CN103498190A - Preparation method of high-purity dendrite FeWO4/FeS core-shell nano structure - Google Patents
Preparation method of high-purity dendrite FeWO4/FeS core-shell nano structure Download PDFInfo
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- CN103498190A CN103498190A CN201310422662.3A CN201310422662A CN103498190A CN 103498190 A CN103498190 A CN 103498190A CN 201310422662 A CN201310422662 A CN 201310422662A CN 103498190 A CN103498190 A CN 103498190A
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Abstract
The invention relates to a preparation method of a high-purity dendrite FeWO4/FeS core-shell nano structure, belonging to the technical field of material preparation. According to the method, a vacuum tube furnace is adopted, tungsten oxide and sulfur powder are used as evaporation sources, and a thermal evaporation method is adopted to synthesize the dendritic FeWO4/FeS ore-shell nano structure on a substrate coated with an iron film under the protection of carrier gas by strictly controlling the evaporation temperature, the distance between the evaporation sources and the substrate, the pressure of the reaction chamber, the carrier gas flow and the like. The method has the advantages of simple synthesis technique and equipment, high controllability on technological parameters, and low cost. Both the core and the shell of the dendritic FeWO4/FeS core-shell nano structure are crystalline, and the diameters of the branches and trunks are distributed uniformly. The dendritic core-shell nano structure has wide application prospects the fields of optical fibers, sensors, semiconductor devices, catalysts and the like.
Description
Technical field
The present invention relates to a kind of high purity dendrite FeWO
4the preparation method of/FeS core-shell nano structure, belong to technical field of material.
Background technology
Tungstate, due to chemistry and the physicals of its excellence, has been applied to many fields, as photoconductive fiber, humidity sensor and catalyzer etc.Wherein, wolframic acid iron, as a kind of p-type semi-conductor, has also shown excellent magnetics and optical property.But, due to the synthetic difficulty of tungstate nano structure, yet there are no the report of tungstate nano structural research work.And iron sulphide is synthetic than being easier to, under vacuum, heating sulphur and iron just can obtain, and generally as catalyzer, are used for oil, the industry of Sweet natural gas equal energy source.
Along with the development of nano material and composite science and technology, scientist finds that the compound or hydridization of two or more material often can produce the excellent properties that single composition material does not have, and this has caused people's extensive concern.Wherein, nano-heterogeneous structure is paid attention to because the function of performance that can strongthener or expansion material is subject to people.For example, nucleocapsid structure has been widely used in electricity, magnetics, optics, catalysis, mechanics and chemical property compound of material as a kind of important heterojunction structure.According to Chen Gong etc., carbon prepared by thermochemical method coats wolframic acid iron particle at 800mA
-1excellent large current discharging capability and long-term circulation ability (Chen Gong have been shown under current cycle, Yu-Jun Bai, Jun Feng, Rui Tang, Yong-Xin Qi, Ning Lun and Run-Hua Fan.Enhanced electrochemical performance of FeWO
4by coating nitrogen-doped carbon.ACS applied materials& Interfaces, 2013,5,4209-4215), and dendritic FeWO
4/ FeS nucleocapsid structure have not been reported.Simultaneously, because the basic device that forms contemporary large-scale integrated circuit generally has the electrode more than 3 or 3, single wire nanostructure can not meet the needs of nanoelectronics to nano material and nano-device performance study.Therefore the synthetic preparation of dendritic nano-structure all has great importance from theory at nano-device aspect practical.
At present, the core-shell nano structure generally adopts the chemical method preparation, but it is difficult to prepare branched structure.In addition, compared to the complexity of chemical reaction and restive, the physical vapor depositions such as thermal evaporation have that cost is low, preparation process simple, the processing parameter controllability is strong and prepare material mostly is the characteristics such as crystal.The present invention utilizes thermal evaporation techniques to prepare high purity dendrite FeWO first
4/ FeS core-shell nano structure.Because it is dendritic constructional feature, will have wide practical use in various electronic devices and components field.
Summary of the invention
The object of the invention is to propose the FeWO of a kind of high purity, dendritic, crystallization
4the preparation method of/FeS core-shell nano structure, the method adopts vacuum tube furnace, with Tungsten oxide 99.999 (WO
3) and sulphur (S) as evaporation source, by the method for thermal evaporation, under carrier gas protection; on the substrate that is coated with the iron film, through strict vaporization temperature, the distance between evaporation source and substrate controlled; reaction chamber pressure, the conditions such as carrier gas air-flow, prepared dendritic FeWO
4/ FeS shell core nanostructure.The method have reaction conditions strictly controlled, equipment and process is simple, product yield is high, the advantage such as with low cost.The dendritic FeWO that obtains
4/ FeS core-shell nano structure, branch and dry equal diameter are even, the well-crystallized, and their kernel is the FeWO of highly crystalline
4, shell is the FeS of highly crystalline; Kernel in nanostructure and the diameter Distribution of shell are all very even, and diameter is controlled.Product surface clean, purity are high.
The dendritic FeWO that the present invention proposes
4/ FeS core-shell nano structure preparation method, is characterized in that, described method is synthetic dendritic FeWO on the substrate that is coated with the iron film by thermal evaporation Tungsten oxide 99.999 and sulphur
4/ FeS core-shell nano structure comprises the following steps:
(1), in vacuum tube furnace, will WO be housed respectively
3the alumina ceramic crucible of powder and S powder or WO is housed
3be placed on the heating region of stove central authorities with the alumina ceramic crucible of S powder mix, in its airflow downstream distance, WO be housed
3the crucible 15-25mm place lower regional placement surface of temperature of powder is coated with the substrate of Fe film;
(2) before heating, first whole system is vacuumized, then in system, pass into high-purity inert carrier gas, and repeatedly, with the air in removal system; Then be warmed up to maximum heating temperature with 10-30 ℃/min speed, and be incubated a few hours; In heat-processed; keeping carrier gas flux is that in 100-300 standard cubic centimeter per minute, tube furnace, vacuum tightness is-0.01 arrive-0.1MPa; and whole heat-processed completes under the inert carrier gas protection; finally naturally cool to room temperature, can on substrate, obtain the FeWO of high purity, dendritic, highly crystalline
4/ FeS core-shell nano structure.
In above-mentioned preparation method, the evaporation source in described step (1) is commercially available analytical pure WO
3powder and sulphur powder.
In above-mentioned preparation method, in described step (1), if WO will be housed
3the alumina ceramic crucible of powder and S powder is placed on respectively the different heating zone and is heated, and WO will be housed
3the alumina ceramic crucible of powder is placed on the highest heating region of central temperature of stove, in its air-flow upstream or downstream distance WO is housed
3the alumina ceramic crucible that the S powder is housed is placed in the zone that the crucible 5-15mm place Heating temperature of powder is lower.
In above-mentioned preparation method, in described step (1), if WO will be housed
3the heating region that is placed on stove central authorities with the alumina ceramic crucible of S powder mix is heated, WO wherein
3the mass ratio of powder and S powder is controlled at 10:1 between 150:1.
In above-mentioned preparation method, to be coated with Fe film thickness on the substrate of Fe film be 5-50nm on surface in described step (1).
In above-mentioned preparation method, to be coated with the substrate of Fe film be a kind of among silicon chip, gallium arsenide film, single-crystal silicon carbide sheet on surface in described step (1).
In above-mentioned preparation method, in described step (2), high-purity inert carrier gas is a kind of among argon gas, nitrogen.
In above-mentioned preparation method, the inert carrier gas in described step (2) is high-purity gas, and purity is more than 99.99vol.%.
In above-mentioned preparation method, the maximum heating temperature in described step (2) is 1000-1200 ℃.
In above-mentioned preparation method, in described step (2) under maximum heating temperature soaking time be 1-5 hour.
Adopt present technique to prepare dendritic FeWO
4/ FeS core-shell nano structure, have that equipment and process is simple, reaction conditions strictly controlled, product yield is high, the characteristics such as with low cost, the dendritic FeWO obtained
4/ FeS core-shell nano structure branch and dry equal diameter are even, and the kernel in nucleocapsid structure and shell crystallization are all good, and kernel and shell are even along the nanostructure growth orient diameter, and length is controlled, purity is high.
The accompanying drawing explanation
Fig. 1 is the prepared dendritic FeWO of the embodiment of the present invention 1
4the stereoscan photograph of/FeS core-shell nano structure
Fig. 2 is the prepared single dendritic FeWO of the embodiment of the present invention 1
4the transmission electron microscope photo of/FeS core-shell nano structure
Fig. 3 is the prepared single dendritic FeWO of the embodiment of the present invention 1
4the high-resolution-ration transmission electric-lens photo of/FeS core-shell nano structure
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further.
The present invention proposes a kind of high purity dendrite FeWO
4the preparation method of/FeS core-shell nano structure, is characterized in that, described method is synthetic dendritic FeWO on the substrate that is coated with the iron film by thermal evaporation Tungsten oxide 99.999 and sulphur
4/ FeS core-shell nano structure, and comprise the steps and content:
(1) evaporation source that adopts is commercially available analytically pure WO
3powder and sulphur powder.
(2) depositing a layer thickness by the method for magnetron sputtering coater or electric arc evaporation on clean silicon chip, gallium arsenide film or single-crystal silicon carbide sheet in advance is the metal Fe film that 5-50nm is thick.
(3), in vacuum tube furnace, will WO be housed respectively
3the alumina ceramic crucible of powder and S powder or WO is housed
3be placed on the heating region of stove central authorities with the alumina ceramic crucible of S powder mix, in its airflow downstream distance, WO be housed
3the crucible 15-25mm place lower regional placement surface of temperature of powder is coated with the substrate of Fe film;
(4) in the evaporation source put procedure, if WO will be housed
3the alumina ceramic crucible of powder and S powder is placed on respectively the different heating zone and is heated, and WO will be housed
3the alumina ceramic crucible of powder is placed on the highest heating region of central temperature of stove, in its air-flow upstream or downstream distance WO is housed
3the alumina ceramic crucible that the S powder is housed is placed in the zone that the crucible 5-15mm place Heating temperature of powder is lower.
(5) in the evaporation source put procedure, if WO will be housed
3the heating region that is placed on stove central authorities with the alumina ceramic crucible of S powder mix is heated, WO wherein
3the mass ratio of powder and S powder is controlled at 10:1 between 150:1.
(6) before heating, first whole system is vacuumized, then in system, pass into high-purity inert carrier gas, and repeatedly, with the air in removal system; Then be warmed up to maximum heating temperature with 10-30 ℃/min speed, and be incubated a few hours; In heat-processed; keeping carrier gas flux is that in 100-300 standard cubic centimeter per minute, tube furnace, vacuum tightness is-0.01 arrive-0.1MPa; and whole heat-processed completes under the inert carrier gas protection; finally naturally cool to room temperature, can on substrate, obtain the FeWO of high purity, dendritic, highly crystalline
4/ FeS core-shell nano structure.
(7) testing inert carrier gas used is high-purity argon gas or nitrogen, and whole experiment heat-processed completes under the carrier gas protection.
(8) maximum heating temperature of experiment is 1000-1200 ℃, and soaking time is 1-5 hour.
Resulting dendritic FeWO
4/ FeS core-shell nano structure is green film in appearance.
Under scanning electronic microscope, can observe a large amount of dendritic nano-structure, and can obviously observe FeWO transmission electron microscope is next
4/ FeS nucleocapsid structure.High-resolution-ration transmission electric-lens the analysis showed that, the kernel of this nucleocapsid structure and shell well-crystallized, and kernel is monocrystalline FeWO
4, shell is monocrystalline FeS.In a word, can obtain high purity, dendritic crystallization FeWO by present technique
4/ FeS core-shell nano structure, wherein kernel is monocrystalline FeWO
4, shell is monocrystalline FeS.
Embodiment 1: 0.4g analytical pure WO will be housed
3the alumina ceramic crucible of powder is placed on the central heating zone of vacuum tube furnace, in its air-flow upstream distance, WO is housed
3the alumina ceramic crucible that 0.01g analytical pure S powder is housed is placed at the crucible 14mm place of powder, in its airflow downstream distance, WO is housed
3the crucible 14mm place placement surface of powder is coated with the silicon chip of 5nm Fe film.
Before heating, first whole system is vacuumized, then in system, pass into high-purity argon gas, and repeat 2 times, with the air in removal system.Then be warmed up to 1050 ℃ with 15 ℃/min speed, insulation 2h.In heat-processed, keeping carrier gas flux is that in 300 standard cubic centimeter per minutes (sccm), tube furnace, vacuum tightness is-0.04MPa, finally naturally cools to room temperature, can on substrate, obtain dendritic FeWO
4/ FeS core-shell nano structure.
The nanostructure of synthesized is dendritic obviously, and branch and dry equal diameter be (being shown in Fig. 1) evenly.Can obviously observe nucleocapsid structure under microscope, nanometer rod external diameter 120-200nm, internal diameter is 60-160nm (seeing Fig. 2).The FeWO that kernel is monocrystalline
4, shell is monocrystalline FeS (seeing Fig. 3).
Claims (2)
1. high purity dendrite FeWO
4the preparation method of/FeS core-shell nano structure is characterized in that: described dendritic core-shell nano structure kernel is monocrystalline FeWO
4, shell is monocrystalline FeS; Described method is by thermal evaporation WO
3powder and S powder be synthetic dendritic FeWO on the substrate that is coated with the iron film
4/ FeS core-shell nano structure comprises the following steps:
(1), in vacuum tube furnace, will WO be housed respectively
3the alumina ceramic crucible of powder and S powder or WO is housed
3be placed on the heating region of stove central authorities with the alumina ceramic crucible of S powder mix, in its airflow downstream distance, WO be housed
3the crucible 15-25mm place lower regional placement surface of temperature of powder is coated with the substrate of Fe film;
(2) before heating, first whole system is vacuumized, then in system, pass into high-purity inert carrier gas, and repeatedly, with the air in removal system; Then with 10-30 ℃/min speed intensification maximum heating temperature, and insulation a few hours; In heat-processed; keeping carrier gas flux is that in 100-300 standard cubic centimeter per minute, tube furnace, vacuum tightness is-0.01 arrive-0.1MPa; and whole heat-processed completes under the inert carrier gas protection; finally naturally cool to room temperature, can on substrate, obtain the FeWO of high purity, dendritic, highly crystalline
4/ FeS core-shell nano structure.
2. according to preparation method claimed in claim 1, it is characterized in that: WO in step (1) described in described step (1)
3the heating evaporation method of powder and S powder is evaporation or mixing evaporation respectively, WO while wherein evaporating respectively
3powder is placed on heat district in stove and the S powder is placed on low-temperature heat district in stove, and the two is at a distance of 5-15mm; And mix while evaporating, need WO
3the mass ratio of powder and S powder is controlled at 10:1 between 150:1; Substrate in described step (1) is silicon chip, gallium arsenide film, single-crystal silicon carbide sheet; Deposited the thick Fe film of one deck 5-50nm on substrate in described step (1); In described step (2), maximum heating temperature is 1000-1200 ℃, soaking time 1-5 hour; In described step (2), carrier gas flux is that in 100-300 standard cubic centimeter per minute, tube furnace, vacuum tightness is-0.01 arrive-0.1MPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741224A (en) * | 2014-01-17 | 2014-04-23 | 中国地质大学（北京） | Preparation method for high-purity and high-density WS2 lamellar nano structure |
| CN106215954A (en) * | 2016-07-27 | 2016-12-14 | 中国地质大学（北京） | A kind of carbon fiber@bis-tungsten selenide nanometer sheet core-shell structure and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| CN101353816A (en) * | 2008-07-08 | 2009-01-28 | 中山大学 | Growth method of tungsten oxide pencil-shaped nanostructured array |
| CN101603200A (en) * | 2009-07-10 | 2009-12-16 | 中南大学 | The preparation method of the tungsten crystal whisker array of a kind of diameter and length controlled |
| US20100112349A1 (en) * | 2008-11-05 | 2010-05-06 | National Taipei University Of Technology | Nanomaterial With Core-Shell Structure |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353816A (en) * | 2008-07-08 | 2009-01-28 | 中山大学 | Growth method of tungsten oxide pencil-shaped nanostructured array |
| US20100112349A1 (en) * | 2008-11-05 | 2010-05-06 | National Taipei University Of Technology | Nanomaterial With Core-Shell Structure |
| CN101603200A (en) * | 2009-07-10 | 2009-12-16 | 中南大学 | The preparation method of the tungsten crystal whisker array of a kind of diameter and length controlled |
Non-Patent Citations (1)
| Title |
|---|
| YUNHO BAEK ET AL: "Controlled Growth and Characterization of Tungsten Oxide Nanowires Using Thermal Evaporation of WO3 Powder", 《J. PHYS. CHEM. C》, vol. 111, no. 3, 3 January 2007 (2007-01-03), pages 1213 - 1218 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741224A (en) * | 2014-01-17 | 2014-04-23 | 中国地质大学（北京） | Preparation method for high-purity and high-density WS2 lamellar nano structure |
| CN103741224B (en) * | 2014-01-17 | 2016-04-13 | 中国地质大学（北京） | High-purity high-density WS 2the preparation method of lamellar nanostructure |
| CN106215954A (en) * | 2016-07-27 | 2016-12-14 | 中国地质大学（北京） | A kind of carbon fiber@bis-tungsten selenide nanometer sheet core-shell structure and preparation method thereof |
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