CN104807859B - The method of low-temperature original position growth nanostructure metal oxide semiconductor and application - Google Patents
The method of low-temperature original position growth nanostructure metal oxide semiconductor and application Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 6
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- PXDRFTPXHTVDFR-UHFFFAOYSA-N propane;titanium(4+) Chemical compound [Ti+4].C[CH-]C.C[CH-]C.C[CH-]C.C[CH-]C PXDRFTPXHTVDFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 25
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
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- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The present invention discloses method and the application of a kind of low-temperature original position growth nanostructure metal oxide semiconductor.It is to deposit the polymer nanofiber containing inorganic salt solution in substrate by method of electrostatic spinning, then carried out hydro-thermal process, so that the inorganic salts converted in-situ being contained in polymer nanofiber is to be tightly combined with substrate, the metal oxide semiconductor with nanostructure.The present invention is with equipment is simple, step is easy, low energy consumption, is not necessarily to high-temperature heat treatment, it can be at relatively low temperatures, less than 180 DEG C, realize the advantages that obtaining metal oxide semiconductor nano material in situ on different substrates, it can be used for using polymer as the preparation of the flexible semiconductor metal oxide device of substrate, and it can further easily realize that metal oxide semiconductor nano material and organic macromolecule are well compound, organic/metal oxide semiconductor nanocomposite and device are prepared, is had a good application prospect in nano photoelectric devices field.
Description
Technical field
The present invention relates to field of nanometer material technology, and in particular to one kind is heat-treated at low temperature, is realized former on different substrates
The method of position growth nanostructure inorganic semiconductor metal oxide.
Background technology
Metal oxide semiconductor has great scientific research value and actual techniques application value.More there are commonly
SnO2、ZnO、TiO2、Fe2O3Deng.These metal oxide semiconductors are mostly the N-shaped multifunctional semiconductor with wide energy band, are had
It is very excellent electrical properties, photocatalysis property, electrochemical properties, optical and electrical properties, gas sensing, humidity sensor, optical
Matter etc.（L.b. Luo, F.x. Liang and J.s. Jie, Nanotechnology, 2011, 22, 485701; M.
Batzill, K. Katsiev, J. M. Burst, U. Diebold, A. M. Chaka and B. Delley,
Physical Review B, 2005, 72, 165414; H. Zhang, Q. He, X. Zhu, D. Pan, X. Deng
and Z. Jiao, CrystEngComm, 2012, 14, 3169-3176.）.Due to these excellent properties, research work
Persons expand the research applied in every field, such as solar cell, super capacitor to the metal oxide semiconductor
Device, optoelectronic device, transistor, lithium ion battery, humidity sensor and gas sensor etc..
Nano structural material has special nano effect so that it is many unique that it has relative to conventional bulk material
Performance and advantage.For example, nano structural material in sensor field in application, since it is with the much bigger ratio of bulk material
Surface area helps to improve the sensitivity of response in sensor field in application, more reactivity sites can be provided,
The diffusion that detection molecules can be also conducive to simultaneously, to accelerate to respond and improve response invertibity.And nanostructure is formed also
It can promote electric charge transfer, sensitivity is promoted to improve.The metal oxide semiconductor of preparation nanostructure, which also becomes, widens its application
The effective means of its performance is improved in field.
Presently, there are the preparation method of metal oxide semiconductor nano material mainly have thermal evaporation techniques, calcining, molten
Glue-gel method, electrochemical synthesis, atomic layer deposition method, chemical vapour deposition etc., these methods are more special toward needing
Technology, large-scale instrument, high-temperature process（It is ~ 500 DEG C, prosperous referring to the summer, the system of the porous SnO2 nanofibers of Niu Xiao, Zhou Huimin
It is standby with characterization, textile journal, 2014,35 (7):13-17.）Deng cost is higher and energy consumption is larger.In addition, making in this way
Standby metal oxide semiconductor nano material generally requires after disperse again, redeposited in can be just used to prepare in substrate
Electronic device.Therefore, metal oxide semiconductor nano material prepares intermediate demand to device and carries out transfer step, in this way, increasing
The process for having added device to prepare, and if in preparation process nano material evenly dispersed and deposition control it is bad, also can shadow
The consistency of Chinese percussion instrument part.It is combined in addition, often existing between nano material and substrate by device prepared by dispersed deposition again
Imperfect problem makes it there are larger contact impedance and influences charge transfer process in this way, will be to the photoelectricity work(of preparation
The performance of energy device adversely affects.（I.D. Kim, A. Rothschild, Nanostructured metal oxide
gas sensors prepared by electrospinning, Polym. Adv. Technol. 22 (2011) 318–
325.)
On the other hand, the preparation method of conventional metal oxide semiconductor nano material usually requires high-temperature process, and
Flexible organic and polymer material substrate can not often be resistant to high temperature, and which has limited the uses of flexible polymer substrate, to flexibility
The development and application of photoelectric device bring difficulty.
Invention content
In view of the deficiencies of the prior art, the present invention provides the side of low-temperature original position growth nanostructure metal oxide semiconductor
Method and application.
The present invention adopts the following technical scheme that：
A kind of method of Low Temperature Heat Treatment growth in situ nanostructure metal oxide semiconductor, including electrostatic spinning and water
Two steps are heat-treated, the Nanowire containing metal oxide semiconductor presoma is deposited in substrate using method of electrostatic spinning
Dimension, then by hydro-thermal process, is translated into the nanostructure metal oxide semiconductor of the growth in situ in substrate.
The substrate is flexible material or rigid material, including but not limited to polyethylene terephthalate, poly- four
Vinyl fluoride, polypropylene, Kynoar, glass, ceramics, silicon chip, ito glass.
Spinning-aid agent used in the spinning solution of the electrostatic spinning is oil-soluble polymers, including is selected from one or more of：
Polyvinyl butyral, Kynoar, polyvinyl chloride.
The metal oxide semiconductor presoma by used in metal salt, the electrostatic spinning spinning-aid agent and solvent it is equal
Even to be mixed to get, the metal salt includes but not limited to stannous chloride, butter of tin, butyl titanate, tetra isopropyl titanium, chlorination
Zinc, zinc acetate, ferric trichloride, ferric nitrate.
Specifically comprise the following steps：
1) it prepares metal oxide semiconductor presoma and the mixed solution of spinning-aid agent obtains spinning solution, spinning solution is led to
After the method for crossing electrostatic spinning forms nanofibres deposit to substrate surface, naturally dry；
2) deposition obtained in the step 1) has the substrate of nanofiber by hydro-thermal process, obtains in substrate
The metal oxide semiconductor with nanostructure of growth in situ.
Step 1）Described in metal oxide semiconductor precursor concentration be 10 ~ 300 mg/mL, the spinning-aid agent is a concentration of
40 ~ 100 mg/mL, flow velocity preferably 0.1 ~ 1 mL/h of the electrostatic spinning；It is preferably 5 ~ 30 cm to receive distance；Spinning voltage
Preferably 5 ~ 30 kV；Receiving time is preferably 0.5 ~ 30 min.
Step 2）Described in hydro-thermal process temperature be preferably 120 ~ 180 DEG C；Hydrothermal conditions are preferably 6 ~ 24 h.
The nanostructure metal oxide semiconductor of growth in situ in the substrate that the method obtains.
The nanostructure metal oxide semiconductor is used to prepare gas sensor.
The sensor is flexible gas sensor.
The beneficial effects of the invention are as follows：
1. simple, step that the present invention provides a kind of equipment is conveniently, low energy consumption, in arbitrary substrate semiconductor-on-insulator metal oxygen
Compound growth in situ, especially growth in situ on a flexible substrate, semiconductor alloy oxygen the advantages that convenient for preparing flexible device
The growing method of compound nanostructure has widened the metal oxide semiconductor application field, has become the semiconductor significantly
A kind of necessary means of the metal oxide in the preparation nanostructure of each application field.
2. the preparation method is that low-temperature epitaxy（120-180℃）, this method is good with controllability, reaction condition
Mildly, the metal oxide semiconductor nanostructure growth is uniform, and energy-output ratio is less, can reduce environmental pollution etc. all
More advantages, particularly, cryogenic conditions are especially suitable for the direct easy preparation of flexible device.
3. the preparation method is that growth in situ, can realize that nanostructure metal oxide semiconductor material exists
Being prepared in situ in different base can then reduce preparation section, directly obtain required photoelectric functional device, and nano material
Growth in situ be also beneficial to promote material and substrate combination, reduce contact impedance, promote electric charge transfer, improve stability
Deng.To push application of the nanostructure metal oxide semiconductor in function element.The metal oxide semiconductor is received
It is Ohmic contact between rice structure and substrate, metal oxide semiconductor nanostructure and conducting polymer, it can be effectively
Improve sensitivity, repeatability and the stability of prepared sensor.
4. the present invention uses method of electrostatic spinning, in-situ deposition contains the nanofiber of metal salt directly in substrate, then
Pass through lower temperature（Less than 180 DEG C）Hydro-thermal process so that contained metal salt converted in-situ is nano junction in nanofiber
Structure metal oxide.Hereby it is achieved that nanostructured metal oxides are former in the direct low temperature of substrate surface in water-heat process
Position growth, and significantly enhance its binding ability with substrate.
5. the present invention has prepared the metal oxide semiconductor nanostructure comprising this method multiple with conducting polymer
There is very superior gas sensitization performance after conjunction（High sensitivity, recovery are good）The advantages that gas sensor.
6. the I-V curve of metal oxide semiconductor nanostructure and conducting polymer prepared by the present invention, cycle volt
Peace curve shows between the metal oxide semiconductor nanostructure and conducting polymer there are strong interaction, can be with
The charge migration of electric conductivity and promotion at room temperature at room temperature is improved using this synergistic effect, the two exists very close
Synergistic effect, while adjoint tunneling effect, and the metal oxide semiconductor nanostructure and substrate, semi-conductive metal oxide
It is Ohmic contact between object nanostructure and conducting polymer.
Description of the drawings
Fig. 1 is the surface shape of growth in situ metal oxide semiconductor nanostructure obtained through the embodiment of the present invention
The stereoscan photograph of looks；
Fig. 2 is that the scanning electron microscope of the surface topography of gas sensor functional layer obtained through the embodiment of the present invention is shone
Piece；
Fig. 3 is the high strength ammonia gas dynamic response curve of the sensor prepared using the embodiment of the present invention；
Fig. 4 is response test result figure of the sensor for low concentration ammonia of preparation of the embodiment of the present invention；
Fig. 5 is round robin test result figure of the embodiment of the present invention to 5ppm ammonias.
Specific implementation mode
Further illustrate that method part of the invention is by electrostatic spinning and hydro-thermal process below in conjunction with drawings and examples
Two steps collectively constitute, and the electrostatic spinning spinning solution is that spinning-aid agent and metal oxide precursor collectively constitute.Described
Electrostatic spinning technique enables to metal oxide semiconductor presoma to be deposited on substrate surface in the form of nanofiber, water
Heat treatment technics can make metal oxide semiconductor presoma change under the action of pressure and temperature, in substrate table
Face growth in situ goes out metal oxide semiconductor nanostructure.Two steps one in front and one in back, complement each other, indispensable.It is in situ
The metal oxide semiconductor nanostructure grown contacts well with substrate, and Ohmic contact property is presented, especially suitable for system
Standby gas sensor, especially flexible gas sensor.
Embodiment 1
The production method of the method for the present invention, includes the following steps：
1. preparing the mixed solution of stannous chloride and polyvinyl butyral, i.e. spinning solution, the concentration of the stannous chloride
For 85 mg/mL, a concentration of 40 mg/mL of polyvinyl butyral；Wherein stannous chloride, which can be any one, can be dissolved in spinning
Liquid solvent, and have with spinning-aid agent the metal salt of excellent compatibility, including but not limited to stannous chloride, butter of tin, four fourth of metatitanic acid
Ester, tetra isopropyl titanium, zinc chloride, zinc acetate, ferric trichloride, ferric nitrate；Polyvinyl butyral can be any one or
A variety of oil-soluble polymers, including but not limited to polyvinyl butyral, Kynoar, polyvinyl chloride；
2. by step 1. in electrostatic spinning liquid flow velocity be 0.2mL/h；It is 15cm to receive distance；Spinning voltage is 8
kV；It is deposited in ceramic bases in the form of nanofiber under the electrospinning conditions that receiving time is 3 min；Wherein ceramic base
Bottom can be flexible material or rigid material, including but not limited to polyethylene terephthalate, polytetrafluoroethylene (PTFE), poly- third
Alkene, Kynoar, glass, ceramics, silicon chip, ito glass；
3. by step 2. in it is obtained deposition there is the substrate of nanofiber to dry after at 135 DEG C 8 h of hydro-thermal process, obtain
There is the substrate of metal oxide semiconductor nanostructure to growth in situ, method is made；
4. by step, 3. the obtained substrate in-situ polymerization with the metal oxide semiconductor nanostructure is grown
Go out polypyrrole, gas sensor is made.
Using it is described 1.~4. the step of can form a film on a ceramic substrate, be made in this way as the biography of functional layer
Sensor；The sensor surface figure is as shown in Figure 1, obtained metal oxide semiconductor nanostructured surface pattern such as Fig. 2
Shown, metal oxide semiconductor nanostructure is evenly distributed, and size is uniform, and obtained sensor has excellent air-sensitive special
Property, response diagram to high concentration range (5-200 ppm) is as shown in figure 3, response diagram to low concentration (1-10 ppm) ammonia
As shown in Figure 4, it can be seen that the ammonia concentration information in the method energy Sensitive Detection environment utilizes under 10 ppm concentration
FormulaSensitivity S=75% (note can be calculated：R1To be passed through the resistance value after ammonia, R0Before being passed through ammonia
Resistance value).In addition, the response cycle figure of the method is as shown in Figure 5, it can be seen that its is with good stability and replys
Property.
Embodiment 2
1. the mixed solution of zinc acetate and polyvinyl butyral, i.e. spinning solution are prepared, a concentration of the 10 of the zinc acetate
Mg/mL, a concentration of 100 mg/mL of polyvinyl butyral；
2. step 1. in electrostatic spinning liquid flow velocity be 0.1mL/h；It is 5cm to receive distance；Spinning voltage is 5kV；It connects
PET substrate is deposited in the form of nanofiber under the electrospinning conditions between time receiving being 30 min
On；
3. by step 2. in it is obtained deposition there is the substrate of nanofiber to dry after at 180 DEG C 24 h of hydro-thermal process,
Obtaining growth in situ has the substrate of metal oxide semiconductor nanostructure, and method is made；
4. by step, 3. the obtained substrate in-situ polymerization with the metal oxide semiconductor nanostructure is grown
Go out polypyrrole, gas sensor is made.
Resistance of obtained method under the conditions of low concentration (≤10 ppm) is relatively low, less than 170 kilo-ohms, to ammonia have compared with
Good response, under 10 ppm concentration, sensitivity reaches 62%.
Embodiment 3
1. preparing the mixed solution of stannic chloride and polyvinyl chloride, i.e. spinning solution, a concentration of 300 mg/ of the stannic chloride
ML, a concentration of 40 mg/mL of polyvinyl chloride；
2. by step 1. in electrostatic spinning liquid flow velocity be 1 mL/h；It is 30 cm to receive distance；Spinning voltage is 30
kV；It is deposited in the form of nanofiber in polytetrafluoroethylene (PTFE) substrate under the electrospinning conditions that receiving time is 0.5 min；
3. by step 2. in it is obtained deposition there is the substrate of nanofiber to dry after at 120 DEG C 6 h of hydro-thermal process, obtain
There is the substrate of metal oxide semiconductor nanostructure to growth in situ, method is made；
4. by step, 3. the obtained substrate in-situ polymerization with the metal oxide semiconductor nanostructure is grown
Go out polypyrrole, gas sensor is made.
Impedance of obtained method under the conditions of low concentration (≤10 ppm) is relatively low, less than 200 kilo-ohms, to ammonia have compared with
Good response, under 10 ppm concentration, sensitivity reaches 73%.
Embodiment 4
1. prepare the mixed solution of butyl titanate and polyvinyl chloride, i.e. spinning solution, the butyl titanate it is a concentration of
300 mg/mL, a concentration of 40 mg/mL of polyvinyl chloride；
2. by step 1. in electrostatic spinning liquid flow velocity be 1mL/h；It is 30cm to receive distance；Spinning voltage is 30 kV；
It is deposited in polypropylene substrate in the form of nanofiber under the electrospinning conditions that receiving time is 0.5 min；
3. by step 2. in it is obtained deposition there is the substrate of nanofiber to dry after at 180 DEG C hydro-thermal process 6h, obtain
There is the substrate of metal oxide semiconductor nanostructure to growth in situ, method is made；
4. by step, 3. the obtained substrate in-situ polymerization with the metal oxide semiconductor nanostructure is grown
Go out polypyrrole, gas sensor is made.
Impedance of obtained method under the conditions of low concentration (≤10 ppm) is relatively low, less than 100 kilo-ohms, to ammonia have compared with
Good response, under 10 ppm concentration, sensitivity reaches 93%.
Embodiment 5
1. prepare the mixed solution of tetra isopropyl titanium and polyvinyl chloride, i.e. spinning solution, the tetra isopropyl titanium it is a concentration of
300 mg/mL, a concentration of 40 mg/mL of polyvinyl chloride；
2. by step 1. in electrostatic spinning liquid flow velocity be 1mL/h；It is 30cm to receive distance；Spinning voltage is 30 kV；
It is deposited in the form of nanofiber in Kynoar substrate under the electrospinning conditions that receiving time is 0.5 min；
3. by step 2. in it is obtained deposition there is the substrate of nanofiber to dry after at 120 DEG C hydro-thermal process for 24 hours, obtain
There is the substrate of metal oxide semiconductor nanostructure to growth in situ, method is made；
4. by step, 3. the obtained substrate in-situ polymerization with the metal oxide semiconductor nanostructure is grown
Go out polypyrrole, gas sensor is made.
Impedance of obtained method under the conditions of low concentration (≤10 ppm) is relatively low, less than 150 kilo-ohms, to ammonia have compared with
Good response, under 10 ppm concentration, sensitivity reaches 65%.
Embodiment 6
1. the mixed solution of zinc chloride and vinylidene, i.e. spinning solution are prepared, a concentration of 85mg/mL of the zinc chloride,
Poly- a concentration of 40 mg/mL of Kynoar；
2. step 1. in electrostatic spinning liquid flow velocity be 0.2mL/h；It is 15cm to receive distance；Spinning voltage is 8 kV；
It is deposited in substrate of glass in the form of nanofiber under the electrospinning conditions that receiving time is 3 min；
3. step 2. in it is obtained deposition there is the substrate of nanofiber to dry after at 135 DEG C hydro-thermal process 8h, obtain
Growth in situ has the substrate of metal oxide semiconductor nanostructure, and method is made；
4. by step, 3. the obtained substrate in-situ polymerization with the metal oxide semiconductor nanostructure is grown
Go out polypyrrole, gas sensor is made.
Impedance of obtained method under the conditions of low concentration (≤10 ppm) is relatively low, less than 200 kilo-ohms, to ammonia have compared with
Good response, under 10 ppm concentration, sensitivity reaches 74%.
Embodiment 7
1. preparing the mixed solution of ferric trichloride and polyvinyl butyral, i.e. spinning solution, the concentration of the ferric trichloride
For 85 mg/mL, a concentration of 40 mg/mL of polyvinyl butyral；
2. step 1. in electrostatic spinning liquid flow velocity be 0.2mL/h；It is 15cm to receive distance；Spinning voltage is 8 kV；
It is deposited in the form of nanofiber in silicon chip substrate under the electrospinning conditions that receiving time is 3 min；
3. by step 2. in it is obtained deposition there is the substrate of nanofiber to dry after at 135 DEG C hydro-thermal process 8h, obtain
There is the substrate of metal oxide semiconductor nanostructure to growth in situ, method is made；
4. by step, 3. the obtained substrate in-situ polymerization with the metal oxide semiconductor nanostructure is grown
Go out polypyrrole, gas sensor is made.
Impedance of obtained method under the conditions of low concentration (≤10 ppm) is relatively low, less than 100 kilo-ohms, to ammonia have compared with
Good response, under 10 ppm concentration, sensitivity reaches 51%.
Embodiment 8
1. the mixed solution of ferric nitrate and polyvinyl butyral, i.e. spinning solution are prepared, a concentration of the 85 of the ferric nitrate
Mg/mL, a concentration of 40 mg/mL of polyvinyl butyral；
2. step 1. in electrostatic spinning liquid flow velocity be 0.2mL/h；It is 15cm to receive distance；Spinning voltage is 8 kV；
It is deposited in the form of nanofiber in ito glass substrate under the electrospinning conditions that receiving time is 3 min；
3. by step 2. in it is obtained deposition there is the substrate of nanofiber to dry after at 135 DEG C hydro-thermal process 8h, obtain
There is the substrate of metal oxide semiconductor nanostructure to growth in situ, method is made；
4. by step, 3. the obtained substrate in-situ polymerization with the metal oxide semiconductor nanostructure is grown
Go out polypyrrole, gas sensor is made.
Impedance of obtained method under the conditions of low concentration (≤10 ppm) is relatively low, less than 10 kilo-ohms, to ammonia have compared with
Good response, under 10 ppm concentration, sensitivity reaches 72%.
Above example is only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it should also be understood that, reading
After the content of the invention lectured, those skilled in the art can make various modifications or changes to the present invention, these shapes of equal value
Formula is also fallen within the scope of the appended claims of the present application.
Claims (8)
1. a kind of method of low-temperature original position growth nanostructure metal oxide semiconductor, it is characterised in that：Including electrostatic spinning
With two steps of hydro-thermal process, the Nanowire containing conductor oxidate presoma is deposited in substrate using method of electrostatic spinning
Dimension, then by hydro-thermal process, under the action of pressure and temperature, is translated into the nanostructure of the growth in situ in substrate
Metal oxide semiconductor；
Specifically comprise the following steps：
1) it prepares metal oxide semiconductor presoma and the mixed solution of spinning-aid agent obtains spinning solution, spinning solution is passed through quiet
After the method for Electrospun forms nanofibres deposit to substrate surface, naturally dry；
2) deposition obtained in the step 1) has the substrate of nanofiber by hydro-thermal process, obtains in situ in substrate
The metal oxide semiconductor with nanostructure of growth；
Step 2）Described in hydro-thermal process temperature be 120 ~ 180 DEG C；Hydrothermal conditions are 6 ~ 24 h.
2. according to the method described in claim 1, it is characterized in that：The substrate be flexible material or rigid material, including
But it is not limited to polyethylene terephthalate, polytetrafluoroethylene (PTFE), polypropylene, Kynoar, glass, ceramics, silicon chip, ITO
Glass.
3. according to the method described in claim 1, it is characterized in that：Spinning-aid agent used in the spinning solution of the electrostatic spinning is that oil is molten
Property polymer, including it is selected from one or more of：Polyvinyl butyral, Kynoar, polyvinyl chloride.
4. according to the method described in claim 1, it is characterized in that：The conductor oxidate presoma is by metal salt, described
Spinning-aid agent and solvent used in electrostatic spinning are uniformly mixed to get, and the metal salt includes but not limited to stannous chloride, tetrachloro
Change tin, butyl titanate, tetra isopropyl titanium, zinc chloride, zinc acetate, ferric trichloride, ferric nitrate.
5. according to the method described in claim 1, it is characterized in that：Step 1）Described in metal oxide semiconductor presoma it is dense
Degree is 10 ~ 300 mg/mL, a concentration of 40 ~ 100 mg/mL of spinning-aid agent, flow velocity preferably 0.1 ~ 1 mL/ of the electrostatic spinning
h；It is preferably 5 ~ 30 cm to receive distance；Spinning voltage is preferably 5 ~ 30 kV；Receiving time is preferably 0.5 ~ 30 min.
6. the nanostructure semiconductor of growth in situ in a kind of substrate obtained according to claim 1-5 any one of them methods
Metal oxide.
7. a kind of gas sensor prepared by nanostructure metal oxide semiconductor according to claim 6.
8. gas sensor according to claim 7, it is characterised in that：The gas sensor senses for flexible gas
Device.
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