WO2006099776A1 - Preparing a single component metal nanowire directly by physical vapor phase method - Google Patents

Preparing a single component metal nanowire directly by physical vapor phase method Download PDF

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Publication number
WO2006099776A1
WO2006099776A1 PCT/CN2005/000378 CN2005000378W WO2006099776A1 WO 2006099776 A1 WO2006099776 A1 WO 2006099776A1 CN 2005000378 W CN2005000378 W CN 2005000378W WO 2006099776 A1 WO2006099776 A1 WO 2006099776A1
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metal
substrate
preparing
molybdenum
nanowires
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PCT/CN2005/000378
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French (fr)
Chinese (zh)
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Ningsheng Xu
Jun Zhou
Shaozhi Deng
Jun Chen
Juncong She
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Zhongshan University
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Priority to PCT/CN2005/000378 priority Critical patent/WO2006099776A1/en
Publication of WO2006099776A1 publication Critical patent/WO2006099776A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
    • H01L21/2855—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by physical means, e.g. sputtering, evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors

Definitions

  • the invention relates to a technique for directly preparing metal nanowires by physical vapor deposition.
  • Metal materials such as molybdenum, tungsten, niobium, tantalum, niobium, tantalum and niobium have many excellent properties, such as high melting point, good mechanical properties at high temperature, good chemical stability at high temperature, and excellent electrical conductivity. These excellent properties make them
  • vacuum microelectronic devices In particular, one-dimensional metal nanowires will have broad application space in future nanoelectronic components and their integrated circuits. For example, they can be used not only as a component of nanoelectronic components, but also as wires to connect nanoelectronic elements.
  • the device is composed of circuit units.
  • Method 1 synthesis of metal nanowires by electrochemical deposition combined with template method
  • Method 2 first synthesis of metal oxide nanowires, and then reduction
  • Method 3 obtaining a metal nanowire by decomposing a metal organic substance
  • Method 4 obtaining a metal nanowire by a chemical reaction in a solution
  • Method 5 obtaining a metal nanowire by sputtering
  • Method 6 The method of evaporation obtains metal nanowires.
  • the above preparation method can prepare metal nanowires, the obtained nanowire components are impure, mixed with a large amount of oxides, and the process is complicated and expensive. Therefore, we explore a method for the synthesis of metal nanowires that is simple in process and controllable in composition.
  • the present invention employs the following process steps:
  • the metal source and substrate are rapidly cooled to room temperature in a mixed atmosphere of inert and reducing gases.
  • a metal boat, a metal sheet, and a metal powder are used as the metal source.
  • Stainless steel sheets, silicon wafers, alumina sheets, ceramics, and other high temperature resistant materials are used as the substrate, and the geometry of the substrate is not limited.
  • Metal finger They are materials such as molybdenum, tungsten, niobium, tantalum, niobium, tantalum and niobium.
  • the metal molybdenum and tungsten nanowires directly grown by the method are analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), etc., and the results show that the obtained nano material has a single component and is highly controllable. , perpendicular to the substrate and ordered.
  • the method can also synthesize other metal nanowires, such as ruthenium, osmium, iridium, osmium and iridium, etc., the production process is simple, the process parameters are easy to control, and the cost is low and the production efficiency is high.
  • Figure la is an XRD pattern of molybdenum nanowires grown on a stainless steel substrate.
  • Figure lb is an XRD pattern of molybdenum nanowires grown on an alumina substrate.
  • Figure 2a is a high-resolution SEM image of a molybdenum nanowire grown on a stainless steel substrate at a molybdenum boat temperature of 1350 °C for 20 minutes.
  • Figure 2b is a low resolution SEM image of a molybdenum nanowire grown on a stainless steel substrate at a molybdenum boat temperature of 1350 °C for 20 minutes.
  • Figure 3a is an SEM image of molybdenum nanowires grown on a stainless steel substrate at a temperature of 1350 °C for 5 minutes.
  • Figure 3b shows the molybdenum nanowires grown on a stainless steel substrate at a temperature of 1350 °C for 10 minutes.
  • Figure 3c shows the molybdenum boat temperature of 1350.
  • C SEM image of molybdenum nanowires grown on a stainless steel substrate at 20 minutes of incubation.
  • Figure 4a is an SEM image of a molybdenum nanowire grown on an alumina substrate with a molybdenum boat temperature of 1400 °C and a holding time of 20 minutes.
  • Figure 4b shows the molybdenum boat temperature of 1500.
  • C SEM image of a molybdenum nanowire grown on an alumina substrate at a holding time of 20 minutes.
  • Figure 4c shows the molybdenum boat temperature of 1600.
  • C SEM image of a molybdenum nanowire grown on an alumina substrate at a holding time of 20 minutes.
  • Figure 5a is a TEM image of a molybdenum nanowire.
  • Figure 5b is an ultra-high resolution TEM image of molybdenum nanowires and the corresponding Fourier transform.
  • Figure 6 is an XRD pattern of a tungsten nanowire and a ceramic substrate.
  • Fig. 7 is an SEM image of a tungsten nanowire grown on a ceramic sheet at a tungsten boat temperature of 1600 ° C and a holding time of 120 minutes.
  • a stainless steel sheet or an alumina sheet was used as the substrate, which was ultrasonically cleaned in acetone for 5 minutes, and then ultrasonically cleaned in anhydrous ethanol for 5 minutes.
  • the metal molybdenum nanowires grown in the above examples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The following is further described in conjunction with the drawings.
  • the obtained nanowire is a body-centered cubic structure of molybdenum. No diffraction peaks of oxides of molybdenum were observed in the map, indicating that the molybdenum nanowires grown were relatively pure. As can be seen from the two figures, the molybdenum nanowires grown on the stainless steel substrate have the same effect as the molybdenum nanowires grown on the alumina substrate. ,
  • Fig. 2a and Fig. 2b are SEM images of molybdenum nanowires grown on a stainless steel substrate at a temperature of 1350 °C for 20 minutes.
  • the molybdenum nanowires are found to be highly ordered, with nanowires having a diameter of about 40 nm and a length of about 8 ⁇ .
  • Figures 3a, 3b, and 3c are SEM images of molybdenum nanowires grown on stainless steel substrates at a molybdenum boat temperature of 1350 °C and holding times of 5 minutes, 10 minutes, and 20 minutes, respectively. We can see that molybdenum nanowires are not ordered at the beginning of growth, but only grow as time increases.
  • Figure 4 is an SEM image of molybdenum nanowires grown on an alumina substrate at a temperature of 1400 °C, 1500 °C, and 1600 °C for 20 minutes. We found that as the growth temperature increases, the number of molybdenum nanowires on the substrate becomes less and less, but the nanowires become more straight and the surface becomes cleaner.
  • Figure 5a is a TEM image of a single molybdenum nanowire with many nanoparticles attached to the surface of the nanowire.
  • Figure 5b shows the ultra-high resolution TEM image of the molybdenum nanowires and the corresponding Fourier transform.
  • the distance between the parallel crystal faces is about 0.22 nm, which corresponds to the ⁇ 110 ⁇ crystal face family of the body-centered cubic structure molybdenum.
  • the interplanar spacing indicates that the nanowires prepared above are elemental molybdenum nanowires.
  • Ceramic sheets were used as the substrate, which were ultrasonically cleaned in acetone for 5 minutes and then ultrasonically cleaned in absolute ethanol for 5 minutes.
  • the substrate was placed on a tungsten boat.
  • the vacuum heating device is pre-vacuumed to ⁇ 5 10 - 2 Torr, then argon gas is introduced as a shielding gas, the gas flow rate is 200 standard cubic centimeters per second, and hydrogen gas is introduced at the same time, and the gas flow rate is 100 standard cubic centimeters per second.
  • Fig. 6 (a) is an XRD pattern of a ceramic substrate before growing tungsten nanowires, and (b) is an XRD pattern after growing tungsten nanowires, and no significant tungsten oxidation is observed except for the tungsten peak of the body-centered cubic structure. The peak of the object exists.
  • Figure 7 is an SEM image of a tungsten nanowire grown on a ceramic sheet. It can be seen that the bottom of the tungsten nanowire is also disordered, but it becomes very orderable at the top, and the surface of the tungsten nanowire is also not smooth.
  • the present method is also applicable to ruthenium, osmium, iridium, osmium and iridium.

Abstract

The present invention discloses a method for preparing a single component metal nanowire directly by physical vapor deposition, metal tungsten or molybdenum nanowires produced by the present method were analyzed by X-ray diffraction analysis (XRD) , scanning electron microscope (SEM) , transmission electron microscope (TEM) or the like, the results indicate that the obtained nanosize material have single component, high degree of controllability, verticality to substrate and good order. The method may also be used to synthesis several other metal nanowires, such as technetium, ruthenium, iridium, rhenium and osmium or the like, the process for producing metal nanowires is simple and process parameters are easy to control, also, the process has low cost and high production efficiency.

Description

物理气相沉积法直接生长成份单一的金属纳米线  Direct growth of single metal nanowires by physical vapor deposition
本发明所属技术领域 Technical field to which the present invention pertains
本发明涉及物理气相沉积法直接制备金属纳米线的技术。  The invention relates to a technique for directly preparing metal nanowires by physical vapor deposition.
在本发明之前的现有技术 Prior art prior to the present invention
钼、 钨、 锝、 钌、 铱、 铼和锇等金属材料具有很多优良的性质， 如熔点高， 髙 温下机械性能好， 高温化学稳定好， 导电率离等， 这些优异的性能使得它们在真空 微电子器件中有着广阔的应用。 尤其是一维金属纳米线， 它在未来纳电子元器件及 其集成电路中将有着广阔的应用空间， 例如它们不仅可以作为纳电子元器件的组成 单元， 而且还可以作为导线连接各纳电子元器件以组成电路单元。  Metal materials such as molybdenum, tungsten, niobium, tantalum, niobium, tantalum and niobium have many excellent properties, such as high melting point, good mechanical properties at high temperature, good chemical stability at high temperature, and excellent electrical conductivity. These excellent properties make them There are wide applications in vacuum microelectronic devices. In particular, one-dimensional metal nanowires will have broad application space in future nanoelectronic components and their integrated circuits. For example, they can be used not only as a component of nanoelectronic components, but also as wires to connect nanoelectronic elements. The device is composed of circuit units.
至今为止，有很多关于合成金属纳米线方法的报道， 它们主要包括如下几种： 方 法一， 通过电化学沉积结合模板的方法合成金属纳米线； 方法二， 先合成金属氧化 物纳米线， 再还原获得金属纳米线； 方法三， 通过分解金属有机物获得金属纳米线； 方法四， 通过在溶液里发生化学反应获得金属纳米线； 方法五， 通过溅射的方法获 得金属纳米线； 方法六， 通过热蒸发的方法获得金属纳米线。 上述的制备方法虽然 能够制备出金属纳米线， 但是所获得的纳米线成份不纯， 混有大量的氧化物， 并且 工艺复杂， 成本昂贵。 因此我们探索工艺简单、 且成份可控的的合成制备金属纳米 线的方法。  So far, there have been many reports on methods for synthesizing metal nanowires, which mainly include the following: Method 1, synthesis of metal nanowires by electrochemical deposition combined with template method; Method 2, first synthesis of metal oxide nanowires, and then reduction Obtaining a metal nanowire; Method 3, obtaining a metal nanowire by decomposing a metal organic substance; Method 4, obtaining a metal nanowire by a chemical reaction in a solution; Method 5, obtaining a metal nanowire by sputtering; Method 6 The method of evaporation obtains metal nanowires. Although the above preparation method can prepare metal nanowires, the obtained nanowire components are impure, mixed with a large amount of oxides, and the process is complicated and expensive. Therefore, we explore a method for the synthesis of metal nanowires that is simple in process and controllable in composition.
发明目的 Purpose of the invention
本发明的目的是提供一种直接生长成份单一的金属纳米线的方法。  It is an object of the present invention to provide a method of directly growing a single metal nanowire of a composition.
本发明采用的技术方案 Technical solution adopted by the invention
为了实现上述发明目的， 本发明采用了如下工艺步骤：  In order to achieve the above object, the present invention employs the following process steps:
(A) 在真空条件下、在惰性和还原气体的混合气氛中加热金属源和衬底至高于 该金属相应氧化物发生歧化分解反应的温度， 以使金属源发生蒸发； (A) heating the metal source and the substrate in a mixed atmosphere of inert and reducing gas under vacuum to a temperature higher than a disproportionation reaction of the corresponding oxide of the metal to cause evaporation of the metal source;
(B) 在上述反应温度下、在惰性和还原气体的混合或只有它们之中一种气体的 气氛中保温 5~240分钟，相关产物在衬底上发生沉积直接生长单质金属纳 米线； (B) holding at room temperature for 5 to 240 minutes in an atmosphere of a mixture of inert and reducing gases or only one of them, and the related product is deposited on the substrate to directly grow the elemental metal nanowire;
(C) 在惰性和还原气体的混合气氛中， 将金属源和衬底快速降温至室温。 在上述工艺中， 采用金属舟、 金属片和金属粉作为金属源。 采用不锈钢片、 硅 片、 氧化铝片、 陶瓷及其它耐高温的材料作为衬底， 衬底的几何形状不限。 金属指 的是钼、 钨、 锝、 钌、 铱、 铼和锇等材料。 (C) The metal source and substrate are rapidly cooled to room temperature in a mixed atmosphere of inert and reducing gases. In the above process, a metal boat, a metal sheet, and a metal powder are used as the metal source. Stainless steel sheets, silicon wafers, alumina sheets, ceramics, and other high temperature resistant materials are used as the substrate, and the geometry of the substrate is not limited. Metal finger They are materials such as molybdenum, tungsten, niobium, tantalum, niobium, tantalum and niobium.
通过本方法直接生长的金属钼、钨纳米线， 经过用 X射线衍射（XRD)、扫描电 镜 （SEM)、 透射电镜 （TEM)等进行分析， 结果表明所获得的纳米材料成份单一、 高度可控、 垂直于衬底和有序。 该方法还可以合成其它几种金属纳米线， 如锝、 钌、 铱、 铼和锇等， 其生产工艺简单， 工艺参数易于控制， 并且成本低和生产效率高。 附图说明  The metal molybdenum and tungsten nanowires directly grown by the method are analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), etc., and the results show that the obtained nano material has a single component and is highly controllable. , perpendicular to the substrate and ordered. The method can also synthesize other metal nanowires, such as ruthenium, osmium, iridium, osmium and iridium, etc., the production process is simple, the process parameters are easy to control, and the cost is low and the production efficiency is high. DRAWINGS
图 la是生长在不锈钢衬底的钼纳米线的 XRD图。  Figure la is an XRD pattern of molybdenum nanowires grown on a stainless steel substrate.
图 lb是生长在氧化铝衬底上的钼纳米线的 XRD图。  Figure lb is an XRD pattern of molybdenum nanowires grown on an alumina substrate.
图 2a是钼舟温度为 1350 °C， 保温 20分钟时生长在不锈钢衬底上的钼纳米线的 高分辨的 SEM图。  Figure 2a is a high-resolution SEM image of a molybdenum nanowire grown on a stainless steel substrate at a molybdenum boat temperature of 1350 °C for 20 minutes.
图 2b是钼舟温度为 1350 °C， 保温 20分钟时生长在不锈钢衬底上的钼纳米线的 低分辨的 SEM图。  Figure 2b is a low resolution SEM image of a molybdenum nanowire grown on a stainless steel substrate at a molybdenum boat temperature of 1350 °C for 20 minutes.
图 3a是钼舟温度为 1350 °C， 保温 5分钟时生长在不锈钢衬底上的钼纳米线的 SEM图。  Figure 3a is an SEM image of molybdenum nanowires grown on a stainless steel substrate at a temperature of 1350 °C for 5 minutes.
图 3b是钼舟温度为 1350 °C， 保温 10分钟时生长在不锈钢衬底上的钼纳米线的 Figure 3b shows the molybdenum nanowires grown on a stainless steel substrate at a temperature of 1350 °C for 10 minutes.
SEM图。 SEM image.
图 3c是钼舟温度为 1350。C， 保温 20分钟时生长在不锈钢衬底上的钼纳米线的 SEM图。  Figure 3c shows the molybdenum boat temperature of 1350. C, SEM image of molybdenum nanowires grown on a stainless steel substrate at 20 minutes of incubation.
图 4a是钼舟温度为 1400 °C， 保温时间为 20分钟时生长在氧化铝衬底上的钼纳 米线的 SEM图。  Figure 4a is an SEM image of a molybdenum nanowire grown on an alumina substrate with a molybdenum boat temperature of 1400 °C and a holding time of 20 minutes.
图 4b是钼舟温度为 1500。C, 保温时间为 20分钟时生长在氧化铝衬底上的钼纳 米线的 SEM图。  Figure 4b shows the molybdenum boat temperature of 1500. C, SEM image of a molybdenum nanowire grown on an alumina substrate at a holding time of 20 minutes.
图 4c是钼舟温度为 1600。C， 保温时间为 20分钟时生长在氧化铝衬底上的钼纳 米线的 SEM图。  Figure 4c shows the molybdenum boat temperature of 1600. C, SEM image of a molybdenum nanowire grown on an alumina substrate at a holding time of 20 minutes.
图 5a是钼纳米线的 TEM像。  Figure 5a is a TEM image of a molybdenum nanowire.
图 5b是钼纳米线的超高分辨 TEM像以及相应的傅立叶变换。  Figure 5b is an ultra-high resolution TEM image of molybdenum nanowires and the corresponding Fourier transform.
图 6是钨纳米线以及陶瓷衬底的 XRD图。'  Figure 6 is an XRD pattern of a tungsten nanowire and a ceramic substrate. '
图 7是钨舟温度为 1600 °C， 保温时间为 120分钟时生长在陶瓷片上的钨纳米线 的 SEM图。 实施例 Fig. 7 is an SEM image of a tungsten nanowire grown on a ceramic sheet at a tungsten boat temperature of 1600 ° C and a holding time of 120 minutes. Example
实施例 1 (制备钼纳米线）： Example 1 (Preparation of molybdenum nanowires):
( 1 ) 选用不锈钢片或氧化铝片作为衬底， 先在丙酮中超声清洗 5分钟， 然后在无 水乙醇中超声清洗 5分钟。  (1) A stainless steel sheet or an alumina sheet was used as the substrate, which was ultrasonically cleaned in acetone for 5 minutes, and then ultrasonically cleaned in anhydrous ethanol for 5 minutes.
(2) 用钼舟 （ 150x15x0.3 mm ) 作为钼源， 将钼舟放在真空加热装置中 ( φ350χ400ΐΉΐη ) , 将衬底放在钼舟里面。 先将真空加热装置预抽真空至〜 5xlO'2 Torr, 然后通入氩气作为保护气体， 气流量为 200标准立方厘米每秒， 同时通入氢气， 气流量为 100标准立方厘米每秒。 (2) Using a molybdenum boat (150x15x0.3 mm) as the molybdenum source, place the molybdenum boat in a vacuum heating device (φ350χ400ΐΉΐη) and place the substrate in the molybdenum boat. The vacuum heating device is pre-vacuumed to ~5xlO' 2 Torr, then argon gas is introduced as a shielding gas, the gas flow rate is 200 standard cubic centimeters per second, and hydrogen gas is introduced at the same time, and the gas flow rate is 100 standard cubic centimeters per second.
(3 ) 给钼舟升温， 最后分别升温至 1350 °C、 1400 °C、 1500 °C和 1600 °C。  (3) Warm the molybdenum boat and finally heat up to 1350 °C, 1400 °C, 1500 °C and 1600 °C.
(4) 关闭氢气， 此时真空气压为〜 0.7 Torr。 ·  (4) Turn off the hydrogen gas at a vacuum pressure of ~ 0.7 Torr. ·
(5 ) 分别保温 5分钟、 10分钟和 20分钟。  (5) Keep 5 minutes, 10 minutes and 20 minutes respectively.
(6) 再次通入氢气， 并降温（5分钟内降到 400 °C以下）， 直至冷却至室温。  (6) Pass hydrogen again and cool down (down to 400 °C in 5 minutes) until it is cooled to room temperature.
对于上面实施例中所生长的金属钼纳米线，利用 X射线衍射（XRD)、扫描电镜 (SEM)、 透射电镜 （TEM)进行分析。 以下结合附图作进一步说明。  The metal molybdenum nanowires grown in the above examples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The following is further described in conjunction with the drawings.
如图 la和图 lb所示， 分别是生长在不绣钢衬底和氧化铝衬底上的钼纳米线的 As shown in Figures la and lb, respectively, molybdenum nanowires grown on a stainless steel substrate and an alumina substrate
XRD图， 通过图谱可以知道所获得的纳米线是体心立方结构的钼。 在图谱中没有观 察到明显钼的氧化物的衍射峰存在， 说明所生长的钼纳米线成份比较纯。 从两图比 较可知， 不锈钢衬底上生长的钼纳米线与氧化铝衬底上生长的钼纳米线具有同样的 效果。 ， XRD pattern, it can be known from the map that the obtained nanowire is a body-centered cubic structure of molybdenum. No diffraction peaks of oxides of molybdenum were observed in the map, indicating that the molybdenum nanowires grown were relatively pure. As can be seen from the two figures, the molybdenum nanowires grown on the stainless steel substrate have the same effect as the molybdenum nanowires grown on the alumina substrate. ,
图 2a和图 2b是钼舟温度为 1350 °C， 保温 20分钟时生长在不锈钢衬底上的钼 纳米线的 SEM图。 图中发现钼纳米线高度有序， 纳米线的直径约为 40 nm， 长度约 为 8 μπΐο  Fig. 2a and Fig. 2b are SEM images of molybdenum nanowires grown on a stainless steel substrate at a temperature of 1350 °C for 20 minutes. The molybdenum nanowires are found to be highly ordered, with nanowires having a diameter of about 40 nm and a length of about 8 μπΐ.
图 3a、 3b和 3c是钼舟温度为 1350 °C， 保温时间分别为 5分钟、 10分钟和 20 分钟时生长在不锈钢衬底上的钼纳米线的 SEM图。我们可以发现钼纳米线在生长初 期时并不是有序的， 只是随着生长时间增加才会长得有序。  Figures 3a, 3b, and 3c are SEM images of molybdenum nanowires grown on stainless steel substrates at a molybdenum boat temperature of 1350 °C and holding times of 5 minutes, 10 minutes, and 20 minutes, respectively. We can see that molybdenum nanowires are not ordered at the beginning of growth, but only grow as time increases.
图 4是钼舟温度分别为 1400 °C、 1500°C和 1600°C， 保温时间为 20分钟时生长 在氧化铝衬底上的钼纳米线的 SEM图。我们发现随着生长温度的增加， 衬底上钼纳 米线的数量会越来越少， 但是纳米线会越来越直， 表面越来越干净。  Figure 4 is an SEM image of molybdenum nanowires grown on an alumina substrate at a temperature of 1400 °C, 1500 °C, and 1600 °C for 20 minutes. We found that as the growth temperature increases, the number of molybdenum nanowires on the substrate becomes less and less, but the nanowires become more straight and the surface becomes cleaner.
图 5a是单根钼纳米线的 TEM像， 可以着到纳米线的表面附有很多纳米颗粒。 图 5b是钼纳米线的超高分辨的 TEM像及相应的傅立叶变换， 测得平行的晶面之间 的距离约为 0.22 nm， 刚好对应了体心立方结构钼的 {110}晶面族的面间距， 说明上 述所制备的纳米线是单质的钼纳米线。 Figure 5a is a TEM image of a single molybdenum nanowire with many nanoparticles attached to the surface of the nanowire. Figure 5b shows the ultra-high resolution TEM image of the molybdenum nanowires and the corresponding Fourier transform. The distance between the parallel crystal faces is about 0.22 nm, which corresponds to the {110} crystal face family of the body-centered cubic structure molybdenum. The interplanar spacing indicates that the nanowires prepared above are elemental molybdenum nanowires.
实施例 2 (制备钨纳米线）： Example 2 (Preparation of tungsten nanowires):
( 1 ) 选用陶瓷片作为衬底， 先在丙酮中超声清洗 5分钟， 然后在无水乙醇中超声 清洗 5分钟。  (1) Ceramic sheets were used as the substrate, which were ultrasonically cleaned in acetone for 5 minutes and then ultrasonically cleaned in absolute ethanol for 5 minutes.
(2) 以钨舟 （ 150x15x0.3 mm ) 作为钨 ， 将钨舟放在真空加热装置中 (2) Using a tungsten boat (150x15x0.3 mm) as tungsten, place the tungsten boat in a vacuum heating device
(φ350χ400ιηηι),将衬底放在钨舟上。先将真空加热装置预抽真空至〜 5 10—2 Torr, 然后通入氩气作为保护气体， 气流量为 200标准立方厘米每秒， 同时通 入氢气， 气流量为 100标准立方厘米每秒。 (φ350χ400ιηηι), the substrate was placed on a tungsten boat. The vacuum heating device is pre-vacuumed to ~ 5 10 - 2 Torr, then argon gas is introduced as a shielding gas, the gas flow rate is 200 standard cubic centimeters per second, and hydrogen gas is introduced at the same time, and the gas flow rate is 100 standard cubic centimeters per second.
(3 ) 给钨舟升温， 最后分别升温至 1600 °C， 衬底的温度为 1500 °C ~1600 °C。 (3) The tungsten boat is heated up, and finally heated to 1600 °C, and the substrate temperature is 1500 °C ~ 1600 °C.
(4) 关闭氢气， 此时真空气压为〜 0.7 Torr。 (4) Turn off the hydrogen gas at a vacuum pressure of ~ 0.7 Torr.
(5 ) 分别保温 120分钟。  (5) Keep warm for 120 minutes.
(6) 再次通入氢气， 并降温（5分钟内降到 400 °C以下）， 直至冷却至室温。  (6) Pass hydrogen again and cool down (down to 400 °C in 5 minutes) until it is cooled to room temperature.
对于上面实施例中所生长的金属钨纳米线， 利用 X射线衍射（XRD)、 扫描电镜 For the metal tungsten nanowires grown in the above examples, using X-ray diffraction (XRD), scanning electron microscopy
(SEM)、 透射电镜 （TEM)进行分析。 以下结合附图作进一歩说明。 (SEM) and transmission electron microscopy (TEM) were used for analysis. The following description will be made in conjunction with the accompanying drawings.
图 6中， （a)是生长钨纳米线之前陶瓷衬底的 XRD图， （b)是生长钨纳米线之 后的 XRD图， 除了体心立方结构的钨的峰外没有发现明显的钨的氧化物的峰存在。  In Fig. 6, (a) is an XRD pattern of a ceramic substrate before growing tungsten nanowires, and (b) is an XRD pattern after growing tungsten nanowires, and no significant tungsten oxidation is observed except for the tungsten peak of the body-centered cubic structure. The peak of the object exists.
图 7是生长在陶瓷片上的钨纳米线的 SEM图，可以发现钨纳米线的底部也是杂 乱无章的， 但是到了顶部就变得非常有序了， 同时也可以看到钨纳米线的表面不光 滑。  Figure 7 is an SEM image of a tungsten nanowire grown on a ceramic sheet. It can be seen that the bottom of the tungsten nanowire is also disordered, but it becomes very orderable at the top, and the surface of the tungsten nanowire is also not smooth.
除了上述实施例 1和实施例 2中所列举的金属钼和金属钨纳米线的生成以外， 本法还适用于锝、 钌、 铱、 铼和锇。  In addition to the formation of the metal molybdenum and metal tungsten nanowires listed in the above Examples 1 and 2, the present method is also applicable to ruthenium, osmium, iridium, osmium and iridium.

Claims

权 利 要 求 、 一种制备金属钠米线的方法， 包括以下步骤-(A) 在真空条件下、 在惰性和还原气体的混合气氛中加热金属源和衬 底至高于该金属相应氧化物发生歧化分解反应的温度， 以使金属 源发生蒸发； (B) 在上述反应温度下、 在惰性和还原气体的混合或只有它们之中一 种气体的气氛中保温 5~240分钟， 相关产物在衬底上发生沉积直 接生长单质金属纳米线； . (C) 在惰性和还原气体的混合气氛中， 将金属源和衬底快速降温至室 温。 、 按权利要求 1所述的制备金属钠米线的方法， 其特征在于： 所述的金属为钼、 钨、 锝、 钌、 铱、 铼和锇等。 、 按权利要求 1所述的制备金属钠米线的方法， 其特征在于： 所述金属源是指 相应金属的金属片、 金属舟或金属粉。 、 按权利要求 1所述的制备金属钠米线的方法， 其特征在于： 所述的衬底是耐 高温的材料， 几何形状不限， 如不锈钢片、 硅片、 氧化铝片、 陶瓷、 玻璃等。 、 按权利要求 1至 4任一权利要求所述的制备金属钠米线的方法， 其特征包括 以下工艺步骤： ' Claims, a method of preparing a metal sodium noodle, comprising the steps of: (A) heating a metal source and a substrate under a vacuum in a mixed atmosphere of inert and reducing gases to a disproportionation reaction above a corresponding oxide of the metal The temperature is such that the metal source evaporates; (B) is incubated at a temperature of the above reaction temperature in a mixture of inert and reducing gases or only one of them for 5 to 240 minutes, and the related product occurs on the substrate. Depositing directly grown elemental metal nanowires; (C) Rapidly lowering the metal source and substrate to room temperature in a mixed atmosphere of inert and reducing gases. The method for preparing a sodium metal rice noodle according to claim 1, wherein the metal is molybdenum, tungsten, rhenium, ruthenium, osmium, iridium, osmium or the like. The method for preparing a sodium metal rice noodle according to claim 1, wherein the metal source refers to a metal piece, a metal boat or a metal powder of a corresponding metal. The method for preparing a metal sodium noodle according to claim 1, wherein: the substrate is a high temperature resistant material, and the geometric shape is not limited, such as a stainless steel sheet, a silicon wafer, an alumina sheet, a ceramic, a glass, or the like. . A method of preparing a sodium metal rice noodle according to any one of claims 1 to 4, characterized by the following process steps:
( 1 ) 清洗衬底， 除去衬底上的杂质；  (1) cleaning the substrate to remove impurities on the substrate;
(2) 将金属源和衬底放在真空加热装置， 预抽至一定的真空度以上， 然后 往真空加热装置通入惰性气体和还原气体并保持恒定流速；  (2) placing the metal source and the substrate in a vacuum heating device, pre-pumping to a certain degree of vacuum, and then introducing an inert gas and a reducing gas into the vacuum heating device and maintaining a constant flow rate;
(3) 将金属源和衬底加热至高于该金属相应氧化物发生歧化分解反应的 温度；  (3) heating the metal source and the substrate to a temperature higher than a disproportionation reaction of the corresponding oxide of the metal;
(4) 在惰性和还原气体的混合或只有它们之中一种气体的气氛中， 将真空 腔的气压降低至一定真空度以下， 并保温 5分钟至 240分钟； 在惰性 和还原气体的混合气氛中， 将金属源和衬底快速降温， 直至冷却至室 温  (4) In an atmosphere of a mixture of inert and reducing gases or only one of them, reduce the pressure of the vacuum chamber to below a certain degree of vacuum and keep it for 5 minutes to 240 minutes; in a mixed atmosphere of inert and reducing gases Medium, quickly cool the metal source and substrate until cooled to room temperature
PCT/CN2005/000378 2005-03-25 2005-03-25 Preparing a single component metal nanowire directly by physical vapor phase method WO2006099776A1 (en)

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