CN102874876A - Method for preparing tungsten trioxide nanosheets by thermal oxidation - Google Patents

Method for preparing tungsten trioxide nanosheets by thermal oxidation Download PDF

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CN102874876A
CN102874876A CN2012103776091A CN201210377609A CN102874876A CN 102874876 A CN102874876 A CN 102874876A CN 2012103776091 A CN2012103776091 A CN 2012103776091A CN 201210377609 A CN201210377609 A CN 201210377609A CN 102874876 A CN102874876 A CN 102874876A
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thermal oxidation
slice
chamber
trioxide nano
rare gas
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CN102874876B (en
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陈军
许卓
邓少芝
许宁生
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Sun Yat Sen University
National Sun Yat Sen University
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National Sun Yat Sen University
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Abstract

The invention discloses a method for preparing tungsten trioxide nanosheets by thermal oxidation. Raw metallic tungsten is heated to certain temperature without adding any catalyst and is kept at the temperature; oxygen content in oxidization environment is controlled to be lower than 10% by introducing inert gases such as N2 and Ar; and after temperature holding, natural cooling or cooling with introduced protective gases is performed to obtain the tungsten trioxide nanosheets. By metallic tungsten films prepared by localization, the tungsten trioxide nanosheets are prepared by localization. The method can be used to prepare tungsten trioxide nanosheets on various substrates at low temperature without using any catalyst.

Description

A kind of method for preparing tungstic trioxide nano-slice with thermal oxidation method
Technical field
The present invention relates to a kind ofly prepare tungstic oxide (WO with thermal oxidation method 3) method of nanometer sheet, belong to field of nanometer material technology.
Background technology
WO 3Be a kind of important semiconductor material, in fields such as air-sensitive, catalysis, opto-electronic conversion, emissions important application arranged.Tungstic trioxide nano-slice with two-dirnentional structure because it has unique photoelectric characteristic, more and more receives people's concern in recent years.
At present, two-dirnentional structure WO 3The preparation method of nanometer sheet mainly comprises chemosynthesis, chemical stripping or uses the catalyzer thermal oxidation process.Wherein the report of the method for chemosynthesis is more.For example, the human hairs such as Tran Duc Luong understand and a kind ofly to utilize the method that hydrothermal method prepares tungstic trioxide nano-slice (Chinese invention patent: ZL200710054544.6), the method is with laminate structure wolframic acid (H 2W 2O 7XH 2O) and alkylamine (CH 3(CH 2) nNH 2) be raw material, prepare area through magnetic agitation reaction and baking and be the nm of (100-800) nm * (100-800), apparent thickness is the WO of 5-40nm 3Nanometer sheet.The human W powder such as Jinmin Wang are raw material, with H 2O 2The method of chemosynthesis has prepared WO 3Nanometer sheet, the size of nanometer sheet is about 500 nanometers [Jinmin Wang, et al, Journal of Crystal Growth, 311,316 (2009)].The people such as Mollie RWaller adopt chemical stripping Bi 2W 2O 9Method made monocrystalline WO 3Sheet structure [Mollie R Waller, et al, Chemistty of Materials, 24 (4), 698 (2012)].Preparing with thermal oxidation process aspect the nanometer sheet, only having at present the people such as the Jing Xiao report of Peking University.They use potassiumiodide as catalyzer, grow WO by thermooxidizing at the tungsten of block 3Nanometer sheet [Jing Xiao, et al, Proc.8th IVESC and Nanocarbon (IVESC), 2010, p316].
In above-mentioned preparation method, utilize the general reaction that all needs through liquid phase of chemical process preparation, easily introduce impurity.And the employing catalytic oxidation, the existence of catalyzer also can be introduced impurity.And the prepared WO of present method 3The size of nanometer sheet is less, the long and wide hundreds of nanometer that generally is no more than.
Summary of the invention
The present invention proposes a kind of any catalyzer that do not adopt, the directly thermal oxidation tungsten prepares the method for tungstic oxide nano-sheets.The method has easy, the good characteristics of controllability, and can realize the localization preparation, the area of prepared tungstic oxide nano-sheets is larger.
Preparation WO of the present invention 3The raw material of the method for nanometer sheet is tungsten, comprises bulk metal tungsten and the tungsten film that is prepared on the substrate.
When being prepared in tungsten film on the substrate as raw material, its preparation process of method for preparing tungstic trioxide nano-slice with thermal oxidation method is as follows:
1) cleans substrate;
2) metallizing W film on substrate;
3) sample that step 2 is obtained is put into the chamber that can heat, and passes into N in chamber 2, or rare gas element, or oxygen and N 2, or the mixed gas of oxygen and rare gas element, make the interior oxygen concentration of chamber be reduced to less than 10% the preferred Ar gas of described rare gas element;
4) temperature is increased to 400 ℃ ~ 800 ℃ in the chamber, and insulation, in this process, need pass into N 2Perhaps Ar gas, flow is little than step 3 generally;
5) stuffiness is lowered the temperature or the cooling of logical rare gas element naturally, until room temperature.
Specifically, the thickness of tungsten film is 200nm ~ 2 μ m in the step 2.Preferred 500 ~ 800nm.
Oxygen concentration preferably is controlled at 1 ~ 10% in the step 3.
Can adopt magnetron sputtering or electron beam evaporation or electro-plating method etc. to carry out the plated film of tungsten film in the step 2.
When raw material was the tungsten film that is prepared on the substrate, the tungsten film can prepare on substrate by full wafer, also can localization prepare on substrate in the step 2.When adopting localization to prepare, select the mode localization such as photolithography, mask means or silk screen print method to prepare the W film figure.
Described substrate can be selected Si sheet or glass or ito glass or metal or pottery.Described ito glass refers on the basis of sodium calcium base or silicon boryl substrate glass, utilizes the method for magnetron sputtering to plate indium oxide layer tin (ITO) film.
Can adopt box-type furnace or tube furnace or hot plate that chamber is heated in the step 3.
Soaking time in the step 4 is 10min ~ 5h.Preferred 1 ~ 2h.
When take bulk metal tungsten as raw material, its preparation process of method for preparing tungstic trioxide nano-slice with thermal oxidation method is as follows:
1) tungsten of bulk is put into the chamber that can heat, in chamber, pass into N 2, or rare gas element, or pass into oxygen and N 2, or the mixed gas of oxygen and rare gas element, make the interior oxygen concentration of chamber be reduced to less than 10% the preferred Ar gas of described rare gas element;
2) temperature is increased to 400 ℃ ~ 800 ℃ in the chamber, and insulation, in this process, need pass into N 2Perhaps Ar gas;
3) stuffiness is lowered the temperature or the cooling of logical rare gas element naturally, until room temperature.
During method, step 1 can adopt box-type furnace or tube furnace or hot plate that chamber is heated in the employing.Soaking time in the step 2 is 10min ~ 5h, preferred 1 ~ 2h.
In the above-mentioned steps, pass into N 2The perhaps purpose of Ar or other rare gas element mainly is to be environment below 10% in order to keep sample to be in oxygen concentration, also can reach this effect by vacuumizing.The preparation WO that the present invention proposes 3The principle of the method for nanometer sheet is, by the oxygen in the control growth atmosphere, and the thermooxidizing of control W film, the reaction heat that thermooxidizing produces provides WO 3Molecule carries out fast transferring, generates the structure of nanometer sheet.It is not enough that oxygen concentration is crossed low then reaction heat, can not form larger nanometer sheet, and the easy over oxidation of the too high then sample of oxygen concentration does not become nanometer sheet.Therefore, logical N 2Perhaps the principle that should follow of Ar or other rare gas elementes is, the scope that keeps the environment oxygen concentration being fit to.The WO for preparing according to this method 3Nanometer sheet can obtain having by changing annealing conditions the nanometer sheet of different crystallinity and lattice imperfection density.
Preparation WO of the present invention 3The method of nanometer sheet need not complicated micro fabrication, and making method is easy, and can be by the pattern of control thermooxidizing time and the parameter Effective Regulation samples such as temperature, shield gas flow rate, and controllability is good.
The WO of the present invention's preparation 3Nanometer sheet can be applied to large-area field emitting cold cathode, also can be applied to the fields such as air-sensitive, catalysis, microelectronic device, electrooptical device.
Description of drawings
Fig. 1 a ~ Fig. 1 f adopts photoetching method at the processing step schematic diagram of glass substrate preparation W film pattern array.
Wherein: 1. glass substrate; 2.ITO film; 3. photoresist material; 4.W film; 5.WO 3Nanometer sheet.
Fig. 2 adopts the logical shielding gas of thermal oxidation method to prepare WO 3The device schematic diagram of nanometer sheet.
Wherein: 100. box-type furnaces; 200. sample; 300. hot-plate.
Fig. 3 is the WO that adopts the thermal oxidation process preparation 3The Raman spectrum of nanometer sheet.
Fig. 4 a ~ 4b is the WO that adopts the thermal oxidation process preparation 3The low magnification SEM figure of nanometer sheet, wherein Fig. 4
A represents the W film spot formation looks after the thermooxidizing; Fig. 4 b represents the W film spot battle array WO under the low range amplification 3The homogeneity situation of nanometer sheet growth.
Fig. 5 a ~ 5b is the WO that adopts the thermal oxidation process preparation 3The high-amplification-factor SEM figure of nanometer sheet, wherein Fig. 5 a represents WO 3Growth distribution and the pattern of nanometer sheet on single localization point, Fig. 5 b have reflected that high magnification amplifies lower monolithic WO 3The pattern of nanometer sheet and thickness.
Fig. 6 a ~ 6b is the WO that adopts the thermal oxidation process preparation 3The TEM figure of nanometer sheet, wherein Fig. 6 a represents WO 3The pattern picture of nanometer sheet under transmission electron microscope, Fig. 6 b represent the reflection WO that observes under the transmission electron microscope 3The high resolution picture of Nano lamellite lattice structure.
Embodiment
Make WO in order more clearly to provide the above-mentioned method of passing through thermooxidizing 3The method of nanometer sheet, Fig. 1 has provided take glass as substrate, prepares WO take the tungsten film of localization preparation as parent material 3The step of nanometer sheet.
At first clean glass substrate (Fig. 1 (a)).Plate one deck ito thin film as conductive layer (Fig. 1 (b)) in glass substrate, then being coated with resist coating on the substrate of ito thin film, behind overexposure and developing process, formed photoetching agent pattern (Fig. 1 (c)) on the substrate.Adopt magnetron sputtering, electron beam evaporation equal vacuum film coating method plating tungsten film (Fig. 1 (d)).With organic solvent such as acetone, with the photoresist material dissolving, namely obtain tungsten film pattern (Fig. 1 (e)).Above-mentioned sample is put into the baking oven that can ventilate, pass into N 2Or the rare gas element such as Ar gas, be heated to 400 ~ 800 ℃, and insulation 10min ~ 5h, naturally lower the temperature at last.Can lead to shielding gas in the temperature-fall period.Through behind the above-mentioned thermal oxidation process, substrate surface can generate tungstic oxide nano-sheets (Fig. 1 (f)).
Fig. 2 is that a kind of method of thermooxidizing is made WO 3The schematic diagram of the device of nanometer sheet.This device is a kind of box baking oven that can ventilate, and it has inlet mouth and venting port, and other parts are airtight.Substrate places the middle part of baking oven.In preparation process, pass into the rare gas elementes such as N2 or Ar by inlet mouth, make the oxygen content in the stove be brought down below 10%.
Embodiment
The present embodiment is given in that localization prepares WO on the glass substrate 3The detailed process of nanometer sheet.At first, used respectively acetone, ethanol and deionized water ultrasonic cleaning glass substrate each 15 minutes, dry up with nitrogen.Plate ito thin film with magnetron sputtering in glass substrate, the thickness of film is 200nm; Use photoresist spinner, apply photoresist material at ito thin film, photoresist material thickness is about 1 micron, and baking, 120 ℃ of storing temperatures.Adopting ultraviolet exposure machine to see through mask plate exposes to photoresist material.With developing solution the sample after exposing is developed, and use washed with de-ionized water, dry up with nitrogen.Sample after the photoetching is put into magnetron sputtering metal tungsten film, and thickness is 600nm approximately.After removing photoresist with acetone soln, use successively again acetone, alcohol and washed with de-ionized water clean.At last, above-mentioned sample is put into box baking oven, at first pass into the N that flow is 2slm 2Flow continues 1.5h, reduces flow to 200sccm again, is heated to 540 ℃ from room temperature, and at 540 ℃ of insulation 1h, takes out sample after naturally being cooled to room temperature at last.
With the component of the sample after the Raman spectrometer measurement oxidation, it is the laser of 514nm that the exciting light of test adopts wavelength.Fig. 3 is the WO that adopts the thermal oxidation process preparation 3The Raman spectrum of nanometer sheet.Four peak positions in the spectrum are in 135cm -1, 273cm -1, 714cm -1, 808cm -1, be WO 3Characteristic peak.Illustrate that the product after the oxidation is WO 3, do not have other dephasign.
Use respectively scanning electronic microscope (SEM) and transmission electron microscope (TEM) to observe the WO of thermooxidizing preparation 3The surface topography of nanometer sheet and structure.Fig. 4 and Fig. 5 are respectively the WO that adopts the thermal oxidation process preparation 3The low magnification of nanometer sheet and the SEM photo of high-amplification-factor.Can see that the center line average that grows the tungstic trioxide nano-slice nanometer sheet on the W film of localization preparation is 3 μ m, thickness is about 10nm.Fig. 6 is the WO that adopts the thermal oxidation process preparation 3The TEM photo of nanometer sheet.Can find out that from the TEM photo prepared tungstic trioxide nano-slice has single crystal structure.

Claims (10)

1. method for preparing tungstic trioxide nano-slice with thermal oxidation method, its preparation process is as follows:
1) cleans substrate;
2) metallizing W film on substrate;
3) sample that step 2 is obtained is put into the chamber that can heat, and passes into N in chamber 2, or rare gas element, or oxygen and N 2, or the mixed gas of oxygen and rare gas element, make in the chamber oxygen concentration be reduced to less than
10%, the preferred Ar gas of described rare gas element;
4) temperature is increased to 400 ℃ ~ 800 ℃ in the chamber, and insulation, in this process, need pass into N 2Perhaps Ar gas;
5) stuffiness is lowered the temperature or the cooling of logical rare gas element naturally, until room temperature.
2. a kind of method for preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 1, it is characterized in that: the thickness of tungsten film is 200nm ~ 2 μ m in the step 2.
3. a kind of method for preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 1 is characterized in that: adopt the preparation of magnetron sputtering or electron beam evaporation or electro-plating method in the step 2.
4. a kind of method for preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 1 is characterized in that: the preparation of tungsten film full wafer is on substrate in the step 2, and perhaps the localization preparation is on substrate.
5. a kind of method for preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 4 is characterized in that: described localization preparation refers to select the localization such as photolithography, mask means or silk screen print method to prepare the W film figure.
6. a kind of method for preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 1, it is characterized in that: described substrate is selected Si sheet or glass or ito glass or metal or pottery.
7. a kind of method for preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 1 is characterized in that: adopt box-type furnace or tube furnace or hot plate that chamber is heated in the step 3.
8. a kind of method for preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 1, it is characterized in that: the soaking time in the step 4 is 10min ~ 5h.
9. method for preparing tungstic trioxide nano-slice with thermal oxidation method, its preparation process is as follows:
1) tungsten of bulk is put into the chamber that can heat, in chamber, pass into N 2, or rare gas element, or pass into oxygen and N 2, or the mixed gas of oxygen and rare gas element, make the interior oxygen concentration of chamber be reduced to less than 10% the preferred Ar gas of described rare gas element;
2) temperature is increased to 400 ℃ ~ 800 ℃ in the chamber, and insulation, in this process, need pass into N 2Perhaps Ar gas;
3) stuffiness is lowered the temperature or the cooling of logical rare gas element naturally, until room temperature.
10. a kind of method for preparing tungstic trioxide nano-slice with thermal oxidation method according to claim 9, it is characterized in that: the soaking time in the step 2 is 10min ~ 5h.
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Cited By (1)

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CN101638781A (en) * 2009-04-24 2010-02-03 中山大学 Method for directly heating metal membrane to grow oxide nanowires in array-type arranged microcavity structure, and application thereof
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Publication number Priority date Publication date Assignee Title
CN105154812A (en) * 2015-09-22 2015-12-16 五邑大学 Preparation method for micro-nano material adopting metal and metal oxide core-shell structure

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