CN102765743A - Preparation of corn-shaped multilevel structure zinc oxide nanorod array film on zinc sheet substrate - Google Patents
Preparation of corn-shaped multilevel structure zinc oxide nanorod array film on zinc sheet substrate Download PDFInfo
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- CN102765743A CN102765743A CN2012102439917A CN201210243991A CN102765743A CN 102765743 A CN102765743 A CN 102765743A CN 2012102439917 A CN2012102439917 A CN 2012102439917A CN 201210243991 A CN201210243991 A CN 201210243991A CN 102765743 A CN102765743 A CN 102765743A
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Abstract
The invention discloses a method for preparing a corn-shaped multilevel structure zinc oxide nanorod array film, which is characterized by comprising the following steps: putting a zinc sheet in a muffle furnace with a certain temperature, and holding to obtain a ZnO nanoparticle seed layer; dissolving equal mol of zinc nitrate hexahydrate and hexamethylenetetramine to prepare an array growth system solution; vertically inserting the zinc sheet into the array growth system solution, and keeping the temperature in a water bath to grow, wherein sulfhydrylsuccinic acid is added in the growth period; and finally, taking out the zinc sheet, flushing, and airing to obtain the corn-shaped multilevel structure zinc oxide nanorod array film, wherein the rod core diameter is 40-200nm, the shell particle size is 10-80nm, and the rod length is 0.2-2 mu m. By regulating the holding temperature and time of the zinc sheet in the muffle furnace, the concentration of the array growth system solution and the water bath holding temperature, the invention can effectively control the growth size of the multilevel structure ZnO nanorod to form a film, so that the ZnO array film has more practical meanings.
Description
Technical field
The invention relates to the method that a kind of method, especially solution method that on the metal zinc metal sheet, prepares corn shape multilevel hierarchy ZnO nano-stick array thin film prepares the ZnO nano-stick array thin film.Belong to the inorganic nanometer functional technical field of material.
Background technology
Zinc oxide (ZnO) is a kind of important semiconductor material with wide forbidden band, and energy gap is 3.37eV under the room temperature, and exciton bind energy all has broad application prospects in fields such as photoelectricity, information and sensings up to 60meV.And nano ZnO material has advantages such as specific surface area is big, chemicalstability is strong, specific conductivity is high, electrochemical activity have good biocompatibility, biological safety and biological degradability etc. simultaneously.In addition, nano-ZnO has very strong self-organizing growth ability, under stable preparation condition, its molecular interaction clearly, molecular energy is in strict accordance with the lattice arrangement epitaxy, forms the structure that composition is single, proportioning is complete.ZnO nano material through difference growth means preparations has abundant pattern: particle, flower-shaped, banded, needle-like, sheet, tower shape, cage shape and many composite structures; The nano-device accurate for the designing and preparing microscale structure provides condition, photoelectricity, information, and field such as sensing all have broad application prospects.
Prepare at present the main gas phase transportation act of method, thermal evaporation, electrochemical deposition method, hydrothermal solution method, sol-gel method, the precipitator method of ZnO nano material etc.Present most of ZnO nano material compound method is owing to there is gas phase to participate in, and preparation temperature is high, and conversion unit is complicated, and preparation cost is high, so liquid phase is synthetic more and more comes into one's own.Especially being used in combination of multiple synthesizing mean, more universal in the preparation of ZnO nano-array material.For example lift, be spin-coated on preparation crystal Seed Layer on the base material, again through the precipitator method or means such as hydrothermal method, electrochemical deposition two one-step growth ZnO nanometer stick arrays with magnetron sputtering or Sol-Gel method.The two-step method making complicacy that the process of sublayer has that makes preparations for sowing needs meticulous repetitive operation; The cost that has is higher, needs high-temperature high-pressure apparatus.
The present invention with the metal zinc metal sheet as base material; Can directly obtain layer of ZnO nano particle Seed Layer through high temperature oxidation; And obtain being orientated good ZnO nanometer stick array at growth from solution; Through during nanorod growth, adding the structure directing agent dimercaptosuccinic acid, be that nanometer rod is that core, shell are the multistage ZnO nanometer rod of corn shape of ZnO crystal grain stacked in multi-layers in the middle of obtaining at last, and can mass preparation become array film simultaneously.The more important thing is; Adopt the multilevel hierarchy nanometer stick array of this method preparation; Its shell intercrystalline has active hydroxy-acid group, carries out surface chemical modification easily, and nano material firmly is connected with chemical molecular or biomolecules; So that this film has more Practical significance widely, can be used for electronic information, photosignal, bioinformation detection and medical diagnosis on disease and analyze.
Summary of the invention
The objective of the invention is in order to make the ZnO nanometer rod of forming array film grow into the multi-level nano-structure of corn shape through modification; Use metal zinc metal sheet has been proposed first as base material; Simplified obtaining of crystal seed layer through high-temperature oxidation process, and added the method for dimercaptosuccinic acid modification in the ZnO crystal process of growth.
A kind of method that adopts the hydrothermal chemistry sedimentation on zinc metal sheet, to prepare corn shape multilevel hierarchy ZnO nano-stick array thin film is characterized in that may further comprise the steps:
(a) at first zinc metal sheet is polished, cleaned, be placed on 150 ~ 380 again
o0.3 ~ 1.5h is handled in insulation in the retort furnace of C, thereby obtains the ZnO nano particle Seed Layer of about 0.2 ~ 1 μ m of thickness on the zinc metal sheet surface;
(b) equimolar zinc nitrate hexahydrate and hexamethylenetetramine are dissolved in the zero(ppm) water, being made into concentration is the array growth system solution of 0.01 ~ 0.5mol/mL;
(c) with the vertical insertion 60 ~ 95 of the zinc metal sheet after the above-mentioned processing
oInsulation growth in the array of the C growth system solution, when 0.5 ~ 8h, adding concentration is the dimercaptosuccinic acid solution of 0.0005 ~ 0.01 mol/L, it is 1 ~ 3:10 with array growth system solution volume ratio, continues cooling and taking-up zinc metal sheet behind insulation growth 6 ~ 14h then;
(d) using temperature is 30 ~ 80
oArray on the distilled water flushing zinc metal sheet of C 3 ~ 5 times at room temperature dries then, and promptly having obtained excellent core diameter on the zinc metal sheet surface is that 40 ~ 200nm, shell particle diameter are that 10 ~ 80nm, rod length are the corn shape multilevel hierarchy ZnO nano-stick array thin film of 0.2 ~ 2 μ m.
The invention has the beneficial effects as follows; In control ZnO nanorod growth process (excellent core diameter from 50 nanometers to 200 nanometers; To 80 nanometers, the nanometer rod total length is between 200 nanometers to 2 micron from 10 nanometers for shell crystal grain); Can control the nanostructure pattern that ZnO crystal is formed again, and in finishing useful organo-functional group.This method has shortened technical process, has practiced thrift the energy, can realize the scale prodn application, has Practical significance widely.
Description of drawings
Fig. 1. the ZnO nanometer stick array of corn shape multilevel hierarchy is overlooked electron scanning micrograph;
Fig. 2. the corn shape multilevel hierarchy ZnO nanometer stick array side electron scanning micrograph of excellent core 50nm, shell grain-size 20 * 60nm, the long 500nm of rod.
Embodiment
Below in conjunction with embodiment and comparative example the present invention is done detailed elaboration, but therefore do not limit the present invention within the described scope of embodiments.
At first zinc metal sheet is polished, cleaned, be placed on 250 again
oBe incubated 1h in the retort furnace of C, obtain ZnO nano particle Seed Layer on the zinc metal sheet surface.With equimolar zinc nitrate hexahydrate (ZnO (NO
3)
26H
2O), hexamethylenetetramine ((CH
3)
6N
4) be dissolved in the zero(ppm) water, stir, obtaining concentration is the array growth system solution of 0.025mol/mL.Pretreated zinc metal sheet is vertically inserted array growth system solution, 85
oThe C water bath heat preservation adds properties-correcting agent dimercaptosuccinic acid (MSA) 0.002 mol/L when 5h, properties-correcting agent and array growth solution volume ratio are 1:10, and lowering the temperature behind the continuation insulation 7h stops growing.Take out zinc metal sheet, with 60
oC distilled water flushing 5 times, room temperature is dried, and promptly obtains corn shape multilevel hierarchy ZnO nano-stick array thin film on the zinc metal sheet surface.
The present invention compared with prior art, the key distinction is to use the metal zinc metal sheet to be the array substrate material, through simple high-temperature oxidation process, has simplified the preparation time and the Financial cost of ZnO nano particle Seed Layer; And on existing solution method technical foundation, added dimercaptosuccinic acid as structure modifier, the ZnO wafer can be grown in the outer stack of ZnO nanometer rod, the formation nanometer rod is a core, and stratiform crystal grain is the corn shape multi-level nano-structure of shell.Hydroxy-acid group between the ZnO crystal grain layer makes film more easily by chemical modification.Practical implementation of the present invention and comparative example are seen table 1 for details.
Table 1
Used zinc metal sheet is all 350 in the table 1
oThe retort furnace insulation 45min of C; Used MSA concentration is 0.002 mol/L, and itself and array growth system solution volume ratio are 1.5:10.
Claims (1)
1. method that adopts the hydrothermal chemistry sedimentation on zinc metal sheet, to prepare corn shape multilevel hierarchy ZnO nano-stick array thin film is characterized in that may further comprise the steps:
(a) at first zinc metal sheet is polished, cleaned, be placed on 150 ~ 380 again
o0.3 ~ 1.5h is handled in insulation in the retort furnace of C, thereby obtains the ZnO nano particle Seed Layer of about 0.2 ~ 1 μ m of thickness on the zinc metal sheet surface;
(b) equimolar zinc nitrate hexahydrate and hexamethylenetetramine are dissolved in the zero(ppm) water, being made into concentration is the array growth system solution of 0.01 ~ 0.5mol/mL;
(c) zinc metal sheet with above-mentioned processing vertically inserts 60 ~ 95
oInsulation growth in the array of the C growth system solution, when 0.5 ~ 8h, adding concentration is the dimercaptosuccinic acid solution of 0.0005 ~ 0.01 mol/L, it is 1 ~ 3:10 with array growth system solution volume ratio, continues cooling and taking-up zinc metal sheet behind insulation growth 6 ~ 14h then;
(d) using temperature is 30 ~ 80
oArray on the distilled water flushing zinc metal sheet of C 3 ~ 5 times at room temperature dries then, and promptly having obtained excellent core diameter on the zinc metal sheet surface is that 40 ~ 200nm, shell particle diameter are that 10 ~ 80nm, rod length are the corn shape multilevel hierarchy ZnO nano-stick array thin film of 0.2 ~ 2 μ m.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043707A (en) * | 2013-01-14 | 2013-04-17 | 四川大学 | Preparation method of perpendicular array ZnO nanowire |
| CN104096560A (en) * | 2014-07-21 | 2014-10-15 | 安徽师范大学 | ZnO/Pt heterogeneous nano array structural material as well as preparation method and application thereof |
| CN104155284A (en) * | 2014-08-15 | 2014-11-19 | 中国工程物理研究院化工材料研究所 | ZnO-Ag surface enhanced Raman scattering chip, and making method, preserving method and use thereof |
| CN112158875A (en) * | 2020-10-09 | 2021-01-01 | 南京信息工程大学 | Preparation method of isolated ZnO micron rod |
| CN113828298A (en) * | 2021-09-09 | 2021-12-24 | 四川轻化工大学 | Method for improving ZnO surface photovoltage |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1763263A (en) * | 2005-09-27 | 2006-04-26 | 清华大学 | Oriented ZnO nanorod or nanowire film and preparation process thereof |
| CN101045991A (en) * | 2007-04-30 | 2007-10-03 | 四川大学 | Transition metal salt dopping process for preparing magnetic nanometic zinc oxide rod array film |
| CN101234855A (en) * | 2007-02-01 | 2008-08-06 | 四川大学 | On-site chemical modification method for preparing zinc oxide nano-stick array thin film and use thereof |
-
2012
- 2012-07-16 CN CN2012102439917A patent/CN102765743A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1763263A (en) * | 2005-09-27 | 2006-04-26 | 清华大学 | Oriented ZnO nanorod or nanowire film and preparation process thereof |
| CN101234855A (en) * | 2007-02-01 | 2008-08-06 | 四川大学 | On-site chemical modification method for preparing zinc oxide nano-stick array thin film and use thereof |
| CN101045991A (en) * | 2007-04-30 | 2007-10-03 | 四川大学 | Transition metal salt dopping process for preparing magnetic nanometic zinc oxide rod array film |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043707A (en) * | 2013-01-14 | 2013-04-17 | 四川大学 | Preparation method of perpendicular array ZnO nanowire |
| CN103043707B (en) * | 2013-01-14 | 2014-08-13 | 四川大学 | Preparation method of perpendicular array ZnO nanowire |
| CN104096560A (en) * | 2014-07-21 | 2014-10-15 | 安徽师范大学 | ZnO/Pt heterogeneous nano array structural material as well as preparation method and application thereof |
| CN104155284A (en) * | 2014-08-15 | 2014-11-19 | 中国工程物理研究院化工材料研究所 | ZnO-Ag surface enhanced Raman scattering chip, and making method, preserving method and use thereof |
| CN112158875A (en) * | 2020-10-09 | 2021-01-01 | 南京信息工程大学 | Preparation method of isolated ZnO micron rod |
| CN113828298A (en) * | 2021-09-09 | 2021-12-24 | 四川轻化工大学 | Method for improving ZnO surface photovoltage |
| CN113828298B (en) * | 2021-09-09 | 2023-08-22 | 四川轻化工大学 | Method for improving surface photovoltage of ZnO |
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Application publication date: 20121107 |