1312410 九、發明說明： 【發明所屬之技術領域】 本發明係涉及一種奈米碳管陣列與基底結合力之測量 方法。 【先前技術】 奈米碳管係九十年代初發現的一種新型一維奈米材 料，其具有優良之綜合力學性能，如高彈性模量、高楊氏 模量與低密度，以及優異之電學性能、熱學性能及吸附性 月匕。由於奈米碳管具有理想之一維結構以及於力學、電學、 熱學等領域之優良性質，其於材料科學、化學、物理學等 父又學科領域已展現出廣闊之應用前景，而形成於導電基 底上之奈米碳管陣列因其中之奈米碳管排列整齊有序，更 廣泛應用於真空電子器件、場發射平板顯示、熱傳導等諸 多領域。 奈米碳管陣列之實際應用中，尤其於場發射領域之應 用中，確保奈米碳管陣列與基底間具有足夠結合力係人們 較爲關注之問題。當奈米碳管陣列與基底間結合力較弱 時，奈米碳管陣列與基底於使用中會導致短路、放電等不 良問題從而使場發射失敗。故而，於奈米碳管陣列之實際 應用之前，爲確保其與基底間具有足夠之結合力，如何能 夠準確測量奈米碳管陣列與基底結合力之大小亦為一有待 解決之問題。 按’測量奈米碳管陣列與基底結合力之方法主要爲採 用原子力顯微鏡測量之方法以及採用毫牛（mN)測力計測 1312410 量之方法。 時二η:員微鏡測量奈米碳管陣列與基底結合力 =母根或少數幾根奈来碳管與基底間之結 二力，測纽率較低；另，因奈米碳管相互之間存在之凡 ί瓦耳力’其對於剛量值影響較大，從而降低二 毫牛===量!:，陣列與基底結合力時’ 之Η在疋噪音，同時，因奈米碳管相互 之間存在之凡錢耳力，科測 低，從而降低測量之準確度。 』里L號雜訊比較 乎碳==其，必要提供一種克服以上缺點之測量奈 米石厌官陣列與基底結合力的方法。 【發明内容】 與基二說明-種奈米碳管陣列 夕㈣地 以方法_里方法可提高測量過程中 紙’同時，亦可降低奈米碳管之間存在之凡德 ^耳力對測量過程的影響，從而有效提高測量結果之準確 度。 :種奈米與基歧合力之測量方法，其測量 碳管陣列中奈米碳管間具有一定的間隙，該測量方 法包括： 臂之Ϊ牛測力計’該測力計具有-測力臂，該測力 f .而固疋一測力探針，該測力探針具有平整之測力端 曲， 1312410 於測力探針之測力端面上塗覆一粘性膠層；以及 將塗覆有粘性膠之測力端面逐漸靠近待測之奈米碳管 ，，的上表面並緊密接觸，然後將測力探針逐漸拔離奈米 炭ΐϋ車列表面，測力探針之測力端面將粘附一定數量之奈 :厌s，藉由測力計顯示之力數值以及拔出奈米碳管之數 里阿知出奈米碳管陣列與#附著基底之結合力數值。 麵力探針爲細絲’細絲之末端面經過抛光處理作爲 平整光滑之測力端面。 °亥、、’田絲末端之截面直徑不小於微米。 该測力探針係直徑爲500微米之鎢絲。 山該测力探針爲條狀體，其具有平整末端面以作爲測力 化面且末咖財不小於15()微米糊微米。 該測力探針爲切成長條形狀之矽片。 該測力探針藉由錄膠固定於測力臂之末端。 —該奈米碳管陣列包括複數呈矩形方陣形式排列之小單 之間具有間隙且各單元之戴面尺寸約爲50微米 與先前技術相較，本發明奈米碳管陣列與基底之測量 方法中於測力計之測力臂末端設置—測力探針，該測力探 針具有平整域_較大之測力翻，每次可測量較多之 奈米碳管，從而提高測量之信號雜訊比；同時，本發明測 量之奈米碳管陣列具有特定之間隙，該蚊間隙可降低奈 米碳官1存在之凡德瓦耳力_量過程之影響，進而可 有效提南測量之準確度。 1312410 【實施方式】 、下面將結合關對本發明奈米碳管陣顺基底結合力 之測量方法作進一步之詳細說明。 旦3 4閱圖1，本發明奈米碳管陣列與基底結合力之測 里方法大致包括以下幾個步驟： (7)提供—毫牛測力計，該測力計具有一測力臂10, =測力# 10之末端固定一測力探針2〇，該測力探針卯具 平2且截面積較大之測力端面（圖中未標號）。 偏止2 勒探針2G可選用細絲’該細絲之末端面經過 之恭2從而平整储以作爲測力端面。爲確保具有較大 優選餘末端之絲直徑應不小於微米，如， 亦可_條狀體微ί之鶴絲作爲測力探針20。測力探針20 端面，h “條狀體應具有平整之末端面作爲測力 不小於咖料保具有較大之截面積，該測力端面之尺寸應 作爲測力探針7微米’如’優選切成長條形狀之石夕片 用先於測力計之測力臂1G上之方法可採 測力臂10上 可採用枯性膠將測力探針20枯接於 3〇 〇 1力探針2G之測力端面上塗覆-紐膠層 奈米碳管^^，膠30之測力端面逐漸靠近待測之 漸拔離奈米料並緊密测後，將測力探針20逐 lJ 40表面，測力探針20之測力端面將 1312410 #附-=數:^之奈米碳管，藉由測力計顯示力之數值以及 ， 拔出奈米碳管之數量即可得出奈米礙管陣列40與其附著 基底50之結合力大小。 “其中，待測之奈米碳管陣列4〇具有特定圖樣，從而使 奈米碳管陣列40間具有特定間隙，該奈米礙管陣列4〇中 特定之_可防止凡德瓦耳力於啦過程巾制量精度之 影響。奈米碳管陣列40之圖樣可為任意規則之圖形，爲確 .保測！_之更向精度，本實施例中優選複數重復排列之小單 元，如呈矩形方陣形式排列之複數小單元。各單元之間具 有間隙且各單元之設置細力探針2Q之測力端面的尺寸 相對應，如，當測力探針2〇之測力端面的尺寸約爲π。微 米x250微米或直徑約爲3〇〇微米時，奈米碳管陣列4〇中 各單元之截面尺寸約爲50微米χ5〇微米（請參閱圖2以及 圖3)。 奈米碳管陣列40可預先藉由化學氣相沈積法、電弧放 . 電法或鐳射蒸發法等先前技術製備。本實施例中優選化學 氣相沈積法製備奈米碳管陣列，首先於基底上形成具有特 定圖案之催化劑，該催化劑之圖案與所需之奈米碳管陣列 之圖樣相對應；然後於高溫下通入破源氣以形成奈米碳管 陣列。該催化劑包括鐵、錄、銘、把等過渡金屬。該碳源 氣包括曱烧、乙稀、丙稀、乙快、甲醇及乙醇等。 於計算奈米碳管陣列40與基底50結合力之數值時， 力之數值可由測力計直接讀出，拔出奈米碳管之數目以及 面積可於光學顯微鏡或電子掃描電鏡下觀察計算得到，故 11 1312410 、而單位面積之奈米碳管與基底結合力之數值可計算得出， - 進而獲得所測奈米碳管陣列40與基底50結合力之大小。 本發明奈米碳官陣列與基底之測量方法中於測力計之 .. 測力臂末端設置一測力探針，該測力探針具有平整且截面 積較大之測力端面，每次可以測量較多之奈米碳管，從而 提高測量過程之信號雜訊比；同時，本發明測量之奈米碳 管陣列具有特定間隙，該特定間隙可降低奈米碳管之間存 在之凡德瓦耳力對測量過程之影響，進而有效提高測量之 • 準確度。 綜上所述’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例， 自不能以此_本案之申請專纖圍。舉凡熟悉本案技藝 =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】 • θ圖1係本發明實施例奈米碳管陣列與基底結合力之測 量方法之流程示意圖。 圖2係本發明實施例中所測之奈米碳管陣列之照片。 【主要元件符號說明】 測力臂 10 測力探針 20 粘性膠層 30 奈米碳管陣列 40 圖3係圖2巾奈米碳管陣列之俯視照片。 1312410 50 基底1312410 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for measuring the binding force of a carbon nanotube array to a substrate. [Prior Art] A new type of one-dimensional nanomaterial discovered in the early 1990s, which has excellent comprehensive mechanical properties such as high elastic modulus, high Young's modulus and low density, and excellent electrical properties. Performance, thermal performance and adsorption month. Because the carbon nanotubes have an ideal one-dimensional structure and excellent properties in the fields of mechanics, electricity, heat, etc., they have shown broad application prospects in the fields of materials science, chemistry, physics, etc. The carbon nanotube array on the substrate is arranged in a neat and orderly manner, and is widely used in many fields such as vacuum electronic devices, field emission flat panel display, heat conduction and the like. In practical applications of carbon nanotube arrays, especially in the field of field emission applications, ensuring sufficient binding between the carbon nanotube array and the substrate is a concern. When the bonding force between the carbon nanotube array and the substrate is weak, the carbon nanotube array and the substrate may cause short-circuit, discharge, and the like in use, thereby causing field emission failure. Therefore, before the practical application of the carbon nanotube array, in order to ensure sufficient binding force with the substrate, how to accurately measure the binding force of the carbon nanotube array and the substrate is also a problem to be solved. The method of measuring the binding force of the carbon nanotube array to the substrate is mainly a method using an atomic force microscope measurement and a method of measuring the amount of 1312410 using a millin (mN) dynamometer.二二: The micro-mirror measures the binding force between the carbon nanotube array and the substrate = the root of the mother or a few knots between the carbon nanotubes and the substrate, and the rate of detection is low; in addition, the carbon nanotubes are mutually There is a difference between the watts of the force, which has a greater influence on the magnitude of the material, thus reducing the amount of two milligrams ===!: When the array is bonded to the substrate, the noise is 疋, while the carbon nanotubes The mutual existence of the money, the low measurement, thus reducing the accuracy of the measurement. The L-number of noise is more carbon==, and it is necessary to provide a method for measuring the binding force of the nano-analytic array to the substrate to overcome the above disadvantages. [Description of the invention] and the base two description - the carbon nanotube array (4) in the method _ the method can improve the paper during the measurement process, and can also reduce the presence of the van der Waals between the carbon nanotubes The impact of the measurement, thus effectively improving the accuracy of the measurement results. : A method for measuring the combined force of a nanometer and a base, which measures a certain gap between the carbon nanotubes in the carbon tube array, and the measurement method includes: an arm yak dynamometer 'the dynamometer has a - force arm The force measuring f is a fixed force measuring probe having a flat force measuring end, 1312410 is coated with an adhesive layer on the measuring end face of the force measuring probe; and the coating is coated The measuring end face of the viscous glue gradually approaches the upper surface of the carbon nanotube to be tested, and is in close contact with each other, and then the force probe is gradually pulled out of the surface of the nano anthracite vehicle, and the measuring end face of the force measuring probe will be Adhere to a certain amount of nai: 厌 s, by the force value displayed by the dynamometer and the number of pull-out carbon nanotubes, the value of the binding force between the carbon nanotube array and the #attach substrate. The force probe is the end surface of the filament 'filament, which is polished to be a smooth and smooth end face. The cross-sectional diameter of the end of the _, , , ,,,,,,,,,,,,, The force probe is a tungsten wire having a diameter of 500 microns. The force measuring probe is a strip having a flat end surface as a force measuring surface and having a margin of not less than 15 (micrometers). The force measuring probe is a septum cut into a strip shape. The force probe is fixed to the end of the force measuring arm by a recording glue. - the carbon nanotube array comprises a plurality of small squares arranged in a rectangular square array with a gap between each other and the wearing size of each unit is about 50 micrometers. Compared with the prior art, the carbon nanotube array and the substrate of the present invention are measured. The force measuring probe is arranged at the end of the measuring arm of the dynamometer, and the measuring probe has a flat field _ large measuring force flip, and more carbon nanotubes can be measured at a time, thereby improving the signal of the measurement At the same time, the carbon nanotube array measured by the invention has a specific gap, and the mosquito gap can reduce the influence of the van der Waals force-quantity process of the carbon carbon 1 and can effectively improve the accuracy of the South measurement. degree. 1312410 [Embodiment] The measurement method of the bonding strength of the nanocarbon tube array of the present invention will be further described in detail below. Referring to FIG. 1, the method for measuring the binding force between the carbon nanotube array and the substrate of the present invention generally comprises the following steps: (7) Providing a milligram dynamometer, the dynamometer having a force measuring arm 10 , = The end of the measuring force # 10 is fixed with a measuring probe 2〇, and the measuring probe has a measuring end face with a flat section and a large cross-sectional area (not labeled in the figure). The second end of the probe 2G can be selected from the filaments. The end face of the filament passes through the knuckle 2 to be flattened and stored as a force measuring end face. In order to ensure that the diameter of the wire having the larger preferred end is not less than micrometer, for example, the wire of the strip-shaped body may be used as the force measuring probe 20. Force probe 20 end face, h "The strip body should have a flat end face as the force measurement is not less than the coffee material to have a larger cross-sectional area, and the size of the force measuring end face should be used as a force measuring probe 7 micron 'such as ' Preferably, the shape of the strip is cut by the force measuring arm 1G of the dynamometer. The force measuring arm 10 can be used to test the force probe 20 to the 3 〇〇 1 force probe. The measuring end face of the needle 2G is coated with a neodymium layer carbon nanotube ^^, and the measuring end face of the glue 30 is gradually approached to be measured and pulled out of the nano material and closely measured, and the force measuring probe 20 is lJ 40 On the surface, the end face of the force measuring probe 20 will be 1312410 #附-=数:^ the carbon nanotubes, the force value is displayed by the dynamometer, and the number of carbon nanotubes can be extracted to obtain the nai. The size of the bonding force between the array of 40 and its attached substrate 50. "Where the carbon nanotube array 4 to be tested has a specific pattern, so that there is a specific gap between the carbon nanotube arrays 40, the nano tube array The specific _ in the 〇 can prevent the influence of Van der Waals force on the precision of the process towel. The pattern of the carbon nanotube array 40 can be any regular pattern, for sure! For the more precise precision, in the present embodiment, a plurality of small units repeatedly arranged, such as a plurality of small units arranged in a rectangular square array, are preferred. There is a gap between the units and the dimensions of the force measuring end faces of the fine force probes 2Q of the respective units are corresponding, for example, when the measuring force end face of the force measuring probe 2 is about π. When the micrometer x 250 micrometers or the diameter is about 3 micrometers, the cross-sectional dimension of each unit in the carbon nanotube array 4 is about 50 micrometers χ 5 micrometers (see Fig. 2 and Fig. 3). The carbon nanotube array 40 can be prepared in advance by a prior art such as chemical vapor deposition, arc discharge, or laser evaporation. In this embodiment, the carbon nanotube array is preferably prepared by chemical vapor deposition, firstly forming a catalyst with a specific pattern on the substrate, the pattern of the catalyst corresponding to the pattern of the desired carbon nanotube array; and then at a high temperature A source gas is introduced to form a carbon nanotube array. The catalyst includes transition metals such as iron, ruthenium, imprint, and the like. The carbon source gas includes teriyaki, ethylene, propylene, ethyl acetate, methanol, and ethanol. When calculating the value of the binding force between the carbon nanotube array 40 and the substrate 50, the value of the force can be directly read by the dynamometer, and the number and area of the extracted carbon nanotubes can be calculated under an optical microscope or an electron scanning electron microscope. Therefore, 11 1312410, and the value of the binding force of the carbon nanotubes per unit area to the substrate can be calculated, and the magnitude of the binding force between the carbon nanotube array 40 and the substrate 50 is obtained. The measuring method of the nano carbon official array and the substrate of the invention is used in the dynamometer: a measuring force probe is arranged at the end of the measuring arm, and the measuring probe has a flat end face with a large cross-sectional area, each time More carbon nanotubes can be measured to increase the signal-to-noise ratio of the measurement process; at the same time, the carbon nanotube arrays measured by the present invention have specific gaps, which can reduce the presence of virgins between the carbon nanotubes The influence of the watt force on the measurement process, which in turn increases the accuracy of the measurement. In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application in accordance with the law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to use this application alone. Equivalent modifications or variations made by persons in accordance with the spirit of the present invention are intended to be within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method for measuring the binding force between a carbon nanotube array and a substrate in the embodiment of the present invention. Figure 2 is a photograph of a carbon nanotube array as measured in an embodiment of the present invention. [Main component symbol description] Force arm 10 Force probe 20 Adhesive layer 30 Carbon nanotube array 40 Figure 3 is a top view of the 2 carbon nanotube array of Figure 2. 1312410 50 base
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