CN104807859A - Low-temperature in-situ growing method of semiconducting metal oxide with nano-structure as well as application - Google Patents
Low-temperature in-situ growing method of semiconducting metal oxide with nano-structure as well as application Download PDFInfo
- Publication number
- CN104807859A CN104807859A CN201510112493.2A CN201510112493A CN104807859A CN 104807859 A CN104807859 A CN 104807859A CN 201510112493 A CN201510112493 A CN 201510112493A CN 104807859 A CN104807859 A CN 104807859A
- Authority
- CN
- China
- Prior art keywords
- metal oxide
- substrate
- oxide semiconductor
- spinning
- situ
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a low-temperature in-situ growing method of a semiconducting metal oxide with a nano-structure as well as an application. According to the method, polymeric nanofibers containing an inorganic salt solution are deposited on a substrate with an electrospinning method, and then are subjected to hydro-thermal treatment, so that inorganic salt contained in the polymeric nanofibers is converted into the semiconducting metal oxide with the nano-structure in situ, and the semiconducting metal oxide is tightly combined with the substrate. The method has the advantages as follows: equipment is simple, steps are simple and convenient, the energy consumption is low, high-temperature thermal treatment is not required, a semiconducting metal oxide nano material is obtained on different substrates in situ at the relatively low temperature lower than 180 DEG C and the like; the method can be used for preparation of a flexible semiconducting metal oxide device with polymer as the substrate, further realizes good composition of the semiconducting metal oxide nano material and organic polymer conveniently, can be used for preparation of organic/semiconducting metal oxide nanocomposite materials and devices, and has a good application prospect in the field of nano photoelectric devices.
Description
Technical field
The present invention relates to field of nanometer material technology, be specifically related to one thermal treatment at low temperatures, realize the method for growth in situ nanostructured inorganic semiconductor metal oxide on different substrates.
Background technology
Metal oxide semiconductor has great scientific research value and actual techniques using value.Comparatively conventional has SnO
2, ZnO, TiO
2, Fe
2o
3deng.These metal oxide semiconductors mostly are has the wide N-shaped multifunctional semiconductor that can be with; there is (the L.b. Luo such as very excellent electrical properties, photocatalysis property, electrochemical properties, optical and electrical properties, gas sensing, humidity sensor, optical property; 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 the character of these excellences, researchers expand the research in every field application to described metal oxide semiconductor, such as solar cell, ultracapacitor, optoelectronic device, transistor, lithium ion battery, humidity sensor and gas sensor etc.
Nano structural material has special nano effect, makes it have a lot of unique performance and advantage relative to the bulk material of routine.Such as, nano structural material is when sensor field is applied, because it has the much bigger specific surface area of bulk material, when sensor field is applied, more reactivity site can be provided, contribute to the sensitivity improving response, also can be conducive to the diffusion of detection molecules simultaneously, thus add fast-response and improve response reversibility.And nanostructured formation also can promote Charger transfer, promote that sensitivity improves.The metal oxide semiconductor of preparation nanostructured also becomes widens its application, improves the effective means of its performance.
The preparation method of the metal oxide semiconductor nano material of current existence mainly contains thermal evaporation techniques, calcining, sol-gel process, electrochemical synthesis, atomic layer deposition method, chemical vapour deposition etc., these methods are toward needing more special technology, large-scale instrument, pyroprocessing (~ 500 DEG C, prosperous see the summer, Niu Xiao, Zhou Huimin. the UV absorber of porous SnO2 nanofiber, textile journal, 2014,35 (7): 13-17.) etc., cost is higher and energy resource consumption is larger.In addition, after the metal oxide semiconductor nano material of preparation so often needs again to disperse, then be deposited on could for the preparation of electron device in substrate.Therefore, metal oxide semiconductor nano material is prepared intermediate demand to device and is carried out transfer step, like this, adds operation prepared by device, and if in preparation process nano material dispersed and deposition control bad, also can affect the consistance of device.In addition, often exist between nano material and substrate in conjunction with imperfect problem through the device that again prepared by dispersed deposition, make it there is larger contact impedance and affect charge transfer process like this, the performance of the photoelectric functional device to preparation is caused adverse effect.（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 needs pyroprocessing usually, and flexible organic and polymer material substrate often cannot withstand high temperatures, which has limited the use of flexible polymer substrate, bring difficulty to the development and application of flexible photoelectric device.
Summary of the invention
For the deficiencies in the prior art, the invention provides method and the application of low-temperature original position growth nanostructured metal oxide semiconductor.
The present invention adopts following technical scheme:
A kind of method of Low Temperature Heat Treatment growth in situ nanostructured metal oxide semiconductor, comprise electrostatic spinning and hydrothermal treatment consists two steps, adopt method of electrostatic spinning in substrate, deposit the nanofiber containing metal oxide semiconductor presoma, then by hydrothermal treatment consists, the nanostructured metal oxide semiconductor of growth in situ in substrate is translated into.
Described substrate is flexible material or rigid material, includes but not limited to polyethylene terephthalate, teflon, polypropylene, Kynoar, glass, pottery, silicon chip, ito glass.
The spinning liquid spinning-aid agent used of described electrostatic spinning is oil-soluble polymers, comprise be selected from following one or more: polyvinyl butyral, Kynoar, Polyvinylchloride.
Described metal oxide semiconductor presoma is obtained by slaine, described electrostatic spinning spinning-aid agent used and solvent Homogeneous phase mixing, and described slaine includes but not limited to stannous chloride, butter of tin, butyl titanate, tetra isopropyl titanium, zinc chloride, zinc acetate, ferric trichloride, ferric nitrate.
Specifically comprise the steps:
1) mixed solution preparing metal oxide semiconductor presoma and spinning-aid agent obtains spinning liquid, after spinning liquid is formed nanofibres deposit to substrate surface by the method for electrostatic spinning, naturally dries;
2) described step 1) in the obtained substrate depositing nanofiber by hydrothermal treatment consists, obtain the metal oxide semiconductor with nanostructured of growth in situ in substrate.
The precursor concentration of metal oxide semiconductor described in step 1) is 10 ~ 300 mg/mL, and described spinning-aid agent concentration is 40 ~ 100 mg/mL, flow velocity preferably 0.1 ~ 1 mL/h of described electrostatic spinning; Receiving range is preferably 5 ~ 30 cm; Spinning voltage is preferably 5 ~ 30 kV; Time of reception is preferably 0.5 ~ 30 min.
Step 2) described in hydrothermal treatment consists temperature be preferably 120 ~ 180 DEG C; Hydrothermal conditions is preferably 6 ~ 24 h.
The nanostructured metal oxide semiconductor of growth in situ in the substrate that described method obtains.
Described nanostructured metal oxide semiconductor is for the preparation of gas sensor.
Described sensor is flexible gas sensor.
The invention has the beneficial effects as follows:
1. the invention provides that a kind of equipment is simple, step is convenient, energy consumption is low, at any substrate semiconductor-on-insulator metal oxide growth in situ, especially growth in situ on a flexible substrate, be convenient to the growing method of the metal oxide semiconductor nanostructured preparing the advantages such as flexible device, greatly widen described metal oxide semiconductor application, become a kind of necessary means of described metal oxide semiconductor in the preparation nanostructured of each application.
2. preparation method of the present invention is low-temperature epitaxy (120-180 DEG C), it is good that the method has controllability, reaction conditions is gentle, described metal oxide semiconductor nanostructure growth is even, energy-output ratio is less, can reduce the plurality of advantages such as environmental pollution, especially, cryogenic conditions is especially applicable to the direct simple preparation of flexible device.
3. preparation method of the present invention is growth in situ, the original position preparation on different substrates of nanostructured metal oxide semiconductor material can be realized, then preparation section can be reduced, photoelectric functional device needed for direct acquisition, and the growth in situ of nano material is also conducive to the combination promoting material and substrate, reduce contact impedance, promote Charger transfer, improve stability etc.Thus promote the application of nanostructured metal oxide semiconductor in function element.Described metal oxide semiconductor nanostructured and substrate, between metal oxide semiconductor nanostructured and conducting polymer, be Ohmic contact, effectively can improve the sensitivity of prepared sensor, repeatability and stability.
4. the present invention adopts method of electrostatic spinning, directly in substrate, in-situ deposition contains the nanofiber of slaine, subsequently by the hydrothermal treatment consists of lower temperature (lower than 180 DEG C), slaine converted in-situ contained in nanofiber is made to be nanostructured metal oxides.Thus, achieve nanostructured metal oxides direct low-temperature original position growth at substrate surface in water-heat process, and significantly enhance the binding ability of itself and substrate.
5. the present invention prepared the metal oxide semiconductor nanostructured that comprises the method with conducting polymer compound after there is the gas sensor of the advantages such as very superior gas sensitization performance (highly sensitive, recovery good).
6. the metal oxide semiconductor nanostructured prepared by the present invention and the I-V curve of conducting polymer, cyclic voltammetry curve show to there is strong interaction between described metal oxide semiconductor nanostructured and conducting polymer, this synergy can be utilized to improve electric conductivity at room temperature and the charge migration under promoting room temperature, there is very close synergy in the two, simultaneously with tunneling effect, and described metal oxide semiconductor nanostructured and substrate, between metal oxide semiconductor nanostructured and conducting polymer, be Ohmic contact.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the surface topography by the growth in situ metal oxide semiconductor nanostructured obtained by the embodiment of the present invention;
Fig. 2 is the stereoscan photograph of the surface topography by the gas sensor functional layer obtained by the embodiment of the present invention;
Fig. 3 is the high strength ammonia gas dynamic response curve of the sensor adopting the embodiment of the present invention to prepare;
Fig. 4 is the response test result figure of the sensor prepared of the embodiment of the present invention for low concentration ammonia;
Fig. 5 is the round robin test result figure of the embodiment of the present invention to 5 ppm ammonias.
Embodiment
Further illustrate below in conjunction with drawings and Examples, method part of the present invention is made up of jointly electrostatic spinning and hydrothermal treatment consists two steps, and described electrostatic spinning spinning liquid is that spinning-aid agent and metal oxide precursor form jointly.Described electrostatic spinning technique can make metal oxide semiconductor presoma deposit on substrate surface with the form of nanofiber, hydrothermal technology can make metal oxide semiconductor presoma change under the effect of pressure and temperature, goes out metal oxide semiconductor nanostructured at substrate surface growth in situ.Two steps one in front and one in back, complement each other, indispensable.The metal oxide semiconductor nanostructured that growth in situ goes out and substrate contact well, present Ohmic contact character, are particularly useful for making gas sensor, especially flexible air dependent sensor.
embodiment 1
The method for making of method of the present invention, comprises the following steps:
1. prepare the mixed solution of stannous chloride and polyvinyl butyral, i.e. spinning liquid, the concentration of described stannous chloride is 85 mg/mL, and polyvinyl butyral concentration is 40 mg/mL; Wherein stannous chloride can be that any one can be dissolved in spinning liquid solvent, and have the slaine of excellent compatibility with spinning-aid agent, include but not limited to stannous chloride, butter of tin, butyl titanate, tetra isopropyl titanium, zinc chloride, zinc acetate, ferric trichloride, ferric nitrate; Polyvinyl butyral can be any one or multiple oil-soluble polymers, includes but not limited to polyvinyl butyral, Kynoar, Polyvinylchloride;
2. by step 1. in electrostatic spinning liquid be 0.2 mL/h at flow velocity; Receiving range is 15 cm; Spinning voltage is 8 kV; Time of reception is deposit in ceramic bases with the form of nanofiber under the electrospinning conditions of 3 min; Wherein ceramic bases can be flexible material or rigid material, includes but not limited to polyethylene terephthalate, teflon, polypropylene, Kynoar, glass, pottery, silicon chip, ito glass;
3. by step 2. in the substrate depositing nanofiber that obtains dry after at 135 DEG C hydrothermal treatment consists 8 h, obtain the substrate that growth in situ has metal oxide semiconductor nanostructured, obtained method;
4. the substrate in-situ polymerization of described metal oxide semiconductor nanostructured there is is to grow polypyrrole the length that step is 3. obtained, obtained gas sensor.
1. ~ step 4. described in employing can film forming on a ceramic substrate, obtained in this way as the sensor of functional layer; Described sensor surface figure as shown in Figure 1, obtained metal oxide semiconductor nanostructured surface pattern as shown in Figure 2, metal oxide semiconductor nanostructured is evenly distributed, size is homogeneous, obtained sensor has excellent gas-sensitive property, it to the response diagram of high concentration range (5-200 ppm) as shown in Figure 3, to the response diagram of low concentration (1-10 ppm) ammonia as shown in Figure 4, the ammonia concentration information in described method energy Sensitive Detection environment can be found out, under 10 ppm concentration, utilize formula
sensitivity S=75% (note: R can be calculated
1for passing into the resistance value after ammonia, R
0for passing into the resistance value before ammonia).In addition, the response cycle figure of described method as shown in Figure 5, can find out that it has good stability and recovery.
embodiment 2
1. prepare the mixed solution of zinc acetate and polyvinyl butyral, i.e. spinning liquid, described acetic acid zinc concentration is 10 mg/mL, and polyvinyl butyral concentration is 100 mg/mL;
2. step 1. in electrostatic spinning liquid be 0.1 mL/h at flow velocity; Receiving range is 5 cm; Spinning voltage is 5 kV; Time of reception is deposit on PET substrate with the form of nanofiber under the electrospinning conditions of 30 min;
3. by step 2. in the substrate depositing nanofiber that obtains dry after at 180 DEG C hydrothermal treatment consists 24 h, obtain the substrate that growth in situ has metal oxide semiconductor nanostructured, obtained method;
4. the substrate in-situ polymerization of described metal oxide semiconductor nanostructured there is is to grow polypyrrole the length that step is 3. obtained, obtained gas sensor.
The resistance of the method obtained under low concentration (≤10 ppm) condition is lower, less than 170 kilo-ohms, has good response to ammonia, and under 10 ppm concentration, its sensitivity reaches 62%.
embodiment 3
1. prepare the mixed solution of tin chloride and Polyvinylchloride, i.e. spinning liquid, the concentration of described tin chloride is 300 mg/mL, and Polyvinylchloride concentration is 40 mg/mL;
2. by step 1. in electrostatic spinning liquid be 1 mL/h at flow velocity; Receiving range is 30 cm; Spinning voltage is 30 kV; Time of reception is deposit in teflon substrate with the form of nanofiber under the electrospinning conditions of 0.5 min;
3. by step 2. in the substrate depositing nanofiber that obtains dry after at 120 DEG C hydrothermal treatment consists 6 h, obtain the substrate that growth in situ has metal oxide semiconductor nanostructured, obtained method;
4. the substrate in-situ polymerization of described metal oxide semiconductor nanostructured there is is to grow polypyrrole the length that step is 3. obtained, obtained gas sensor.
The impedance of the method obtained under low concentration (≤10 ppm) condition is lower, less than 200 kilo-ohms, has good response to ammonia, and under 10 ppm concentration, its sensitivity reaches 73%.
embodiment 4
1. prepare the mixed solution of butyl titanate and Polyvinylchloride, i.e. spinning liquid, the concentration of described butyl titanate is 300 mg/mL, and Polyvinylchloride concentration is 40 mg/mL;
2. by step 1. in electrostatic spinning liquid be 1 mL/h at flow velocity; Receiving range is 30 cm; Spinning voltage is 30 kV; Time of reception is deposit in polypropylene substrate with the form of nanofiber under the electrospinning conditions of 0.5 min;
3. by step 2. in the substrate depositing nanofiber that obtains dry after at 180 DEG C hydrothermal treatment consists 6 h, obtain the substrate that growth in situ has metal oxide semiconductor nanostructured, obtained method;
4. the substrate in-situ polymerization of described metal oxide semiconductor nanostructured there is is to grow polypyrrole the length that step is 3. obtained, obtained gas sensor.
The impedance of the method obtained under low concentration (≤10 ppm) condition is lower, less than 100 kilo-ohms, has good response to ammonia, and under 10 ppm concentration, its sensitivity reaches 93%.
embodiment 5
1. prepare the mixed solution of tetra isopropyl titanium and Polyvinylchloride, i.e. spinning liquid, the concentration of described tetra isopropyl titanium is 300 mg/mL, and Polyvinylchloride concentration is 40 mg/mL;
2. by step 1. in electrostatic spinning liquid be 1 mL/h at flow velocity; Receiving range is 30 cm; Spinning voltage is 30 kV; Time of reception is deposit in Kynoar substrate with the form of nanofiber under the electrospinning conditions of 0.5 min;
3. by step 2. in the substrate depositing nanofiber that obtains dry after at 120 DEG C hydrothermal treatment consists 24 h, obtain the substrate that growth in situ has metal oxide semiconductor nanostructured, obtained method;
4. the substrate in-situ polymerization of described metal oxide semiconductor nanostructured there is is to grow polypyrrole the length that step is 3. obtained, obtained gas sensor.
The impedance of the method obtained under low concentration (≤10 ppm) condition is lower, less than 150 kilo-ohms, has good response to ammonia, and under 10 ppm concentration, its sensitivity reaches 65%.
embodiment 6
1. prepare the mixed solution of zinc chloride and vinylidene, i.e. spinning liquid, described chlorination zinc concentration is 85 mg/mL, and poly-Kynoar concentration is 40 mg/mL;
2. step 1. in electrostatic spinning liquid be 0.2 mL/h at flow velocity; Receiving range is 15 cm; Spinning voltage is 8 kV; Time of reception is deposit in substrate of glass with the form of nanofiber under the electrospinning conditions of 3 min;
3. step 2. in the substrate depositing nanofiber that obtains dry after at 135 DEG C hydrothermal treatment consists 8 h, obtain the substrate that growth in situ has metal oxide semiconductor nanostructured, obtained method;
4. the substrate in-situ polymerization of described metal oxide semiconductor nanostructured there is is to grow polypyrrole the length that step is 3. obtained, obtained gas sensor.
The impedance of the method obtained under low concentration (≤10 ppm) condition is lower, less than 200 kilo-ohms, has good response to ammonia, and under 10 ppm concentration, its sensitivity reaches 74%.
embodiment 7
1. prepare the mixed solution of ferric trichloride and polyvinyl butyral, i.e. spinning liquid, the concentration of described ferric trichloride is 85 mg/mL, and polyvinyl butyral concentration is 40 mg/mL;
2. step 1. in electrostatic spinning liquid be 0.2 mL/h at flow velocity; Receiving range is 15 cm; Spinning voltage is 8 kV; Time of reception is deposit at the bottom of silicon wafer-based with the form of nanofiber under the electrospinning conditions of 3 min;
3. by step 2. in the substrate depositing nanofiber that obtains dry after at 135 DEG C hydrothermal treatment consists 8 h, obtain the substrate that growth in situ has metal oxide semiconductor nanostructured, obtained method;
4. the substrate in-situ polymerization of described metal oxide semiconductor nanostructured there is is to grow polypyrrole the length that step is 3. obtained, obtained gas sensor.
The impedance of the method obtained under low concentration (≤10 ppm) condition is lower, less than 100 kilo-ohms, has good response to ammonia, and under 10 ppm concentration, its sensitivity reaches 51%.
embodiment 8
1. prepare the mixed solution of ferric nitrate and polyvinyl butyral, i.e. spinning liquid, the concentration of described ferric nitrate is 85 mg/mL, and polyvinyl butyral concentration is 40 mg/mL;
2. step 1. in electrostatic spinning liquid be 0.2 mL/h at flow velocity; Receiving range is 15 cm; Spinning voltage is 8 kV; Time of reception is deposit in ito glass substrate with the form of nanofiber under the electrospinning conditions of 3 min;
3. by step 2. in the substrate depositing nanofiber that obtains dry after at 135 DEG C hydrothermal treatment consists 8 h, obtain the substrate that growth in situ has metal oxide semiconductor nanostructured, obtained method;
4. the substrate in-situ polymerization of described metal oxide semiconductor nanostructured there is is to grow polypyrrole the length that step is 3. obtained, obtained gas sensor.
The impedance of the method obtained under low concentration (≤10 ppm) condition is lower, less than 10 kilo-ohms, has good response to ammonia, and under 10 ppm concentration, its sensitivity reaches 72%.
Above embodiment is only not used in for illustration of the present invention and limits the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Claims (10)
1. the method for a low-temperature original position growth nanostructured metal oxide semiconductor, it is characterized in that: comprise electrostatic spinning and hydrothermal treatment consists two steps, adopt method of electrostatic spinning in substrate, deposit the nanofiber containing conductor oxidate presoma, then by hydrothermal treatment consists, the nanostructured metal oxide semiconductor of growth in situ in substrate is translated into.
2. method according to claim 1, it is characterized in that: described substrate is flexible material or rigid material, include but not limited to polyethylene terephthalate, teflon, polypropylene, Kynoar, glass, pottery, silicon chip, ito glass.
3. method according to claim 1, is characterized in that: the spinning liquid spinning-aid agent used of described electrostatic spinning is oil-soluble polymers, comprise be selected from following one or more: polyvinyl butyral, Kynoar, Polyvinylchloride.
4. method according to claim 1, it is characterized in that: described conductor oxidate presoma is obtained by slaine, described electrostatic spinning spinning-aid agent used and solvent Homogeneous phase mixing, and described slaine includes but not limited to stannous chloride, butter of tin, butyl titanate, tetra isopropyl titanium, zinc chloride, zinc acetate, ferric trichloride, ferric nitrate.
5. method according to claim 1, is characterized in that: specifically comprise the steps:
1) mixed solution preparing metal oxide semiconductor presoma and spinning-aid agent obtains spinning liquid, after spinning liquid is formed nanofibres deposit to substrate surface by the method for electrostatic spinning, naturally dries;
2) described step 1) in the obtained substrate depositing nanofiber by hydrothermal treatment consists, obtain the metal oxide semiconductor with nanostructured of growth in situ in substrate.
6. method according to claim 5, is characterized in that: the precursor concentration of metal oxide semiconductor described in step 1) is 10 ~ 300 mg/mL, and described spinning-aid agent concentration is 40 ~ 100 mg/mL, flow velocity preferably 0.1 ~ 1 mL/h of described electrostatic spinning; Receiving range is preferably 5 ~ 30 cm; Spinning voltage is preferably 5 ~ 30 kV; Time of reception is preferably 0.5 ~ 30 min.
7. method according to claim 5, is characterized in that: step 2) described in hydrothermal treatment consists temperature be preferably 120 ~ 180 DEG C; Hydrothermal conditions is preferably 6 ~ 24 h.
8. the nanostructured metal oxide semiconductor of growth in situ in the substrate that obtains of the method according to any one of claim 1-7.
9. a nanostructured metal oxide semiconductor according to claim 8 is for the preparation of gas sensor.
10. according to the sensor described in claim 9, it is characterized in that: described sensor is flexible gas sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510112493.2A CN104807859B (en) | 2015-03-16 | 2015-03-16 | The method of low-temperature original position growth nanostructure metal oxide semiconductor and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510112493.2A CN104807859B (en) | 2015-03-16 | 2015-03-16 | The method of low-temperature original position growth nanostructure metal oxide semiconductor and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104807859A true CN104807859A (en) | 2015-07-29 |
| CN104807859B CN104807859B (en) | 2018-08-21 |
Family
ID=53692868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510112493.2A Active CN104807859B (en) | 2015-03-16 | 2015-03-16 | The method of low-temperature original position growth nanostructure metal oxide semiconductor and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104807859B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105092658A (en) * | 2015-08-18 | 2015-11-25 | 浙江大学 | Polyaniline/zinc oxide nano composite resistor type material sensor and preparation method thereof |
| CN105136869A (en) * | 2015-08-18 | 2015-12-09 | 浙江大学 | Polyaniline/iron oxide nano composite resistance-type material sensor, and preparation method thereof |
| CN106521678A (en) * | 2016-11-01 | 2017-03-22 | 华南协同创新研究院 | Preparation method of polymer fiber-based ZnO nanowire fiber |
| CN108138367A (en) * | 2016-08-30 | 2018-06-08 | 高丽大学校产学协力团 | Nanofiber-nanowire composite and its production method |
| CN108666588A (en) * | 2018-05-10 | 2018-10-16 | 东北师范大学 | A kind of three-dimensional substrates material load Ag doping titanium dioxide optical catalyst and the preparation method and application thereof |
| CN109668911A (en) * | 2017-10-13 | 2019-04-23 | 香港理工大学 | A kind of method of in situ TEM observation nanoparticle growth |
| CN113325043A (en) * | 2021-07-19 | 2021-08-31 | 东北师范大学 | Flexible inorganic semiconductor resistance type room temperature gas sensor and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947415A (en) * | 2010-08-13 | 2011-01-19 | 东华大学 | Combination of electrostatic spinning and electrostatic spraying for preparing nanofibre base composite separation membrane |
| CN102134761A (en) * | 2010-01-23 | 2011-07-27 | 中国科学院合肥物质科学研究院 | Iron-containing polymer composite nanofiber and preparation method thereof |
| CN102557477A (en) * | 2010-12-24 | 2012-07-11 | 中国科学院兰州化学物理研究所 | Preparation method of in-situ vertically grown titanium dioxide nanosheet film |
| CN102786072A (en) * | 2012-08-16 | 2012-11-21 | 东华大学 | Method for preparing electrostatic spinning alumina hollow micro/nano tube |
| KR101493444B1 (en) * | 2014-02-24 | 2015-02-16 | 충남대학교산학협력단 | Polycaprolactone nano-fibers comprising physiological active substance and manufacturing method thereof |
-
2015
- 2015-03-16 CN CN201510112493.2A patent/CN104807859B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134761A (en) * | 2010-01-23 | 2011-07-27 | 中国科学院合肥物质科学研究院 | Iron-containing polymer composite nanofiber and preparation method thereof |
| CN101947415A (en) * | 2010-08-13 | 2011-01-19 | 东华大学 | Combination of electrostatic spinning and electrostatic spraying for preparing nanofibre base composite separation membrane |
| CN102557477A (en) * | 2010-12-24 | 2012-07-11 | 中国科学院兰州化学物理研究所 | Preparation method of in-situ vertically grown titanium dioxide nanosheet film |
| CN102786072A (en) * | 2012-08-16 | 2012-11-21 | 东华大学 | Method for preparing electrostatic spinning alumina hollow micro/nano tube |
| KR101493444B1 (en) * | 2014-02-24 | 2015-02-16 | 충남대학교산학협력단 | Polycaprolactone nano-fibers comprising physiological active substance and manufacturing method thereof |
Non-Patent Citations (4)
| Title |
|---|
| D.-Y.CHOI ET AL.: "Characterization of TiO2 fibers by combined electrospinning method and hydrothermal reaction", 《MATERIALS LETTERS》 * |
| XIAOBIN DONG ET AL.: "Fabrication of ZnO nanorod arrays via electrospinning assisted hydrothermal method", 《MATERIALS LETTERS》 * |
| 王丽芳 等: "静电纺丝制备超疏水TiO2纳米纤维网膜", 《高等学校化学学报》 * |
| 王峰等: "原位生长法制备PET/TIO2纳米杂化纤维及其光催化活性研究", 《科学通报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105092658A (en) * | 2015-08-18 | 2015-11-25 | 浙江大学 | Polyaniline/zinc oxide nano composite resistor type material sensor and preparation method thereof |
| CN105136869A (en) * | 2015-08-18 | 2015-12-09 | 浙江大学 | Polyaniline/iron oxide nano composite resistance-type material sensor, and preparation method thereof |
| CN105136869B (en) * | 2015-08-18 | 2018-04-03 | 浙江大学 | Polyaniline/ferric oxide nano composite resistance type material sensors and preparation method thereof |
| CN108138367A (en) * | 2016-08-30 | 2018-06-08 | 高丽大学校产学协力团 | Nanofiber-nanowire composite and its production method |
| CN106521678A (en) * | 2016-11-01 | 2017-03-22 | 华南协同创新研究院 | Preparation method of polymer fiber-based ZnO nanowire fiber |
| CN109668911A (en) * | 2017-10-13 | 2019-04-23 | 香港理工大学 | A kind of method of in situ TEM observation nanoparticle growth |
| CN109668911B (en) * | 2017-10-13 | 2021-09-24 | 香港理工大学 | Method for observing growth of nano particles by in-situ transmission electron microscope |
| CN108666588A (en) * | 2018-05-10 | 2018-10-16 | 东北师范大学 | A kind of three-dimensional substrates material load Ag doping titanium dioxide optical catalyst and the preparation method and application thereof |
| CN113325043A (en) * | 2021-07-19 | 2021-08-31 | 东北师范大学 | Flexible inorganic semiconductor resistance type room temperature gas sensor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104807859B (en) | 2018-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104807859A (en) | Low-temperature in-situ growing method of semiconducting metal oxide with nano-structure as well as application | |
| Patil et al. | Electrospinning: A versatile technique for making of 1D growth of nanostructured nanofibers and its applications: An experimental approach | |
| TWI274424B (en) | Electrode, photoelectric conversion element, and dye-sensitized solar cell | |
| Zhang et al. | High-power and high-energy-density flexible pseudocapacitor electrodes made from porous CuO nanobelts and single-walled carbon nanotubes | |
| Archana et al. | Structural and electrical properties of Nb‐doped anatase TiO2 nanowires by electrospinning | |
| CN108447915A (en) | A kind of thin film field effect transistor type gas sensor and preparation method thereof | |
| Du et al. | Tailoring all-inorganic cesium lead halide perovskites for robust triboelectric nanogenerators | |
| CN102412369B (en) | Organic/inorganic hybrid solar cell and preparation method thereof | |
| Xie et al. | Electrochemical capacitance performance of polyaniline/tin oxide nanorod array for supercapacitor | |
| Chen et al. | SnO2 nanoparticles/TiO2 nanofibers heterostructures: In situ fabrication and enhanced gas sensing performance | |
| CN102718408A (en) | Method for preparing gas-sensitive film | |
| Ryu et al. | Ethanedithiol-treated manganese oxide nanoparticles for rapidly responsive and transparent supercapacitors | |
| CN105651828B (en) | Based on polyaniline/stannic oxide composite nano fiber gas sensor and preparation method thereof | |
| CN105336861B (en) | A kind of organic solar batteries and preparation method thereof | |
| Zhang et al. | Polypyrrole/ZnS core/shell coaxial nanowires prepared by anodic aluminum oxide template methods | |
| CN106783201B (en) | A kind of molybdenum sulfide/ferric oxide composite material and its preparation method and application | |
| CN102175724A (en) | Composite resistance NH3 gas-sensitive gas sensor and preparation method thereof | |
| Zhu et al. | High-performance room-temperature NO2 sensors based on CH3NH3PbBr3 semiconducting films: Effect of surface capping by alkyl chain on sensor performance | |
| CN104198560A (en) | Preparation method of graphene modified porous titanium dioxide composite film | |
| Su et al. | Free-standing nitrogen-doped TiO2 nanorod arrays with enhanced capacitive capability for supercapacitors | |
| CN105810820A (en) | Porous structure organic field effect transistor photosensitive memory and preparation method thereof | |
| CN105136869B (en) | Polyaniline/ferric oxide nano composite resistance type material sensors and preparation method thereof | |
| CN108459054A (en) | A kind of preparation method of silicon nanowires-Pt/Polypyrrole composite material | |
| Das et al. | High performance BiFeO3 ferroelectric nanostructured photocathodes | |
| CN104638034B (en) | A kind of flexible thin-film solar cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |