201041006 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種奈米碳管場發射源之製造方法，特別是指一種 I 製造多方向的電子發射路徑之奈米碳管發射源之製造方法。 【先前技術】 奈米碳管自90年代被發現以來，由於其具有奈米等級的尺寸與很 大的表面基’且具有由六方碳原子點陣構成之特殊圓柱管結構，以及 具有獨特的電、磁、光學特性和應用潛力，因此特別受到褐目。奈米 碳管具有極小的尖端曲率半控、極小尺寸、中空狀、高化學穩定度以 及高機械強度，可提供多元化的應用，例如場發射源、儲氫的載具、 至溫時的電晶體等，特別是高的管徑長度比與高化學穩定度，使其成 為較具前_場發射源’所以奈米碳管有著極佳的場發射特性，在較 低電壓下所產生的電場可引發出大的電流密度，使其成為場發射陰極 發射源的最佳材料。 目刖製作奈米碳管陰極結構的方式主要有兩種方式，一種是直接 利用化學氣相沉積法(CVD)法在玻璃基板上直接成長奈米碳管，但合 成溫度超過基板的軟化溫度，同時對於大面積顯示器的應用亦受到限 〇制，另—種方式是利用網版印刷的方式直接將奈米碳管漿料網印於基 板上’與CVD法相比，網印法不僅成本較低，製作相對簡單，且可以 大面積印刷生產。但是奈米碳管漿料在網印於基板後，在高溫燒結過 釭十’奈米碳管會與漿料中之有機載體(〇rganjcvehjc|e)反應而造成質 量損失很大，奈米碳管的發射穩定性變差，另外利用網印法所製造之 結構’發射源無方向性，因此需要進—步的活化，常見的方式為膠帶 (adhesive tap丨ng)將平坦之礙管拉起而與基板垂直，但此方法會將膠帶 ^的化學物賊留於陰極結構中而造成二次污染，且直接接觸也會破 壞結構而影響場發射穩定性、壽命等。 有鑑於此，本發明遂提出一種奈米碳管場發射源之製造方法，以 201041006 改善存在於先前技術中之該些缺失。 【發明内容】 本發明的主要目的在於提供一種奈米碳管場發射源之製造方法， 可省略後續的活化步驟，以簡化奈米碳管場發射源的製程，進而降低 製造成本。 本發明之另一目的係提供一種可於較低溫下進行反應，且不需外 加碳氫化合物氣體之奈米碳管場發射源之製造方法，以減低製造上的 危險性。 本發明之再一目的係提供一種可應用於場發射顯示器或高效能發 光元件上的奈米碳管場發射源之方法。 為達到上述目的，本發明提供一種奈米碳管場發射源之製造方 法’包含提供一基板；設置一電極層於該基板上；提供一混合物，其 係由奈米碳管漿料及碳粉混和而成；以及利用網印將混合物塗佈於電 極層上’並燒結以進行熱裂解反應而形成一刺螺狀奈米碳簽結構之奈 米碳管發射層。 另外’本發明製造的奈米碳管場發射源可應用於場發射顯示器或 高效能發光元件上，以場發射顯示器為例，依照上述步驟獲得陰極板 後，可組裝一場發射顯示器，其方法包含：提供一陰極板，其上表面 設置一電極層，而電極層上具有刺蜎狀奈米碳簇結構之奈米碳管發射 層；於陰極板上設置一空間支撐器；於空間支撐器的一頂緣設置一陽 極板’使空間支撐器介於陰極板及陽極板之間；以及將陰極板、空間 支撐器與陽極板置入於一真空腔體内，並進一步地對該陰極板、空間 支撐器及陽極板進行封裝；依上述步驟即可完成場發射顯示器。 為使對本發明的目的、特徵及其功能有進一步的了解，茲配合圖 式詳細說明如下： 口 【實施方式】 请參閱第一圖，為本發明之奈米碳管場發射源之製造方法之步驟 201041006 流，圖。請-併參閱第二圖，為本發明製造陰極板之結構剖視圖。於 第圖中’奈米碳管場發射源之步驟流程包含：步驟Si〇:提供一基 板211而基板211係為玻璃基板、塑膠基板、陶竟基板或石夕基板者。 步驟sn :設置一電極層212於基板211上，其中電極層212 $製作過程包含下列步驟’將一感光性導電漿料塗佈於此基板211的 一表面上’利用光微影製程，將圖案作出，且燒結(sintering)後完成電 極層212，微影製程包括經麟後以光罩定義_，並作曝光和顯影。 步驟S12 :提供-由奈米碳錄料及雜混和喊之混合物，其 中混合物係_—三賴裝置將奈米碳管雜與碳粉均句混合而成， 〇奈米碳管漿料係包含多壁奈米碳管(MWCNTs)、有機載體(〇rganjc vehicle) ’例如松油醇(terpine〇l)或乙基纖維素(EC)、黏結劑，例如玻 璃柘(frits)、導電粉末及分散劑，例如聚乙醇基紛_員界面活性劑⑽⑽ X 100)。本發明所選用的碳粉可由回收的碳粉閘中取得，而碳粉係包 含磁性粒子、高分子及碳黑枝，< 粉於高溫的侧下高分子會裂解 成碳原子與鐵、鈷及鎳等粒子反應生成奈米碳管。 步驟S13 :利用網版印刷方式將混合物塗佈於電極層212上。 步驟S14 . it行Hx使混合物騎減解反應祕成—刺螺狀 奈米碳簇結構之奈米碳管發射層213。 〇 #巾’於步驟S14巾’混合物係藉由複數階段不肖加練溫溫度 的升溫加齡驟使魏行鋪解反應，騎溫至室溫，魏結步驟包 含：對混合物進行加熱’使其升溫至第-階段的加熱溫度並持溫-段 時間，使高分子進行第-階段除氫、去除不需要的揮發產物之反應。 於本發明中，第-階段的加熱恒溫溫度較佳為在3〇〇〜35(rc之間，自 。室溫加熱至，-階段的加熱恆溫溫度的升溫速率較佳為每分鐘2〜5 C。待完成第-階段的加熱溫度加織，接著再升溫至第三階段的加 熱奴並持溫-段時間，使高分子進行第二階段的熱裂解反應，此時 石反粉與奈米碳管漿料中的高分子在熱裂解反應中所裂解出的碳當作碳 源’可生長卿狀奈米碳麟構之奈米碳管發射層213 ，因此，不需 5 201041006 外加碳氫化合物氣體，以減低習知技術所製造奈米碳管場發射源的危 險性。於本發明中，第二階段的加熱恆溫溫度較佳為在35〇〜5〇(rc之 間，自室溫加熱至第二階段的加熱恆溫溫度的升溫速率較佳為每分鐘 2〜5°C 〇 由於碳粉之裂解溫度較低，當碳粉與奈米碳管漿料中的多壁奈米 碳管進行裂解反應時，除了可降低多壁奈米碳管被氧化的機率，同時 也可以合成出有利於場發射效果的碳簇材料，此材料的特點為刺蜎狀 碳簇的結構可使其始終有一面朝向陽極，因此，可以減少後續的一些 表面處理步驟，而解決現今製備及活化陰極結構程序複雜化的缺點， 換句話說，即可得到高電流密度之場發特性，此外，更可以達到縮短 製作程序及製㈣間崎低成本之優點，域可有聽用於大面積製 程製作場發射平面顯示器或高效能發光元件上。 此外，為使可獲得產量較多的刺蜎狀奈米碳簇，亦可將混合物進 行熱裂解反應的步驟，其包含—通人氣體的步職先於鮮解反應中 升溫至第-P桃的加熱溫度恆溫前，於通人氮氣前先通人空氣，待溫 度升至第二階段的加熱溫度後改通入氮氣以置換反應室中的空氣藉 此，依照上述之製造步驟，在燒結的過程巾，氣體、溫度及混合物能 夠促使奈米碳管的生成，除了能夠保護原本的奈米碳管不受破壞外， 亦同時可以成長出綱狀奈米碳竊結構之奈米碳管發射層213，待燒 結元成之後，即可完成一陰極板21。 请參閱第二圖及第四圖，當經由上述燒結以使混合物進行熱裂解 反應完的產物後’可使崎描錢子臟鏡(SEM)進行觀察本發明所 =之製造方法所製造出的刺·奈米碳蔟結構之影像圖。由於奈米 碳管是呈現網狀向四面八方發射出電子，因此，本發明所製造出刺 螺狀奈米碳_構係為多方向之電子發射路徑之奈米碳管發射層，所 以不須經過活化的步驟’即可達到高電流密度、低起始電壓(turn_〇n voltage)之特性。 本發明製造的奈米碳管場發獅可應場發射赫ϋ或高效能 201041006 發光元件上，讀職場發棚4為例，依照第—圖之夺 發射源的製造雜轉喊得陰缺21後，可絲—% 如第五圖所示’場發射顯示器5〇係包含：提供—基板211，其上 設置有-電極層作為-陰極層212，而陰極層211上具有刺螺狀太 碳簇結構之奈純料_ 213,接祕陰極板21上設i複數* = 樓器(spa峰1，並於此些空間支樓器51的一頂緣設置一陽極 使空間支撑器51介於陰極板21及_板52之間，陽極板 Ο 明導電玻璃_-9_，其中，陽極板52下表面設置有一透明導2 作為陽極層53，且陽極層53對應於與陰極板21，並於陽極層5 網印一層營光體(__)54，螢光體54是可因應電路設計的需长， 而為下述兩種型態：第-種是形成呈紅綠藍(簡稱RGB)三原色 別獨立没置第二種是將RGB三原色同時形成在單一螢光體 ο t併參閱第五圖及第六圖’第六圖為本發_試場發射顯示器 之不思圖’將陰極板21、空間支撐器51及陽極板52置人於—真空腔 體61内’射，可利用幫浦將腔體的壓力抽至10-5T〇rr以下’並進 極板21、空間支撐器52及陽極板53進行封裝，即可完成 G。本發明可個-電壓供應裝置62(例如最高可提 H V)提供一電壓於陰極板21及陽極板52之間用以加速自陰 反上U碳〗發射層213以多方向發射出電子並撞擊到陽極 板52的螢光體54上，則螢光體54即會激發出可見光源。 以上所述之實施例僅係為說明本發明之技術思想及特點，其目的 、使熟習此項技藝之人士能夠瞭解本發明之内容並據以實施，當不能 發明之專利範圍，即大凡依本發明所揭示之精神所作之均 專變化或修飾，健减在本發明之補範圍内。 【圖式簡單說明】 第一圖為本_之奈米碳管場贿狀觀方法之步職程圖。 201041006 第二圖為本發a·猶極板之結構剖視圖。 第三圖為本發明使用掃描式電子顯微鏡(SEM)進行觀察刺蜎狀卉 簇結構之影像圖。 T/、厌 米後 簇結構之影像圖 第四圖為本發明使用掃描式電子顯微鏡(SEM)進行觀察刺蜎狀太 第五圖為本發明應用於場發射顯示器之剖視圖。 第六圖為本發明測試場發射顯示器之示意圖。 【主要元件符號說明】 21陰極板 211基板 212陰極層 213奈米碳管發射層 50場發射顯示器 51空間支撐器 52陽極板 53陽極層 54螢光體 61真空腔體 62電壓供應裝置201041006 VI. Description of the Invention: [Technical Field] The present invention relates to a method for manufacturing a carbon nanotube field emission source, and more particularly to a method for manufacturing a carbon nanotube emission source for manufacturing a multi-directional electron emission path. method. [Prior Art] Since the discovery of the carbon nanotubes in the 1990s, due to its nano-scale size and large surface base, and a special cylindrical tube structure composed of hexagonal carbon atom lattices, and unique electrical , magnetic, optical properties and application potential, so it is particularly affected by brown eyes. Nano carbon tubes have a small tip curvature half control, very small size, hollow shape, high chemical stability and high mechanical strength, which can provide a variety of applications, such as field emission sources, hydrogen storage vehicles, and temperature-to-temperature Crystals, etc., especially high tube diameter ratio and high chemical stability, make it a more front-field emission source' so the carbon nanotubes have excellent field emission characteristics, and the electric field generated at lower voltage It can induce a large current density, making it the best material for the field emission cathode emission source. There are two main ways to produce the cathode structure of the carbon nanotubes. One is to directly grow the carbon nanotubes directly on the glass substrate by chemical vapor deposition (CVD), but the synthesis temperature exceeds the softening temperature of the substrate. At the same time, the application of large-area display is limited, and the other way is to use the screen printing method to directly print the nano-carbon tube slurry on the substrate. Compared with the CVD method, the screen printing method is not only cheaper. , the production is relatively simple, and can be printed on a large area. However, after the carbon nanotube slurry is screen printed on the substrate, the high temperature sintering of the 釭10' carbon nanotubes reacts with the organic carrier in the slurry (〇rganjcvehjc|e), resulting in a large mass loss, nanocarbon The emission stability of the tube is deteriorated, and the structure manufactured by the screen printing method has a non-directionality of the emission source, so that activation is required, and the common method is that the tape is pulled up by the adhesive tape. And perpendicular to the substrate, but this method will leave the chemical thief of the tape ^ in the cathode structure and cause secondary pollution, and direct contact will also damage the structure and affect the field emission stability, life and so on. In view of this, the present invention proposes a method of manufacturing a carbon nanotube field emission source, which improves the defects existing in the prior art with 201041006. SUMMARY OF THE INVENTION A primary object of the present invention is to provide a method for fabricating a carbon nanotube field emission source, which can omit subsequent activation steps to simplify the process of the carbon nanotube field emission source, thereby reducing manufacturing costs. Another object of the present invention is to provide a method for producing a carbon nanotube field emission source which can be reacted at a relatively low temperature without the need for an additional hydrocarbon gas to reduce the manufacturing risk. Still another object of the present invention is to provide a method of applying a carbon nanotube field emission source to a field emission display or a high performance light-emitting element. In order to achieve the above object, the present invention provides a method for manufacturing a carbon nanotube field emission source, comprising: providing a substrate; disposing an electrode layer on the substrate; and providing a mixture which is mixed with a carbon nanotube slurry and a carbon powder. And forming a carbon nanotube emitting layer of a thorn-like nanocarbon carbon-nickel structure by coating the mixture on the electrode layer by screen printing and sintering for thermal cracking reaction. In addition, the nano carbon nanotube field emission source manufactured by the invention can be applied to a field emission display or a high-performance light-emitting element. Taking a field emission display as an example, after obtaining the cathode plate according to the above steps, a field emission display can be assembled, and the method includes Providing a cathode plate having an electrode layer on the upper surface thereof and a carbon nanotube emitting layer having a thorn-like carbon nano-cluster structure on the electrode layer; a space supporter on the cathode plate; and a space supporter a top edge is provided with an anode plate' such that the space support is interposed between the cathode plate and the anode plate; and the cathode plate, the space supporter and the anode plate are placed in a vacuum chamber, and further the cathode plate, The space support and the anode plate are packaged; the field emission display can be completed according to the above steps. In order to further understand the objects, features and functions of the present invention, the following detailed description will be given with reference to the following: Port [Embodiment] Please refer to the first figure, which is a manufacturing method of a carbon nanotube field emission source of the present invention. Step 201041006 Flow, figure. Please refer to the second drawing for a cross-sectional view of the structure of the cathode plate of the present invention. The step flow of the 'nanocarbon tube field emission source in the figure includes: Step Si: providing a substrate 211 and the substrate 211 is a glass substrate, a plastic substrate, a ceramic substrate or a stone substrate. Step sn: an electrode layer 212 is disposed on the substrate 211, wherein the electrode layer 212$ fabrication process comprises the following steps of: applying a photosensitive conductive paste to a surface of the substrate 211 by using a photolithography process to pattern After the sintering is completed, the electrode layer 212 is completed, and the lithography process includes a reticle defined by the lining, and is exposed and developed. Step S12: providing - a mixture of nano carbon recording material and miscellaneous mixing and shouting, wherein the mixture is made up of a mixture of carbon nanotubes and carbon powder, and the carbon nanotube slurry comprises a plurality of walls. Carbon nanotubes (MWCNTs), organic carriers (〇rganjc vehicle) such as terpineol or ethyl cellulose (EC), binders, such as glass frits, conductive powders and dispersants, For example, a polyglycol based surfactant (10) (10) X 100). The carbon powder selected by the invention can be obtained from the recovered toner gate, and the carbon powder comprises magnetic particles, a polymer and a carbon black branch, and the powder is cracked into carbon atoms and iron and cobalt under the high temperature side. It reacts with particles such as nickel to form a carbon nanotube. Step S13: The mixture is applied onto the electrode layer 212 by screen printing. Step S14. The line Hx causes the mixture to ride on the decomposing reaction to form a carbon nanotube emitting layer 213 of a thorn-like nanocarbon cluster structure. 〇#巾'in the step S14 towel' mixture is caused by a plurality of stages of temperature increase and temperature increase of the ageing step, so that Wei Xing will dissolve the reaction, riding to warm to room temperature, and the Wei-junction step includes: heating the mixture to make it The temperature is raised to the heating temperature of the first stage and held for a period of time to allow the polymer to undergo a first-stage dehydrogenation reaction to remove unwanted volatile products. In the present invention, the first-stage heating constant temperature is preferably between 3 〇〇 and 35 (rc, from room temperature heating to, - the stage heating temperature is preferably 2 to 5 per minute. C. To complete the first stage of the heating temperature and weave, and then heat up to the third stage of the heating slave and hold the temperature for a period of time, so that the polymer undergoes the second stage of thermal cracking reaction, at this time, stone anti-powder and nano carbon The carbon cleavage of the polymer in the tube slurry in the thermal cracking reaction is used as a carbon source to grow the carbon nanotube emitting layer 213 of the sapphire nanocarbon arsenic. Therefore, it is not necessary to add 5 201041006 to the hydrocarbon. The gas is used to reduce the risk of the carbon nanotube field emission source produced by the prior art. In the present invention, the second stage heating temperature is preferably between 35 〇 and 5 〇 (rc, heated from room temperature to The heating rate of the second stage of the heating constant temperature is preferably 2 to 5 ° C per minute. 〇 Since the cracking temperature of the carbon powder is low, the carbon nanotubes and the carbon nanotubes in the carbon nanotube slurry are lysed. In addition to reducing the probability of oxidation of multi-walled carbon nanotubes, It is possible to synthesize a carbon cluster material which is advantageous for the field emission effect, and the material is characterized in that the structure of the hedgehog carbon cluster can have one side facing the anode at all times, thereby reducing the subsequent surface treatment steps and solving the current preparation and The disadvantage of the complicated process of activating the cathode structure is that, in other words, the field emission characteristics of the high current density can be obtained, and in addition, the advantages of shortening the production process and the system (4) the low cost of the room can be achieved, and the domain can be used for large-area processes. The production field emits a flat panel display or a high-performance light-emitting element. In addition, in order to obtain a high-yield locust-shaped nanocarbon cluster, the mixture may be subjected to a thermal cracking reaction step, which includes a stepping of the gas Before the temperature of the fresh-reacting reaction is raised to the heating temperature of the first-P peach, the air is passed before the nitrogen gas is passed, and the temperature is raised to the heating temperature of the second stage, and then the nitrogen is replaced to replace the air in the reaction chamber. Thereby, according to the above manufacturing steps, in the process towel of sintering, the gas, the temperature and the mixture can promote the formation of the carbon nanotubes, in addition to protecting the original The carbon nanotubes are not damaged, and at the same time, the carbon nanotube emitting layer 213 of the nano-carbon stealing structure can be grown. After the sintering is completed, a cathode plate 21 can be completed. In the fourth figure, after the above-mentioned sintering is carried out to thermally pyrolyze the mixture, the thorn-nanocarbonium produced by the manufacturing method of the present invention can be observed by the SEM. The image of the structure. Since the carbon nanotubes emit electrons in all directions in a mesh shape, the carbon nanotube emission layer of the electron-emitting path of the multi-directional is produced by the present invention. Therefore, the characteristics of high current density and low starting voltage (turn_〇n voltage) can be achieved without the step of activation. The carbon nanotube field lion manufactured by the invention can be used for field emission or high performance. 201041006 On the illuminating element, read the workplace 4 as an example. According to the production of the source of the ray, the yoke of the source is smashed by 21, and the wire is as shown in the fifth figure. : providing a substrate 211 on which an -electrode layer is disposed It is a cathode layer 212, and the cathode layer 211 has a thorn-like carbon cluster structure of neat material _ 213, and the cathode cathode plate 21 is provided with i complex number* = floor stone (spa peak 1, and these space branches) A top edge of the floor 51 is provided with an anode such that the space support 51 is interposed between the cathode plate 21 and the plate 52, and the anode plate is provided with a conductive glass _-9_, wherein a transparent guide 2 is disposed on the lower surface of the anode plate 52. The anode layer 53 and the anode layer 53 correspond to the cathode plate 21, and a layer of the camping body (__) 54 is screen printed on the anode layer 5. The phosphor 54 is required to be designed according to the circuit design, and is the following two types. Type: The first type is formed in red, green and blue (abbreviated as RGB). The three primary colors are independent. The second is to form RGB three primary colors simultaneously in a single phosphor. ο and see the fifth and sixth figures. For the hair _ test field emission display, the cathode plate 21, the space support 51 and the anode plate 52 are placed in the vacuum chamber 61, and the pressure of the cavity can be pumped to the 10- G is completed by encapsulating 5' rrrr below 'parallel plate 21, space support 52 and anode plate 53. The present invention can provide a voltage-supply device 62 (e.g., up to HV) to provide a voltage between the cathode plate 21 and the anode plate 52 for accelerating the self-injection of the U-carbon emission layer 213 to emit electrons in multiple directions and collide. Upon reaching the phosphor 54 of the anode plate 52, the phosphor 54 excites a source of visible light. The embodiments described above are only for explaining the technical idea and the features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the contents of the present invention and implement them according to the scope of patents that cannot be invented. The variations or modifications made by the spirit of the invention are within the scope of the invention. [Simple description of the diagram] The first picture is the step-by-step diagram of the method of bribery. 201041006 The second figure is a cross-sectional view of the structure of the a. The third figure is an image of the present invention using a scanning electron microscope (SEM) to observe the structure of the hedgehog cluster. Image of T/, anatomical cluster structure The fourth figure is a view of the present invention using a scanning electron microscope (SEM) to observe the shape of the hedgehog. The fifth figure is a cross-sectional view of the present invention applied to a field emission display. The sixth figure is a schematic diagram of the test field emission display of the present invention. [Main component symbol description] 21 cathode plate 211 substrate 212 cathode layer 213 carbon nanotube emission layer 50 field emission display 51 space support 52 anode plate 53 anode layer 54 phosphor 61 vacuum chamber 62 voltage supply device