劑黏結於第二電極22上，從而使其更好地固定於 第一電極21和第二電極22之間。 本實施例與第一實施例奈米碳管陣列傳感器10之製備方法 22 201031586 管陣列23之實轉於奈米碳 管陣列23之第二端234形成複數第二導電=:於奈米碳 本實施例中該複數第一導電' 鍵或磁控騎法形成於該第鍵、電 端232相對之表面，該複數第二導電金屬層μ 之第 電鍍或磁錢躲形缺該帛 〜過化學鍍、 二端故相對之表面。第一電極22與奈米碳管陣列23之第 參 可以理解，所述第-導電金屬層 可以分卿成在所料m和料 ^ 234，或分卿成麵縣 管230的第一端232和第二電極22。 τ不木反 本發明提供的奈轉管陣簡❹及錢備綠具有以下優 點：該奈米碳管_傳心㈣備綠無需採科電轉使争来 碳管與第-電極和第二_實職連接，且所製備的奈米碳管陣 ❹列職II中的奈米碳管的第—端和第二端分別沈積有第 層和第二親金屬層，且該第-親金屬層和第二親金屬層不僅鮮 米碳管具有很好的浸潤性，且與第一導電材料層和第二導電材料 也有良好的浸潤性，因此，該奈米碳管陣列與第一電極和第二電 極結合牢固’保證了奈米碳管陣列傳感器工作的可靠性和穩定 性，提高了該奈米碳管陣列傳感器的工作壽命。 综上所述，本發明確已符合發明專利之要件，遂依法提出專 利申請。惟’以上所述者僅為本發明之較佳實施方式，自不能以 201031586 -- 此限制本案之申請專利範圍。舉凡熟悉本案技藝之人士援依本發 ： 明之精神所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍 .内。 【圖式簡單說明】 圖1係本發明第一實施例之奈米碳管陣列傳感器之 剖視圖。 圖2係本發明第一實施例奈米碳管陣列傳感器之製 備工藝流程圖。 ❿ 圖3係本發明第一實施例奈米碳管陣列傳感器之製 備方法流程圖。 圖4係本發明第二實施例之奈米碳管陣列傳感器之 剖視圖。 圖5係本發明第二實施例奈米碳管陣列傳感器之製 備工藝流程圖。 【主要元件符號說明】 奈米碳管陣列傳感器 10 ' 20 第一電極 11、21 第二電極 12、22 奈米碳管陣列 13、23 奈米碳管 130 > 230 第一端 132、232 第二端 134 、 234 第一親金屬層 136 、 236 第二親金屬層 138 、 238 24 201031586 第一導電金屬層 14 > 24 第二導電金屬層 15、25 支撐體 16 ' 26 基底 17 ' 27The electrical connection method may be that a plurality of second conductive gold riders 25 are formed in the second end 234 of the carbon nanotube 23 in the carbon nanotube array 23, and the second conductive gold 25 is electrically connected to the second electrode. Specifically, firstly, a second conductive metal layer 25 ′ is formed on the second end 234 of the carbon nanotube 23 ( ) in the carbon nanotube array 23 by chemical ore, electric key or magnetron method. method. Next, the second conductive metal layer 25' on the second end 234 of the carbon nanotube 23 in the nano tube array 23 is heated to melt the second conductive metal layer 25. Finally, the second end 234 of the carbon nanotube array carbon nanotube 230 having the second electrophilic layer 238 (four) fused to the second conductive metal layer 25 is in contact with one surface of the second electrode 22, and is subjected to After bonding, the second conductive gold (four)% is rapidly cooled, so that the carbon nanotube array 23 is firmly bonded to the second electrode and maintains a good electrical connection. The step further includes adhering the above-mentioned support body % formed on the first electrode 21 to the second electrode 22 by a common bonding agent so as to be better fixed between the first electrode 21 and the second electrode 22. The present embodiment and the first embodiment of the carbon nanotube array sensor 10 preparation method 22 201031586 The actual implementation of the tube array 23 to the second end 234 of the carbon nanotube array 23 forms a plurality of second conductivity =: on the carbon In the embodiment, the plurality of first conductive 'keys or magnetically controlled riding methods are formed on the opposite surface of the first key and the electric terminal 232, and the plurality of second conductive metal layers μ are electroplated or magnetically deficient. Plated, two ends and opposite surfaces. It can be understood from the first electrode 22 and the first embodiment of the carbon nanotube array 23 that the first conductive metal layer can be divided into the first end 232 of the material m and the material 234, or the first end of the county tube 230. And the second electrode 22. τ 不木 反 The invention provides the neat transfer tube array and the money reserve green has the following advantages: the carbon nanotube _ Chuan Xin (four) green preparation does not need to use the electric power to make the carbon tube and the first electrode and the second _ The first and second metalophilic layers are deposited on the first end and the second end of the carbon nanotubes in the prepared carbon nanotubes, respectively, and the first and second metalophilic layers are respectively The second metal-friendly layer not only has good wettability of the fresh rice carbon tube, but also has good wettability with the first conductive material layer and the second conductive material, and therefore, the carbon nanotube array and the first electrode and the second electrode The combination of the electrodes firmly ensures the reliability and stability of the operation of the carbon nanotube array sensor and improves the working life of the carbon nanotube array sensor. In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is filed according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to use 201031586 - this limits the scope of patent application in this case. Anyone who is familiar with the skill of this case should be included in the scope of the following patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a carbon nanotube array sensor according to a first embodiment of the present invention. Fig. 2 is a flow chart showing the preparation process of the carbon nanotube array sensor of the first embodiment of the present invention. Figure 3 is a flow chart showing the preparation method of the carbon nanotube array sensor of the first embodiment of the present invention. Figure 4 is a cross-sectional view showing a carbon nanotube array sensor of a second embodiment of the present invention. Fig. 5 is a flow chart showing the preparation process of the carbon nanotube array sensor of the second embodiment of the present invention. [Main component symbol description] Carbon nanotube array sensor 10' 20 First electrode 11, 21 Second electrode 12, 22 Carbon nanotube array 13, 23 Carbon nanotube 130 > 230 First end 132, 232 Two ends 134, 234 first metal layer 136, 236 second metal layer 138, 238 24 201031586 first conductive metal layer 14 > 24 second conductive metal layer 15, 25 support 16 ' 26 substrate 17 ' 27
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