TWI343591B - Field emission componet and method for making same - Google Patents
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1343591 _ •办 100年03月21日梭正替換頁 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明係涉及一種場發射元件及其製備方法，尤其涉及 一種奈米碳管場發射元件及其製備方法。 【先前技術】 [0002] 奈米碳管（Carbon Nanotube，CNT)係一種新型碳材料 ，由日本研究人員Iijima在1991年發現，請參見"He卜 ical Microtubules of Graphitic Carbon", S.1343591 _•Operation on March 21st, 2001, the replacement of the page, the invention description: [Technical field of the invention] [0001] The present invention relates to a field emission element and a preparation method thereof, and more particularly to a carbon nanotube field Emitter element and method of preparing the same. [Prior Art] [0002] Carbon Nanotube (CNT) is a new type of carbon material discovered by Japanese researcher Iijima in 1991. Please refer to "He ical Microtubules of Graphitic Carbon", S.
Iijima，Nature, vol. 354，p56 ( 1 991 )。奈米碳管 具有極優異的導電性能、良好的化學穩定性和較大的長 - 徑比，且其具有幾乎接近理論極限的尖端表面積（尖端表 . 面積愈小，其局部電場愈集中），故奈米碳管在場發射領 域具有潛在的應用前景。當前的研究表明，奈米碳管係 已知的最好的場發射材料之一，它的尖端尺寸只有幾奈 米至幾十奈米，具有極低的場發射電壓（小於100伏）， 可傳輸極大的電流密度，並且電流極穩定，使用壽命長 Φ ，因此非常適合作爲一種極佳的場發射元件，應用於場 發射顯示器等設備的電子脊射部件中。 [0003] 傳統的奈米碳管場發射元件一般至少包括一導電陰極電 極和作爲發射端的奈米碳管，該奈米碳管形成於該導電 陰極電極上。目前，奈米碳管場發射元件的製備方法主 要包括機械方法和原位生長法。其中，機械方法包括絲 網印刷法和膠粘法。絲網印刷法一般通過將奈米碳管粉 末混合到漿料裏，再通過絲網印刷的方式印刷到導電陰 極上。此種方法通常需要配置分散均勻的奈米碳管漿料 095123830 表單編號A0101 第3頁/共18頁 1003097669-0 1343591 100年03月21日梭正替换苜 ，在印刷後需要烘乾、摩擦、除粉塵 '燒結等步驟，工 藝複雜，且印刷法不適於製作大電流或高精度的場發射 元件。粘膠法係通過原子力顯微鏡操縱已經合成的奈米 碳管，將奈米碳管用導電膠固定到導電陰極上，此種方 法程式簡單，但操作繁雜且效率低。製備出的發射體電 流承載能力一般較低，另，在粘膠法的操作過程中，化 學膠層會滲透到微小的奈米碳管間隙中，其表面張力容 易改變奈米碳管發射體的形狀。另，由於化學膠一般情 況下無法承受電子真空部件所需的:封接或排氣溫度（一 般爲30(TC~50(TC)，:故、應用受到限制 ' * . -V.. . 5 - V . ' *1^- ： ·ί · [0004]Iijima, Nature, vol. 354, p56 (1 991). The carbon nanotubes have excellent electrical conductivity, good chemical stability and large aspect ratio, and they have a tip surface area close to the theoretical limit (tip table. The smaller the area, the more concentrated the local electric field), Therefore, carbon nanotubes have potential application prospects in the field of field emission. Current research shows that one of the best field emission materials known for the carbon nanotube system, its tip size is only a few nanometers to tens of nanometers, with very low field emission voltage (less than 100 volts). It transmits extremely large current density, and its current is extremely stable and has a long service life of Φ. Therefore, it is very suitable as an excellent field emission element for use in electronic ridge parts of devices such as field emission displays. A conventional carbon nanotube field emission element generally includes at least a conductive cathode electrode and a carbon nanotube as a transmitting end, and the carbon nanotube is formed on the conductive cathode electrode. At present, the preparation methods of the carbon nanotube field emission elements mainly include mechanical methods and in situ growth methods. Among them, mechanical methods include screen printing and gluing. Screen printing is generally performed by mixing a carbon nanotube powder into a slurry and printing it onto a conductive cathode by screen printing. This method usually requires a uniform distribution of carbon nanotube slurry 095123830 Form No. A0101 Page 3 / 18 pages 1003097669-0 1343591 On March 21, 100, the shuttle is replacing the crucible, which needs to be dried, rubbed after printing. In addition to the steps of dust 'sintering, the process is complicated, and the printing method is not suitable for making a large current or high-precision field emission element. The viscose method manipulates the synthesized carbon nanotubes by atomic force microscopy and fixes the carbon nanotubes to the conductive cathode with a conductive paste. This method is simple, but complicated and inefficient. The prepared emitter has a low current carrying capacity. In addition, during the operation of the viscose method, the chemical layer penetrates into the tiny carbon nanotube gap, and the surface tension easily changes the carbon nanotube emitter. shape. In addition, because chemical glue can not withstand the requirements of electronic vacuum components under normal conditions: sealing or exhaust temperature (generally 30 (TC ~ 50 (TC),: Therefore, application is limited ' * . -V.. . 5 - V . ' *1^- : · ί · [0004]
原位生長法係先於導電陰極，然後通 過化學氣相沈積、電弧放電或鐳射燒祕驗綠方法在導電 \：i： :··.'： 陰極上直接生長出奈米碳管，此種方;_作簡單，奈米 碳管與導電陰極的電接觸H。，奈管與導電陰 極的結合能力較弱，於使甩 落或被電場The in-situ growth method precedes the conductive cathode, and then directly grows a carbon nanotube on the conductive \:i: :··.': cathode by chemical vapor deposition, arc discharge, or laser burnt green method. Square; _ simple, the electrical contact H of the carbon nanotubes with the conductive cathode. The binding ability of the tube to the conductive cathode is weak, so that it is collapsed or is affected by the electric field.
力拔出，從而導致場發射元作袠。立’，由於該方法不The force is pulled out, causing the field emission element to work. Lie, because the method is not
Oitice 易控制奈米碳管的生長數量和方向，故仍存在效率低且 可控性差的問題。另，原位生長法對陰極基底材料有所 選擇，需要採用不影響化學氣相條件的矽、氧化鋁、氧 化矽、高熔點金屬等，或者基底表面塗敷一層隔離層。 且，基底材料還需要能夠耐受奈米碳管生長的高溫範圍 ，因此該方法成本較高，不利於實際應用。 有鑒於此，提供一種容易固定於導電陰極、電性連接良 好、電流承載能力高且生産和操作簡易、易於實際應用 095123830 表單編號A0101 第4頁/共18頁 1003097669-0 [0005] 1343591 100年03月21日核正替换頁 的場發射元件及其製備方法實為必要。 【發明内容】 [0006] 以下，將以若干實施例說明一種場發射元件及其製備方 法，其具有容易固定於導電陰極、電性連接良好、易於 生産和操作、易於實際應用的特點。 [0007] —種場發射元件，該場發射元件包括一支撐體線材及一 奈米碳管場發射層，該奈米碳管場發射層爲纏繞於所述 支撐體線材外表面的單層或多層奈米碳管薄膜構成。 [0008] 所述奈米碳管薄膜包括複數個奈米碳管束，該多個奈米 碳管束端部首尾相連沿同一方向排列。 [0009] 所述奈米碳管薄膜是從奈米碳管陣列中抽拉獲得。 [0010] 該奈米碳管場發射層還可爲單層或多層奈米碳管薄膜， 則該奈米碳管薄膜的厚度爲5奈米~10微米。 [0011] 該奈米碳管薄膜包括複數奈米碳管。 [0012] 該奈米碳管直徑爲0. 5奈米〜100奈米。 [0013] 該支撐體線材材料爲銅、銀、金、鎳、鉬、玻璃或陶瓷 [0014] 一種場發射元件的製備方法，其包括以下步驟：提供一 支撐體線材；在該支撐體線材外表面形成一奈米碳管場 發射層；按照預定長度切割該外表面形成有奈米碳管場 發射層的支撐體線材，並在切割後對其進行表面處理， 形成場發射元件。 [0015] 該切割方法包括機械剪切或鐳射切割。 095123830 表單編號 A0101 第 5 頁/共 18 頁 1003097669-0 fM3591 [0016] [0017] [0018] [0019] [0020] [0021] 095123830 100年03月21日梭正替换哀 该表面處理方法包括鐳射照射、機械摩擦或大電流場發 射老化。 該奈米碳管場發射層爲奈米碳管薄膜層。 δ亥奈米碳管薄膜層作爲奈米碳管場發射層的製備方法包 括以下步驟：通過一錯子夾住或用膠帶枯取奈米碳管陣 列中—定寬度的一束奈米碳管，施加外力抽拉形成一帶 狀奈米碳管薄膜；將該帶狀奈米碳管薄膜纏繞於支撐體 線材的外表面；將纏繞後的支撐體線材浸入有機溶劑， #成奈米碳管場發射層 該帶狀奈米碳聲薄膜可在纏繞單層 或多層Oitice is easy to control the amount and direction of growth of carbon nanotubes, so there are still problems of low efficiency and poor controllability. In addition, the in-situ growth method has a choice of cathode substrate materials, such as ruthenium, aluminum oxide, ruthenium oxide, high melting point metal, etc., which do not affect the chemical vapor phase conditions, or a layer of isolation on the surface of the substrate. Moreover, the base material also needs to be able to withstand the high temperature range in which the carbon nanotubes grow, so the method is costly and unfavorable for practical use. In view of this, it is easy to fix to a conductive cathode, has good electrical connection, high current carrying capacity, and is easy to manufacture and operate, and is easy to be practically applied. 095123830 Form No. A0101 Page 4 / 18 pages 1003097669-0 [0005] 1343591 100 years It is necessary to correct the field emission element of the replacement page and the preparation method thereof on March 21st. SUMMARY OF THE INVENTION [0006] Hereinafter, a field emission element and a method of fabricating the same will be described in several embodiments, which have the characteristics of being easily fixed to a conductive cathode, having good electrical connection, being easy to produce and operate, and being easy to practically apply. a field emission element comprising a support body wire and a carbon nanotube field emission layer, the nano carbon tube field emission layer being a single layer wound around an outer surface of the support body wire or A multilayer carbon nanotube film is constructed. [0008] The carbon nanotube film comprises a plurality of carbon nanotube bundles, and the ends of the plurality of carbon nanotube bundles are arranged end to end in the same direction. [0009] The carbon nanotube film is obtained by drawing from a carbon nanotube array. [0010] The carbon nanotube field emission layer may also be a single layer or a plurality of layers of carbon nanotube film, and the carbon nanotube film has a thickness of 5 nm to 10 μm. [0011] The carbon nanotube film comprises a plurality of carbon nanotubes. 5纳米〜100纳米。 [0012] The diameter of the carbon nanotubes is 0. 5 nanometers ~ 100 nanometers. [0013] The support wire material is copper, silver, gold, nickel, molybdenum, glass or ceramic [0014] A method for preparing a field emission element, comprising the steps of: providing a support wire; outside the support wire A carbon nanotube field emission layer is formed on the surface; the support wire of the carbon nanotube field emission layer is formed by cutting the outer surface according to a predetermined length, and is surface-treated after cutting to form a field emission element. [0015] The cutting method includes mechanical shearing or laser cutting. 095123830 Form No. A0101 Page 5 of 18 1003097669-0 fM3591 [0016] [0018] [0020] [0021] 095123830 On March 21, 100, the shuttle is replacing the surface treatment method including laser Irradiation, mechanical friction or large current field emission aging. The carbon nanotube field emission layer is a carbon nanotube film layer. The preparation method of the δHenne carbon nanotube film layer as the nano carbon tube field emission layer comprises the following steps: clamping a bundle of carbon nanotubes in a carbon nanotube array by a wrong one or by tape Applying external force to form a strip of carbon nanotube film; wrapping the strip of carbon nanotube film on the outer surface of the support wire; immersing the wound support wire in an organic solvent, #成奈米碳管Field emission layer The ribbon-shaped nanocarbon acoustic film can be wound in a single layer or multiple layers
::¾ 麵：y.. mo 相較於先前技術，所述的包含支撐體緣綱#r奈米碳管場 發射層的場發射元件，其優點在於：读魏'，使用奈米碳 管場發射層作爲發射體發1電^子jI*利g ^,碳管本身優 良的電子發射性能；其次，貧1i米碳管場發Γ ί 〇ρΘ?… 射層形成的場發射元件具，利用支撐體線材 對奈米碳管場發射層之固定和支撐作用，使場發射元件 具有良好的機械性能，易於固定於陰極電極，容易操作 ，能夠大量生産並且方便地應用於各種真空場發射器件 【實施方式】 下面將結合附圖對本發明作進一步的詳細說明。 請參閱圖1和圖2，本發明實施例提供一種場發射元件10 ，該場發射元件ι〇包括一支撐體線材12及一包覆在該支 表單編號Α0101 第6頁/共18頁 1003097669-0::3⁄4 face: y.. mo Compared to the prior art, the field emission element comprising the support body edge #r nanocarbon field emission layer has the advantages of reading Wei', using carbon nanotubes The field emission layer acts as an emitter to generate an electron beam jI*li g ^, and the carbon tube itself has excellent electron emission performance; secondly, the 1i meter carbon tube field is Γ 〇 ΘρΘ?... the field emission component formed by the shot layer, The fixing and supporting effect of the support wire on the carbon nanotube field emission layer makes the field emission element have good mechanical properties, is easy to be fixed on the cathode electrode, is easy to operate, can be mass-produced and is conveniently applied to various vacuum field emission devices. [Embodiment] Hereinafter, the present invention will be further described in detail with reference to the accompanying drawings. Referring to FIG. 1 and FIG. 2, an embodiment of the present invention provides a field emission device 10, which includes a support body wire 12 and a cover sheet number Α0101, page 6 / 18 pages 1003097669- 0
[0022] 100年03月21日修正替換頁 撐體線材12外表面的> . 場發射層則於發^米料場發射層14。該奈米碳管 管場發射川提供機^飞切體線材12對該奈米碳 支待與保護作用，也可以提供導 電作用。 [〇〇23]該支撐體線材丨2可選用銅、 ^ -V- ^ ^ s J 銀、金、錄、雜或其他金屬 材料’也可㈣喊或料。該支擇體線材㈣狀爲線 狀，其直徑可根據實際需要而敎，本實施例優選爲幾 十微米到幾毫米。 剛該奈㈣管if發射層14可_奈切卜聚合物複合材 料或奈米碳營一玻璃複合材料，其厚度爲丨微米〜1〇〇〇微 米0 [0025]線狀奈米碳管一聚合物複合材料包括聚合物材料和均勻 分散於該聚合物材料中的奈米碳管。本實施例聚合物材 料可選自聚對笨二甲酸乙二醇酯（卩〇1丫6七以16116了61^_ phthalate，PET)、聚碳酸醋（p〇iyCarbonate，PC) 、丙烯腈一丁二烯丙烯一笨乙烯共聚物 (Acrylonitrile-Butadiene Styrene Terpolymer, ABS)、聚碳酸酯/丙烯腈—丁二烯一苯乙烯共聚物 (PC/ABS)等高分子材料。其中，奈米碳管在該複合材料 中的質量百分含量爲〇. 2%〜10%，本實施例優選爲2%。 [0〇26] 奈米碳管一坡璃複合材料爲含奈米碳管和導電金屬顆粒 的玻璃’奈米碳管和導電金屬顆粒均勻地分散在玻璃中 。導電金屬微粒可以選用銀或氧化銦錫，優選地，導電 金屬微粒由銀製成，且銀的重量約爲玻璃重量的15倍。 095123830 表單編號A0101 第7頁/共18頁 1003097669-0 «43591 [0027] [0028] [0029] [0030] [0031] 095123830 100年03月21日核正替换寅 爲獲得較佳的分散性能，本實施例優選長度爲〇. 1微米 〜20微米、直徑爲0. 5奈米〜100奈米的奈米碳管、其在玻 璃和導電金屬微粒中的重量百分比爲0. 2%〜10°/〇。 另，本實施例奈米碳管場發射層14也可選用帶狀奈米碳 管薄膜包覆於支撐體線材1 2外表面形成場發射元件1 0。 奈米碳管薄膜係由超順排奈米碳管陣列以一定寬度拉出 連續的奈米碳管線形成的帶狀奈米碳管薄膜，其包含有 大量奈米碳管。該奈米碳管之間彼此通過凡德瓦力緊密 結合。本實施例該奈米碟管轉;餐味:爹米碳管的直徑爲〇· 5 奈米〜100奈米，優參奈米碳管薄膜的厚 度爲5奈米-1J梭米[0022] Correction replacement page on March 21, 100. The outer surface of the support wire 12 is > the field emission layer is emitted from the emission field 14 of the rice field. The carbon nanotube field launching machine provides a mechanism for the support and protection of the nano carbon, and also provides a conductive effect. [〇〇23] The support wire 丨2 can be selected from copper, ^ -V- ^ ^ s J silver, gold, recorded, miscellaneous or other metal materials. The shape of the wire (four) is linear, and its diameter can be twisted according to actual needs. This embodiment is preferably several tens of micrometers to several millimeters. Just the Nai (4) tube if the emissive layer 14 can be _Nicheb polymer composite material or nano carbon camp glass composite material, the thickness of which is 丨 micron ~ 1 〇〇〇 micron 0 [0025] linear carbon nanotube-polymerization The composite material comprises a polymeric material and a carbon nanotube uniformly dispersed in the polymeric material. The polymer material of this embodiment may be selected from the group consisting of polyethylene terephthalate (卩〇1丫6-7 to 1611661X phthalate, PET), polycarbonate (p〇iyCarbonate, PC), acrylonitrile A polymer material such as Acrylonitrile-Butadiene Styrene Terpolymer (ABS), polycarbonate/acrylonitrile-butadiene-styrene copolymer (PC/ABS). Wherein, the mass percentage of the carbon nanotubes in the composite material is 0.2% to 10%, and in this embodiment, it is preferably 2%. [0〇26] The carbon nanotube-glass composite material is a glass of carbon nanotubes and conductive metal particles containing carbon nanotubes and conductive metal particles uniformly dispersed in the glass. The conductive metal particles may be selected from silver or indium tin oxide. Preferably, the conductive metal particles are made of silver, and the weight of silver is about 15 times the weight of the glass. 095123830 Form No. A0101 Page 7 / Total 18 Page 1003097669-0 «43591 [0027] [0030] [0031] 095123830 On March 21, 100, the core was replaced by 寅 in order to obtain better dispersion performance, 2%〜10° The weight percentage of the glass and the conductive metal particles is 0.2%~10°, the weight percentage of the glass and the conductive metal particles is 0.2%~10°. /〇. In addition, the carbon nanotube field emission layer 14 of the present embodiment may also be coated with a strip of carbon nanotube film on the outer surface of the support wire 1 2 to form the field emission element 10 . The carbon nanotube film is a ribbon-shaped carbon nanotube film formed by pulling a continuous nano carbon line with a width of a super-sequential carbon nanotube array, which contains a large number of carbon nanotubes. The carbon nanotubes are tightly coupled to each other by Van der Waals. In the present embodiment, the nano-disc tube is rotated; the taste of the rice: the diameter of the carbon nanotubes is 〇·5 nm to 100 nm, and the thickness of the carbon nanotube film of the ginseng rice is 5 nm-1 J.
IEQ 本實施例場發射元件ίο於需要將單個 或多個場發射元件ίο通過其支撐體線材4¾固定於陰極電 極上以形成單個場發射電子源或平面陣列排列的場發射 電子源，並使得奈米碳管，電極電性相 連，通過陰極電極直接施:奇求碳管場發射層14 ，或通過支撐體線材12施米碳管場發射層14 ，可利用奈米碳管材料本身優異的電子場發射性能發射 電子。 請參閱圖3，本發明實施例場發射元件的製備方法包括以 下步驟： (一）提供一支撐體線材。 該支撐體線材可選用銅、銀、金、鎳、鉬或其他金屬材 料，也可選用陶瓷或玻璃。該支撐體線材形狀爲線狀， 表單編號A0101 第8頁/共18頁 1003097669-0IEQ The field emission element of the present embodiment is required to fix a single or a plurality of field emission elements ίο via its support body wire 436 to the cathode electrode to form a single field emission electron source or a field array electron source of a planar array arrangement, and The carbon nanotubes are electrically connected to each other, and are directly applied through the cathode electrode: the carbon nanotube field emission layer 14 is obtained, or the carbon nanotube field emission layer 14 is applied through the support wire 12, and the excellent electrons of the carbon nanotube material itself can be utilized. Field emission performance emits electrons. Referring to FIG. 3, a method for fabricating a field emission device according to an embodiment of the present invention includes the following steps: (1) providing a support body wire. The support wire can be made of copper, silver, gold, nickel, molybdenum or other metal materials, or ceramic or glass. The shape of the support wire is linear, Form No. A0101 Page 8 of 18 1003097669-0
1343591 __ • 100年D3月21日梭正替换頁 其直徑可根據實際需要而選定，本實施例優選爲幾十微 米到幾毫米。 [0032] (二）在該支撐體線材外表面形成一奈米碳管場發射層 [0033] 該奈米碳管場發射層材料可選用奈米碳管一聚合物複合 材料、奈米碳管一玻璃複合材料或奈米碳管薄膜。 [0034] 本實施例以奈米碳管一聚合物複合材料作爲奈米碳管場 發射層的製備方法包括以下步驟··將奈米碳管加入熔融 的聚合物材料中，通過混輾攪拌的方式均勻分散；將該 混合物塗敷於支撐體線材外表面」冷卻後形成奈米碳管 場發射層。 、： [0035] 奈米碳管的製備方法可採用先前技術中的化學氣相沈積 法、電弧放電法、鐳射燒蝕法等，本實施例採用化學氣 相沈積法，所用的奈米碳管直徑範圍爲0. 5奈米〜100奈米1343591 __ • 100 years D3, 21st, the shuttle replacement page The diameter can be selected according to actual needs, and the embodiment is preferably several tens of micrometers to several millimeters. [0032] (2) forming a carbon nanotube field emission layer on the outer surface of the support wire [0033] The carbon nanotube field emission layer material may be selected from a carbon nanotube-polymer composite material, a carbon nanotube A glass composite or carbon nanotube film. [0034] The preparation method of the carbon nanotube-polymer composite material as the nano carbon tube field emission layer in the embodiment includes the following steps: adding a carbon nanotube to the molten polymer material, stirring and stirring The method is uniformly dispersed; the mixture is applied to the outer surface of the support wire" to form a carbon nanotube field emission layer after cooling. [0035] The preparation method of the carbon nanotubes can adopt the chemical vapor deposition method, the arc discharge method, the laser ablation method and the like in the prior art, and the carbon nanotubes used in the present embodiment are used in the chemical vapor deposition method. The diameter range is 0. 5 nm ~ 100 nm
[0036] 本實施例聚合物材料可選自聚嘶笨二甲酸乙二醇酯 (Polyethylene Terephthalate，PET)、聚碳酸酯 (Polycarbonate, PC)、丙豨腈一丁二稀丙稀一笨乙稀 共聚物（Acrylonitrile-Butadiene Styrene Terpolymer, ABS)、聚碳酸酯/丙烯腈一丁二烯一苯乙 烯共聚物（PC/ABS)等高分子材料。本實施例獲得的奈米 碳管聚合物複合材料中奈米碳管在該複合材料中的質量 百分含量爲0. 2%〜10%，本實施例優選爲2%。 本實施例以奈米碳管一玻璃複合材料作爲奈米碳管場發 095123830 表單編號A0101 第9頁/共18頁 1003097669-0 [0037] 1343591 100年03見21日核正替換•再 射層的製備方法包括以下步驟： [0038] 首先，提供一定量的奈米碳管、導電金屬顆粒、有機載 體與玻璃粉； [0039] 其中，有機載體係預先將作爲溶劑質量百分比約爲95%的 松油醇和作爲穩定劑質量百分比約爲5 %的乙基纖維素水 浴80°C形成的混合劑。奈米碳管可以預先通過化學氣相 沈積法、電弧放電法或鐳射燒蝕法等先前技術製備，其 長度爲0. 1微米〜20微米，直徑爲0. 5奈米〜100奈米。 / [0040] [0041] 其次，混合奈米碳驚· 粉形成漿料；$ 優選地，形成的漿料中有 f機載體和玻璃 約爲20%[0036] The polymer material of this embodiment may be selected from the group consisting of polyethylene terephthalate (PET), polycarbonate (Polycarbonate, PC), acrylonitrile, butadiene propylene A polymer material such as a copolymer (Acrylonitrile-Butadiene Styrene Terpolymer, ABS) or a polycarbonate/acrylonitrile-butadiene-styrene copolymer (PC/ABS). The carbon nanotube polymer composite material obtained in the present embodiment has a mass percentage of the carbon nanotubes in the composite material of 0.2% to 10%, preferably 2% in this embodiment. In this embodiment, the carbon nanotube-glass composite material is used as the carbon nanotube field 095123830. Form No. A0101 Page 9/18 pages 1003097669-0 [0037] 1343591 100 years 03 see 21 nuclear replacement • re-shooting layer The preparation method comprises the following steps: [0038] First, a certain amount of carbon nanotubes, conductive metal particles, organic carrier and glass powder are provided; wherein the organic carrier is preliminarily used as a solvent mass percentage of about 95%. Terpineol and a mixture formed as a stabilizer having a mass percentage of about 5% in an ethylcellulose water bath at 80 °C. 5纳米〜100纳米。 The carbon nanotubes can be prepared by a chemical vapor deposition method, an arc discharge method or a laser ablation method, the length of 0. 1 micron to 20 microns, a diameter of 0. 5 nanometers ~ 100 nanometers. [0041] Next, the nano-carbon powder is mixed to form a slurry; preferably, the formed slurry has an organic carrier and glass of about 20%.
導電金屬顆粒154的質量百分比約爲791#敏璃粉的質量 .· ：v'k. 百分比約爲5%。奈米碳管相對於導電金fr顆粒和玻璃粉 的質量百分比約爲0. 2%〜1The mass percentage of the conductive metal particles 154 is about 791# the mass of the sensitive glass powder. · :v'k. The percentage is about 5%. 2%〜1 The mass percentage of the carbon nanotubes relative to the conductive gold fr particles and the glass powder is about 0. 2%~1
Intel lech [0042]Intel lech [0042]
最後，將上述混合漿料塗材的外表面，並 經過烘乾、摩擦、除’塵、谬從而形成場發射元 件。 [0043] 本實施例優選爲在3 0 0〜6 0 0 ° C下進行烘乾和焙燒從而形 成場發射元件。烘乾的目的在於使有機載體揮發。焙燒 的目的在於使玻璃粉熔融從而將導電金屬微粒和奈米碳 管粘結。 [0044] 本實施例以奈米碳管薄膜作爲奈米碳管場發射層14的製 備方法包括以下步驟： 095123830 表單編號A0101 第10頁/共18頁 1003097669-0 1D0年D3月21日核正替换頁 [〇〇45] 首先，提供一帶狀奈米碳管薄膜。 [0046] 本實施例製備該奈米碳管薄膜的方法包括以下步驟：提 供一奈米碳管陣列，按一定的寬度用一鑷子夾住或用膠 帶粘取超順排奈米碳管陣列中的一束奈米碳管，施加外 力抽拉。由於凡德瓦力的作用，奈米碳管束端部首尾連 接在一起，沿柚拉方向形成一帶狀奈米碳管薄膜。 [0047] 其次，將該帶狀奈米碳管薄膜纏繞於支撐體線材的外表 面，形成場發射元件。 [0048] 本實施例可在支撐體線材的外表面纏繞單層或多層的奈 米碳管薄膜，以包覆整個支撐體線材巧外表面，並通過 在有機溶劑中浸沒以使奈米碳’管薄膜牢固地粘覆於支撐 體線材的外表面。本實施例所選用的有機溶劑爲乙醇。 [0049] 上述能抽拉奈米碳管薄膜的奈米碳管陣列，需滿足以下 三個條件：基底表面平整光滑；生長速率高；反應前體 分壓低。 [0050] 另，帶狀奈米碳管薄膜的寬度和厚度可由抽拉工具的尖. .... - ' 端尺寸或膠帶的尺寸控制，帶狀奈米碳管薄膜的長度由 奈米碳管陣列的面積決定。抽拉奈米碳管的力的大小由 奈米碳管線的寬度和厚度決定，寬度和厚度越大，所需 的力越大。本實施例帶狀奈米碳管薄膜的厚度範圍優選 爲5奈米〜10微求® [0051] 本實施例場發射元件可根據實際需要直接製成所需場發 射元件的長度，可替代地，爲製作方便也可先製成長線 ，再通過機械剪切或鐳射切割的方法切短成所需長度的 表單蝙號A0101 第11頁/共18頁 1003097669-0 1343591 100年03月21日孩正替换K 場發射元件。進一步地，本實施例場發射元件還可經過 —表面處理過程，如通過鐳射照射或機械摩擦處理該場 發射元件，以使得分散在聚合物或玻璃材料中的奈米碳 管露頭以提高場發射性能。另’該場發射元件還可經過 大電流場發射老化等方式進行處理以使得該場發射元件 能充分發揮奈米碳管本身的場發射性能。 [0052] 本發明包含支撐體線材和奈米碳管場發射層的場發射元 件’其優點在於：首先，使用奈米碳管場發射層作爲發 射體發射電子可利用奈米碳备本參，良#電子發射性能 ，其次’支撲體線#采鐵成的場發射Finally, the outer surface of the above mixed slurry is coated, and dried, rubbed, dust removed, and ruthenium to form a field emission element. [0043] This embodiment preferably performs drying and firing at 300 to 600 ° C to form a field emission element. The purpose of drying is to volatilize the organic vehicle. The purpose of the calcination is to melt the glass frit to bond the conductive metal particles and the carbon nanotubes. [0044] The preparation method of the carbon nanotube film as the carbon nanotube field emission layer 14 in the embodiment includes the following steps: 095123830 Form No. A0101 Page 10 / Total 18 Page 1003097669-0 1D0 Year D March 21 Replacement page [〇〇45] First, a strip of carbon nanotube film is provided. [0046] The method for preparing the carbon nanotube film of the embodiment comprises the steps of: providing an array of carbon nanotubes, clamping or smearing a super-aligned carbon nanotube array with a tape at a certain width; A bundle of carbon nanotubes is applied by external force. Due to the effect of van der Waals force, the ends of the carbon nanotube bundles are connected end to end, forming a strip of carbon nanotube film along the direction of the grapefruit. [0047] Next, the strip-shaped carbon nanotube film is wound around the outer surface of the support wire to form a field emission element. [0048] In this embodiment, a single-layer or multi-layered carbon nanotube film may be wound on the outer surface of the support wire to cover the outer surface of the entire support wire and immersed in an organic solvent to make the nanocarbon' The tube film is firmly adhered to the outer surface of the support wire. The organic solvent selected for this example is ethanol. [0049] The above-mentioned carbon nanotube array capable of drawing a carbon nanotube film needs to satisfy the following three conditions: the surface of the substrate is smooth and smooth; the growth rate is high; and the partial pressure of the reaction precursor is low. [0050] In addition, the width and thickness of the strip-shaped carbon nanotube film can be controlled by the tip of the drawing tool, .... - 'end size or tape size, and the length of the strip-shaped carbon nanotube film is made up of carbon nanotubes The area of the array is determined. The force of the carbon nanotubes is determined by the width and thickness of the carbon nanotubes. The greater the width and thickness, the greater the force required. The thickness of the strip-shaped carbon nanotube film of the embodiment is preferably in the range of 5 nm to 10 μm. [0051] The field emission element of the embodiment can be directly formed into the length of the required field emission element according to actual needs, or alternatively For the convenience of production, it can be made into a long line first, and then cut into the required length by mechanical shearing or laser cutting. The bat number A0101 Page 11 / 18 pages 1003097669-0 1343591 100 years old March 21 The K field emission element is being replaced. Further, the field emission element of the present embodiment may also be subjected to a surface treatment process such as laser irradiation or mechanical rubbing to process the field emission element such that the carbon nanotubes are dispersed in the polymer or glass material to improve field emission. performance. The field emission element can also be processed by means of large current field emission aging or the like to enable the field emission element to fully utilize the field emission performance of the carbon nanotube itself. [0052] The present invention includes a field emission element of a support wire and a carbon nanotube field emission layer, which has the advantage that, first, a nanocarbon carbon nanotube field emission layer is used as an emitter to emit electrons, and a nanocarbon preparation ginseng can be utilized. Liang #electron emission performance, followed by 'supporting body line# mining field into the field
元件具有宏觀太寸，利用 層固定和支撐作用，使場考 管場發射 機械性能 ’容易操作，能夠大量生産並且方便)1|_带於各種真空 場發射器件。 卞 [0053] 綜上所述，本發明確已符代是丨f，遂依法提 出專利申請。惟，以上所月之較佳實施例 ，自不能以此限制本案之申〔〔多f專㈤够圍。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。 [0054] [0055] [0056] 【圖式簡單說明】 圖1係本發明實施例的場發射元件的立體示意囷。 圖2係圖1沿11 -11線的剖面示意圓。 圖3係本發明實施例的場發射元件的製備方法的流程示意 圖。 095123830 表單碥號A0101 第丨2頁/共18頁 1003097669-0 1343591 _ ，· 100年03月21日修正替换頁 【主要元件符號說明】 [0057] 場發射元件10，20 [0058] 支撐體線材12, 22 [0059] 奈米碳管場發射層14，24 095123830 表單編號A0101 第13頁/共18頁 1003097669-0The components are macroscopically too large, using layer fixing and support to make the field test field launch mechanical performance 'easy to operate, mass production and convenient) 1|_ with various vacuum field emission devices.综 [0053] In summary, the present invention has indeed been replaced by 丨f, and patent applications are filed according to law. However, the preferred embodiment of the above month can not limit the application of this case ([multi-f (5) is sufficient). Equivalent modifications or variations made by those skilled in the art to the spirit of the invention are intended to be included within the scope of the following claims. [0056] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a field emission element according to an embodiment of the present invention. Figure 2 is a schematic cross-sectional view of Figure 1 taken along line 11-11. Fig. 3 is a flow chart showing a method of preparing a field emission element of an embodiment of the present invention. 095123830 Form nickname A0101 Page 2 of 18 Page 303097669-0 1343591 _ , · March 21, 2011 Correction replacement page [Key element symbol description] [0057] Field emission element 10, 20 [0058] Support body wire 12, 22 [0059] Nano Carbon Tube Emission Layer 14, 24 095123830 Form No. A0101 Page 13 of 18 Page 1003097669-0
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| CN101567230B (en) | 2008-04-25 | 2012-06-20 | 清华大学 | Preparation method of transparent conductive thin film |
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