CN104743602A - Hydrothermal synthesis method of zinc oxide nanomaterial and zinc oxide nanomaterial - Google Patents
Hydrothermal synthesis method of zinc oxide nanomaterial and zinc oxide nanomaterial Download PDFInfo
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Abstract
The present invention discloses a hydrothermal synthesis method of a zinc oxide nanomaterial, and the method is as follows: under the conditions of hydrothermal synthesis, a reaction solution containing a zinc salt and an alkali is contacted with a growth substrate in a reactor to prepare a ZnO nanostructure array on the growth substrate, the reaction solution also contains an ammonium salt. The invention also provides the zinc oxide nanomaterial prepared by the method, the near band edge emission intensity and defect state emission intensity ratio in the light induced luminescence spectra of the zinc oxide nanomaterial is greater than 6, preferably greater than 10, and more preferably greater than 20. The defect density of the ZnO nanostructure synthesized by the method is significantly reduced, and the optical quality of the ZnO nanostructure array is greatly improved. In addition, the length of the ZnO nanostructure array synthesized by the method in same growth period is increased significantly, and the growth rate of the ZnO nanostructure array is greatly improved.
Description
Technical field
The present invention relates to a kind of hydrothermal synthesis method and nano zinc oxide material of nano zinc oxide material.
Background technology
Zinc oxide is a kind of semiconductor material of excellent performance, has good optics, electricity and catalysis characteristics.Nano zinc oxide material performance is various, of many uses.The preparation method of nano zine oxide comprises vapor phase process and liquid phase method, and wherein, hydrothermal method is a kind of important method of Liquid preparation methods nano structure of zinc oxide.
Hydrothermal method is also known as hydrothermal method, refer in special closed reactor (autoclave), adopt the aqueous solution as reaction system, by heating reaction system, produce the environment of a High Temperature High Pressure, speeding-up ion reaction and facilitation of hydrolysis reaction, in the aqueous solution or steam flow, prepare oxide compound, realization response is rapid under hydrothermal conditions can to make some thermodynamical reaction that speed of reaction is very slow at normal temperatures and pressures.
The photoluminescence spectrogram of ZnO nano-structure array generally has two emission peaks, one at about 380nm, one at about 540nm.It is generally acknowledged that the emission peak of about 380nm is the nearly band-edge emission of wide bandgap semiconductor ZnO; And yellowish green photoemissive reason exists multiple explanation, wherein the defect that there is Lacking oxygen in ZnO is thought in a kind of explanation.
But adopt the nano structure of zinc oxide array defect density of conventional hydrothermal method growth higher, optical quality is not high, and growth velocity is low.
Summary of the invention
It is not high that the present invention is intended to overcome the higher optical quality that causes of nano structure of zinc oxide array defect density adopting conventional hydrothermal method to obtain, and the low defect of growth velocity and provide hydrothermal synthesis method and the ZnO nano material of a kind of new optical quality of raising nano structure of zinc oxide array and the ZnO nano material of growth velocity.
To achieve these goals, the invention provides a kind of hydrothermal synthesis method of ZnO nano material, the method comprises: under hydrothermal synthesizing condition, contact containing zinc salt in a kettle. with growth substrate with the reaction soln of alkali, with ZnO nano-structure array obtained in described growth substrate, wherein, described reaction soln is also containing ammonium salt.
Present invention also offers and a kind ofly adopt method of the present invention to synthesize the ZnO nano material obtained, wherein, in the photoluminescence collection of illustrative plates of described ZnO nano material, nearly band-edge emission intensity and defect state emissive porwer ratio are greater than 6, are preferably greater than 10, are more preferably and are greater than 20.
Can be found by photoluminescence (PL) test, adopt method of the present invention to synthesize nearly band-edge emission intensity and defect state emissive porwer ratio in the photoluminescence collection of illustrative plates of the ZnO nano material obtained and be greater than 6, be preferably greater than 10, be more preferably and be greater than 20.Illustrate thus, the defect concentration of the ZnO nano-structure adopting method of the present invention to synthesize significantly reduces, thus drastically increases the optical quality of ZnO nano-structure array.In addition, adopt method of the present invention to be omitted annealing steps in conventional hydrothermal synthetic method, not only simplify operation steps, also assures that the good optical property of the ZnO nano material of synthesis simultaneously.Thus provide extensive prospect for the application of ZnO nano-structure array in the fields such as solar cell, gas sensor, photorectifier.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the photoluminescence collection of illustrative plates of the ZnO nano-structure array adopting the method for comparative example 1 and the method for embodiment 1-3 to prepare; Wherein, the result of the corresponding comparative example 1 of spectrogram a, the result of the corresponding embodiment 1-3 of spectrogram b, c, d difference;
Fig. 2 is scanning electronic microscope (SEM) photo of the ZnO nano-structure array adopting the method for comparative example 1 and the method for embodiment 1-3 to prepare; Wherein, a is the SEM sectional view of the ZnO nano-structure array adopting the method for comparative example 1 to prepare, and b is the SEM exterior view of the ZnO nano-structure array adopting the method for comparative example 1 to prepare; C, e, g are respectively the SEM sectional view of the ZnO nano-structure array adopting the method for embodiment 1-3 to prepare; D, f, h are respectively the SEM exterior view of the ZnO nano-structure array adopting the method for embodiment 1-3 to prepare;
Fig. 3 is the photoluminescence collection of illustrative plates of the ZnO nano-structure array adopting the method for comparative example 1 and embodiment 4-6 to prepare; Wherein, the result of the corresponding comparative example 1 of spectrogram a, the result of the corresponding embodiment 4-6 of spectrogram b, c, d difference;
Fig. 4 is the electron scanning micrograph of the ZnO nano-structure array adopting the method for embodiment 4-6 to prepare; Wherein, a, c, e are respectively the SEM sectional view of the ZnO nano-structure array adopting the method for embodiment 4-6 to prepare; B, d, f are respectively the SEM exterior view of the ZnO nano-structure array adopting the method for embodiment 4-6 to prepare;
Fig. 5 is the photoluminescence collection of illustrative plates of the ZnO nano-structure array adopting the method for embodiment 7 to prepare;
Fig. 6 is the electron scanning micrograph of the ZnO nano-structure array adopting the method for embodiment 7 to prepare; Wherein, a is the SEM sectional view of ZnO nano-structure array; B is the SEM exterior view of ZnO nano-structure array;
Fig. 7 is the photoluminescence collection of illustrative plates of the ZnO nano-structure array adopting the method for comparative example 2 to prepare;
Fig. 8 is the electron scanning micrograph of the ZnO nano-structure adopting the method for comparative example 2 to prepare, and wherein, a is the SEM sectional view of ZnO nano-structure array; B is the SEM exterior view of ZnO nano-structure array.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to the present invention, the hydrothermal synthesis method of described ZnO nano material comprises: under hydrothermal synthesizing condition, contact containing zinc salt in a kettle. with growth substrate with the reaction soln of alkali, with ZnO nano-structure array obtained in described growth substrate, wherein, also ammonium salt is contained in described reaction soln.
Method of the present invention by adding ammonium salt in the reaction soln containing zinc salt and alkali, the defect concentration of the ZnO nano-structure of this water heat transfer is adopted significantly to reduce, under identical growth time, length significantly increases, thus drastically increases optical quality and the growth velocity of ZnO nano-structure array.
According to the present invention, the selectable range of the kind of described ammonium salt is wider, under preferable case, described ammonium salt be selected from ammonium sulfate, ammonium nitrate, ammonium chloride and ammonium acetate one or more, be more preferably ammonium nitrate and/or ammonium acetate.
According to the present invention, although add the object that namely described ammonium salt can realize improving the nano structure of zinc oxide array defect adopting water heat transfer, but, under preferable case, in order to realize goal of the invention of the present invention better, the described concentration containing ammonium salt in the reaction soln of zinc salt and alkali is 0.0005M-1M, more preferably, the mol ratio of described ammonium salt and zinc salt is 0.1-50:1, is more preferably 2-20:1.
According to the present invention, the kind of described zinc salt can be the various zinc salt being applied to nano zinc oxide material synthesis known in those skilled in the art, such as, described zinc salt can be selected from zinc nitrate, zinc acetate, zinc sulfate and zinc chloride one or more.More preferably, in described reaction soln, the concentration of zinc salt is 0.0005M-1M.Wherein, the solvent in described reaction soln is water.
According to the present invention, the kind of described alkali can be the various alkali being applied to nano zinc oxide material synthesis known in those skilled in the art, such as, described alkali can be selected from one or more in the mineral alkali such as sodium hydroxide, ammoniacal liquor and the organic bases such as hexamethylenetetramine and diethylenetriamine.More preferably, in described reaction soln, paper mill wastewater is 0.0005M-1M.
In the present invention, hydrothermal method refers to and adopts the aqueous solution as reaction medium, by reactor heating, creates high temperature, a reaction under high pressure environment.According to the present invention, the condition of described Hydrothermal Synthesis can be hydrothermal synthesizing condition known in those skilled in the art, such as, the condition of described Hydrothermal Synthesis comprises temperature of reaction and reaction times, wherein, described temperature of reaction can be 70 DEG C-120 DEG C usually, and the reaction times can be 1 hour-48 hours usually.In addition, described hydrothermal synthesis reaction at closed environment, also can carry out in open environment.Closed environment can provide by adopting conventional closed reactor such as autoclave, the structure of the reactor of described closed environment is provided to be conventionally known to one of skill in the art, it can be the reactor of various applicable hydrothermal synthesis reaction, in the present invention, under preferable case, the stainless steel cauldron that closed environment is tetrafluoroethylene by liner provides.
According to the present invention, described growth substrate can be the various growth substrate preparing nano zinc oxide material that can be applied to known in those skilled in the art, such as, described growth substrate can be at least one in transparent conductive oxide, metal, fiber, polymkeric substance and carbon material, is preferably transparent conductive oxide.Wherein, described transparent conductive oxide (TCO) substrate be preferably selected from tin indium oxide (ITO), Al-Doped ZnO (AZO), mix indium zinc oxide (IZO), gallium-doped zinc oxide (GZO), boron-doping zinc oxide (BZO) and mix in the tindioxide (FTO) of fluorine one or more.Described metal base is preferably selected from gold and silver, copper or their alloy.Described fibrous substrate is preferably staple or optical fiber.Described carbon material substrate is preferably carbon nanotube or Graphene.Described growth substrate can also comprise the organic or inorganic substrate of other any suitable hydrothermal method.The zinc-oxide film that described growth substrate surface coverage has or do not cover native oxide zinc film or other metals (as aluminium, indium, gallium, boron etc.) to adulterate.Described zinc-oxide film or other metal-doped zinc oxide films retes can cover the surface of growth substrate by this area usual manner, such as, by the mode of vacuum sputtering coating.The thickness of described zinc-oxide film or other metal-doped zinc-oxide films can be selected according to practical situation, is preferably 30nm-100nm.
According to the present invention, under preferable case, after the method also comprises reaction, growth substrate cooling, the washing also drying of ZnO nano-structure array will be attached with.Usually, be down to room temperature, such as 20-35 DEG C, washing, dry method and condition can, with reference to the common practise of this area, can adopt deionized water to wash usually, adopt inert atmosphere, as nitrogen dries up.
Adopt method of the present invention to synthesize nearly band-edge emission intensity and defect state emissive porwer ratio in the photoluminescence collection of illustrative plates of the ZnO nano material obtained and be greater than 6, be preferably greater than 10, be more preferably and be greater than 20.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below will be described the present invention by embodiment.
Al-Doped ZnO (AZO) transparent conducting film glass used in following embodiment and comparative example, AZO thickness is 700-800nm.
PL spectrogram adopts He-Cd laser apparatus to measure at 325 nm wavelength.PL testing apparatus is the LABRAM HR of HoribaJobin Yvon company.The mean diameter of ZnO nano-structure array and mean length are by the assess and determine of scanning electron microscope, and testing apparatus is the Quanta scanning electronic microscope of FEI Co..
Embodiment 1-3
The present embodiment is for illustration of the synthetic method of nano zinc oxide material provided by the invention.
In the ultrasonic bath of organic solvent (acetone and ethanol), clean Al-Doped ZnO (AZO) transparent conducting film glass as growth substrate, then use water ultrasonic cleaning clean.
The zinc acetate (0.005M) and the hexamethylenetetramine (0.005M) that by mol ratio are 1:1 are soluble in water, ultrasonic dissolution mixes, configuration obtains mixing solutions, and add the ammonium nitrate of different concns wherein, ultrasonic dissolution mixes, the concentration of ammonium nitrate in the described aqueous solution is respectively 0.01M, 0.05M and 0.1M, and the mol ratio of ammonium nitrate and zinc acetate is difference 2:1,10:1 and 20:1.
Above-mentioned growth substrate is put into the reactor of the mixing solutions filled containing zinc salt, alkali and ammonium salt, reactor is put into air dry oven and carries out reacting by heating, temperature of reaction is 90 DEG C, reaction times is 6 hours, room temperature is down to after reaction terminates, namely grow ZnO nano-structure array, take out rear deionized water rinsing, dry up with nitrogen.
Comparative example 1
According to the method synthesizing zinc oxide nano material of embodiment 1-3, unlike, do not add ammonium salt in described mixing solutions, acetic acid zinc concentration is 0.005M, and the concentration of hexamethylenetetramine is 0.005M.
Fig. 1 is the photoluminescence collection of illustrative plates of the ZnO nano-structure array adopting the method for embodiment 1-3 and comparative example 1 to prepare; Wherein, a is the photoluminescence collection of illustrative plates of ZnO nano-structure array prepared by the reaction soln only containing zinc salt and alkali, b, c, d is respectively and adds 0.01M in zinc salt and alkali, the photoluminescence collection of illustrative plates of ZnO nano-structure array prepared by the reaction soln of 0.05M, 0.1M ammonium nitrate;
Fig. 2 is the ZnO nano-structure SEM photo adopting the method for embodiment 1-3 and comparative example 1 to prepare; Wherein, a is the SEM sectional view of ZnO nano-structure array prepared by the reaction soln only containing zinc salt and alkali, and b is the SEM exterior view of ZnO nano-structure array prepared by the reaction soln only containing zinc salt and alkali; C, e, g are respectively and add 0.01M in zinc salts and alkali, the SEM sectional view of ZnO nano-structure array prepared by the reaction soln of 0.05M, 0.1M ammonium nitrate; D, f, h are respectively and add 0.01M in zinc salts and alkali, the SEM exterior view of ZnO nano-structure array prepared by the reaction soln of 0.05M, 0.1M ammonium nitrate.
Design parameter is as shown in table 1 below.
Table 1
The data conclusion that the photoluminescence collection of illustrative plates of embodiment 1-3 and comparative example 1 and electron scanning micrograph draw is summarized in table 1, can be found by photoluminescence collection of illustrative plates, the nearly band-edge emission intensity of synthesizing ZnO nano-structure array according to comparative example 1 is better than defect state emissive porwer, and its ratio is 6.And according to the method for embodiment 1-3, by adding 0.01M, 0.05M, the nearly band-edge emission intensity of ZnO nano-structure prepared by the reaction soln of 0.1M ammonium nitrate and the ratio of defect state emissive porwer are respectively 9,27 and 17, improve 50%, 350% and 183% respectively compared with comparative example 1, draw thus, the ZnO nano-structure prepared by adding ammonium nitrate has higher optical quality.
Observed can be found by electron scanning micrograph, the ZnO nano-structure array synthesized according to comparative example 1 is hexagonal taper, and length is 320nm, and diameter is 110nm.According to the method for embodiment 1-3, by adding 0.01M, ZnO nano-structure array prepared by the reaction soln of 0.05M, 0.1M ammonium nitrate changes hexagonal column into from hexagonal taper gradually, length is respectively 350nm, 650nm and 630nm, improve 9%, 103% and 97% respectively compared with comparative example 1, illustrate thus, along with the increase of ammonium nitrate concn, the length of ZnO nano-structure increases, therefore, adding of ammonium nitrate, the growth velocity improving ZnO nano-structure array is contributed to.
Embodiment 4-6
The present embodiment is for illustration of the synthetic method of nano zinc oxide material provided by the invention.
In the ultrasonic bath of organic solvent (acetone and ethanol), clean Al-Doped ZnO (AZO) transparent conducting film glass as growth substrate, then use water ultrasonic cleaning clean.
The zinc acetate (0.005M) and the hexamethylenetetramine (0.005M) that by mol ratio are 1:1 are soluble in water, ultrasonic dissolution mixes, configuration obtains mixing solutions, and add the ammonium acetate of different concns wherein, ultrasonic dissolution mixes, the concentration of ammonium acetate in the described aqueous solution is 0.04M, 0.05M, 0.08M, and the mol ratio of ammonium acetate and zinc acetate is respectively 8:1,10:1 and 16:1.
Above-mentioned growth substrate is put into the reactor of the mixing solutions filled containing zinc salt, alkali and ammonium salt, reactor is put into air dry oven and carries out reacting by heating, temperature of reaction is 90 DEG C, reaction times is 6 hours, room temperature is down to after reaction terminates, namely grow ZnO nano-structure array, take out rear deionized water rinsing, dry up with nitrogen.
Fig. 3 is the photoluminescence collection of illustrative plates of the ZnO nano-structure array adopting the method for embodiment 4-6 and comparative example 1 to prepare; Wherein, a is the photoluminescence collection of illustrative plates of ZnO nano-structure array prepared by the reaction soln only containing zinc salt and alkali, b, c, d is respectively and adds 0.04M in zinc salt and alkali, the photoluminescence collection of illustrative plates of ZnO nano-structure array prepared by the reaction soln of 0.05M, 0.08M ammonium acetate;
Fig. 4 is the SEM photo of the ZnO nano-structure adopting the method for embodiment 4-6 to prepare; Wherein, a, c, e are respectively and add 0.04M in zinc salts and alkali, the SEM sectional view of ZnO nano-structure array prepared by the reaction soln of 0.05M, 0.08M ammonium acetate; B, d, f are respectively and add 0.04M in zinc salts and alkali, the SEM exterior view of ZnO nano-structure array prepared by the reaction soln of 0.05M, 0.08M ammonium acetate.
Design parameter is as shown in table 2 below.
Table 2
The data conclusion that the photoluminescence collection of illustrative plates of embodiment 4-6 and comparative example 1 and electron scanning micrograph draw is summarized in table 2, can be found by photoluminescence collection of illustrative plates, the nearly band-edge emission intensity of synthesizing ZnO nano-structure array according to comparative example 1 is better than defect state emissive porwer, and its ratio is 6.And according to the method for embodiment 4-6, by adding 0.04M, 0.05M, the nearly band-edge emission intensity of ZnO nano-structure prepared by the reaction soln of 0.08M ammonium acetate and the ratio of defect state emissive porwer are respectively 14,16 and 21, improve 133%, 167% and 250% respectively compared with comparative example 1, draw thus, the ZnO nano-structure prepared by adding ammonium acetate has higher optical quality.
Observed can be found by electron scanning micrograph, synthesizing ZnO nano-structure array according to comparative example 1 is hexagonal taper, and length is 320nm, and diameter is 110nm.According to the method for embodiment 4-6, by adding 0.04M, ZnO nano-structure array prepared by the reaction soln of 0.05M, 0.08M ammonium acetate is hexagonal column, length is respectively 615nm, 600nm and 650nm, improve 92%, 88% and 103% respectively compared with comparative example 1, illustrate thus, along with the increase of ammonium acetate concentration, the length of ZnO nano-structure increases, therefore, adding of ammonium acetate, the growth velocity improving ZnO nano-structure array is contributed to.
Embodiment 7
The present embodiment is for illustration of the synthetic method of nano zinc oxide material provided by the invention.
Nano zinc oxide material is prepared according to the method for embodiment 4-6, unlike, the mol ratio of ammonium acetate and zinc acetate is 1:1.
Fig. 5 is the photoluminescence collection of illustrative plates of the ZnO nano-structure array adopting the method for embodiment 7 to prepare;
Fig. 6 is scanning electronic microscope (SEM) photo of the ZnO nano-structure adopting the method for embodiment 7 to prepare; Wherein, a is the SEM sectional view of ZnO nano-structure array; B is the SEM exterior view of ZnO nano-structure array.
Can be found by photoluminescence collection of illustrative plates, be 6.4 according to the nearly band-edge emission intensity of the method synthesis ZnO nano-structure array of embodiment 7 and defect state emissive porwer ratio.
Observed can be found by electron scanning micrograph, synthesizing ZnO nano-structure array according to embodiment 7 is hexagonal column, and length is 360nm, and diameter is 120nm, and the length of ZnO nano-structure adds 13% compared with comparative example 1.
Comparative example 2
This comparative example is for illustration of the synthetic method of the nano zinc oxide material of prior art.
Nano zinc oxide material is prepared according to the method for embodiment 1, unlike, described nitric acid zinc concentration is 0.01M, and not containing ammonium salt in reaction soln.
Fig. 7 is the photoluminescence collection of illustrative plates of the ZnO nano-structure array adopting the method for comparative example 2 to prepare;
Fig. 8 is the electron scanning micrograph of the ZnO nano-structure adopting the method for comparative example 2 to prepare, and wherein, a is the SEM sectional view of ZnO nano-structure array; B is the SEM exterior view of ZnO nano-structure array.
Can be found by photoluminescence collection of illustrative plates, be only 1.4 according to the nearly band-edge emission intensity of the method synthesis ZnO nano-structure array of comparative example 2 and defect state emissive porwer ratio, illustrate thus, this ZnO nano-structure defect concentration is higher, and optical quality is poor.
Observed can be found by scanning electronic microscope (SEM) photo, be hexagonal taper according to comparative example 2-in-1 one-tenth ZnO nano-structure array, length is only 260nm, illustrates thus, and the growth velocity of this ZnO nano-structure is lower.
To sum up, as can be seen from photoluminescence (PL) Fig. 1 c(embodiment 2) with the contrast of Fig. 7 (comparative example 2), significantly improve compared with comparative example 2 with the ratio of defect state emissive porwer according to the nearly band-edge emission intensity of embodiment 2-in-1 one-tenth ZnO nano-structure array, draw thus, the defect concentration of the nano structure of zinc oxide adopting method of the present invention to prepare significantly reduces, and has higher optical quality.
As can be seen from scanning electronic microscope (SEM) Fig. 2 e and 2f(embodiment 2) with the contrast of the scanning electron photomicrograph of Fig. 8 (comparative example 2), the nano structure of zinc oxide array that the adding of ammonium salt can make to obtain is under identical growth time, length significantly increases, therefore, ammonium salt add the growth velocity contributing to improving ZnO nano-structure array.
Illustrate thus, method of the present invention greatly can improve optical quality and the growth velocity of ZnO nano-structure array.
Claims (10)
1. the hydrothermal synthesis method of a ZnO nano material, the method comprises: under hydrothermal synthesizing condition, contact containing zinc salt in a kettle. with growth substrate with the reaction soln of alkali, with ZnO nano-structure array obtained in described growth substrate, it is characterized in that, described reaction soln is also containing ammonium salt.
2. method according to claim 1, wherein, described ammonium salt be selected from ammonium sulfate, ammonium nitrate, ammonium chloride and ammonium acetate one or more, be preferably ammonium nitrate and/or ammonium acetate.
3. method according to claim 1 and 2, wherein, in described reaction soln, the concentration of ammonium salt is 0.0005M-1M.
4. according to the method in claim 1-3 described in any one, wherein, the mol ratio of described ammonium salt and zinc salt is 0.1-50:1, is preferably 2-20:1.
5. method according to claim 4, wherein, described zinc salt be selected from zinc nitrate, zinc acetate, zinc sulfate and zinc chloride one or more, in described reaction soln, the concentration of zinc salt is 0.0005M-1M.
6. method according to claim 1, wherein, described alkali be selected from sodium hydroxide, ammoniacal liquor, hexamethylenetetramine and diethylenetriamine one or more, in described reaction soln, paper mill wastewater is 0.0005M-1M.
7. according to the method in claim 1-6 described in any one, wherein, the condition of described Hydrothermal Synthesis comprises: temperature of reaction is 70 DEG C-120 DEG C, and the reaction times is 1 hour-48 hours.
8. method according to claim 1, wherein, described growth substrate is at least one in transparent conductive oxide, metal, fiber, polymkeric substance and carbon material, described transparent conductive oxide substrate be selected from tin indium oxide, Al-Doped ZnO, mix indium zinc oxide, gallium-doped zinc oxide, boron-doping zinc oxide and mix in the tindioxide of fluorine one or more, described metal is gold and silver, copper or their alloy, described fiber is staple or optical fiber, and described carbon material is carbon nanotube or Graphene; Described growth substrate surface coverage has or the zinc-oxide film of not capping oxidation zinc film or doping.
9. according to the method in claim 1-8 described in any one, wherein, the method also comprises: will be attached with growth substrate cooling, the washing also drying of ZnO nano-structure array after reaction.
10. the ZnO nano material obtained is synthesized according to the method in claim 1-9 described in any one, it is characterized in that, in the photoluminescence collection of illustrative plates of described ZnO nano material, nearly band-edge emission intensity and defect state emissive porwer ratio are greater than 6, are preferably greater than 10, are more preferably and are greater than 20.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108249474A (en) * | 2018-03-13 | 2018-07-06 | 江苏巨珩新材料科技有限公司 | Method for preparing three-dimensional zinc oxide nano self-assembly structure |
| CN108557868A (en) * | 2018-02-09 | 2018-09-21 | 神华（北京）光伏科技研发有限公司 | Nano-structure array and preparation method thereof and device |
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| JP2020503228A (en) * | 2016-12-20 | 2020-01-30 | ロッテ アドバンスト マテリアルズ カンパニー リミテッド | Composition for artificial marble |
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-
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- 2013-12-30 CN CN201310744538.9A patent/CN104743602B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 宋玉哲等: ""ZnO纳米棒阵列的水热法制备及其光学性质"", 《功能材料》 * |
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