200822187 九、發明說明： 發明所屬之技術領域 本發明揭示一種適合置於熱化學氣相沉積反應器内的 一平面加熱底板上的氣體流動控制及預熱裝置，及使用此 裝置在玻璃基板上低溫且均勻的生長奈米碳管的方法。 先前技術 區人’州專利申清案Ep 1061041 A1揭示一種低溫熱cvD 设備和利用設備合成奈米碳管的方法，是將該設備中的反 應管分成在空間上鄰接氣體輸入部分、用於熱分解輸入氣 體的第一區，和空間上鄰接排氣部分、用於利用前述的分 解氣體合成奈米碳管第二區，並且，保持兩區的溫度，使 第二區的溫度低於第一區的溫度。在奈米碳管之生成反應 區使用兩種不同之觸媒基板，其中一片作為助觸媒使用， 主要作用為加速乙炔裂解，成份為Pd、心及^等，另一片 則沉積有鐵、鈷、鎳或其合金觸媒膜，是主要生成奈米碳 管的觸媒。將具有鐵、鈷、鎳或其合金觸媒膜的觸媒基板 用餘刻氣腐|虫，形成奈米級催化性顆粒，利用上述設備先 於第一區高熱分解碳源氣，然後，通過第二區在等於或低 於基片形變溫度的溫度下使用被助觸媒分解的碳源氣，經 熱化學氣相沉積反應，在基板上每個隔離的奈米級催化性 金屬顆粒上生長垂直排列的碳奈米管。此前案技術除了使 用攝氏450至650度的低溫反應區段外，仍須使用攝氏7〇〇 至1〇〇〇度的高溫進行碳源氣的熱分解（第一區），並非是純 5 200822187 低溫製程，也因此此前案技術必須使用特殊的CVD反應 器。此外於此前案技術中必須於兩基材上形成兩種不同的 金屬觸媒層，再將此兩種基材以金屬層相對的方式間隔著 一段距離放置於熱CVD反應器中。很明顯的，此前案技術 的製程複雜、成本高、且不容易實施。 歐洲專利申請案EP 1061043 A1揭示一種利用金屬觸 媒層低溫合成碳奈米管的方法。在該合成方法中，在基材 上开> 成金屬觸媒層，該金屬觸媒層被餘刻形成隔離的奈米 級催化性金屬顆粒。然後，通過在等於或低於基片形變溫 度的溫度下用被分解的碳源氣，經熱化學汽相沈積，在基 片上每個隔離的奈米級催化性金屬顆粒上生長垂直排列的 石反奈米官。該被分解的碳源氣係使用一碳源氣分解金屬觸 媒層。於此前案技術中必須於兩基材上形成兩種不同的金 屬觸媒層，再將此兩種基材以金屬層相對的方式間隔著一 段距離放置於熱CVD反應器中。很明顯的，此前案技術為 改進EP1061041 A1之製程專利，主要的進步性為將兩段式 加熱系統更改為一段式加熱系統’但對於觸媒系統並無明 顯之進步性’仍需在兩片基板上制兩種Μ之觸媒系統。 我國發明專们237064揭示-種適用於低溫（低於 熱化學氣相沉積合成奈米碳管的負载金屬觸媒，包 含作為擔體的粒徑介於0.01至1〇微米的貴金屬顆粒及 沉積於該貴金屬顆粒上的金屬觸媒，丨中 旦㈣其寻之合金，及該金屬觸媒對該貴金屬粒子 里比介於0.1:100至10:100之間。該發明專利亦揭示 6 200822187 使用該擔體金屬觸媒的一種於基材上直接低溫合成奈米碳 管的方法’其中於合成奈米碳管後不需去除觸媒擔體。 要在玻璃基板表面直接以低溫熱化學氣相沉積方式來 成長奈米碳管除了需要考量，包括整體製程溫度要低於玻 璃形變溫度、表面觸媒之製備方式、觸媒活性提昇之前處 方式專專技術外’而右要能真正實際應用時更需要考虞 到在大面積玻璃基板上成長奈米複管所容易遭遇到基板表 面碳管成長不均勻與奈米碳管電子放射性質不佳的問題。 此問題很可能是在大面積基板反應時會相對放大反應氣體 積體及氣體流量，易造成反應空間中活性碳分子分布不 均、氣流溫度下降等問題。 發明内容 本發明的一主要目的在提供一種用於熱化學氣相沉積 的氣體流動控制及預熱裝置，其可有效的改善基板表面奈 米碳管成長之均勻性，及提高奈米碳管電子放射性質。 為了達成上述本發明目的，依本發明内容所完成的一 種氣體流動控制及預熱裝置包含：包含一罩蓋，該罩蓋内 叹有一分隔板將此罩蓋分隔成一頂部空間及一底部空間， 其中该分隔板的一側與罩蓋相連，另一側被留有一間隙， 且該頂部空間及底部空間僅能通過該間隙相通；一被設於 該罩蓋上的進氣埠，其用於將氣體導入該頂部空間；及在 相對於該間隙的一側的該罩蓋上設有多個出氣孔，且該多 個出氣孔係位於該分隔板下方與該底部空間流體相通，當 200822187 該氣體流動控制及預熱裝置被蓋於一平面加熱底板上且氣 體由該進氣埠被導入該頂部空間時，該氣體將流過該分隔 板上方，通過該間隙進入該底部空間，流過該平面加熱底 板上’最後由該多個出氣孔流出氣體流動控制及預熱裝 置’於是氣體被充分的加熱並以一層流方式通過該平面加 熱底板上方。 依本發明内容所完成的另一種氣體流動控制及預熱裝 f f k 置包含：一罩蓋，該罩蓋包含一頂板及圍壁；結合於該罩 蓋内並且大體上平行於該頂板的二片分隔板，其中每一片 分隔板的一側分別與該圍壁的一側留有一間隙，而相對的 另一側則密接於該頂板近中央處，其餘的側則密接於該圍 壁’於是該圍壁内部被該二片分隔板分隔成二個頂部空間 及一底部空間，且該二個頂部空間及該底部空間僅能通過 該二個間隙流體相通；二個被設於該頂板上的進氣埠，其 用於將氣體分別導入該二個頂部空間；及被設於該頂板中 央處的多個出氣孔，且該多個出氣孔位於該二片分隔板之 間舁省底#空間流體相通，當氣體流動控制及預熱裝置被 瓜於平面加熱底板上且氣體由該二個進氣埠被導入該二 個頂部空間時，該氣體將流過該二片分隔板上方，通過 二個間隙進人該底部空間，流過該平面加熱底板上，最 由该多個出氣孔流出該氣體流動控制及預熱裝置，於是 體被充分的加熱並以-層流方式通過該平面加熱底板上 方0 8 200822187 本發明亦提供一種低溫熱化學氣相沉積反應器，包含 一平面加熱底板，其具有一進氣管及一出氣管；一可密閉 的罩住該平面加熱底板的活動式上蓋，於是可在該平面加 熱底板上形成一反應艙；及一個如上述的本發明氣體流動 控制及預熱裝置；其中該氣體流動控制及預熱裝置被蓋於 該平面加熱底板上且其進氣埠與該進氣管連接。 較佳的，該平面加熱底板的内部被設有一加熱單元。 以上介紹的兩篇歐洲專利所使用之高溫爐皆為上下端 皆加熱之高溫爐且皆未提及其基材表面之奈米碳管成長之 均勻性及所生長之奈米碳管電子放射性質。本發明與此兩 前案相較具有以下之優點⑴使用—平面式底板式加熱高 溫爐，可降低加熱所需要之能耗；⑺引人_氣體流動控制 及預熱裝置，反應氣體僅需要充滿該裝置之空間即可，不 需充滿整個反應器加熱腔體，降低反應氣體用量；（3)減少 反應之時間，增加產出速率，由於碳管成長需在低氡狀態 下，反應器腔體需先進行吹除之動作，以降低氧含量，由 於本發明的氣體流動控制及預熱裝置之體積遠較反應器腔 體體積小’故可縮短吹除之時間，力口快產出之速率·，（4)不 而要另外使用氣體預加熱系統，本發明的氣體流動控制及 預熱裝置為一雙層空間，且上層空間之溫度較下層空間為 低，當氣體進入上層空間時會被預先加熱及活化，再經由 上下層間之間隙流動到下層空間進行反應；（5)活化系統與 反應系統可同時設計在一加熱區中，可簡化設備；（㈨由於 本發明的氣體流動控制及預熱裝置具有預加熱及活化效果 200822187 故基板表面之觸媒僅使用單一觸媒系統即可；（7)具有連續 式生產之潛力，可將加熱爐與本發明的氣體流動控制及預 熱裝置设計成为離活動式’而進行連續生產，不需長時間 等待加熱及冷卻爐體；及（8)使用本發明的氣體流動控制及 預熱裝置所產製之低溫奈米碳管基板電子放射性質佳且均 勻性隹。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention discloses a gas flow control and preheating device suitable for placement on a flat heating substrate in a thermal chemical vapor deposition reactor, and the use of the device for low temperature on a glass substrate And a uniform method of growing carbon nanotubes. A method for synthesizing a carbon nanotube by using a low-temperature thermal cvD device and a device for synthesizing a carbon nanotube by using a device in the prior art is disclosed in the method of dividing the reaction tube in the device into a spatially adjacent gas input portion. a first zone for thermally decomposing the input gas, and a spatially adjacent exhaust portion for synthesizing the second zone of the carbon nanotubes using the aforementioned decomposition gas, and maintaining the temperature of the two zones such that the temperature of the second zone is lower than The temperature of the first zone. Two different catalyst substrates are used in the reaction zone of the carbon nanotubes. One of them is used as a cocatalyst. The main function is to accelerate the cracking of acetylene, the components are Pd, heart and ^, and the other is deposited with iron and cobalt. , nickel or its alloy catalyst film, is the catalyst that mainly produces carbon nanotubes. A catalyst substrate having a catalyst film of iron, cobalt, nickel or an alloy thereof is formed into a nano-sized catalytic particle by using a residual gas rot | worm, and the carbon source gas is decomposed by the above-mentioned equipment before the first zone, and then passed through The second zone is grown on each of the isolated nano-sized catalytic metal particles on the substrate by a thermal chemical vapor deposition reaction using a carbon source gas decomposed by the promoter at a temperature equal to or lower than the deformation temperature of the substrate. Vertically arranged carbon nanotubes. In addition to the low temperature reaction zone of 450 to 650 degrees Celsius, the prior art technology must still use the high temperature of 7 〇〇 to 1 摄 to thermally decompose the carbon source gas (the first zone), not pure 5 200822187 Low temperature processes, and therefore the prior art must use a special CVD reactor. In addition, in the prior art, two different metal catalyst layers must be formed on the two substrates, and the two substrates are placed in the thermal CVD reactor at a distance apart from each other in a metal layer. Obviously, the prior art technology is complicated, costly, and not easy to implement. European Patent Application EP 1061043 A1 discloses a method for the low temperature synthesis of carbon nanotubes using a metal catalyst layer. In this synthesis method, a metal catalyst layer is opened on the substrate, and the metal catalyst layer is left to form isolated nano-sized catalytic metal particles. Then, vertically aligned stones are grown on each of the isolated nano-grade catalytic metal particles on the substrate by thermal chemical vapor deposition using a decomposed carbon source gas at a temperature equal to or lower than the substrate deformation temperature. Anti-nano official. The decomposed carbon source gas decomposes the metal catalyst layer using a carbon source gas. In the prior art, two different metal catalyst layers must be formed on the two substrates, and the two substrates are placed in a thermal CVD reactor at a distance apart in a metal layer. Obviously, the prior art is to improve the process patent of EP1061041 A1. The main progress is to change the two-stage heating system to a one-stage heating system 'but there is no obvious progress for the catalyst system'. Two kinds of catalyst systems are fabricated on the substrate. China's inventions 237,064 disclose a kind of supported metal catalyst suitable for low temperature (lower than thermal chemical vapor deposition synthesis of carbon nanotubes, containing noble metal particles with a particle size of 0.01 to 1 〇 micron as a support and deposited on The metal catalyst on the noble metal particles, 丨中旦(四) the alloy thereof, and the metal catalyst is between 0.1:100 and 10:100 in the precious metal particles. The invention patent also discloses 6 200822187 A method for directly synthesizing a carbon nanotube on a substrate by a metal catalyst of a carrier, wherein the catalyst carrier is not removed after synthesizing the carbon nanotube. The surface of the glass substrate is directly subjected to a low temperature thermal chemical vapor phase. The deposition method to grow carbon nanotubes, in addition to the need to consider, including the overall process temperature is lower than the glass deformation temperature, the preparation of the surface catalyst, the catalyst activity before the promotion of the special technology outside and the right to be truly practical It is also necessary to consider that the growth of the nanotubes on a large-area glass substrate is prone to the problem of uneven growth of the carbon nanotubes on the substrate surface and poor electron radioactivity of the carbon nanotubes. When the large-area substrate reacts, the reaction gas volume and the gas flow rate are relatively enlarged, which tends to cause uneven distribution of the activated carbon molecules in the reaction space, and the temperature of the gas stream is lowered. SUMMARY OF THE INVENTION A main object of the present invention is to provide a heat for use. A gas flow control and preheating device for chemical vapor deposition, which can effectively improve the uniformity of growth of carbon nanotubes on the surface of the substrate, and improve the electron radioactivity of the carbon nanotubes. In order to achieve the above object of the present invention, according to the present invention A gas flow control and preheating device is provided comprising: a cover, the cover is slanted with a partition plate to divide the cover into a head space and a bottom space, wherein the side of the partition plate and the cover The cover is connected, the other side is left with a gap, and the head space and the bottom space can only communicate through the gap; an air intake raft provided on the cover for introducing gas into the head space; The cover is provided with a plurality of air outlets on one side of the gap, and the plurality of air outlets are located in fluid communication with the bottom space below the partition plate. When the gas flow control and preheating device is covered on a flat heating floor and the gas is introduced into the head space by the inlet port, the gas will flow over the partition plate and enter the bottom space through the gap. Flowing through the flat heating plate, 'final flow of gas flow control and preheating device from the plurality of vents', then the gas is sufficiently heated and heated above the floor plate in a layer by flow manner. According to the present invention Another gas flow control and preheating package includes: a cover comprising a top plate and a surrounding wall; two separate sheets joined to the cover and substantially parallel to the top plate, wherein each piece One side of the partition plate has a gap with one side of the surrounding wall, and the other side is closely adjacent to the center of the top plate, and the other side is in close contact with the surrounding wall. Then the inside of the surrounding wall is The two partition plates are divided into two top spaces and a bottom space, and the two top spaces and the bottom space can only be in fluid communication through the two gaps; two are disposed on the top plate An intake port for introducing gas into the two head spaces; and a plurality of air outlet holes disposed at a center of the top plate, and the plurality of air outlet holes are located between the two partition plates The space fluid is in communication. When the gas flow control and preheating device is placed on the flat heating floor and the gas is introduced into the two head spaces by the two inlet ports, the gas will flow over the two partition plates. Passing through the two gaps into the bottom space, flowing through the flat heating base plate, and the gas flow control and preheating device is most discharged from the plurality of air outlet holes, so that the body is sufficiently heated and passes through the plane in a laminar flow manner Heating the upper surface of the bottom plate 0 8 200822187 The present invention also provides a low temperature thermal chemical vapor deposition reactor comprising a planar heating bottom plate having an air inlet pipe and an air outlet pipe; and a closable activity of covering the planar heating floor plate Cap, so that a reaction chamber can be formed on the flat heating floor; and a gas flow control and preheating device of the invention as described above; wherein the gas flow control and preheating device is covered Heating the soleplate plane and which is connected to the intake port of the intake pipe. Preferably, the interior of the planar heating floor is provided with a heating unit. The high temperature furnaces used in the two European patents described above are high temperature furnaces which are heated at both upper and lower ends and do not mention the uniformity of growth of the carbon nanotubes on the surface of the substrate and the electron radioactivity of the carbon nanotubes grown. . Compared with the two previous cases, the invention has the following advantages: (1) using a flat bottom plate type heating high temperature furnace, which can reduce the energy consumption required for heating; (7) introducing a gas flow control and a preheating device, the reaction gas only needs to be filled The space of the device can be no need to fill the entire reactor heating chamber to reduce the amount of reaction gas; (3) reduce the reaction time, increase the output rate, and the reactor cavity needs to be in a low-lying state due to the growth of the carbon tube. It is necessary to perform the blowing action first to reduce the oxygen content. Since the gas flow control and the preheating device of the present invention are much smaller than the reactor cavity volume, the blowing time can be shortened, and the rate of the force output is fast. (4) Instead of using a gas preheating system, the gas flow control and preheating device of the present invention is a two-layer space, and the temperature of the upper space is lower than that of the lower space, and when the gas enters the upper space, it is Preheating and activation, and then flowing to the lower space through the gap between the upper and lower layers for reaction; (5) The activation system and the reaction system can be simultaneously designed in a heating zone, which simplifies the equipment. ((9) Since the gas flow control and preheating device of the present invention has the effect of preheating and activation 200822187, the catalyst on the surface of the substrate can be used only by a single catalyst system; (7) has the potential for continuous production, and the furnace can be heated And the gas flow control and preheating device of the present invention is designed to be continuously operated from the movable type, without waiting for heating and cooling the furnace body for a long time; and (8) using the gas flow control and preheating device of the present invention The low-temperature carbon nanotube substrate produced by the substrate has good electron radioactivity and uniformity.
實施方式 依本發明的一第一較佳具體實施例所完成的一低溫熱 化學氣相沉積反應器，如圖丨所示，主要包括一平面加熱 底板20，其具有一進氣管21及一出氣管22 ; 一可密閉的 罩住該平面加熱底板的活動式上蓋3〇，於是可在該平面加 熱底板20上形成一反應艙31 ;及一具有可均勻預加熱及 層W作用之氣體流動控制及預熱裝置丨〇。將預定進行奈米 石反官成長之觸媒粉體或是含有表面塗佈有觸媒之玻璃基板 40置於該平面加熱底板2〇的表面上，再以該氣體流動控 制及預熱裝置10覆蓋住。此襞置10可對反應氣體進行預 加熱，增加活性碳分子的量，提高氣體之反應性，同時使 、人刀子均勻的與塗佈在基板表面之高活性觸媒接觸， 生成具有優異電子放射性質之奈米碳管。 、該氣體流動控制及預熱裝置10，如圖2及3所示，其 為扁平的方形罩蓋100,該罩蓋包含一連續的四面直立 圍壁1彳.U Λ ，…5 Κ該圍壁的頂端並氣密的蓋住該圍壁的一頂 板12，一結合於該圍壁内並且大體上平行於該頂板的分隔 200822187 板1 3，其中該分隔板1 3的左側與該圍壁11的左壁被留有 一間隙14，其餘的側則密接於該圍壁11，於是該圍壁内部 被該分隔板13分隔成一頂部空間1 5及一底部空間i 6，且 該頂部空間15及底部空間16僅能通過該間隙14流體相 通；一被設於該頂板上的進氣埠1 7，其用於將氣體導入該 頂部空間1 5 ;及被設於該圍壁的右壁的下方的多個出氣孔 1 8，且該多個出氣孔i 8位於該分隔板！ 3的下方與該底部 空間1 6流體相通，當該氣體流動控制及預熱裝置1 〇被蓋 於該平面加熱底板20上且氣體由該進氣埠！ 7被導入該頂 部空間1 5時，該氣體將流過該分隔板13上方，通過該間 隙14進入該底部空間16，流過該平面加熱底板2〇上，最 後由s亥多個出氣孔1 8流出’於是氣體被充分的加熱並以一 層流方式流過該平面加熱底板2〇表面上的玻璃基板4〇。 當預定進行奈米礙管成長之具有觸媒塗層.之基板4 〇 被置於该平面加熱底板20表面上，並以該氣體流動控制及 預熱裝置1 0蓋住後，該進氣埠17被與該進氣管21相連 接。將该平面加熱底板2 0加熱至設定之溫度，並將進行化 學氣相沉積之氣體自該進氣管2 1及進氣埠1 7導入該裝置 10内’於是在該基板40上生成奈米碳管。反應後之氣體 自該裝置10之多個出氣孔18逸出至該反應艙31，並自該 出氣管22排放。 該平面加熱底板20其内部被設有一加熱單元23，而 加熱底板之材質可為不鏽鋼、銅鐵合金，石英或陶瓷等具 11 200822187 有良，熱傳導及均溫性之材料。反應器之活動式上蓋3〇益 加熱早7L，而是充填斷熱材料作為保溫。 …、 該氣體流動控制及預熱褒置1()之罩蓋⑽的材 不鏽鋼_鐵合金’石英或陶瓷等具有良好熱傳導及均： 性之材料，以不鏽鋼為較佳。該罩蓋1〇〇為長寬均為25: 分。當该罩蓋100被置於兮承 «於料面加熱底板20時，該分隔板 13人该平面加熱底板2〇之距離為〇 3〜i 5公分以… 公分為較佳’在此實施例中為G 6公分。該頂板12與該分 隔板Π的距離約等於該分隔板13與該平面加熱底板2〇之 距離。而該間隙14的寬度為〇.5〜5公分，以卜3公分為較 佳’在此實施例中為2公分。 適合使用於本發明的熱化學氣相沉積反應之觸媒可選 自鐵、鈷、鎳或其合金，而表面具有觸媒塗層之基板可為 玻璃、石英、氧化銘或氧化石夕等材料所製成者。本發明奈 米反笞之熱化學氣相沉積反應係於一介於400至600°C的 反應溫度及一介於〇·5至2大氣壓的壓力進行一介於1至 120分鐘的反應時間。被導入熱化學氣相沉積反應室的氣 體包括惰性氣體（例如氧、氬、氮氣）、氫氣及碳源氣體。 可使用的碳源氣體包括碳氫化合物或一氧化碳。 依本發明的第二較佳具體實施例所完成的一氣體流動 控制及預熱裝置10，被示於圖4及5，其中類似於圖2及 3的部件以相同的標號表示。此第二實施例係參考第一實 方e例的没叶加予修改成_適於更大面積的基板的奈米碳管 熱化學氣相沉積反應。如圖4及5所示，多個出氣孔1 8被 12 200822187 設於該頂板12的中央處’而相對於該中央處的一垂直面呈 互相對稱的設有二片分隔板13 a及13 b，二個頂部空間1 $ a 及15b，一共通的底部空間16 ;及二個進氣埠na及丨％。 该分隔板1 3 a的左側與該圍壁11的左壁被留有一間严爭 14a，右側密接於該頂板12，另兩側則密接於該圍壁^。 該分隔板13b的右侧與該圍壁！ 1的右壁被留有一間隙 1 4b，左側始、接於该頂板1 2，另兩側則密接於該圍壁1丄。 進氣埠17a及17b在其底端分別具有一歧管連通於該二個 頂部空間15&及15b。當罩蓋100被蓋於一平面加熱底板上 且氣體由該二個進氣埠17a及17b被導入該二個頂部空間 15a及15b時，該氣體將流過該二片分隔板na及i3b上 方，通過該二個間隙14a及14b進入該底部空間，流過該 平面加熱底板上，最後由該多個出氣孔18流出該罩蓋丨〇〇。 貫施例1 本實施例使用圖1至3所示的反應器及裝置。取一塗 佈有奈米鎳觸媒之玻璃基板，玻璃基板之尺寸為4吋⑼土 角）’塗佈之方式可為網印、濺鍍或旋轉塗佈，以網印為佳。 塗佈之圖案為平行之長條，且分為含有觸媒之陰極線及不 f媒之閘極線’線寬約為川〜工〇〇微米，陰極 線距約80〜1〇〇微乎，夂 深 、， 木母一陰極與閘極對之距離為10〇〇微 米。反應器之活動式上蓋為氣動式開啟，丨 以快速將反應艙内处今4丄人 ^ 專庸 内工虱抽除。接著將惰性氣體灌入，達到 低氧含量之要求。掣 版^中可同時引入及分別控制3種不同 13 200822187 乱體之机里（乙炔、氫氣、氬氣）。平面加熱底板的高溫爐 的加熱速率為600t： /hr，最高可加熱至65〇。〇。 進行反應時先將基板樣品40置於加平面加熱底板2〇 上再將氣體流動控制及預熱裝置1〇之罩蓋1〇〇蓋上，將進 氣琿17接上進氣管21，將上蓋3〇降下後即可開始加熱， 亚啟動真空幫浦直到反應艙3丨達到6〇 mmHg之真空度即 可將氬軋灌入並持續3〇分鐘，等到達所設定溫度分鐘 後即可開始進行反應。先進行還原反應，其條件為：溫度 Ar /爪里1 〇 〇〇 sccm，h2流量1 5 〇 s c cm，反應時間2 0 分鐘。接著再將一碳源氣體C2H2通入，其流量為5〇sccm， 繼續反應20分鐘。以上之反應皆在i大氣壓下進行。反應 後在觸媒擔體表面生成奈米碳管，其管徑分佈於“2⑻奈 米之間。 對照例1 重覆貫施例1的步驟，但不使用本發明的氣體流動控 制及預熱裝置10。表一列出對照例丨及實施例丨所製備的 成長有奈米後管之場發射光源陰極裝置的性質。 表一 _#碳管型態 P線變色情況 Et〇 (V/μπι) Ethr TV/ um^ 對照例1 Ι^τλ 1 彎曲且短 不明顯且不均勻 3.3 ^tiir V v 1 ) 7.2 實施例1 —--------- 長 均勻變色 1.8 3.0Embodiment A low temperature thermal chemical vapor deposition reactor according to a first preferred embodiment of the present invention, as shown in FIG. ,, mainly includes a planar heating bottom plate 20 having an intake pipe 21 and An air outlet tube 22; a movable upper cover 3 罩 which covers the planar heating base plate, so that a reaction chamber 31 can be formed on the flat heating base plate 20; and a gas having uniform preheating and layer W action Flow control and preheating device 丨〇. The catalyst powder or the glass substrate 40 coated with the catalyst coated on the surface of the planar heating substrate 2 is placed on the surface of the planar heating substrate 2, and the gas flow control and preheating device 10 is used. Covered. The device 10 can preheat the reaction gas, increase the amount of activated carbon molecules, improve the reactivity of the gas, and simultaneously make the human knife uniformly contact with the highly active catalyst coated on the surface of the substrate to generate excellent electron radioactivity. Quality carbon nanotubes. The gas flow control and preheating device 10, as shown in Figures 2 and 3, is a flat square cover 100 comprising a continuous four-sided upright wall 1 U.U Λ , ... 5 Κ a top end of the wall and a gas-tight cover of a top plate 12 of the surrounding wall, a partition in the surrounding wall and substantially parallel to the partition 200822187 plate 13 of the top plate, wherein the left side of the dividing plate 13 and the circumference The left wall of the wall 11 is left with a gap 14 , and the other side is closely adhered to the surrounding wall 11 , so that the inside of the surrounding wall is divided by the partition plate 13 into a head space 15 and a bottom space i 6 , and the head space 15 and the bottom space 16 can only be in fluid communication through the gap 14; an intake port 17 is provided on the top plate for introducing gas into the head space 15; and is disposed on the right wall of the wall A plurality of air outlets 8 8 below, and the plurality of air outlets i 8 are located on the partition plate! The bottom of the 3 is in fluid communication with the bottom space 16 when the gas flow control and preheating device 1 is covered on the planar heating floor 20 and the gas is vented by the intake! When 7 is introduced into the head space 15 5 , the gas will flow over the partition plate 13 , enter the bottom space 16 through the gap 14 , flow through the flat heating base plate 2 , and finally vent multiple holes 1 8 flows out' then the gas is sufficiently heated and flows through the plane to heat the glass substrate 4 on the surface of the bottom plate 2 in a laminar flow. When the substrate 4 having the catalytic coating for the growth of the nano tube is placed on the surface of the planar heating substrate 20 and covered by the gas flow control and preheating device 10, the inlet 埠17 is connected to the intake pipe 21. The planar heating substrate 20 is heated to a set temperature, and a gas for chemical vapor deposition is introduced into the device 10 from the inlet pipe 21 and the inlet port 117. Thus, a nanometer is formed on the substrate 40. Carbon tube. The reacted gas escapes from the plurality of vent holes 18 of the apparatus 10 to the reaction chamber 31 and is discharged from the outlet pipe 22. The flat heating base plate 20 is internally provided with a heating unit 23, and the material of the heating base plate can be made of stainless steel, copper-iron alloy, quartz or ceramic, etc. 11 200822187 Good heat conduction and temperature uniformity. The movable upper cover of the reactor 3 heats up 7L earlier, but fills the heat-insulating material as insulation. ..., the gas flow control and the material of the cover (10) of the preheating device 1 () stainless steel _ iron alloy 'quartz or ceramic material having good heat conduction and uniformity, preferably stainless steel. The cover 1 is 25:length and width. When the cover 100 is placed on the support surface to heat the bottom plate 20, the partition plate 13 has a distance of 平面3~i 5 cm from the flat heating base plate. The centimeters are preferably 'implemented here' In the example, it is G 6 cm. The distance between the top plate 12 and the partition plate 约 is approximately equal to the distance between the partition plate 13 and the planar heating base plate 2〇. The width of the gap 14 is 〇5 to 5 cm, and the division of the 3 cm is preferable, which is 2 cm in this embodiment. The catalyst suitable for use in the thermal chemical vapor deposition reaction of the present invention may be selected from the group consisting of iron, cobalt, nickel or alloys thereof, and the substrate having a catalyst coating on the surface may be glass, quartz, oxidized or oxidized stone. Made by. The thermal chemical vapor deposition reaction of the present invention is carried out at a reaction temperature of from 400 to 600 ° C and a pressure of from 5 to 2 atm for a reaction time of from 1 to 120 minutes. The gas introduced into the thermal chemical vapor deposition reaction chamber includes an inert gas (e.g., oxygen, argon, nitrogen), hydrogen, and a carbon source gas. Carbon source gases that can be used include hydrocarbons or carbon monoxide. A gas flow control and preheating device 10 constructed in accordance with a second preferred embodiment of the present invention is illustrated in Figures 4 and 5, wherein components similar to those of Figures 2 and 3 are designated by the same reference numerals. This second embodiment is referred to the carbon nanotube thermal chemical vapor deposition reaction of the substrate of the first embodiment e modified to a substrate suitable for a larger area. As shown in FIGS. 4 and 5, a plurality of air outlets 18 are provided at the center of the top plate 12 by 12200822187, and two partition plates 13a are provided symmetrically with respect to a vertical plane at the center. 13 b, two headspaces 1 $ a and 15b, a common bottom space 16 ; and two intake 埠 na and 丨 %. The left side of the partition plate 13 3 a and the left wall of the surrounding wall 11 are left with a strict competition 14a, the right side is in close contact with the top plate 12, and the other sides are in close contact with the surrounding wall. The right side of the partition plate 13b and the surrounding wall! The right wall of 1 is left with a gap 1 4b, the left side is connected to the top plate 12, and the other sides are closely connected to the surrounding wall 1丄. The intake ports 17a and 17b have a manifold at their bottom ends respectively communicating with the two head spaces 15 & and 15b. When the cover 100 is covered on a flat heating floor and gas is introduced into the two head spaces 15a and 15b by the two intake ports 17a and 17b, the gas will flow through the two partition plates na and i3b. Above, the two gaps 14a and 14b enter the bottom space, flow through the plane to heat the bottom plate, and finally flow out of the cover 丨〇〇 by the plurality of air outlets 18. Example 1 This example uses the reactor and apparatus shown in Figures 1 to 3. A glass substrate coated with a nano nickel catalyst is used, and the size of the glass substrate is 4 吋 (9) earth angle. The coating method may be screen printing, sputtering or spin coating, and screen printing is preferred. The coated pattern is a parallel strip, and is divided into a cathode line containing a catalyst and a gate line of a non-f dielectric. The line width is about 0.5 to 〇〇 micron, and the cathode line is about 80 to 1 〇〇, 夂Deep, the distance between the cathode and the gate of the mica is 10 〇〇 micron. The movable top cover of the reactor is pneumatically opened, so that the inside of the reaction chamber can be quickly removed. The inert gas is then poured in to achieve the low oxygen content requirement.掣 ^ 中 can be introduced and separately controlled in three different 13 200822187 chaotic machine (acetylene, hydrogen, argon). The high temperature furnace of the flat heating floor has a heating rate of 600t: /hr and can be heated up to 65〇. Hey. When the reaction is carried out, the substrate sample 40 is first placed on the flat heating substrate 2, and the cover of the gas flow control and preheating device 1 is covered, and the intake port 17 is connected to the intake pipe 21, After the upper cover 3〇 is lowered, the heating can be started. The vacuum pump can be started until the reaction chamber 3丨 reaches a vacuum of 6〇mmHg, and the argon rolling can be poured in for 3 minutes, and then it can be started after reaching the set temperature. Carry out the reaction. The reduction reaction is first carried out under the following conditions: temperature Ar / 1 〇 〇〇 sccm in the claw, h2 flow rate 1 5 〇 s c cm, reaction time 20 minutes. Then, a carbon source gas C2H2 was introduced, and the flow rate was 5 〇sccm, and the reaction was continued for 20 minutes. The above reactions were all carried out at i atmosphere. After the reaction, a carbon nanotube was formed on the surface of the catalyst carrier, and the diameter of the tube was distributed between "2 (8) nm. Comparative Example 1 repeated the procedure of Example 1, but without using the gas flow control and preheating of the present invention. Device 10. Table 1 lists the properties of the cathode device of the field emission light source grown in the comparative example and the sample prepared by the embodiment. Table 1_#Carbon tube type P line discoloration condition Et〇(V/μπι Ethr TV/ um^ Comparative Example 1 Ι^τλ 1 Bending and short inconspicuous and uneven 3.3 ^tiir V v 1 ) 7.2 Example 1 —--------- Long uniform color change 1.8 3.0
Et。及Ethr刀別為電流密度為1 的啟動電場(灿工-⑽fidd) 及電流雄、度為10 mA/cm2的臨界電場(threshold field) 14 200822187 從表一 置可以藉由 長奈米碳管 極裝置。 可以看出使用本發明 ^ ^ 軋體&動控制及預埶| 低恤熱化學氣相沉積反應在麵 、、、衣 ，及製備出電子放射性質N 9勾成 貝k良的場發射光源陰 圖式簡單說明 21顯示依本發明的第-較佳具體實施例所完成的-低Z皿”、、化學氣相沉積反應器的部份剖面示意圖。 圖、員不圖1中的反應器的氣體流動控制及預熱裝置 1 〇的示意透視圖。 圖3顯示依圖2中的3_3線的剖面示意圖。 圖4顯示依本發明的第二較佳具體實施例所完成的氣 體流動控制及預熱裝置10的示意透視圖。 圖5顯示依圖2中的5_5線的剖面示意圖。 主要元件之符號說明 20.•平面加熱底板；21··進氣管；22··出氣管；23··加熱草元， 30··活動式上蓋；31··反應艙；4〇··玻璃基板； 10 ··氣體流動控制及預熱裝置；i丨··圍壁；12 ·.頂板， 13、13a、13b··分隔板；14、I4a、i4b··間隙； 15、15a、15b··頂部空間；16··底部空間； 17、17a、17b··進氣埠；18··出氣孔；1〇〇·.罩蓋 15Et. And the Ethr knife is a starting electric field with a current density of 1 (can--(10) fidd) and a critical electric field with a current of 10 mA/cm2. 14 200822187 From the table one can be made by a long carbon nanotube Device. It can be seen that the use of the present invention ^ ^ rolling body & dynamic control and pre-twisting | low-tie thermal chemical vapor deposition reaction in the surface,, clothing, and the preparation of electronic radioactive material N 9 hook into a good field emission source BRIEF DESCRIPTION OF THE DRAWINGS Fig. 21 is a partial cross-sectional view showing a low-dish dish, a chemical vapor deposition reactor, which is completed in accordance with a first preferred embodiment of the present invention. A schematic perspective view of a gas flow control and preheating device 1 。 Figure 3 shows a cross-sectional view taken along line 3_3 of Figure 2. Figure 4 shows a gas flow control performed in accordance with a second preferred embodiment of the present invention Fig. 5 shows a schematic cross-sectional view of the preheating device 10. Fig. 5 shows a schematic cross-sectional view taken along line 5-5 of Fig. 2. Symbols of main components: 20. Flat heating floor; 21··intake pipe; 22··exhaust pipe; · heating grass, 30 · · movable top cover; 31 · · reaction cabin; 4 〇 · · glass substrate; 10 · · gas flow control and preheating device; i 丨 · · wall; 12 ·. roof, 13, 13a, 13b·· partition plate; 14, I4a, i4b·· clearance; 15, 15a, 15b··top space ; ·· bottom space 16; 17,17a, 17b ·· intake ports; 18 ·· vent;. * Cover 15 1〇〇