CN100436661C - Method for in situ growth for preparing semiconductor nanotube - Google Patents
Method for in situ growth for preparing semiconductor nanotube Download PDFInfo
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- CN100436661C CN100436661C CNB2006100026806A CN200610002680A CN100436661C CN 100436661 C CN100436661 C CN 100436661C CN B2006100026806 A CNB2006100026806 A CN B2006100026806A CN 200610002680 A CN200610002680 A CN 200610002680A CN 100436661 C CN100436661 C CN 100436661C
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Abstract
The invention relates to a method for preparing semi conductive nanometer pipe without using mould and on different base material with good degree of crystallization. It comprises following steps: (1) putting base material coated with metal film or metal foil into evacuated container, ventilating mixing gas of inert gas and reacting gas, said reacting gas is the gas that can react with metal and produce semiconductor; (2) introducing low- temperature plasma to promote reacting gas to generate active matter, and maintain temperature for base material and metal film at a certain range to make semi conductive nanometer grow, said temperature is not lower than 200 Deg. C and not higher than 200 Deg. C of fusion temperature of metal foil or metal film, said positive ion of semiconductor comes from metal foil or metal film, negative ion come from reacting gas; (3) keeping mixing gas ventilation until reaction is finished.
Description
Technical field
The present invention relates to the preparation method of semiconducting nanotubes, in more detail, the present invention relates to use simple experimental apparatus and technology, is supplementary means with the plasma body, and growth in situ goes out to have the method for the semiconductor nano tube material of good crystallization degree in the substrate of unlike material.
Background technology
The character of semiconductor nano material is to determine by the factor of its chemical ingredients, size and dimension three aspects is common.Taught since finding carbon nanotube in 1991 since Japanese scientist's Sumio Iijima, nano tubular structure has just caused great research interest.One dimension Nano structure is considered to the smallest dimension that can realize that electronics and exciton effectively transport, and is the ideal element of nano functional device.Simultaneously, the hollow structure of nanotube provides big specific surface area, thereby is being with a wide range of applications aspect transmitter, catalyzer and the material storage.By adopting different semiconductor materials to make nano tube structure, everyways such as its light, electricity, magnetic, catalysis, mechanical property have different performances, thereby have a wide range of applications in different fields.
But, up to now by spontaneous growth synthetic nano tube structure mainly be confined to possess laminate structure material (as graphite, h-BN, WS
2, MoS
2Deng).This class material might obtain nano tube structure by curling of atomic shell.And for the material that does not possess laminate structure, a kind of two step process are adopted in the preparation of nano tube structure usually, comprise and at first use certain template (anodised aluminium for example, carbon nanotube, the perhaps nano wire of other materials etc.) makes the deposition of growth raw material present tubulose, and carry out template by burn into dissolved method afterwards and remove.Template is a method in common very, but has some problems on using.At first be that tube wall is not to obtain by spontaneous growth, the crystallization degree of sample is difficult to be guaranteed; Next is that the process of removing template relates to operations such as corrosion or thermal treatment, might cause damage to product.
In addition, in order to obtain functional device, synthetic nanotube product needed is transferred, assembles and be fixed in the substrate through loaded down with trivial details treating processes.As seen for the semiconductor substance that does not possess laminate structure, if can be not by the effect of template and make it in specified substrate, realize spontaneous growth, directly obtain the good nanotube of fixed crystallization degree in substrate, can be very significant work.
Result of study before this shows, because crystalline structure intrinsic anisotropy, the oriented growth pattern is followed in the crystal growth meeting under given conditions, thereby produces one dimension Nano structure (nano wire, nanometer rod etc.).The growth front end of one-dimentional structure always is made of the highest crystal face of energy, and the side that occupies most surface-area then is to be made of the lower stable crystal face of energy.In the prior art, can obtain the solid one dimension Nano structure of growth in situ.
Summary of the invention
At the problems referred to above, the purpose of this invention is to provide a kind of needn't be by template, can be on different base growth in situ go out the method for the good semiconducting nanotubes of crystallization degree.The basic design of technical solution of the present invention is: determined in the solid phase nucleation process under the prerequisite of diameter of product one-dimentional structure, promote the one-dimensional growth of nanocrystal by the activity that improves reactant, and control reactant concn, make product be not enough to fill up the high-energy crystal face and generate unidimensional solid construction (nano wire, nanometer rod etc.), thereby obtain the unidimensional hollow structure, i.e. nanotube.The reaction raw materials that adopts is tinsel or is plated in suprabasil metallic film, the working gas of low-temperature plasma, and reactant gas.Make tinsel and reactant gas reaction by geseous discharge and heater means, grow semiconducting nanotubes.
According to purpose of the present invention, growth in situ semiconducting nanotubes method comprises the steps:
(1) will be coated with the substrate of metallic film or the container that tinsel is put into vacuum-pumping, vacuumize the gas mixture of back input rare gas element and reactant gas, described reactant gas be can with the gas of metal reaction synthesized semiconductor;
Preferably, also can be coated with catalyst film in the described substrate, its role is to the diameter that growth for semiconducting nanotubes provides the nucleation site and controls nanotube.Preferably, described catalyzer is selected from one or more of lead, tin, chromium, manganese, iron, cobalt, nickel, gold and silver;
(2) introducing low-temperature plasma makes reactant gas generate active specy, temperature maintenance with substrate or tinsel makes the semiconducting nanotubes growth within the specific limits simultaneously, described temperature range is not less than 200 ℃, above 200 ℃ of the fusing point that is not higher than this suprabasil metallic film or tinsel, described semi-conductive positively charged ion is from tinsel or metallic film, and negatively charged ion is from reactant gas;
(3) input of maintenance gas mixture is carried out back end fully until reaction.
In above-mentioned steps, the mechanism of growth in situ semiconducting nanotubes is roughly as follows: 1) metallic film or tinsel and reactant gas react under heating and plasma-activated condition, the surface generates the layer of semiconductor film, and forms the growth site of one-dimensional material with nucleation process; 2) semiconductor layer and following metallic film form partial alloy eutectic system at intersection, reactive species in the gas phase and following metallic membrane are constantly to this eutectic system postreaction raw material, semiconductor crystal is separated out from the supersaturation eutectic system, the one-dimensional growth that is orientated; 3) because plasma body provides highly active reaction species, so crystal growth is carried out with very high speed.Therefore the undersupply of raw material carries out with hollow one-dimentional structure growth pattern after initial nucleation stage to keep the growth of solid one-dimentional structure, and the direction of growth remains unchanged.In the process that generates semiconducting nanotubes, for effective growth and the good crystallization degree of acquisition of keeping nanotube, temperature should not be lower than 200 ℃; Because of metal flow enhancing under the high temperature, be difficult for forming the nano tube structure of hollow, simultaneously so system temperature should not be higher than the fusing point of used metal more than 200 ℃.
Wherein, the material of metallic film or tinsel depends on required synthetic semiconductor nano tube material, purpose provide generate positively charged ion in the semiconducting nanotubes; Reactant gas is to generate semi-conductive gas with metal reaction, purpose provides the negatively charged ion in the semiconducting nanotubes, and it is preferable can be all gases that contains the 5th, six, seven main group elements (as nitrogen, phosphorus, arsenic, oxygen, sulphur, selenium, fluorine, chlorine, bromine, iodine etc.).Described semiconductor carbon nanometer tube is preferably nitride, phosphide, arsenide, oxide compound, sulfide, selenide, fluorochemical, muriate, bromide or iodide semi-conductor.The ratio that the branch of reactant gases covers mixed gas is not more than 10%.The crystalline structure of institute's synthetic semiconductor material has determined the geometric shape, particularly cross-sectional shape of the nanotube that generated.In addition, those skilled in the art should understand, and the variation of technical parameters such as the Heating temperature in the semiconducting nanotubes process of growth, plasma power also can produce certain influence to the product pattern.
Further, the low-temperature plasma that adopts in the inventive method is a kind of nonequilibrium plasma, can allow gas phase species have high chemical reactivity under relatively low temperature.Those skilled in the art should be able to understand, and described low-temperature plasma can be but be not limited to the radio-frequency plasma of microwave plasma, capacitive character or inductive couplings.
Further, the maximum length of the nanotube that is generated in aforesaid method also can be regulated and control by controlling reaction time by the thickness decision of suprabasil metallic film simultaneously.Metallic membrane is thick more, and corresponding nanotube maximum length is also long more.Reaction times is long more, and the nanotube length that obtains is also long more.
Technique effect of the present invention is: the present invention adopts tinsel or is plated in suprabasil metallic film is raw material, obtains the semiconductor nano tube material of growth in situ in atmosphere reactive through Cement Composite Treated by Plasma.Entire reaction course is a dry process, does not need template, and step is simple, cleanliness without any pollution, and reaction can be carried out continuously, is applicable to industrial production.Contrast the template of present widespread use, the product that is made by method provided by the invention obtains owing to spontaneous growth, so possess good crystallization degree.And in substrate, directly obtain nano tube structure, save that template is removed and to nanotube shift, assembling and the numerous and diverse operation of fixed, help the structure of the functional device of based semiconductor nano tube structure.And present method is to the pervasive universal method of multiple semiconductor material.In addition, it is few to the present invention relates to operation, and equipment is simple, suitable can the quantity-produced dry process, environmental pollution is few, is fit to industrial application.
Description of drawings
Fig. 1 is the scanning electron microscopy picture that is grown in the suprabasil ZnO nanotube of silicon single crystal (100);
Fig. 2 is the transmission electron microscope image of the ZnO nanotube sample collected from substrate;
Fig. 3 is the high resolution transmission electron microscope image of Fig. 2 sample;
Fig. 4 is the X-ray powder crystal diffractogram of the ZnO nanotube of growth in situ on monocrystal silicon substrate.
Embodiment
Below be described with reference to the accompanying drawings the present invention by specific embodiment, but be not construed as limiting the invention.
Embodiment 1: from Zn film preparation ZnO nanotube, synthesis step is as follows on monocrystal silicon substrate:
(1) Zn metallic membrane on the magnetron sputtering on single crystalline Si (100) substrate, thickness is 300 nanometers.
(2) Si (100) substrate that will be coated with the Zn metallic membrane moves in the silica tube of horizontal positioned.Vacuumize the back and add O
2/ Ar gas mixture, oxygen partial pressure is about 0.5%, and system pressure is kept about 50 pascals.
(3) add radio frequency (13.6MHz) plasma body of jigger coupling in the updrift side of substrate, about 100 watts of power is heated by resistive device to substrate simultaneously and is heated to 350 ℃.
(4) reaction stops heating and plasma body output after 15 minutes, takes out substrate after the system cools, obtains reaction product.
As shown in Figure 1, for present embodiment prepares the scanning electron microscopy picture that is grown in the suprabasil ZnO nanotube of silicon single crystal (100), the ZnO nanotube is grown in the substrate densely as we can see from the figure.Illustration wherein is the feature of a nanotube port, and hexagonal regular profile demonstrates the good crystallization degree of product.As shown in Figure 2, be the transmission electron microscope image of the ZnO nanotube sample collected from substrate, as can be seen from the figure product has bigger length-to-diameter ratio, and even size distribution.As shown in Figure 3, be the high resolution transmission electron microscope image of sample among Fig. 2, the clear lattice that manifests has proved the good crystallization degree of this product mutually.As shown in Figure 4, be the X-ray powder crystal diffractogram of the ZnO nanotube of growth in situ on monocrystal silicon substrate, confirm that product is pure wurtzite zinc oxide nano mitron.
Wherein, heating is to be in the needs of keeping the required temperature of growing semiconductor nanotube to substrate, those skilled in the art will be understood that, the heater means that is adopted in the present embodiment is not a monotechnics feature of the present invention, be not construed as limiting the invention, generate the required temperature of nanotube as long as can keep, also can not heat (when plasma power is large enough to keep temperature of reaction), perhaps adopt other heater meanses.
Embodiment 2: prepare the ZnS nanotube of patterning on conducting glass material tin indium oxide (ITO) substrate from the Zn film of patterning, synthesis step is as follows:
(1) under the effect of copper mast on the conducting glass material Zn film of hot evaporation one deck patterning, thickness is 600 nanometers.
(2) the conducting glass material substrate that will be coated with patterning Zn film is put on the specimen holder of quartz reactor of vertical placement.Vacuumize the back and feed H
2The S/Ar mixed gas, H
2The S dividing potential drop is about 2%, and system pressure is kept about 100 pascals.
(3) updrift side at substrate adds capacity coupled radio frequency (13.6MHz) plasma body, and about 200 watts of power is heated to 380 ℃ to substrate with Infrared heaters simultaneously.
(4) reaction carries out stopping after 20 minutes heating and plasma body output, takes out substrate after the system cools, obtains reaction product.
Embodiment 3: preparing attached to the AlN nanotube on the tungsten tip from the Al film on the tungsten tip, synthesis step is as follows:
(1) plate one deck Al film with molecular beam epitaxial process on tungsten tip, thickness is 400 nanometers.
(2) tungsten tip that will be coated with the Al film is put into the quartz reactor of horizontal positioned, vacuumizes the back and feeds NH
3/ N
2/ Ar mixed gas, NH
3Dividing potential drop is about 5%, N
2Dividing potential drop is about 20%, and system pressure maintains about 10
4Pascal.
(3) introduce microwave (2.45GHz) plasma body at placement substrate place by waveguide, about 400 watts of power, heat effect causes substrate temperature to be about 550 ℃.
(4) reaction carries out stopping after 40 minutes heating and plasma body output, takes out substrate after the system cools, obtains reaction product.
Embodiment 4: from the Ce film, prepare CeO under catalyst action on quartz substrate
2Nanotube, synthesis step is as follows:
(1) magnetron sputtering last layer Ce metallic membrane on quartz substrate, thickness is 400 nanometers.And then magnetron sputtering last layer Sn metallic membrane is as catalyzer in the above, and thickness is 10 nanometers.The effect of Sn coating is to reduce CeO by form low melting point alloy with Ce under heating condition
2Growth temperature, and change the metallic film situation of nucleation of being heated, thereby regulate and control resulting nanotube diameter.
(2) quartz substrate of above-mentioned Ce of being coated with and Sn metallic membrane is put into the quartz reactor of horizontal positioned, vacuumized the back and feed O
2/ He mixed gas, wherein O
2Dividing potential drop is about 1%, and system pressure maintains 100 pascals.
(3) add radio frequency (40.8MHz) plasma body of inductive couplings in the updrift side of substrate, about 100 watts of power.Simultaneously substrate is heated by resistive to 680 ℃.
(4) reaction stops heating and plasma body output after 30 minutes, treats to take out substrate after the system cools, obtains reaction product.
Embodiment 5: from the cadmium sulfide nano pipe of cadmium metal paper tinsel preparation on metal base, synthesis step is as follows:
(1) the cadmium metal paper tinsel is placed on is equipped with plate electrode and resistive heating platform, and in the metal reaction chamber of vacuum-pumping, vacuumize the back and feed H
2The S/Ar mixed gas, H
2The S dividing potential drop is 3%, and system pressure maintains about 100 pascals.
(2) the cadmium metal paper tinsel is heated to 550 ℃, and introduces radio frequency (13.6 MHz) plasma body by the capacitive coupling, power is 100 watts.
(3) reaction carries out stopping after 30 minutes heating and plasma body output, treats to take out substrate after the system cools, obtains reaction product.
Used the substrate that is coated with metallic film among the present invention, but the mode of adhesion metal film belongs to the known technology of this area in substrate, so do not belong to the scope that the present invention discusses.In addition, keeping certain system pressure in reaction vessel is for geseous discharge and the needs of keeping plasmoid take place, and the power effect of plasma body is to control the kind and the concentration of active specy, it is not a monotechnics feature of the present invention, those skilled in the art all can and adjust these parameters according to the known technology grasp in implementation process of the present invention, can realize purpose of the present invention.
Claims (7)
1, a kind of method for preparing semiconducting nanotubes comprises step:
(1) will be coated with the substrate of metallic film or the container that tinsel is put into vacuum-pumping, vacuumize the gas mixture of back input rare gas element and reactant gas, described reactant gas be can with the gas of metal reaction synthesized semiconductor;
(2) introducing low-temperature plasma makes reactant gas generate active specy, simultaneously with the temperature maintenance of substrate or tinsel in specified range with the growing semiconductor nanotube, described specified range is not less than 200 ℃, above 200 ℃ of the fusing point that is not higher than this suprabasil metallic film or tinsel, described semi-conductive positively charged ion is from tinsel or metallic film, and negatively charged ion is from reactant gas;
(3) input of maintenance gas mixture is carried out back end fully until reaction.
2, the method for claim 1 is characterized in that, described reactant gas is the gas that contains following a kind of element: nitrogen, phosphorus, arsenic, oxygen, sulphur, selenium, fluorine, chlorine, bromine, iodine.
3, the method for claim 1 is characterized in that, also is coated with catalyst film in the described substrate, for the growth of semiconducting nanotubes provides the nucleation site and controls the diameter of nanotube.
4, method as claimed in claim 3 is characterized in that, described catalyzer is selected from one or more of lead, tin, chromium, manganese, iron, cobalt, nickel, gold and silver.
5, the method for claim 1 is characterized in that, described semiconducting nanotubes is nitride, phosphide, arsenide, oxide compound, sulfide, selenide, fluorochemical, muriate, bromide or iodide semi-conductor.
6, the method for claim 1 is characterized in that, the ratio that the branch of described reactant gas covers mixed gas is not more than 10%.
7, the method for claim 1 is characterized in that, described low-temperature plasma is a nonequilibrium plasma.
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| CNB2006100026806A CN100436661C (en) | 2006-01-27 | 2006-01-27 | Method for in situ growth for preparing semiconductor nanotube |
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| CNB2006100026806A CN100436661C (en) | 2006-01-27 | 2006-01-27 | Method for in situ growth for preparing semiconductor nanotube |
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| CN100436661C true CN100436661C (en) | 2008-11-26 |
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| CN102260046B (en) * | 2010-05-28 | 2013-04-17 | 中国科学院大连化学物理研究所 | Microwave synthesis method of zinc oxide film with oriented nanorod structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557719A (en) * | 2004-01-19 | 2004-12-29 | 上海交通大学 | Method for preparing zine sulfide nanometer material with orientation arrangement nano-tubes |
| CN1669920A (en) * | 2004-12-29 | 2005-09-21 | 浙江大学 | Method for preparing one-dimensional nanostructure in anode alumina template |
| CN1697132A (en) * | 2004-05-12 | 2005-11-16 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing nano zinc oxide tube by assistance of radiofrequency plasma |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557719A (en) * | 2004-01-19 | 2004-12-29 | 上海交通大学 | Method for preparing zine sulfide nanometer material with orientation arrangement nano-tubes |
| CN1697132A (en) * | 2004-05-12 | 2005-11-16 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing nano zinc oxide tube by assistance of radiofrequency plasma |
| CN1669920A (en) * | 2004-12-29 | 2005-09-21 | 浙江大学 | Method for preparing one-dimensional nanostructure in anode alumina template |
Non-Patent Citations (4)
| Title |
|---|
| Large-Scale Synthesis of ZnO Nanotubes via a SimpleMethod. Li Da-Zhi等.CHINESE JOURNAL OF INORGANIC CHEMISTRY,Vol.21 No.11. 2005 |
| Large-Scale Synthesis of ZnO Nanotubes via a SimpleMethod. Li Da-Zhi等.CHINESE JOURNAL OF INORGANIC CHEMISTRY,Vol.21 No.11. 2005 * |
| 镍基底上生长CN_x纳米管薄膜的研究. 丁佩等.无机材料学报，第20卷第2期. 2005 |
| 镍基底上生长CN_x纳米管薄膜的研究. 丁佩等.无机材料学报，第20卷第2期. 2005 * |
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