CN102998344B - Novel nanosheet film for sensor and preparation method thereof - Google Patents
Novel nanosheet film for sensor and preparation method thereof Download PDFInfo
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- CN102998344B CN102998344B CN201210534982.3A CN201210534982A CN102998344B CN 102998344 B CN102998344 B CN 102998344B CN 201210534982 A CN201210534982 A CN 201210534982A CN 102998344 B CN102998344 B CN 102998344B
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Abstract
The invention belongs to the cross field of semiconductor materials and chemical engineering, relates to a preparation method of a sensor film, and particularly relates to a novel nanosheet film for a sensor and a preparation method thereof. The nanosheet film comprises of 35-100 wt% of one or more selected from nanosheet WO3 and MoO3, and 0-65 wt% of one or more selected from W and Mo. According to the invention, one or more selected from Na2WO4 and Na2MoO4, FeSO4, and (NH4)2C4H4O6 are used to prepare an electrolyte; an alloy coating is prepared by electrodeposition coating; the alloy coating grows on substrate metal sheet in situ; Fe component in the alloy is removed; and the nanosheet deposition film is oxidized to obtain the product. The method provided by the invention does not require sophisticated equipment or dangerous medicine and solvent, and has the advantages of simple process, low production cost, and uniform thickness of the nanosheet WO3 film.
Description
Technical field
The invention belongs to the crossing domain of semiconductor material and chemical technology, relate to the preparation method of colorimetric sensor films, be specifically related to a kind of novel nano sheet film that can be used for sensor and preparation method thereof.
Background technology
Semi-conductor type gas sensor is to utilize gas to be measured to carry out adsorption reaction on inductive material surface, inductive material surface can absorb or emit unnecessary electronics, and the electron density on inductive material surface is changed, therefore cause the variation of inductive material resistance value, decide thus the concentration of gas to be measured according to the variable quantity of its resistance.
Tungstic acid is a kind of n-type metal oxide semiconductor of energy gap, is widely used in as fields such as gas sensor and efficient wide catalyzer as a kind of important functional material.Simultaneously due to its distinguished galvanochemistry and contact performance, WO
3it is a kind of engineering material having a great attraction.WO
3and WO
3based sensor is widely used in surveying NO
2, NO and H
2s gas.
The inductive material of existing tungstic acid sensor is mostly fine and close or many empty particle type WO 3 films, the method of preparation has sol-gal process [Sivakumar R, MosesEzhilRaj A, Subramanian B, et al. Preparation and characterization of spray deposited n-type WO3 thin films for electrochromic devices. Mater ResBull 2004, 39 (10): 1479 – 1489.], chemical vapor deposition [N. Shankar, M.F. Yu, S.P. Vanka, N.G. Glumac, Synthesis of tungsten oxide (WO
3) nanorods using carbon nanotubes as templates by hot filament chemical vapor deposition, Mater. Lett. 2006,60:771 – 774.], magnetron sputtering [Stankova M, Vilanova X, Llobet E, et al. Influence of the annealing and operating temperatureson the gas-sensing properties of rf sputtered WO
3thin-film sensors. Sensors Actuators B 2005,105 (2): 271 – 277] etc.
Publication number is that the Chinese patent of CN101318702 discloses " a kind of tungstic trioxide nano-slice and preparation method thereof ", it is precursor that the method adopts wolframic acid base organic or inorganic stratiform to mix micro-/ nano band (pipe), removes to obtain the after-baking of wolframic acid nanometer sheet after the organism between precursor layer and obtain tungstic oxide nano-sheets dusty material.Publication number is that the Chinese patent of CN1935671 discloses " a kind of tungsten oxide material with nano band array structure and preparation method thereof ", the method adopt tungsten basal body self-heating under low vacuum and outwards the method for the banded tungsten oxide of growing nano on tungsten basal body, directly prepare membraneous material.Publication number is that the Chinese patent of CN1974890 discloses " a kind of nanometer porous tungsten trioxide material and its preparation method and application ", the method adopts constant current anode oxidation tungsten matrix, makes its self assembly form the tungsten trioxide nano material of nanoporous shape.But be also not reporting of growth in situ nano-sheet, relevant air-sensitive performance research also has no its report.
Summary of the invention
For prior art deficiency, the invention provides a kind of novel nano sheet film that can be used for sensor and preparation method thereof.
Basic conception of the present invention is according to the metallic iron of dialling compared with living preferential corrosion and dissolving and tungsten and the molybdenum of the ripple of deviating to stay more not live from alloy gradually in acid solution, then under higher temperature, tungsten and molybdenum and airborne oxygen generation oxidation reaction, by the control to de-alloy extent, the control of high-temperature oxydation temperature and time, and obtain that specific surface area is large, tungsten oxide and the Electrochromic Molybdenum Oxide Coatings material of nano-sheet.
A novel nano sheet film that can be used for sensor, its nanometer sheet film is by the nano-sheet WO that accounts for its quality 35% ~ 100%
3and MoO
3in one or more, and account for one or more compositions in W or the Mo of its quality 0% ~ 65%.
In described nanometer sheet film, nanometer sheet length is 100 nanometer ~ 600 nanometers, and width is 50 nanometer ~ 300 nanometers, and thickness is 20 nanometer ~ 100 nanometers.
The integral thickness of described nanometer sheet film is 1 micron ~ 50 microns.
Can be used for a preparation method for the novel nano sheet film of sensor, with Na
2wO
4and Na
2moO
4in one or more, FeSO
4, (NH4)
2c
4h
4o
6configuration electrolytic solution, prepares alloy layer by electro-deposition, and described alloy layer growth in situ is on parent metal sheet; Obtain product by the deposit film of deviating from the Fe composition rear oxidation nano-sheet in alloy, concrete steps are as follows:
(1) configuration electrolytic solution, wherein electrolytic solution is composed as follows:
Na in electrolytic solution
2wO
4and Na
2moO
4total concentration be 0.15 ~ 0.25mol/L, FeSO
4concentration be 0.02 ~ 0.03 mol/L, (NH
4)
2c
4h
4o
6concentration be 0.2 ~ 0.3 mol/L;
(2) electrodeposition technology:
Matrix is cut into required form, after sand papering, use successively acetone, alcohol and deionized water ultrasonic cleaning 10 min respectively; Then the pH value that regulates electrolytic solution is 3 ~ 5; Then electrolytic solution is put into heating arrangement, heating and temperature control is at 40 DEG C ~ 60 DEG C; Taking matrix as negative electrode, graphite is anode, passes into 0.05 A/cm
2~ 0.4 A/cm
2direct current carry out electro-deposition, electrodeposition time is controlled at 2 min ~ 15 min; The complete coating of electro-deposition dries after washing, i.e. the alloy layer of system;
(3) de-alloying technology:
Compound concentration is the aqueous hydrochloric acid solution of 1 mol/L, at room temperature the alloy layer having deposited is placed in to hydrochloric acid solution, and the Fe composition in alloy layer reacts with HCl and dissolved, and the time of the de-alloy of control was at 3 hours ~ 24 hours; De-alloy is complete through washed with de-ionized water, after naturally drying, obtains deposit film;
(4) deposit film oxidation technology:
Deposit film after de-alloy treatment is placed in to tubular furnace, in air atmosphere at 450 DEG C ~ 700 DEG C sintering, sintering time is controlled at 30 min ~ 240 min, makes nanometer sheet film.
Described matrix is pure tungsten, stainless steel or fine copper metal.
Beneficial effect of the present invention is:
The inventive method does not need to use complicated equipment, also need not use dangerous medicine and solvent, has that technique is simple, production cost is low, nanometer sheet WO
3the advantages such as film thickness is even.
Brief description of the drawings
Fig. 1 is the nano-sheet W scanning electron microscope (SEM) photograph (SEM) of embodiment 1 through de-alloy treatment;
Fig. 2 is the tungsten oxide film scanning electron microscope (SEM) photograph (SEM) of embodiment 1 nanometer sheet;
Fig. 3 is the X-ray diffractogram (XRD) of embodiment 1 nano-sheet tungsten oxide;
Fig. 4 be embodiment 1 nanometer sheet tungsten oxide at 100 DEG C to NO
2response curve.
Embodiment
The invention provides a kind of novel nano sheet film that can be used for sensor and preparation method thereof, below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment 1
The preparation process of the tungstic oxide nano-sheets film taking tungsten sheet as reactive matrix is as follows:
The first step cuts into pure tungsten sheet to be of a size of 15 mm × 15 mm, carefully polishes, successively with acetone and deionized water each 10 min of ultrasonic cleaning respectively through 500#, 1000#, 2000# sand paper.
The analytically pure Na of second step
2wO
42H
2o, FeSO
47H
2o and (NH
4)
2c
4h
4o
6the electrolytic solution of preparation tungstenic, ferric ion, wherein Na
2wO
42H
2o, FeSO
47H
2o and (NH
4)
2c
4h
4o
6concentration be followed successively by 0.25 mol/L, 0.02 mol/L and 0.25 mol/L, regulate electrolyte PH value to 4 with sulfuric acid, electrolytic solution liquid adopts deionized water preparation.
The 3rd step packs the electrolytic solution preparing in beaker into, is placed in water-bath, and negative electrode connects through the pretreated matrix of step 1, and anode connects graphite flake.Start temperature control device for water bath, control temperature and be incubated after 30 min at 60 DEG C, pass into direct current 0.2 A/cm
2carry out electro-deposition, power-off source immediately after electro-deposition 5 min, takes out electrode.
The 4th step is at room temperature placed in the W-Fe alloy layer having deposited the hydrochloric acid solution of 1 mol/L, and the Fe composition in alloy reacts with HCl and deviate from, and the time of controlling de-alloy is 24 hours; De-alloy is complete to be dried after deionization washing.
The matrix after de-alloy treatment is placed in tubular furnace by the 5th step, sintering at 500 DEG C, and sintering time control is 120 min, makes nanometer sheet WO
3film.
The tungsten oxide material of measuring the nano-sheet that obtains, its film thickness is 7 μ m.
The scanning electron microscope (SEM) photograph (as shown in Figure 1) of the tungsten nano-chip arrays film of embodiment 1, is to adopt Hitachi S-4800 scanning electron microscope, and accelerating potential is 20 kV, above matrix, takes.As seen from Figure 1, the tungsten after the de-alloy treatment of HCl presents unordered nano-sheet array structure.
The scanning electron microscope (SEM) photograph (as shown in Figure 2) of the tungstic oxide nano-sheets array film of embodiment 1, is to adopt Hitachi S-4800 scanning electron microscope, and accelerating potential is 20 kV, above matrix, takes.As seen from Figure 2, tungstic oxide nano-sheets film presents unordered array structure.
The X-ray diffractogram (as shown in Figure 3) of the tungstic oxide nano-sheets film of embodiment 1, is to adopt D-8Advanced diffractometer, at 40 kV, under 20 mA conditions, scans, and sweep speed is 0.02 °/S.
Fig. 4 is nanometer sheet tungsten oxide film NO to 1 ppm, 2 ppm, 4 ppm and 8 ppm concentration under the working temperature of 100 DEG C of embodiment 1
2the response curve of gas.
Embodiment 2
The preparation process of the molybdena nanometer sheet film taking metal copper sheet as reactive matrix is as follows:
Copper sheet is cut into 15 mm × 15 mm by the first step, plays acetone, deionized water ultrasonic cleaning before deposition through 500#, 1000#, 2000# sand paper.
Second step is to analyze pure Na
2moO
42H
2o, FeSO
47H
2o and (NH4)
2c
4h
4o
6preparation is containing the electrolytic solution of molybdenum, ferric ion, wherein Na
2moO
42H
2o, FeSO
47H
2o and (NH4)
2c
4h
4o
6concentration be respectively 0.15 mol/L, 0.03 mol/L and 0.3 mol/L, regulate electrolyte PH value to 5.5, electrolytic solution adopts deionized water preparation.
The 3rd step packs the electrolytic solution preparing in beaker into, is placed in water-bath, and negative electrode connects through the pretreated matrix of step 1, and anode connects graphite flake.Start temperature control device for water bath, control temperature and be incubated after 30 min at 50 DEG C, pass into direct current 0.05 A/cm
2carry out electro-deposition, power-off source immediately after electro-deposition 3 min, takes out electrode.
The 4th step is at room temperature placed in the Mo-Fe alloy layer having deposited the hydrochloric acid solution of 1 mol/L, and the Fe composition in alloy reacts with HCl and deviate from, and the time of controlling de-alloy is 12 hours; De-alloy is complete to be dried after deionization washing.
The matrix after de-alloy treatment is placed in tubular furnace by the 5th step, sintering at 600 DEG C, and sintering time control is 90 min, makes thickness and be the nanometer sheet MoO of 2 microns
3film.
Claims (5)
1. a preparation method who can be used for the novel nano sheet film of sensor, is characterized in that, with Na
2wO
4and Na
2moO
4in one or more, FeSO
4, (NH
4)
2c
4h
4o
6configuration electrolytic solution, prepares alloy layer by electro-deposition, and described alloy layer growth in situ is on parent metal sheet; Obtain product by the deposit film of deviating from the Fe composition rear oxidation nano-sheet in alloy, concrete steps are as follows:
(1) configuration electrolytic solution, wherein electrolytic solution is composed as follows:
Na in electrolytic solution
2wO
4and Na
2moO
4total concentration be 0.15～0.25mol/L, FeSO
4concentration be 0.02～0.03mol/L, (NH
4)
2c
4h
4o
6concentration be 0.2～0.3mol/L;
(2) electrodeposition technology:
Matrix is cut into required form, after sand papering, use successively acetone, alcohol and deionized water ultrasonic cleaning 10min respectively; Then the pH value that regulates electrolytic solution is 3～5; Then electrolytic solution is put into heating arrangement, heating and temperature control is at 40 DEG C～60 DEG C; Taking matrix as negative electrode, graphite is anode, passes into 0.05A/cm
2～0.4A/cm
2direct current carry out electro-deposition, electrodeposition time is controlled at 2min～15min; The complete coating of electro-deposition dries after washing, makes alloy layer;
(3) de-alloying technology:
Compound concentration is the aqueous hydrochloric acid solution of 1mol/L, at room temperature the alloy layer having deposited is placed in to hydrochloric acid solution, and the Fe composition in alloy layer reacts with HCl and dissolved, and the time of the de-alloy of control was at 3 hours～24 hours; De-alloy is complete through washed with de-ionized water, after naturally drying, obtains deposit film;
(4) deposit film oxidation technology:
Deposit film after de-alloy treatment is placed in to tubular furnace, in air atmosphere at 450 DEG C～700 DEG C sintering, sintering time is controlled at 30min～240min, makes nanometer sheet film.
2. method according to claim 1, is characterized in that: described matrix is pure tungsten, stainless steel or fine copper metal.
3. method according to claim 1 and 2, is characterized in that: prepared nanometer sheet film is by the nano-sheet WO that accounts for its quality 35%～100%
3and MoO
3in one or more, and account for one or more compositions in W or the Mo of its quality 0%～65%.
4. method according to claim 3, is characterized in that: in described nanometer sheet film, nanometer sheet length is 100 nanometer～600 nanometers, and width is 50 nanometer～300 nanometers, and thickness is 20 nanometer～100 nanometers.
5. method according to claim 3, is characterized in that: the integral thickness of described nanometer sheet film is 1 micron～50 microns.
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| CN102998344B true CN102998344B (en) | 2014-11-26 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105510398A (en) * | 2015-09-08 | 2016-04-20 | 浙江大学 | Film-type alcohol gas-sensitive sensor and preparation method thereof |
| CN106746724B (en) * | 2017-02-21 | 2019-11-12 | 上海第二工业大学 | A kind of molybdenum oxide electrochromism nano thin-film and preparation method thereof |
| CN107522229B (en) * | 2017-07-24 | 2019-10-11 | 桂林理工大学 | One kind (Y1-xLnx)2(MoO4)3The direct preparation method of film |
| CN108107098B (en) * | 2018-01-30 | 2019-12-31 | 集美大学 | Based on WO3Method for detecting alcoholic strength in white spirit by using/FTO photoelectric material |
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| US7816681B2 (en) * | 2008-12-03 | 2010-10-19 | Electronics And Telecommunications Research Institute | Capacitive gas sensor and method of fabricating the same |
| US9721754B2 (en) * | 2011-04-26 | 2017-08-01 | Carl Zeiss Smt Gmbh | Method and apparatus for processing a substrate with a focused particle beam |
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| CN1807492A (en) * | 2005-12-29 | 2006-07-26 | 复旦大学 | Method for preparing inorganic semi-conductor/ conducting polymer composite film by photocatalyzed polymerization |
| CN101456605A (en) * | 2008-12-24 | 2009-06-17 | 苏州纳米技术与纳米仿生研究所 | Organic wastewater advanced treatment apparatus by LED nano photocatalysis |
| CN101799443A (en) * | 2010-03-16 | 2010-08-11 | 天津大学 | Method for preparing multiaperture silicon substrate tungsten oxide nanometer thin film gas sensitive transducer |
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