CN103011257B - Preparation method of P-type zinc oxide micro/nano fibers - Google Patents
Preparation method of P-type zinc oxide micro/nano fibers Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of inorganic micro/nano fiber materials, and particularly relates to a preparation method of P-type zinc oxide micro/nano fibers, which comprises the steps of preparation of spinning precursor solution, electric spinning of micro/nano fibers and high-temperature sintering. The method specifically comprises the following steps: respectively preparing a polyvinylpyrrolidone ethanol solution and a lanthanum nitrate or cerium nitrate solution, and evenly mixing the two solutions to obtain a spinning precursor solution; using an aluminum foil as a collector electrode, putting a square silicon wafer with a silicon oxide insulating layer on the surface onto the aluminum foil, using the prepared precursor solution as the spinning solution, electrically spinning the micro/nano fibers by using a conventional electrostatic spinning device and method, and taking down the silicon wafer with micro/nano fibers for later use after finishing the electric spinning; and putting the silicon wafer with micro/nano fibers in a muffle furnace, and sintering at controlled temperature to obtain the P-type zinc oxide micro/nano fibers. The preparation method is easy and simple to operate, and has the advantages of reliable principle, strong practicality, high speed, high efficiency, low cost favorable product performance and environment friendliness.
Description
Technical field:
The invention belongs to inorganic micro nanometer fiber technical field of material, relate to a kind of preparation method of P type zinc oxide micron/nano fiber, doping vario-property technology based on electrostatic spinning technique and semiconductor material, realizes preparing fast and in batches of P type zinc oxide micron/nano fiber.
Background technology:
In current technology, so-called micro nanometer fiber refers to wire or the tubular material of two dimension in nanoscale on the three-dimensional space yardstick of material, normally diameter, caliber or thickness are nanoscale and the relatively large material of length, and it mainly comprises nano thread, nano wire, nanometer rod, nanotube, nano belt and nano-cable etc.; Because the diameter of nanofiber is reduced to nanometer scale, specific surface area is large, cause its surface energy and activity greatly to strengthen, thereby produce small-size effect, surface or interfacial effect, quantum size effect and macro quanta tunnel effect, made it show a series of special character at chemistry and physics (heat, optical, electrical magnetic etc.) properties.The existing method of preparing micro nanometer fiber comprises: method of electrostatic spinning (United States Patent (USP): 1-975-504,1934), method (the Euro physics Letters that reels off raw silk from cocoons, 42,215 (1998)), template (Chemistry of Materials, 8,1739 (1996)), split-phase method (Journal of Biomedical Materials Research, 46,60 (1999)) and self-assembly method (Science, 295,2418 (2002)) etc., comparatively speaking, electrostatic spinning technique can be prepared long size, even and the diversified nanofiber of composition of diameter Distribution, prepared nanofiber not only can be organism but also can be inorganics, the method has operating procedure simply and the feature such as suitability more widely, existing method of electrostatic spinning is prepared inorganic nano-fiber and is mainly divided into preparation spinning precursor solution, micro nanometer fiber spinning and high temperature sintering are removed organic composition totally three steps, according to the difference of the composition adulterating in spinning precursor solution and sintering temperature, the inorganic nano-fiber of heterogeneity and structure will be obtained.
But the zinc oxide semi-conductor characteristic of eigenstate is N-type, use the haloid elements such as aluminium, gallium, indium grade in an imperial examination III main group element or chlorine and iodine can regulate its N-type semiconductor performance; Zinc oxide to be made to P-type semiconductor and will pass through acceptor doping, available additive comprises the alkali metals such as lithium, sodium, potassium, nitrogen, phosphorus, arsenic grade in an imperial examination V main group element, and the metallic element such as copper, silver, but owing to there being more intrinsic alms giver's defect in zinc oxide, can produce height auto-compensation to acceptor doping, and acceptor impurity solid solubility is very low, being difficult to realize P type changes, cause making the core of semiconducter device---zinc oxide P-N junction structure, has therefore greatly limited the Application and Development of Zinc oxide-base photoelectric device.In current research, Chinese patent (application number: CN200610119424.5), utilizes electromagnetic field constraint jigger coupling to strengthen gas-phase deposition system, obtained the P type zinc-oxide film of nitrogen doping, but the method technology of preparing is too complicated; Application number is that the Chinese patent of CN201110160741.2 passes through magnetron sputtering, taking metallic zinc as target, taking argon gas as sputter gas, oxygen and nitrogen are the P type zinc-oxide film that reactant gases obtains nitrogen doping, after magnetron sputtering without thermal treatment, method is simple, and film quality is better, but is only applicable to the preparation of thin-film material; In Chinese patent (application number: CN200810050450.6) taking the zinc oxide of certain molar percentage and antimony mixed powder as raw material, prepare the P type zinc oxide polycrystalline material of antimony doping by hot pressing sintering method, but the method needs comparatively high temps and larger pressure, be only applicable to larger volume material preparation; Chinese patent (application number: CN200910024218.X), use plasma auxiliary laser molecular beam epitaxial device, adopt two-step approach extension to generate the P type zinc-oxide film of phosphorus doping, the P-type conduction type that has successfully realized primary film changes, but complicated process of preparation, and be all the preparation to P type Zinc oxide film material or bulk, therefore seek to design a kind of simple, fast and the preparation method of the P type zinc oxide micron/nano fiber can be mass, there is good social effect and practical value.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, seeking design provides a kind of preparation method of P type zinc oxide micron/nano fiber, to realize the successful preparation of more stable P type zinc oxide micron/nano fiber.
To achieve these goals, the preparation method who the present invention relates to comprises preparation spinning precursor solution, electrospinning micro nanometer fiber and three steps of high temperature sintering:
(1) preparation spinning precursor solution: first Environment temperature is 15 DEG C, humidity is the preparation occasion of 43%RH, with 8.5 grams of dehydrated alcohols of electronic balance weighing and 1.5 grams of polyvinylpyrrolidone (PVP, molecular weight 1,300,000), in Erlenmeyer flask, mix and blend left standstill 1 hour after 3 hours, obtain the transparent 15wt%PVP ethanolic soln of homogeneous, use again 1.0 grams of zinc acetate solids of electronic balance weighing, 2.0 grams of dehydrated alcohols, 0.2 gram of distilled water and 0.2 gram of lanthanum nitrate or 0.2 gram of cerous nitrate solid, in another Erlenmeyer flask, mix, temperature control 60-80 DEG C is carried out heated and stirred 5-10 minute, after solid in Erlenmeyer flask dissolves completely, this solution is transferred in the 15wt%PVP ethanolic soln having configured and formed mixing solutions with Dispette, then with magnetic stirring apparatus, above-mentioned mixing solutions is at room temperature stirred and within 1 hour, makes two kinds of solution fully mix, obtain spinning precursor solution,
(2) electrospinning micro nanometer fiber: do collector with the square aluminium foil that the length of side is 10 centimetres, it is the silicon chip that the square of 1-2 centimetre and surface band have insulating layer of silicon oxide that aluminium foil upper side is placed the length of side, using the precursor solution of preparing in (1) step as spinning solution, utilize conventional electrostatic spinning apparatus and method to carry out electrospinning micro nanometer fiber, the spinning voltage of its electrostatic spinning apparatus is 18-20 kilovolt, spinning is apart from 7.5-9.5 centimetre, spinning time 10-15 minute, after electrospinning, the silicon chip that is attached with micro nanometer fiber is taken off, be placed in loft drier and save backup,
(3) high temperature sintering: the silicon chip (surface band has insulating layer of silicon oxide) that is attached with micro nanometer fiber in step (2) is placed in to retort furnace, adjusting sintering temperature is 650-750 DEG C, sintering time is 4-5 hour, to be sintered complete and stove in temperature drop to after room temperature, take out silicon chip, now on silicon chip, the organic composition of micro nanometer fiber is removed, and makes the P type zinc oxide micron/nano fiber of doping lanthanum or doped with cerium.
When the made zinc oxide micron/nano fiber of the present invention carries out electrical performance testing, the zinc oxide micron/nano fiber dispersion of doping lanthanum or doped with cerium is had at surface band on the silicon chip of insulating layer of silicon oxide, again silicon chip is transferred on microprobe platform, then under opticmicroscope, operate, metal microprobe is pressed in to the two ends of micro nanometer fiber, taking silicon chip as grid (gate), the micro nanometer fiber two ends that contact with microprobe are respectively source electrode (source) and drain electrode (drain), set test parameter, electrical properties to micro nanometer fiber sample is measured, the zinc oxide micron/nano fiber field-effect curve of the single doping lanthanum recording and doped with cerium all shows that it is typical P-type semiconductor.
The present invention compared with prior art, the method that adopts electrostatic spinning and high temperature sintering to combine, realize the preparation of more stable P type zinc oxide micron/nano fiber, solve zinc oxide and in for example chemical vapour deposition of conventional preparation process, magnetron sputtering, hot pressed sintering and hydrothermal synthesis method, very easily produced more intrinsic alms giver's defect, low to acceptor doping generation height auto-compensation and acceptor impurity solid solubility, be difficult for realizing the problems such as P type transformation; Its preparation method is simple, and principle is reliable, easy and simple to handle, practical, and speed is fast, and efficiency is high, and cost is low, good product performance, environmental friendliness.
Brief description of the drawings:
Fig. 1 is technical process principle schematic of the present invention.
Fig. 2 is the scanning electron microscope sem shape appearance figure of the P type zinc oxide micron/nano fiber of the doping lanthanum that makes of the present invention.
Fig. 3 is the scanning electron microscope sem shape appearance figure of the P type zinc oxide micron/nano fiber of the doped with cerium that makes of the present invention.
Fig. 4 is the field-effect graphic representation of the P type zinc oxide micron/nano fiber of the single doping lanthanum that makes of the present invention.
Fig. 5 is the field-effect graphic representation of the P type zinc oxide micron/nano fiber of the single doped with cerium that makes of the present invention.
Embodiment:
Below in conjunction with accompanying drawing and by embodiment, the present invention is described in further detail.
Embodiment:
The present embodiment adopts the electrospinning process different acceptor impurities that can adulterate, form P type zinc oxide semi-conductor, the zinc oxide micron/nano fiber of preparation has good P-type semiconductor characteristic, and concrete steps comprise preparation spinning precursor solution, electrospinning micro nanometer fiber and three steps of high temperature sintering:
(1) preparation spinning precursor solution: first Environment temperature is 15 DEG C, humidity is the preparation occasion of 43%RH, with 8.5 grams of dehydrated alcohols of electronic balance weighing and 1.5 grams of polyvinylpyrrolidone (PVP, molecular weight 1,300,000), in Erlenmeyer flask, mix and blend left standstill 1 hour after 3 hours, obtain the transparent 15wt%PVP ethanolic soln of homogeneous, use again 1.0 grams of zinc acetate solids of electronic balance weighing, 2.0 grams of dehydrated alcohols, 0.2 gram of distilled water and 0.2 gram of lanthanum nitrate or 0.2 gram of cerous nitrate solid, in another Erlenmeyer flask, mix, temperature control 60-80 DEG C is carried out heated and stirred 5-10 minute, after solid in Erlenmeyer flask dissolves completely, this solution is transferred in the 15wt%PVP ethanolic soln having configured and formed mixing solutions with Dispette, then with magnetic stirring apparatus, above-mentioned mixing solutions is at room temperature stirred and within 1 hour, makes two kinds of solution fully mix, obtain spinning precursor solution,
(2) electrospinning micro nanometer fiber: do collector with the square aluminium foil that the length of side is 10 centimetres, it is the silicon chip that the square of 1-2 centimetre and surface band have insulating layer of silicon oxide that aluminium foil upper side is placed the length of side, using the precursor solution of preparing in (1) step as spinning solution, utilize conventional electrostatic spinning apparatus and method to carry out electrospinning micro nanometer fiber, the spinning voltage of its electrostatic spinning apparatus is 18-20 kilovolt, spinning is apart from 7.5-9.5 centimetre, spinning time 10-15 minute, after electrospinning, the silicon chip that is attached with micro nanometer fiber is taken off, be placed in loft drier and save backup,
(3) high temperature sintering: the silicon chip (surface band has insulating layer of silicon oxide) that is attached with micro nanometer fiber in step (2) is placed in to retort furnace, adjusting sintering temperature is 650-750 DEG C, sintering time is 4-5 hour, to be sintered complete and stove in temperature drop to after room temperature, take out silicon chip, now on silicon chip, the organic composition of micro nanometer fiber is removed, and makes the P type zinc oxide micron/nano fiber of doping lanthanum or doped with cerium, under scanning electron microscope as shown in Figures 2 and 3.
When the made zinc oxide micron/nano fiber of the present embodiment carries out electrical performance testing, the zinc oxide micron/nano fiber dispersion of doping lanthanum or doped with cerium is had at surface band on the silicon chip of insulating layer of silicon oxide, again silicon chip is transferred on microprobe platform, then under opticmicroscope, operate, metal microprobe is pressed in to the two ends of micro nanometer fiber, taking silicon chip as grid (gate), the micro nanometer fiber two ends that contact with microprobe are respectively source electrode (source) and drain electrode (drain), set test parameter, electrical properties to micro nanometer fiber sample is measured, as shown in Figure 4 and Figure 5, the zinc oxide micron/nano fiber field-effect curve of the single doping lanthanum recording and doped with cerium all shows that it is typical P-type semiconductor.
Claims (1)
1. a preparation method for P type zinc oxide micron/nano fiber, is characterized in that concrete steps comprise preparation spinning precursor solution, electrospinning micro nanometer fiber and three steps of high temperature sintering:
(1) preparation spinning precursor solution: first Environment temperature is 15 DEG C, humidity is the preparation occasion of 43%RH, with 8.5 grams of dehydrated alcohols of electronic balance weighing and 1.5 grams of polyvinylpyrrolidones, in Erlenmeyer flask, mix and blend left standstill 1 hour after 3 hours, obtain the transparent 15wt%PVP ethanolic soln of homogeneous, use again 1.0 grams of zinc acetate solids of electronic balance weighing, 2.0 grams of dehydrated alcohols, 0.2 gram of distilled water and 0.2 gram of lanthanum nitrate or 0.2 gram of cerous nitrate solid, in another Erlenmeyer flask, mix, temperature control 60-80 DEG C is carried out heated and stirred 5-10 minute, after solid in Erlenmeyer flask dissolves completely, this solution is transferred in the 15wt%PVP ethanolic soln having configured and formed mixing solutions with Dispette, then with magnetic stirring apparatus, above-mentioned mixing solutions is at room temperature stirred and within 1 hour, makes two kinds of solution fully mix, obtain spinning precursor solution,
(2) electrospinning micro nanometer fiber: do collector with the square aluminium foil that the length of side is 10 centimetres, it is the silicon chip that the square of 1-2 centimetre and surface band have insulating layer of silicon oxide that aluminium foil upper side is placed the length of side, using the precursor solution of preparing in (1) step as spinning solution, utilize conventional electrostatic spinning apparatus and method to carry out electrospinning micro nanometer fiber, the spinning voltage of its electrostatic spinning apparatus is 18-20 kilovolt, spinning is apart from 7.5-9.5 centimetre, spinning time 10-15 minute, after electrospinning, the silicon chip that is attached with micro nanometer fiber is taken off, be placed in loft drier and save backup,
(3) high temperature sintering: the silicon chip that is attached with micro nanometer fiber in step (2) is placed in to retort furnace, adjusting sintering temperature is 650-750 DEG C, sintering time is 4-5 hour, to be sintered complete and stove in temperature drop to after room temperature, take out silicon chip, now on silicon chip, the organic composition of micro nanometer fiber is removed, and makes the P type zinc oxide micron/nano fiber of doping lanthanum or doped with cerium.
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| CN107974732A (en) * | 2016-10-21 | 2018-05-01 | 苏州今道创业投资有限公司 | The preparation method of zinc oxide hollow Nano fiber in use |
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| CN103789875B (en) * | 2014-01-23 | 2015-09-30 | 黑龙江大学 | A kind of preparation method of crystalline phase controllable oxidization zirconium 1-dimention nano fiber |
| CN105261700B (en) * | 2015-09-07 | 2018-05-01 | 武汉理工大学 | Nonvolatile semiconductor memory member based on fiber and preparation method thereof |
| CN105403291B (en) * | 2015-10-29 | 2019-01-18 | 青岛大学附属医院 | Ultraviolet photosensitive sensor of zinc oxide nano fiber QCM and preparation method thereof |
| CN107017307A (en) * | 2017-03-28 | 2017-08-04 | 青岛大学 | A kind of preparation method of low pressure p-type oxide nanofiber field-effect transistor |
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| CN107974732A (en) * | 2016-10-21 | 2018-05-01 | 苏州今道创业投资有限公司 | The preparation method of zinc oxide hollow Nano fiber in use |
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