CN102874876B - 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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CN102874876B
CN102874876B CN201210377609.1A CN201210377609A CN102874876B CN 102874876 B CN102874876 B CN 102874876B CN 201210377609 A CN201210377609 A CN 201210377609A CN 102874876 B CN102874876 B CN 102874876B
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thermal oxidation
slice
chamber
trioxide nano
tungstic trioxide
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CN102874876A (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 of preparing tungstic trioxide nano-slice with thermal oxidation method
Technical field
The present invention relates to one thermal oxidation method and prepare tungstic oxide (WO 3) method of nanometer sheet, belong to field of nanometer material technology.
Background technology
WO 3be a kind of important semiconductor material, have important application in fields such as air-sensitive, catalysis, opto-electronic conversion, transmittings.There is the tungstic trioxide nano-slice of two-dirnentional structure, because it has unique photoelectric characteristic, more and more receive in recent years people's concern.
At present, two-dirnentional structure WO 3the preparation method of nanometer sheet mainly comprises chemosynthesis, chemical stripping or uses 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 a kind of method (Chinese invention patent: ZL200710054544.6) of utilizing hydrothermal method to prepare tungstic trioxide nano-slice, and the method is with laminate structure wolframic acid (H 2w 2o 7xH 2and alkylamine (CH O) 3(CH 2) nnH 2) be raw material, it is (100-800) nm × (100-800) nm that the reaction of process magnetic agitation and baking prepare area, the WO that apparent thickness is 5-40nm 3nanometer sheet.The people such as Jinmin Wang are raw material with W powder, with H 2o 2the method of chemosynthesis has been 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 by thermal oxidation process aspect nanometer sheet, only having at present people's report such as Jing Xiao of Peking University.They use potassiumiodide as catalyzer, grow WO by thermooxidizing on the tungsten of block 3nanometer sheet [Jing Xiao, et al, Proc.8th IVESC and Nanocarbon (IVESC), 2010, p316].
In above-mentioned preparation method, utilize chemical process preparation generally all to need the reaction through liquid phase, easily introduce impurity.And employing catalytic oxidation, the existence of catalyzer also can be introduced impurity.And the prepared WO of current method 3the size of nanometer sheet is less, the long and wide hundreds of nanometer that is generally no more than.
Summary of the invention
The present invention proposes one and do not adopt any catalyzer, directly thermal oxidation tungsten is prepared the method for tungstic oxide nano-sheets.The method has easy, the good feature of controllability, and can realize 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 is prepared in the tungsten film on substrate.
When being prepared in tungsten film on substrate as raw material, its preparation process of method of preparing tungstic trioxide nano-slice with thermal oxidation method is as follows:
1) clean substrate;
2) metallizing W film on substrate;
3) sample step 2 being obtained is put into the chamber that can heat, and in chamber, passes into N 2, or rare gas element, or oxygen and N 2, or the mixed gas of oxygen and rare gas element, the interior oxygen concentration of chamber is reduced to and is less than 10%, the preferred Ar gas of described rare gas element;
4) chamber room temp is increased to 400 DEG C ~ 800 DEG C, and insulation, in this process, need pass into N 2or Ar gas, generally little than step 3 of flow;
5) stuffiness is lowered the temperature or the cooling of logical rare gas element naturally, until room temperature.
Specifically, in step 2, the thickness of tungsten film is 200nm ~ 2 μ m.Preferably 500 ~ 800nm.
In step 3, oxygen concentration is preferably controlled at 1 ~ 10%.
In step 2, can adopt magnetron sputtering or electron beam evaporation or electro-plating method etc. to carry out the plated film of tungsten film.
In step 2, in the time that raw material is the tungsten film being prepared on substrate, tungsten film can be prepared on substrate by full wafer, also can localization prepare on substrate.In the time adopting localization to prepare, select the mode localization such as photolithography, mask means or silk screen print method to prepare 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.
In step 3, can adopt box-type furnace or tube furnace or hot plate to heat chamber.
Soaking time in step 4 is 10min ~ 5h.Preferably 1 ~ 2h.
When taking bulk metal tungsten as raw material, its preparation process of method of 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, the interior oxygen concentration of chamber is reduced to and is less than 10%, the preferred Ar gas of described rare gas element;
2) chamber room temp is increased to 400 DEG C ~ 800 DEG C, and insulation, in this process, need pass into N 2or Ar gas;
3) stuffiness is lowered the temperature or the cooling of logical rare gas element naturally, until room temperature.
In employing, when method, step 1 can adopt box-type furnace or tube furnace or hot plate to heat chamber.Soaking time in step 2 is 10min ~ 5h, preferably 1 ~ 2h.
In above-mentioned steps, pass into N 2or the object of Ar or other rare gas element, is to be mainly the environment below 10% in order to keep sample in oxygen concentration, also can reach this effect by vacuumizing.The preparation WO that the present invention proposes 3the square ratio juris of nanometer sheet is, by controlling the oxygen in growth atmosphere, controls the thermooxidizing of W film, and the reaction heat that thermooxidizing produces provides WO 3molecule carries out fast transferring, generates the structure of nanometer sheet.The too low reaction heat of oxygen concentration deficiency, can not form larger nanometer sheet, and the easy over oxidation of the too high sample of oxygen concentration, does not become nanometer sheet.Therefore, logical N 2or the principle that Ar or other rare gas elementes should be followed is to keep environment oxygen concentration in applicable scope.The WO 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 is without complicated micro fabrication, and making method is easy, and can be by controlling the pattern of the parameter Effective Regulation samples such as thermooxidizing time and temperature, shield gas flow rate, and controllability is good.
WO prepared by the present invention 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.
Brief description of the drawings
Fig. 1 a ~ Fig. 1 f adopts photoetching method in glass substrate, to prepare the processing step schematic diagram of 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 thermal oxidation process to prepare 3the Raman spectrum of nanometer sheet.
Fig. 4 a ~ 4b is the WO that adopts thermal oxidation process to prepare 3the low magnification SEM figure of nanometer sheet, wherein Fig. 4
A represents the W film spot formation looks after thermooxidizing; Fig. 4 b represents the W film spot battle array WO under low range amplification 3the homogeneity situation of nanometer sheet growth.
Fig. 5 a ~ 5b is the WO that adopts thermal oxidation process to prepare 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 has reflected that high magnification amplifies lower monolithic WO 3the pattern of nanometer sheet and thickness.
Fig. 6 a ~ 6b is the WO that adopts thermal oxidation process to prepare 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 represents the reflection WO observing under 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 taking glass as substrate, and the tungsten film of preparing taking localization is prepared WO as parent material 3the step of nanometer sheet.
First clean glass substrate (Fig. 1 (a)).In glass substrate, plate one deck ito thin film as conductive layer (Fig. 1 (b)), then resist coating on the substrate that is coated with ito thin film, after overexposure and developing process, has formed photoetching agent pattern (Fig. 1 (c)) on substrate.Adopt magnetron sputtering, electron beam evaporation equal vacuum film coating method plating tungsten film (Fig. 1 (d))., as acetone photoresist material is dissolved with organic solvent, obtain tungsten film pattern (Fig. 1 (e)).Above-mentioned sample is put into the baking oven that can ventilate, passed into N 2or the rare gas element such as Ar gas, be heated to 400 ~ 800 DEG C, and be incubated 10min ~ 5h, finally naturally lower the temperature.In temperature-fall period, can lead to shielding gas.After 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 is placed in the middle part of baking oven.In preparation process, pass into the rare gas element such as N2 or Ar by inlet mouth, make the oxygen content in stove be brought down below 10%.
Embodiment
The present embodiment is given in localization in glass substrate and prepares WO 3the detailed process of nanometer sheet.First, use respectively acetone, ethanol and deionized water ultrasonic cleaning glass substrate each 15 minutes, dry up with nitrogen.In glass substrate, plate ito thin film with magnetron sputtering, the thickness of film is 200nm; With photoresist spinner, on ito thin film, apply photoresist material, photoresist material thickness is about 1 micron, and baking, 120 DEG C of storing temperatures.Adopting ultraviolet exposure machine to see through mask plate exposes to photoresist material.Sample with developing solution after to exposure develops, and by washed with de-ionized water, dries up with nitrogen.Sample after photoetching is put into magnetron sputtering metal tungsten film, the about 600nm of thickness.After removing photoresist with acetone soln, then use successively acetone, alcohol and washed with de-ionized water clean.Finally, above-mentioned sample is put into box baking oven, first pass into the N that flow is 2slm 2flow, continues 1.5h, then reduces flow to 200sccm, is heated to 540 DEG C from room temperature, and at 540 DEG C of insulation 1h, takes out sample after being finally naturally cooled to room temperature.
Measure the component of the sample after oxidation with Raman spectrometer, the exciting light of test adopts the laser that wavelength is 514nm.Fig. 3 is the WO that adopts thermal oxidation process to prepare 3the Raman spectrum of nanometer sheet.Four peak positions in spectrum are in 135cm -1, 273cm -1, 714cm -1, 808cm -1, be WO 3characteristic peak.Illustrate that the product after oxidation is WO 3, there is no other dephasign.
Use respectively scanning electronic microscope (SEM) and transmission electron microscope (TEM) to observe WO prepared by thermooxidizing 3the surface topography of nanometer sheet and structure.Fig. 4 and Fig. 5 are respectively the WO that adopts thermal oxidation process to prepare 3the low magnification of nanometer sheet and the SEM photo of high-amplification-factor.Can see that the center line average that grows tungstic trioxide nano-slice nanometer sheet on W film prepared by localization is 3 μ m, thickness is about 10nm.Fig. 6 is the WO that adopts thermal oxidation process to prepare 3the TEM photo of nanometer sheet.Can find out that from TEM photo prepared tungstic trioxide nano-slice has single crystal structure.

Claims (10)

1. a method of preparing tungstic trioxide nano-slice with thermal oxidation method, its preparation process is as follows:
1) clean substrate;
2) metallizing W film on substrate;
3) by step 2) sample that obtains puts into the chamber that can heat, and in chamber, passes into N 2, or rare gas element, or oxygen and N 2, or the mixed gas of oxygen and rare gas element, the interior oxygen concentration of chamber is reduced to and is less than 10%;
4) chamber room temp is increased to 400 DEG C～800 DEG C, and insulation, in this process, need pass into N 2or 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 of preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 1, is characterized in that: step 2) in the thickness of tungsten film be 200nm～2 μ m.
3. a kind of method of preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 1, is characterized in that: step 2) middle employing magnetron sputtering or electron beam evaporation or electro-plating method preparation.
4. a kind of method of preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 1, is characterized in that: step 2) middle tungsten film full wafer is prepared on substrate, or localization is prepared on substrate.
5. a kind of method of preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 4, is characterized in that: described localization preparation refers to that selecting photolithography, mask means or silk screen print method to carry out localization prepares W film figure.
6. a kind of method of preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 1, is characterized in that: described substrate is selected Si sheet or ito glass or metal or pottery.
7. a kind of method of preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 1, is characterized in that: in step 3), adopt box-type furnace or tube furnace or hot plate to heat chamber.
8. a kind of method of preparing tungstic trioxide nano-slice with thermal oxidation method claimed in claim 1, is characterized in that: the soaking time in step 4) is 10min～5h.
9. a method of 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, the interior oxygen concentration of chamber is reduced to and is less than 10%;
2) chamber room temp is increased to 400 DEG C～800 DEG C, and insulation, in this process, need pass into N 2or 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 of preparing tungstic trioxide nano-slice with thermal oxidation method according to claim 9, is characterized in that: step 2) in soaking time be 10min～5h.
CN201210377609.1A 2012-10-08 2012-10-08 Method for preparing tungsten trioxide nanosheets by thermal oxidation Active CN102874876B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101580267A (en) * 2009-02-23 2009-11-18 中山大学 Method for growing nanometer zinc oxide structure through low-temperature heating of zinc and catalyst and application thereof
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
CN101805023A (en) * 2010-04-01 2010-08-18 中国科学院宁波材料技术与工程研究所 Method for preparing tungstic oxide nano-sheets

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101580267A (en) * 2009-02-23 2009-11-18 中山大学 Method for growing nanometer zinc oxide structure through low-temperature heating of zinc and catalyst and application thereof
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
CN101805023A (en) * 2010-04-01 2010-08-18 中国科学院宁波材料技术与工程研究所 Method for preparing tungstic oxide nano-sheets

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
Controlled Growth and Characterization of Tungsten Oxide Nanowires Using Thermal Evaporation of WO3 Powder;Yunho Baek et al.;《J. Phys. Chem. C》;20070103;第111卷(第3期);1213-1218 *
DESIGN》.2010,第10卷(第12期),5193-5199. *
Fei Liu et al..A Catalyzed-Growth Route to Directly Form Micropatterned WO2 and WO3 Nanowire Arrays with Excellent Field Emission Behaviors at Low Temperature.《CRYSTAL GROWTH & DESIGN》.2010,第10卷(第12期),5193-5199.
Fei Liu et al..A Catalyzed-Growth Route to Directly Form Micropatterned WO2 and WO3 Nanowire Arrays with Excellent Field Emission Behaviors at Low Temperature.《CRYSTAL GROWTH &amp *
Yunho Baek et al..Controlled Growth and Characterization of Tungsten Oxide Nanowires Using Thermal Evaporation of WO3 Powder.《J. Phys. Chem. C》.2007,第111卷(第3期),1213-1218.
刘飞等.图案化氧化钨纳米线阵列的低温制备工艺及其场发射特性研究.《真空电子技术》.2012,(第3期),4-7、22.
图案化氧化钨纳米线阵列的低温制备工艺及其场发射特性研究;刘飞等;《真空电子技术》;20120331(第3期);4-7、22 *

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