CN101603207B - Method for preparing network branched silicon nitride single crystal nanostructure with high purity and high yield - Google Patents
Method for preparing network branched silicon nitride single crystal nanostructure with high purity and high yield Download PDFInfo
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- CN101603207B CN101603207B CN2009100894605A CN200910089460A CN101603207B CN 101603207 B CN101603207 B CN 101603207B CN 2009100894605 A CN2009100894605 A CN 2009100894605A CN 200910089460 A CN200910089460 A CN 200910089460A CN 101603207 B CN101603207 B CN 101603207B
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Abstract
The invention relates to a method for preparing a network branched silicon nitride single crystal nanostructure with high purity and high yield, and belongs to the technical field of material preparation. The material is the network branched alpha-silicon nitride nanostructure with high purity. The method synthesizes the network branched silicon nitride single crystal nanostructure on a substrate plated with a metal catalyst by by thermally decomposing organic precursor and comprises the following steps of: (1) low-temperature crosslinking curing of polysilazane containing high contents of silicon and nitrogen at a temperature of between 160 and 300DEG C; (2) high-energy ball-milling crushing of amorphous solid after the crosslinking curing in a high wear-resistant utensil; and (3) quick high-temperature thermal decomposition and evaporation of precursor powder obtained after the high-energy ball-milling at protection atmosphere, and precipitation of the precursor powder on the substrate plated with a metal catalyst film. The method has controllable and adjustable components of an evaporation source, simple process and equipment and low cost; and the prepared network branched structure has high yield and high purity, can be used as a reinforcing toughener in a high-performance nanometer composite material, and simultaneously can be used for manufacturing nanoelectronic devices.
Description
Technical field
The present invention relates to the preparation method of a kind of high purity, high yield, network-like branched silicon nitride (Si3N4) monocrystal nanostructure, belong to technical field of material.
Background technology
Nano material is because of its special physical influence such as surface effects, small-size effect, macro quanta tunnel effect, enclosed pasture blocking effect etc. has the physicochemical property that are different from block materials, be widely used in chemical industry, microelectronic device, numerous areas such as fine ceramics, metallurgy, military affairs, nuclear industry and medical science or biotechnology.In the research of nanometer material science, the preparation of nano material occupies very consequence, and the microtexture and the performance of nano material had significant effects.In recent years, synthetic had a nanostructure of controllable appearance, promotes the microminiaturization of electron device, become people's research emphasis.
Silicon nitride has high strength, low density, good shock resistance and antioxidant property and chemical stability, but also be the semiconductor material of a kind of broad stopband (5.3eV), thereby can be used to the nano electron device for preparing high performance composite and under severe rugged environments such as high temperature and high radiation, use.The main method of preparation silicon nitride nano-material has chemical vapour deposition, thermal evaporation, solvent-thermal method, the auxiliary cracking precursor method of catalyzer etc., utilizes these methods people to prepare structures such as beta-silicon nitride nanowire, nano belt, nanometer rod, nano-rings.
Network-like branch nanostructure, be that nano wire forms by the stack that is cross-linked with each other on two-dimentional yardstick, this structure is a kind of good enhancing toughening material, thereby can be used as the performance of the enhancing ingredients raising block materials of ceramic base, metal matrix, polymer based nanocomposites; In addition, this network multiple-branching construction can also be as the nm-class conducting wire in the nano electron device, and parts such as p-n junction play a part to interconnect, transmission electronic.At present, people have synthesized SiC meshed nano structure, have utilized the ion beam irradiation method to prepare the carbon nano wire network-like structure by chemical Vapor deposition process, have synthesized three-dimensional δ-WO with thermal evaporation
3Meshed nano structure etc., but also do not see the bibliographical information of network-like branched silicon nitride nanostructure.
Summary of the invention
The objective of the invention is to propose the network-like branch nanostructure of a kind of silicon nitride Preparation Method, this method obtains highly purified network-like branched silicon nitride single crystal nanostructure fully by the organic polymer precursor system of the high nitrogen of pyrolysis, silicone content.This method has advantages such as evaporation source is formed controlled and adjustable, equipment and technology is simple, synthesis condition is accurately controlled, product yield is high, with low cost, the network-like branch nanostructure of the silicon nitride that is obtained productive rate height, purity height, well-crystallized.
The preparation method of the network branched silicon nitride single crystal nanostructure that the present invention proposes is characterized in that, described method adopts pyrolysis organosilane precursor body method being coated with comprise network shape branched silicon nitride nanostructure on the substrate of catalyzer, may further comprise the steps:
(1) polysilazane of high silicon nitrogen content under high pure nitrogen, argon gas or ammonia atmosphere, through catalysis or do not have the catalysis heat cross-linking and solidified 0.5-2 hour, obtains translucent SiCN amorphous solid under 160-300 ℃;
(2) should in the agate container, smash to pieces by translucent SiCN amorphous solid, mix with the high abrasion zirconium oxide balls then, in the urethane ball grinder, on high energy ball mill, grind 2-24 hour to pulverizing, obtain the non-crystalline state SiCN powder of particle diameter less than 0.2 μ m;
(3) will be placed on corundum crucible through the non-crystalline state SiCN powder that ball milling obtains at the bottom of; the substrate that is coated with catalyzer is placed the top of powder in the crucible; under nitrogen or protection of ammonia; be rapidly heated to 1150-1450 ℃ of heating 20 minutes to 4 hours, can above substrate, obtain a large amount of highly purified network branched silicon nitride single crystal nanostructures.
In above-mentioned preparation method, the unique evaporation source in the described step (1) is the polysilazane of high silicon nitrogen content.
In above-mentioned preparation method, the amorphous solid behind the crosslinking curing in the described step (2) in the high abrasion container, levigate under the effect of high abrasion abrading-ball, can not introduce any other surfactant granules.
In above-mentioned preparation method, the amorphous solid behind the crosslinking curing in the described step (2) is after levigate, and particle diameter is less than 0.2 μ m.
In above-mentioned preparation method, the substrate in the described step (3) is a kind of among silicon chip, gallium arsenide film, sapphire sheet, silicon nitride single crystal sheet, the alumina formwork, and surfacing, and smooth finish is good.
In above-mentioned preparation method, deposited a kind of among layer of even metal catalyst Fe, Co, Ni, the Cu film on the substrate in the described step (3), and thickness is 20-100nm.
In above-mentioned preparation method, the substrate that is used for the network-like branch nanostructure of grown silicon nitride in the described step (3) is 0-20mm from the distance of precursor powder.
In above-mentioned preparation method, the heat-up rate in the described step (3) is 10-50 ℃/minute.
Adopt present technique to prepare network branched silicon nitride single crystal nanostructure, compare with other methods that prepare the meshed nano structure, technology and equipment are simple, product yield is high, with low cost, evaporation source is formed controlled and adjustable, be convenient to mix and the controlled preparation of new texture the network-like branched silicon nitride nanostructure purity height and the well-crystallized that are obtained.Be particularly suitable for the nanometer strongthener and use, also can be used as nanometer electronic device.
Description of drawings
Fig. 1 is the prepared α-Si of the embodiment of the invention
3N
4The x-ray diffraction pattern of network-like branch nanostructure
Fig. 2 is the prepared α-Si of the embodiment of the invention
3N
4The electron scanning micrograph of network-like branch nanostructure
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further.
The present invention proposes a kind of preparation method of network-like branched silicon nitride nanostructure, it is characterized in that, described method adopts the pyrolysis organic precursor being coated with comprise network shape branched silicon nitride single crystal nanostructure on the substrate of catalyzer, and comprises the steps and content:
(1) polysilazane that adopts, silicon, nitrogen content height surpass 15at% and 20at% respectively, and oxygen level is no more than 3at%, and is unique silicon source of described method deposition network branched silicon nitride single crystal nanostructure.
(2) polymer precursor is under high pure nitrogen, argon gas or ammonia air-flow, low temperature 160-300 ℃ of following catalysis or do not have catalytic crosslinking and solidified 0.5-2 hour, decompose simultaneously and remove moisture and most of hydrogen, become the amorphous solid of translucent only siliceous basically, carbon, nitrogen element.
(3) this translucent amorphous solid is smashed to pieces in the agate container of high abrasion, mix with the high abrasion zirconium oxide balls then, in the urethane ball grinder of high abrasion, on high energy ball mill, ground 2-24 hour, obtain the powder of particle diameter less than 0.2 μ m.Whole process is not introduced surfactant granules substantially, is beneficial to presoma and at high temperature evaporates, and can growth in situ do not obtain the nano material of other structures.
(4) be 20-100nm thick metal catalyst Fe, Co, Ni or Cu film with magnetron sputtering coater in any surface finish, through deposition one layer thickness on silicon chip, gallium arsenide film, sapphire sheet, silicon nitride single crystal sheet or the alumina formwork of ultrasonic cleaning in advance.
(5) will be placed on corundum crucible through the precursor powder that ball milling obtains at the bottom of, the substrate that is coated with catalyzer is placed the 0-20mm place, top of powder in the crucible, under nitrogen or protection of ammonia, be rapidly heated to 1150-1450 ℃ of heating 20 minutes to 4 hours.
Resultant network-like branched silicon nitride nanostructure is white solid in appearance.
At microscopically, can observe network-like branched nanostructure, the degree of crosslinking height.
Other analytical tests show that this network-like branch nanostructure is highly purified monocrystalline α-Dan Huagui material.
Embodiment: initial feed is polysilazane perhydropolysilazane, is light yellow viscous liquid under the room temperature, solidifies 2 hours at 180 ℃ of following catalytic crosslinkings, and protective atmosphere is an ammonia, and airshed is 80ml/min, obtains translucent non-crystalline state SiCN solid.Placing agate mortar to smash to pieces gained SiCN solid, is the high abrasion PZT abrading-ball mixing of 2mm with diameter then, in the urethane ball grinder, grinds 10 hours on high energy ball mill.Get the precursor powders of 3 grams through solidifying, pulverizing, be evenly distributed on the corundum crucible bottom, cutting small pieces then, to be coated with thickness be that the silicon chip of the thick Fe film of 40nm is placed on the high ZrO of the powder about 2mm in top
2On the support.Be placed on then and carry out high temperature pyrolysis in the tube furnace; Wherein, protective atmosphere is a nitrogen, and gas flow rate is 60ml/min; 20 ℃/minute of heat-up rates, 1350 ℃ of top temperatures, soaking time 2 hours; Naturally cool to room temperature then.Reaction finishes, and can be observed a large amount of white solids at silicon chip surface.
Institute's synthetic white solid is a high purity alpha-silicon nitride single crystal material (see figure 1) through the X-ray diffraction Analysis and Identification, is network-like branch nanostructure at the microscopically material, and material surface is bright and clean, is density three-dimensional networking crosslinking structure (see figure 2).
Claims (2)
1. the preparation method of network branched silicon nitride single crystal nanostructure with high purity and high yield, it is characterized in that: described method is being coated with comprise network shape branched silicon nitride nanostructure on the substrate of catalyzer by the pyrolysis organic precursor, may further comprise the steps:
(1) silicon, nitrogen surpass 15at% and 20at% respectively, oxygen level is no more than the polysilazane of 3at%, under high pure nitrogen, argon gas or ammonia atmosphere, 160-300 ℃ of following catalysis or do not have the catalysis heat cross-linking and solidified 0.5-2 hour, obtain translucent SiCN amorphous solid;
(2) should in the agate container, smash to pieces by translucent SiCN amorphous solid, mix with the high abrasion zirconium oxide balls then, in the urethane ball grinder, on high energy ball mill, ground 2-24 hour, obtain non-crystalline state SiCN powder;
(3) will be placed on corundum crucible through the precursor powder behind the ball milling at the bottom of; the substrate that is coated with metal catalyst Fe, Co, Ni or Cu film is placed the top of powder in the crucible; under nitrogen or protection of ammonia; be rapidly heated to 1150-1450 ℃ of heating 20 minutes to 4 hours, can on substrate, obtain the network branched silicon nitride single crystal nanostructure of high purity and high yield.
2. according to the described preparation method of claim 1, it is characterized in that: the substrate in the described step (3) is silicon chip, gallium arsenide film, sapphire sheet, silicon nitride single crystal sheet or alumina formwork; Deposited thick metal catalyst Fe, Co, Ni or the Cu film of one deck 20-100nm on the substrate in the described step (3); The substrate of the network-like branched silicon nitride nanostructure growth in the described step (3) is from being 0-20mm by the distance of pyrolytic crosslinking curing powder; Heat-up rate in the described step (3) is 10-50 ℃/minute.
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| CN103833039B (en) * | 2014-01-17 | 2015-11-25 | 中国地质大学（北京） | A kind of preparation method of coralliform silicon-dioxide amorphous nano/micron structure |
| CN105859302B (en) * | 2016-04-08 | 2018-07-03 | 哈尔滨工业大学 | The preparation method of the ceramic material of in-situ preparation carbon nanocoils |
| CN115354322B (en) * | 2022-08-05 | 2023-06-23 | 佳木斯大学 | Preparation method of high-pore thermal barrier coating |
| CN115537928A (en) * | 2022-09-19 | 2022-12-30 | 福建镓镒半导体材料有限公司 | Silicon nitride single crystal material and preparation method thereof |
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| CN101054730A (en) * | 2007-01-30 | 2007-10-17 | 宁波工程学院 | Controllable doping method for Si3N4 single-crystal low-dimension nano material |
| CN101157452A (en) * | 2007-07-30 | 2008-04-09 | 中国地质大学（武汉） | Method for preparing nano silicon carbide |
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| US5785922A (en) * | 1994-11-21 | 1998-07-28 | Honda Giken Kogyo Kabushiki Kaisha | Method for producing composite sintered body of silicon carbide and silicon nitride |
| CN1740406A (en) * | 2004-08-28 | 2006-03-01 | 清华大学 | Nanometer silicon wire structure and its growth process |
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| CN101024904A (en) * | 2007-01-18 | 2007-08-29 | 上海交通大学 | Method for synthesizing single crystal beta Si3N4 nano wire using nano silicon-wire as formboard |
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