CN101049957A - Method for preparing Nano zinc oxide film with different appearances through solution technique - Google Patents
Method for preparing Nano zinc oxide film with different appearances through solution technique Download PDFInfo
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- CN101049957A CN101049957A CN 200710099434 CN200710099434A CN101049957A CN 101049957 A CN101049957 A CN 101049957A CN 200710099434 CN200710099434 CN 200710099434 CN 200710099434 A CN200710099434 A CN 200710099434A CN 101049957 A CN101049957 A CN 101049957A
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Abstract
This invention discloses a solution method for preparing ZnO nanofilms with different morphologies. The molecular beam epitaxy method has a high cost, thus is not suitable for mass production. The thermal evaporation method has a poor controllability due to high temperature requirement. The method comprises: placing electrically conductive glass containing ZnO seeds into a mixture of Zn(NO3)2 and urotropine with pH value in 2.6-10.5, growing under refluxing at 85-95 deg.C for 6 h, washing with distilled water, and drying to obtain ZnO thin films with different sizes and morphologies. Since the whole reaction process is conducted in an inorganic solution, the method has such advantages as low cost, easy operation, no pollution, and controllable ZnO thin film morphologies. The one-dimensional ZnO thin film prepared in quasi-neutral condition can be used in solar cells, photoelectrical devices, sensors and field emitters.
Description
Technical field
The invention belongs to semiconductor nano film preparation field, particularly a kind of method of preparing Nano zinc oxide film with different appearances through solution technique belongs to the inorganic material preparation process technical field.
Background technology
Because factors such as structure, size and pattern have caused people's very big interest to the material impact that material behavior and application thereof have to the morphology control research of inorganic materials.Especially there is quantum confined effect in nano semiconductor material, have potential application aspect photoelectric device, photo-electroluminescence, the biometric image, and this has just improved semiconductor material dependency to size on photoelectric properties.Simultaneously, the height of device is integrated has also proposed more harsh requirement to the size and the pattern of material with microminiaturization.Morphology control research not only requires to give full play to the intrinsic properties of material, also needs by size and morphology control to inorganic materials its character to be carried out cutting and adjustment.Recently between the more than ten years, semiconductor nano material is in information technology, electronics, medical science, play an important role on the biotechnology field, but still can a challenge that exist be effectively controllably prepare nano semiconductor material, this be because a lot of nano materials have with the distinct physicochemical property of kind massive material.By to the size of semiconductor material, the control of pattern, can effectively control the photoelectric properties of semiconductor material.
Zinc oxide (ZnO) structure is a wurtzite structure, at room temperature has bigger exciton bind energy (60meV), is that a kind of energy gap is the semiconductor material with wide forbidden band of 3.37ev.Just because of its special energy band structure, simultaneously, one-dimension zinc oxide is owing to have special energy gap, higher Surface factor, bigger physical strength and stable chemical property, and unique photoelectric properties, at opto-electronic device, nanoelectronic such as gas and biosensor, fields such as opto-electronic device show huge application potential, especially the One-Dimensional ZnO nanometer rod has excellent optical property and electron transport ability, as Graetzel type electrode of solar battery, can accelerate the separation in light induced electron one hole, it is compound obviously to reduce it, improve the utilization ratio of photo-generated carrier, make that preparation big area controllable appearance growing ZnO nanorod film becomes the focus that people study on solid substrate.
Preparation method about zinc-oxide film control reports more in recent years, different chemistry is arranged up to now, preparation method such as physics and electrochemistry, synthesized ZnO nano wire (Yang as usefulness gas-liquid-solid (vapor-liquid-solid) catalyzed reaction growth methods such as Peidong Yang, Pei-dong, Yan, Hao-quan, Mao, Sa-muel, et al.Controlled growth of ZnO nanowires and theiroptical propertyes[J] .Adv Fund Mater, 2002,12 (5): 323.), original position and thickness by control catalyst alloy cluster or gold thin film are controlled the position of ZnO nano-wire array and the diameter of nano wire respectively, and gas-liquid-solid catalyzed reaction growth method is a method relatively preferably, but improve also needing aspect the controllability of nanostructure; Hiroshi Funakubo etc. has studied at polymorph A l
2O
3, rutile (001) face, MgO (100) face, sapphire (102) and (001) face, and substrate such as amorphous silica on structure (the Wenas W W of growing ZnO thin-film, Yamada A, Konagai M et al.Jpn J ApplPhys, 1994,33:L283), though molecular beam epitaxy growing film quality is good, cost is too high, is not suitable for the requirement of scale operation; Thermal evaporation is because its cost is low, easy handling and can prepare advantage such as multiple pattern and become one of main method of preparation ZnO nanostructure, but its shortcoming is: high temperature requires, controllability is relatively poor.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing the different shape zinc oxide nano thin-film with solution method.It can prepare the ZnO film with different-shape and size easy, cheaply.
Concrete preparation process of the present invention is as follows:
1, a kind ofly prepare the method for different shape zinc oxide nano thin-film, it is characterized in that, may further comprise the steps with solution method:
(1) with Zn (NO
3)
2(CH
2)
6N
4Amount of substances such as solution mix, Zn (NO
3)
2(CH
2)
6N
4Strength of solution is 0.025mol/L, and the pH value of using acid or alkali regulator solution fully stirs between 2.6~10.5;
(2) the conductive glass substrate front surface that will have at the bottom of the thermolysis gained zinc oxide kind is put into above-mentioned solution down, is heated to 85~95 ℃, refluxes, constant temperature is after 6 hours, naturally cooling;
(3) substrate is taken out, use distilled water flushing, 60 ℃ of dryings in baking oven, the zinc-oxide film of acquisition different-shape, different size.
The acid of described step (1) usefulness is hydrochloric acid or nitric acid, and used alkali is ammoniacal liquor.
The preparation method who the invention has the beneficial effects as follows proposition is mainly in the conductive glass substrate that covers one deck zinc oxide, pH value by conditioned reaction solution, the zinc-oxide film of the different-shape that generates, this film directional property is good, the degree of crystallinity height, controllability is good, is significant for the shape dependency of studying nano ZnO.Simultaneously, with low cost, pollution-free because entire reaction course all is to carry out in the inorganic solution environment, be a kind of green method of novel eco-friendly preparation controllable semiconductor film.Prepared zinc-oxide film is at film light chemistry solar cell, photoelectric device, and there is purposes widely in fields such as transmitter, feds.
Description of drawings
Fig. 1 is the zinc oxide SEM figure of embodiment 1 resultant similar pencil shape.
Fig. 2 is SEM (side) figure of embodiment 5 resultant directional nano rod zinc-oxide films.
Fig. 3 is the SEM figure of embodiment 8 resultant spherical zinc-oxide films.
Fig. 4 is the XRD figure of embodiment 5 resultant zinc oxide nano-rod films.
Embodiment
The present invention may be better understood by following representative embodiment, although provided these embodiment, also should comprise: do not departing under the scope of the invention condition, disclosed method is carried out the conspicuous various changes of those skilled in the art.
In embodiments of the present invention, the used conductive glass that has at the bottom of the zinc oxide kind is by thermolysis Zn (CH
3COOH)
2The ethanolic soln method obtains: mix fluorine SnO at 1cm * 2cm
2Dripping concentration on the conductive glass is the Zn (CH of 0.005mol/L
3COOH)
2One of ethanolic soln is used alcohol flushing, dries up with nitrogen, repeats the dropping process 4 times, puts into stove, 350 ℃ of constant temperature 20 minutes.Repeat said process, obtain the transparent conductive glass that has at the bottom of the zinc oxide kind.
The acid of described step (1) usefulness is hydrochloric acid or nitric acid, and used alkali is ammoniacal liquor, and its mass percent concentration is 25%.
Embodiment 1
(1) with the Zn (NO of 0.025mol/L
3)
2And 0.025mol/L (CH
2)
6N
4Mole numbers such as solution mix, and the pH value with the nitric acid regulator solution makes pH=2.6, fully stir;
(2) the conductive glass face down that will have at the bottom of the thermolysis gained zinc oxide kind is put into above-mentioned solution, is heated to 85 ℃, refluxes, constant temperature is after 6 hours, naturally cooling.
(3) substrate is taken out, use distilled water flushing, 60 ℃ of dryings are 1 hour in baking oven.
Make the one-dimension zinc oxide rod of similar pencil shape, diameter is about 1.8 μ m, and length is 10 μ m.
Embodiment 2
1) with the Zn (NO of 0.025mol/L
3)
2And 0.025mol/L (CH
2)
6N
4Mole numbers such as solution mix, and the pH value with hydrochloric acid conditioning solution makes pH=2.62, fully stir;
(2) the conductive glass face down that will have at the bottom of the thermolysis gained zinc oxide kind is put into above-mentioned solution, is heated to 90 ℃, refluxes, constant temperature is after 6 hours, naturally cooling;
(3) substrate is taken out, use distilled water flushing, 60 ℃ of dryings are 1.5 hours in baking oven.
Making diameter is 2.5 μ m, and length is six side's one-dimension zinc oxides of 5 μ m.
Embodiment 3
(1) with the Zn (NO of 0.025mol/L
3)
2And 0.025mol/L (CH
2)
6N
4Mole numbers such as solution mix, and the pH value with hydrochloric acid conditioning solution makes pH=4, fully stir;
(2) the conductive glass face down that will have at the bottom of the thermolysis gained zinc oxide kind is put into above-mentioned solution, is heated to 88 ℃, refluxes, constant temperature is after 6 hours, naturally cooling;
(3) substrate is taken out, use distilled water flushing, 60 ℃ of dryings are 1 hour in baking oven.
Making diameter is 700nm, and length is the one-dimension zinc oxide of 6.5 μ m.
Embodiment 4
(1) with the Zn (NO of 0.025mol/L
3)
2And 0.025mol/L (CH
2)
6N
4Mole numbers such as solution mix, and the pH value with hydrochloric acid conditioning solution makes pH=5.36, fully stir;
(2) the conductive glass face down that will have at the bottom of the thermolysis gained zinc oxide kind is put into above-mentioned solution, is heated to 92 ℃, refluxes, constant temperature is after 6 hours, naturally cooling;
(3) substrate is taken out, use distilled water flushing, 60 ℃ of dryings are 2 hours in baking oven.
Making diameter is 250nm, and length is the one-dimension zinc oxide of 2.9 μ m.
Embodiment 5
(1) with the Zn (NO of 0.025mol/L
3)
2And 0.025mol/L (CH
2)
6N
4Mole numbers such as solution mix, and the pH value with hydrochloric acid conditioning solution makes pH=6.4, fully stir;
(2) the conductive glass face down that will have at the bottom of the thermolysis gained zinc oxide kind is put into above-mentioned solution, is heated to 95 ℃, refluxes, constant temperature is after 6 hours, naturally cooling;
(3) substrate is taken out, use distilled water flushing, 60 ℃ of dryings are 1 hour in baking oven.
Making diameter is 150nm, and length is the zinc oxide array of 2.3 μ m.
Embodiment 6
(1) with the Zn (NO of 0.025mol/L
3)
2And 0.025mol/L (CH
2)
6N
4Mole numbers such as solution mix, and the pH value with the ammoniacal liquor regulator solution makes pH=6.93, fully stir;
(2) the conductive glass face down that will have at the bottom of the thermolysis gained zinc oxide kind is put into above-mentioned solution, is heated to 90 ℃, refluxes, constant temperature is after 6 hours, naturally cooling;
(3) substrate is taken out, use distilled water flushing, 60 ℃ of dryings are 1.5 hours in baking oven.
Making diameter is about 150nm, the zinc oxide nano film of length 2.6 μ m.
(1) with the Zn (NO of 0.025mol/L
3)
2And 0.025mol/L (CH
2)
6N
4Mole numbers such as solution mix, and the pH value with the ammoniacal liquor regulator solution makes pH=8, fully stir;
(2) the conductive glass face down that will have at the bottom of the thermolysis gained zinc oxide kind is put into above-mentioned solution, is heated to 90 ℃, refluxes, constant temperature is after 6 hours, naturally cooling;
(3) substrate is taken out, use distilled water flushing, 60 ℃ of dryings are 1 hour in baking oven.
Make the globular zinc-oxide film, diameter is 80-150nm.
Embodiment 8
(1) with the Zn (NO of 0.025mol/L
3)
2And 0.025mol/L (CH
2)
6N
4Mole numbers such as solution mix, and the pH value with the ammoniacal liquor regulator solution makes pH=10.5, fully stir;
(2) the conductive glass face down that will have at the bottom of the thermolysis gained zinc oxide kind is put into above-mentioned solution, is heated to 92 ℃, refluxes, constant temperature is after 6 hours, naturally cooling;
(3) substrate is taken out, use distilled water flushing, 60 ℃ of dryings are 1 hour in baking oven.
Make the globular zinc-oxide film, diameter is 70-120nm.
Claims (2)
1, a kind of solution method prepares the method for different shape zinc oxide nano thin-film, it is characterized in that, may further comprise the steps:
(1) with Zn (NO
3)
2(CH
2)
6N
4Amount of substances such as solution mix, Zn (NO
3)
2(CH
2)
6N
4Strength of solution is 0.025mol/L, and the pH value of using acid or alkali regulator solution fully stirs between 2.6~10.5;
(2) the conductive glass face down that will have at the bottom of the thermolysis gained zinc oxide kind is put into above-mentioned solution, is heated to 85~95 ℃, refluxes, constant temperature is after 6 hours, naturally cooling;
(3) substrate is taken out, use distilled water flushing, 60 ℃ of dryings in baking oven, the zinc-oxide film of acquisition different-shape, different size.
2, preparation method according to claim 1 is characterized in that, the acid of the usefulness of described step (1) is hydrochloric acid or nitric acid, and used alkali is ammoniacal liquor.
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CN102324349A (en) * | 2011-08-07 | 2012-01-18 | 张研 | Zinc oxide (ZnO) nanowire emitter growing on aligned carbon nanotube (ACNT) array template |
CN103395823A (en) * | 2013-07-22 | 2013-11-20 | 中国计量学院 | Preparation method for nano-zinc oxide directional array |
CN103628305A (en) * | 2013-11-28 | 2014-03-12 | 哈尔滨工业大学 | Zinc oxide nanowire modified PBO (Poly-p-phenylenebenzobisthiazole) fiber |
CN106601592A (en) * | 2016-12-22 | 2017-04-26 | 中国科学院理化技术研究所 | Light-transmitting semiconductor material and preparation method thereof |
CN107170881A (en) * | 2017-06-22 | 2017-09-15 | 江苏科技大学 | A kind of many laminated type nanometer piezoelectric devices and preparation method thereof |
CN108949085A (en) * | 2018-07-02 | 2018-12-07 | 合肥萃励新材料科技有限公司 | A kind of preparation method of electrostatic dissipation pressure sensitive adhesive |
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CN110124700A (en) * | 2019-06-11 | 2019-08-16 | 吉林师范大学 | A kind of difunctional MoS2The preparation method of/ZnO composite material |
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CN101857222A (en) * | 2010-05-28 | 2010-10-13 | 常州大学 | Preparation method of large-area and continuous graphen/zinc oxide composite structure |
CN102324349A (en) * | 2011-08-07 | 2012-01-18 | 张研 | Zinc oxide (ZnO) nanowire emitter growing on aligned carbon nanotube (ACNT) array template |
CN102324349B (en) * | 2011-08-07 | 2013-08-28 | 上海康众光电科技有限公司 | Zinc oxide (ZnO) nanowire emitter growing on aligned carbon nanotube (ACNT) array template |
CN103395823A (en) * | 2013-07-22 | 2013-11-20 | 中国计量学院 | Preparation method for nano-zinc oxide directional array |
CN103628305A (en) * | 2013-11-28 | 2014-03-12 | 哈尔滨工业大学 | Zinc oxide nanowire modified PBO (Poly-p-phenylenebenzobisthiazole) fiber |
CN103628305B (en) * | 2013-11-28 | 2016-02-17 | 哈尔滨工业大学 | A kind of pbo fiber of zinc oxide nanowire modification |
CN106601592A (en) * | 2016-12-22 | 2017-04-26 | 中国科学院理化技术研究所 | Light-transmitting semiconductor material and preparation method thereof |
CN106601592B (en) * | 2016-12-22 | 2019-05-07 | 中国科学院理化技术研究所 | Light-transmitting semiconductor material and preparation method thereof |
CN107170881A (en) * | 2017-06-22 | 2017-09-15 | 江苏科技大学 | A kind of many laminated type nanometer piezoelectric devices and preparation method thereof |
CN107170881B (en) * | 2017-06-22 | 2019-08-23 | 江苏科技大学 | A kind of more laminated type nanometer piezoelectric devices and preparation method thereof |
CN108949085A (en) * | 2018-07-02 | 2018-12-07 | 合肥萃励新材料科技有限公司 | A kind of preparation method of electrostatic dissipation pressure sensitive adhesive |
CN109054660A (en) * | 2018-07-02 | 2018-12-21 | 合肥萃励新材料科技有限公司 | A kind of preparation method of PESD function adhesive |
CN110124700A (en) * | 2019-06-11 | 2019-08-16 | 吉林师范大学 | A kind of difunctional MoS2The preparation method of/ZnO composite material |
CN110124700B (en) * | 2019-06-11 | 2022-06-21 | 吉林师范大学 | Dual-functional MoS2Application of/ZnO composite material in bisphenol A trace detection |
CN111792666A (en) * | 2020-07-13 | 2020-10-20 | 成都能太科技有限公司 | Method for realizing evolution of zinc oxide in various nanometer morphologies |
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