CN1129168C - Process for preparing carbon nano tube film cathode by forming catalyst particles - Google Patents

Process for preparing carbon nano tube film cathode by forming catalyst particles Download PDF

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CN1129168C
CN1129168C CN 00135476 CN00135476A CN1129168C CN 1129168 C CN1129168 C CN 1129168C CN 00135476 CN00135476 CN 00135476 CN 00135476 A CN00135476 A CN 00135476A CN 1129168 C CN1129168 C CN 1129168C
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cathode
preparing
carbon
particles
nano
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CN1320952A (en )
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朱长纯
刘卫华
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西安交通大学
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一种利用生成催化剂颗粒的碳纳米管薄膜阴极的制备方法,它是由下述工艺过程制备成:溶胶制备、衬底预处理、制备碳纳米管薄膜阴极、检验、包装。 A method of preparing a thin film of cathode formation of carbon nanotubes using catalyst particles, which is prepared by the following processes to: sol preparation, pre-treated substrate, the carbon nanotube film prepared cathode, testing and packaging. 本发明的碳纳米管生长密度可通过溶胶浓度加以调节。 Growth density of carbon nanotubes of the present invention can be adjusted by a sol concentration. 由于催化剂通过涂敷方法引入衬底表面,可实现大面积生长。 Since the catalyst is introduced into the substrate surface by a coating method, growth of a large area can be realized. 溶胶可转变为凝胶或分散到其它冻状介质中。 Sol may be converted into a gel-like or jelly dispersed in other media. 可通过丝网印刷工艺印制到衬底。 Is printed on the substrate by a screen printing process. 采用本发明生长的碳纳米管大多数为具有开口结构的多层碳纳米管,具有良好的场发射特性和稳定性。 Carbon nanotubes grown using the present invention is a multilayer carbon nanotube most open structure, with good field emission properties and stability.

Description

利用生成催化剂颗粒的碳纳米管薄膜阴极的制备方法 Using the method of film formation of carbon nanotubes cathode catalyst particles

一、技术领域本发明属于半导体技术领域,具体涉及到应用气态化合物的还原或分解产生固态凝结物的至少具有一个跃变势垒或表面势垒的器件的半导体器件的制备或其零部件的制造或处理。 I. Technical Field The present invention belongs to the technical field of semiconductors, particularly to the reduction or decomposition of a gaseous compound generated application condensate having at least a solid preparation for producing semiconductor devices or parts thereof of a transition barrier or surface barrier of the device or treatment.

为达到上述目的,本发明采用的解决方案它是由下述工艺过程制备成:(1)、溶胶制备用铁或钴或镍的盐酸盐或硫酸盐或硝酸盐或醋酸盐加入到100~250倍重量比的水中制成上述盐的水溶液。 To achieve the above object, the present invention is used in solution which is prepared by a process as described below: (1) preparing a sol of iron or hydrochloride or sulfate or a nitrate or acetate of cobalt or nickel was added to 100 ~ aqueous solution of the formed salt in water 250 times by weight ratio.

取去离子水加热至沸腾,边搅拌边加入上述已制备的盐的水溶液,去离子水与上述盐的水溶液的重量比为1/100~2/100,再搅拌加热至沸腾制成溶胶;(2)、衬底预处理用硅片或二氧化硅片或陶瓷片作为衬底,将衬底放入超声波清洗机内,加入无水乙醇浸过衬底,接通超声清洗机的电源,用超声波清洗,然后倒出无水乙醇,再加入去离子水至浸没衬底,接通超声波清洗机的电源,用超声波清洗至表面无杂物无油垢,将衬底浸入溶胶中,取出,在常温下晾干。 Taken away deionized water was heated to boiling with stirring were added an aqueous solution of the salt has been prepared, the weight ratio of deionized water and an aqueous solution of a salt of the above 1/2 ~ 100/100, stirred and heated to boiling prepare a sol; ( 2), or a silica substrate pretreated with a silicon wafer as a substrate sheet or ceramic sheet, placing the substrate in the ultrasonic cleaning machine, adding ethanol-impregnated substrate, power ultrasonic cleaning machine, with ultrasonic cleaning, and then ethanol was decanted, deionized water was added to the immersion of the substrate, power of ultrasonic cleaning machine, ultrasonic cleaning with no debris to the surface without grease, the substrate is immersed in the sol, removed, at room temperature under dry.

(3)碳纳米管薄膜阴极的制备将经过预处理的衬底放置在石英舟上,接通低压化学气体沉积炉的电源升温,当反应室温度接近还原所需温度650°~850℃时,在氮气保护下将石英舟推入该炉的反应室,石英舟与迎气流方向成15°~30°的坡度,还原衬底上的由溶胶颗粒形成的氧化态的铁或钴或镍纳米颗粒,然后进行高温还原,在反应室温度为650℃~850℃时,通入H2与N2的混合气,H2/N2混合气的体积比为4/1~10/1,流量为20ml/min,反应室内气压为20~30乇,还原0.5~2小时,得单质的铁或钴或镍纳米颗粒,接着在反应室炉温为650℃~800℃下通入C2H2与N2混合气体,C2H2/N2的体积比为1/10~1/2,反应室气压在40~80乇,生长1~2小时,在衬底上生成一层黑色碳纳米管薄膜阴极,生长结束后,在氮气保护下,将所制得碳纳米管薄膜阴极拉至反应室口,冷却,然后取出。 Preparation of (3) the carbon nanotube film cathode pretreated substrate is placed on a quartz boat, a low pressure chemical gas deposition power heating furnace, the temperature of 650 ° ~ 850 ℃ the reaction chamber when the temperature is close to the required reduction, under nitrogen the reaction chamber quartz boat pushed into the furnace, and a quartz boat Ying airflow direction gradient 15 ° ~ 30 °, reduction of the oxidation state of iron or cobalt or nickel nanoparticles on a substrate by a sol particles formed , followed by high temperature reduction, in the reaction chamber temperature was 650 ℃ ~ 850 ℃, into H2 mixed gas of N2, H2 / N2 volume ratio of mixed gas of 4/1 ~ 10/1, flow rate 20ml / min, the reaction chamber pressure is 20 to 30 torr, reducing 0.5 to 2 hours, to obtain elemental iron or cobalt or nickel nanoparticles, followed by a reaction chamber furnace temperature was at 650 ℃ ~ 800 ℃ into C2H2 and N2 mixed gas, C2H2 / N2 the volume ratio of 1/10 ~ 1/2, the reaction chamber pressure of 40 to 80 Torr, the growth of 1 to 2 hours to produce a cathode layer of black carbon nanotube film on the substrate, after growth, under nitrogen, the prepared carbon nanotube film is pulled to the cathode chamber inlet, cooled, and then taken out.

(4)、检验、包装将所制得产品进行质量检验,合格后,包装,入库。 (4), inspection, packing the prepared product quality inspection, after passing, packaging, warehousing.

本发明制备工艺的溶液制备中,其中铁或钴或镍的盐酸盐或硫酸盐或硝酸盐或醋酸盐加入到180~220优选重量比的水中制成上述盐的水溶液,去离子水与上述盐的水溶液的优选重量比为2/100制成溶胶;在碳纳米管薄膜阴极的制备中,其中优选还原温度为700°~750℃,通入H2与N2的优选体积比为4/1~6/1的混合气,反应室内气压在20~30乇,优选还原1~1.5小时,然后在反应室优选温度为650°~750℃下通入C2H2与N2的优选体积比为1/5~1/4的混合气,反应室优选气压在50~60乇,优选生长1~1.5小时。 Preparation process of the invention in solution, in which iron, or a hydrochloride or sulfate or nitrate, or cobalt or nickel acetate aqueous solution was added to the above prepared salt preferably 180 to 220 ratio by weight of water, and deionized water the preferred weight aqueous solution of the salt formed sol ratio of 2/100; in the preparation of carbon nanotubes in the cathode film, wherein the reduction temperature is preferably 700 ° ~ 750 ℃, preferably into a volume ratio of H2 to N2 is 4/1 mixed gas ~ 6/1, the pressure in the reaction chamber 20 to 30 Torr, preferably 1 to 1.5 hours reduction, then in the reaction chamber is preferably a temperature of 650 ° ~ 750 ℃ ​​into C2H2 and N2, the volume ratio is preferably 1/5 ~ mixed gas 1/4, the pressure in the reaction chamber is preferably 50 to 60 torr, preferably 1 to 1.5 hours growth.

本发明的制备方法的溶液制备中,其中铁或钴或镍的盐酸盐或硫酸盐或硝酸盐或醋酸盐加入到200倍最佳重量比的水中制成上述盐的水溶液,去离子水与上述盐的水溶液的最佳重量比为1/100制成溶胶;在碳纳米管薄膜阴极的制备中,其中最佳还原温度为720℃,通入H2与N2的最佳体积比为7/1的混合气,反应室内最佳气压在25乇,最佳还原1小时,然后在反应室最佳温度为720℃下通入C2H2与N2的最佳体积比为1/6的混合气,反应室最佳气压为60乇,最佳生长1.5小时。 Preparing a solution of the preparation method of the present invention, wherein the iron or a hydrochloride or sulfate or nitrate or acetate cobalt or nickel salt is added to an aqueous solution prepared above 200 times the optimum ratios by weight of water, deionized water best weight aqueous solution of the salt to prepare a sol ratio of 1/100; in the preparation of carbon nanotubes in the cathode film, wherein the optimum reduction temperature is 720 ℃, H2 and N2 into the optimum volume ratio of 7 / 1 the gas mixture, the optimum pressure in the reaction chamber 25 Torr, the optimum reduction for 1 hour and then the reaction chamber at the optimum temperature of 720 ℃ into optimum volume ratio of C2H2 and N2, a mixed gas of 1/6, the reaction optimum chamber pressure of 60 Torr, optimal growth for 1.5 hours.

本发明与已有的碳纳为管薄膜阴极的称植相比,碳纳米管生长密度可通过溶胶浓度加以调节,利用溶胶则不需要多孔表面衬底,,由于催化剂通过涂敷方法引入衬底表面,可实现大面积生长,溶胶可转变为凝胶或分散到其它冻状介质中,可通过丝网印刷工艺印制到衬底,采用本发明生长的碳纳米管大多数为具有开口结构的多层碳纳米管,具有良好的场发射特性和稳定性。 The present invention is satisfied as compared with the existing carbon planting, the growth density of carbon nanotubes can be adjusted to the tube, it said cathode film by the sol concentration, the sol of the porous surface of the substrate is not required since the catalyst is introduced ,, substrate by a coating method surface, can achieve a large area growth, the sol can be converted into a gel-like or jelly dispersed in other media, may be printed on the substrate by a screen printing process, the present invention uses a carbon nanotube grown mostly open structure having the multilayer carbon nanotubes having good field emission properties and stability.

发明人给出了本发明第一个实施例如下:1.溶胶制备溶液配制:称取2克FeCl3,将其溶入200克水中,制成FeCl3水溶液。 The inventors show the first embodiment of the present invention are as follows: 1. Preparation of the sol solution preparation: Weigh 2 g FeCl3, which was dissolved in 200 g of water to prepare an aqueous solution of FeCl3.

胶体配制:将去离子水功热至沸腾,然后边搅拌边滴入去离子水与已制备FeCl3水溶液,再搅拌加热3分钟得红棕色溶液即配得Fe(OH)3溶液。 Colloid preparation: A reactive hot deionized water to boiling, then added dropwise with stirring an aqueous solution of deionized water was prepared with FeCl3, 3 minutes and then heated with stirring to give a red-brown solution is obtained i.e. with Fe (OH) 3 solution.

还可用氯化钴或硝酸钴或硫酸钴或醋酸钴或氯化镍或硝酸镍或硫酸镍或醋酸镍制成这些盐的溶液。 Solution of these salts may be made with a cobalt chloride or cobalt sulfate or cobalt nitrate or cobalt acetate, nickel chloride or nickel sulfate or nickel nitrate or nickel acetate.

2.衬底预处理衬底清洗:用N型硅片为衬底,将衬底放入超声波清洗机内,将无水乙醇加入到超声波清洗机内至浸没衬底为止,接通超声波清洗机的电源,用超声波清洗,放掉无水乙醇再将去离子水加入到超声波清洗机内至浸没衬底为止,接通超声波清洗机的电源,用超声波清洗,至表面无杂物无油垢止。 2. The substrate cleaning pre-treated substrate: silicon wafer with N-type substrate, the substrate is placed in an ultrasonic cleaning machine, anhydrous ethanol was added until the immersion of the substrate to ultrasonic cleaning machine, ultrasonic cleaning machine is turned on power, ultrasonic cleaning, and then let go of absolute ethanol was added to the deionized water in the ultrasonic cleaning machine to the substrate until the immersion, ultrasonic cleaning machine power supply is turned on, ultrasonic cleaning, no debris to the surface no grease stop.

溶胶的涂附及干燥:将准备好的硅片在配好的Fe(OH)3溶胶中浸一下,平铺阴干,使Fe(OH)3溶胶颗粒均匀分布在硅片表面。 Sol coated and dried: the prepared silicon wafer with a good Fe (OH) 3 at immersed sol, dried tile, so that Fe (OH) 3 sol particles uniformly distributed in the wafer surface.

本实施例的衬底也可用二氧化硅片或陶瓷片作为衬底。 Substrate of the present embodiment, silica may also be used as the substrate sheet or ceramic sheet.

3.碳纳米管薄膜阴极制备入炉:将经过预处理的硅片置于石英舟,当反应室温度达到650℃时,在氮气保护下,将硅片衬底推入反应室中,石英舟在迎气流方向成15°坡度。 3. Preparation of a carbon nanotube film cathode into the furnace: After the wafer was placed in a quartz boat pretreatment, the reaction chamber when the temperature reached 650 ℃, under nitrogen, the silicon substrate into the reactor chamber, the quartz boat Towards the direction of air flow 15 ° slope.

高温还原:在反应室温度为800℃时,通入H2与N2的混合气体,H2/N2的体积流量比4/1,流量为20l/min,反应室气压为20乇,还原30分钟。 High temperature reduction: a reaction chamber at a temperature of 800 deg.] C, a gas mixture of H2 and N2, the volume flow rate of H2 / N2 ratio of 4/1, a flow rate of 20l / min, a reaction chamber pressure of 20 Torr, to restore for 30 minutes.

碳纳米管生长:在反应室内的温度为650℃通入C2H2与N2混合气,C2H2/N2的体积比为1/10,反应室气压为40乇,生长1小时。 Carbon nanotube growth: the temperature in the reaction chamber is 650 ℃ into C2H2 gas and N2 mixture, the volume ratio of C2H2 / N2 1/10, a reaction chamber pressure of 40 Torr, grown for 1 hour.

出炉:生长结束后,在氮气保护下,将所制得碳纳米管薄膜阴极拉致反应室口冷却,然后取出。 Baked: After growth, under nitrogen, the prepared carbon nanotube film cathode chamber port pull actuation reaction was cooled, and then removed.

4.检验、包装将所制得产品的进行质量检验,合格后,包装,入库。 4. inspection, packaging will be the quality of the obtained product testing, after passing, packaging, warehousing.

发明人给出了本发明的第二个实施例。 The inventors gives a second embodiment of the present invention. 在本实施例中,制备溶胶所用的原料为2克FeCl3,加入到500克水中制成该盐的水溶液。 In the present embodiment, the raw materials used sol 2 g of FeCl3, was added to 500 g of water, an aqueous solution of the salt. 取去离子水加热至沸腾,加入去离子水与已制备盐的水溶液重量比为2/100的FeCl3水溶液制成溶胶。 Taken away deionized water was heated to boiling, deionized water was added to the prepared solution by weight ratio of salts made FeCl3 aqueous sol of 2/100. 将经预处理的衬底放在石英舟上放入低压化学气体沉积炉的反应室内,石英舟与迎气流方向成30°的坡度,在反应室的温度为850℃、气压为30乇,通入H2与N2体积比为10/1混合气,先进行还原2小时后,在反应室温度为800℃下再通入C2H2与N2体积比为1/2的混合气,反应室气压为80乇,生长2小时,制备成碳纳米管阴极。 The chemical reaction chamber into a low pressure gas deposition furnace was pre-treated substrate is placed on a quartz boat, and the quartz boat 30 ° Ying airflow direction gradient, the temperature in the reaction chamber is 850 ℃, gas pressure of 30 Torr, through into H2 and N2 gas volume ratio of 10/1 mixture, after the first reduction for 2 hours at room temperature the reaction was again introduced at 800 ℃ volume ratio of C2H2 and N2 mixed gas of 1/2, the reaction chamber pressure is 80 Torr , grown for 2 hours to prepare a carbon nanotube cathode. 本实施例所用的材料以及其它工艺过程与第一个实施例相同。 Materials used in this embodiment as well as other processes same as the first embodiment.

发明人给出了本发明的第三个实施例。 The inventors have given a third embodiment of the present invention. 在本实施例中,制备溶胶所用的原料为2克FeCl3,加入到400克水中制成该盐的水溶液。 In the present embodiment, the raw materials used sol 2 g of FeCl3, was added to 400 g of water, an aqueous solution of the salt. 取去离子水加热至沸腾,加入去离子水与已制备盐的水溶液重量比为1/100的FeCl3水溶液制成溶胶。 Taken away deionized water was heated to boiling, deionized water was added to the prepared solution by weight ratio of FeCl3 salts 1/100 prepare a sol solution. 将经预处理的衬底放在石英舟上放入低压化学气体沉积炉的反应室内,石英舟与迎气流方向成30°的坡度,在反应室的温度为720℃、气压为25乇,通入H2与N2的体积比为7/1混合气,先进行还原1小时后,在反应室温度为720℃下再通入C2H2与N2的混合体积比为1/6的混合气,反应室气压为60乇,生长1.5小时,制备成碳纳米管阴极。 The chemical reaction chamber into a low pressure gas deposition furnace was pre-treated substrate is placed on a quartz boat, and the quartz boat Ying airflow direction of slope of 30 °, the temperature of the reaction chamber 720. deg.] C, 25 Torr pressure, through into H2 and N2 in a volume ratio of 7/1 mixed gas, the first reduction after 1 hour, the reaction chamber at a temperature of 720 ℃ then passed into mixing volume ratio of C2H2 and N2, a mixed gas of 1/6, the reaction chamber pressure to 60 Torr, the growth for 1.5 hours to prepare a carbon nanotube cathode. 本实施例所用的材料以及其它工艺过程与第一个实施例相同。 Materials used in this embodiment as well as other processes same as the first embodiment.

实施例一、二、三中的FeCl3,也可用硫酸铁或硝酸铁或醋酸铁配制成水溶液。 One embodiment, the two or three of FeCl3, ferric sulfate or ferric nitrate can also be used or formulated as an aqueous solution of iron acetate. 还可用氯化钴或硝酸钴或盐酸钴或醋酸钴或氯化镍或硝酸镍或硫酸镍或醋酸镍制成这些盐的水溶液。 It can also be used, or cobalt chloride or cobalt nitrate or cobalt acetate, cobalt or hydrochloric acid nickel chloride or nickel sulfate or nickel nitrate or nickel acetate aqueous solution these salts are made. 衬底也可用二氧化硅片或陶瓷片作为衬底。 Silica substrate can also be used as the substrate sheet or ceramic sheet.

采用本发明第一个实施例制作的碳纳米管阴极经扫描电子显微镜和透射电子显微镜分析结果为:碳纳米管直径为20至50纳米、管长几十微米、绝大部分为多壁碳管,当碳纳米管排列密度达到或超过109/cm2时,碳纳米管开始定向排列。 The first embodiment uses a carbon nanotube cathode embodiment of the present invention is produced by scanning electron microscopy and transmission electron microscopy analysis results: carbon nanotubes 20 to 50 nanometers in diameter, tube length several tens of microns, most of the MWNTs when the carbon nanotube array density reaches or exceeds 109 / cm2, aligned carbon nanotubes starts. 碳纳米管场发射性能见图1,由图可知,在场强图为1.0v/μm时场发射开启,由IV曲线和Fowler Nordheim曲线可看出测量中所得电流为场发射电流,场发射开启的电压很低,说明本工艺所制备的碳纳米管具有良好的场发射特性。 Carbon nanotube field emission properties shown in Figure 1, the figure shows the field intensity graph 1.0v / μm field emission when turned by Fowler Nordheim IV curve and the curve can be seen that the resulting current measured emission current field, field emission opening the voltage is very low, indicating that the carbon nanotubes prepared by the present process has excellent field emission characteristics.

采用本发明第一个实施例制备的碳纳米管阴极经寿命试验表明:在50μA/mm2的发射电流密度下,持续工作4000小时后,场发射性能无明显衰减。 Carbon Nanotubes prepared using a first embodiment of the present invention by the life test showed that: at emission current density 50μA / mm2 after continuous operation for 4000 hours, and field emission properties without significant attenuation.

Claims (3)

  1. 1.一种利用生成催化剂颗粒的碳纳米管薄膜阴极的制备方法,其特征在于它是由下述工艺过程制备成:(1)、溶胶制备用铁或钴或镍的盐酸盐或硫酸盐或硝酸盐或醋酸盐加入到100~250倍重量比的水中制成上述盐的水溶液;取去离子水加热至沸腾,边搅拌边加入上述已制备的盐的水溶液,去离子水与上述盐的水溶液的重量比为1/100~2/100,再搅拌加热至沸腾制成溶胶;(2)、衬底预处理用硅片或二氧化硅片或陶瓷片作为衬底,将衬底放入超声波清洗机内,加入无水乙醇浸过衬底,接通超声清洗机的电源,用超声波清洗,然后倒出无水乙醇,再功入去离子水至浸没衬底,接通超声波清洗机的电源,用超声波清洗至表面无杂物无油垢,将衬底浸入溶胶中,取出,在常温下晾干;(3)碳纳米管薄膜阴极的制备将经过预处理的衬底放置在石英舟上,接通低压化学气体 1. A method for preparing a thin film of cathode formation of carbon nanotubes using catalyst particles, characterized in that it is prepared by a process to: (1) preparing a sol hydrochloride or sulfate of iron or cobalt or nickel or nitrate or acetate is added to 100 to 250 times the weight ratio of water to an aqueous solution of such salts; take away deionized water was heated to boiling with stirring were added an aqueous solution of the salt has been prepared, and such salts deionized water by weight aqueous solution of 1/2 ~ 100/100, stirred and heated to boiling prepare a sol; (2), or a silica substrate pretreated with a silicon wafer as a substrate sheet or ceramic sheet, the substrate is put within the ultrasonic cleaning machine, adding ethanol-impregnated substrate, power ultrasonic cleaning machine, ultrasonic cleaning, and then poured ethanol, then deionized water to the reactive substrate immersion, ultrasonic cleaning machine is turned on power, ultrasonic cleaning no debris to the surface without grease, the substrate is immersed in the sol, removed, dried at room temperature; (3) preparation of a carbon nanotube thin film cathode through the pre-treated substrate is placed in a quartz boat , the gas is turned on a low pressure chemical 积炉的电源升温,当反应室温度接近还原所需温度650°~850℃时,在氮气保护下将石英舟推入该炉的反应室,石英舟与迎气流方向成15°~30°的坡度,还原衬底上的由溶胶颗粒形成的氧化态的铁或钴或镍纳米颗粒,然后进行高温还原,在反应室温度为650℃~850℃时,通入H2与N2的混合气,H2/N2混合气的体积比为4/1~10/1,流量为20ml/min,反应室内气压为20~30乇,还原0.5~2小时,得单质的铁或钴或镍纳米颗粒,接着在反应室炉温为650℃~800℃下通入C2H2与N2混合气体,C2H2/N2的体积比为1/10~1/2,反应室气压在40~80乇,生长1~2小时,在衬底上生成一层黑色碳纳米管薄膜阴极,生长结束后,在氮气保护下,将所制得碳纳米管薄膜阴极拉至反应室口,冷却,然后取出;(4)、检验、包装将所制得产品进行质量检验,合格后,包装,入库。 Product heating power of the furnace, the reaction chamber when the reaction chamber temperature is close to the desired reduction temperature 650 ° ~ 850 ℃, under nitrogen quartz boat is pushed into the furnace, and a quartz boat Ying airflow direction of 15 ° ~ 30 ° slope, iron or cobalt or nickel nanoparticles sol particles by the oxidation state of the reduction of the substrate is formed, followed by high temperature reduction, the reaction chamber at temperature 650 ℃ ~ 850 ℃, into the mixed gas of N2 and H2, H2 / v N2 mixture gas was 4/1 ~ 10/1, flow rate 20ml / min, a reaction chamber pressure of 20 Torr to 30 Torr, reduction of 0.5 to 2 hours, to obtain elemental iron or cobalt or nickel nanoparticles, followed by the reaction chamber at a furnace temperature of 650 ℃ ~ 800 ℃ into a mixed gas of C2H2 and N2, the volume ratio of C2H2 / N2 1/10 ~ 1/2, the reaction chamber pressure of 40 to 80 Torr, the growth of 1 to 2 hours, in generating a carbon nanotube film on a cathode substrate layer of black, after the end of the growth, under nitrogen, the prepared carbon nanotube film is pulled to the cathode chamber inlet, cooled, and then taken out; (4), inspection, packaging will the prepared product quality inspection, after passing, packaging, warehousing.
  2. 2.按照权利要求1所述的利用生成催化剂颗粒的碳纳米管薄膜阴极的制备方法,其特征在于:在溶液制备中,其中铁或钴或镍的盐酸盐或硫酸盐或硝酸盐或醋酸盐加入到180~220倍重量比的水中制成上述盐的水溶液,去离子水与上述盐的水溶液的重量比为2/100制成溶胶;在碳纳米管薄膜阴极的制备中,其中还原温度为700°~750℃,通入H2与N2的体积比为4/1~6/1的混合气,反应室内气压在20~30乇,还原1~1.5小时,然后在反应室温度为650°~750℃下通入C2H2与N2的体积比为1/5~1/4的混合气,反应室气压在50~60乇,生长1~1.5小时。 2. The use of the carbon nanotube film produced at the cathode catalyst particles prepared according to the method according to claim 1, characterized in that: In preparing solutions, wherein the hydrochloride salt of iron or cobalt or nickel or a sulfate or a nitrate or vinegar salt prepared above was added to an aqueous solution of a salt by weight of water 180 to 220 times the ratio of the weight of the aqueous solution with deionized water, such salts formed sol ratio of 2/100; in the preparation of carbon nanotubes in the cathode film, wherein the reduction temperature of 700 ° ~ 750 ℃, into H2 and N2 in a volume ratio of mixed gas 4 / 1-6 / 1, the reaction chamber pressure of 20 Torr to 30 Torr, reducing 1 to 1.5 hours, then the reaction chamber at 650 at 750 ° ~ deg.] C and passed through C2H2 N2 mixed gas volume ratio of 1/5 to 1/4, a reaction chamber pressure of 50 to 60 Torr, the growth of 1 to 1.5 hours.
  3. 3.按照权利要求1或2所述的利用生成催化剂颗粒的碳纳米管薄膜阴极的制备方法,其特征在于:在溶液制备中,其中铁或钴或镍的盐酸盐或硫酸盐或硝酸盐或醋酸盐加入到200倍重量比的水中制成上述盐的水溶液,去离子水与上述盐的水溶液的重量比为1/100制成溶胶;在碳纳米管薄膜阴极的制备中,其中还原温度为720℃,通入H2与N2的体积比为7/1的混合气,反应室内气压在25乇,还原1小时,然后在反应室温度为720℃下通入C2H2与N2的体积比为1/6的混合气,反应室气压在60乇,生长1.5小时。 3. A method for preparing a thin film of cathode formation of carbon nanotubes using catalyst particles of claim 1 or claim 2, characterized in that: In preparing solutions, wherein the hydrochloride salt of iron or cobalt or nickel sulfate or nitrate, or made or acetate is added to water ratio of 200 times the weight of the aqueous solution of the salt, by weight of deionized water and an aqueous solution of salts of the above-described ratio is 1/100 prepare a sol; in the preparation of carbon nanotubes in the cathode film, wherein the reduction 720 ℃ temperature, into N2 and H2 mixed gas in a volume ratio of 7/1, the reaction chamber pressure of 25 Torr, was reduced for 1 hour and then the reaction chamber at a temperature of 720 ℃ into C2H2 and N2 in a volume ratio 1/6 mixed gas, the reaction chamber pressure of 60 Torr, the growth for 1.5 hours.
CN 00135476 2000-12-28 2000-12-28 Process for preparing carbon nano tube film cathode by forming catalyst particles CN1129168C (en)

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JP3935479B2 (en) 2004-06-23 2007-06-20 キヤノン株式会社 The method of manufacturing a manufacturing method and an electron-emitting device using it of the carbon fiber, a manufacturing method of an electronic device, a method of manufacturing an image display device and an information display reproducing apparatus using the image display device
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