CN105551937B - The method of controllable growth nano structure of zinc oxide on doped zinc oxide aluminium electro-conductive glass - Google Patents
The method of controllable growth nano structure of zinc oxide on doped zinc oxide aluminium electro-conductive glass Download PDFInfo
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- CN105551937B CN105551937B CN201510958197.4A CN201510958197A CN105551937B CN 105551937 B CN105551937 B CN 105551937B CN 201510958197 A CN201510958197 A CN 201510958197A CN 105551937 B CN105551937 B CN 105551937B
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Abstract
The method of controllable growth nano structure of zinc oxide, is related to the preparation of nano material on doped zinc oxide aluminium electro-conductive glass.There is provided it is a kind of it is simple for process, at low cost, nontoxic, deposition rate is fast, purity is high, the method for controllable growth nano structure of zinc oxide on doped zinc oxide aluminium electro-conductive glass without adding catalyst.1) substrate is cleaned, removes surface contaminant；2) substrate after cleaning is put into the corundum boat for filling zinc powder, is then placed in centralised temperature area in chemical vapor deposition stove and starts to vacuumize；3) it when the vacuum degree in chemical vapor deposition stove reaches 8.6mbar, starts to warm up, for three-temperature-zone chemical vapor deposition stove, stove both sides temperature is raised to 250 DEG C respectively, and center temperature is raised to 650 DEG C；It is passed through the mixed gas gas of oxygen and argon gas again；4) after step 3) completion, system cools down, you can obtains uniform nano structure of zinc oxide.
Description
Technical field
The present invention relates to the preparations of nano material, more particularly, to one kind on doped zinc oxide aluminium electro-conductive glass controllable growth
The method of nano structure of zinc oxide.
Background technology
Zinc oxide is a kind of II-VI race's oxide semiconductor material, since it has high binding energy and broad-band gap, low dielectric
Constant and other excellent photoelectricity, piezoelectric properties, be widely used in always for many years piezoelectricity conversion, transparent electrode, photonic crystal,
The numerous areas such as solar energy, while it is also a kind of ep-type material of nontoxic and pollution-free low cost.[1-3]Al doping zinc-oxides are thin
Film (AZO) is since its light transmittance is high, stability is good, and non-toxic, material is easy to get, the cheap indium tin that gradually substituting aoxidizes
Object film (ITO).[4-5]Nano structure of zinc oxide, theoretically it may be speculated that its exciton bind energy is bigger, exciton resonance is stronger
It is strong, thus it absorbs and shines and transition spectrum is waited more to narrow, the interaction of light and substance is more effective, it means that zinc-oxide nano
Structure has superior performance in terms of photovoltaic applications, therefore the nano structure of zinc oxide for preparing high quality is caused and widely ground
Study carefully interest.
The technology of preparing of nano structure of zinc oxide has much at present, for example sol-gel method (sol-gel), metal are organic
Vapor phase epitaxial growth (MOVPE), the catalysis reaction growth method of gas-liquid-solid (VLS) mechanism, aqua-solution method, chemical vapor deposition
Method (CVD), wet chemistry method etc..Chinese patent CN101555035 is reported to be received using sol-gel method (sol-gel) preparation
Rice zinc oxide obtains the relatively high Zinc oxide nanoparticle of purity, but this method requires to compare to reaction mixture condition
Harshness, long preparation period, it is of high cost the shortcomings of；Chinese patent CN101700903A combines chemical precipitation method and solid reaction process
Nano zine oxide is prepared, the sample grown has many advantages, such as that grain size is small, purity is high, is not easy to reunite, but the process synthesized needs
Surfactant is added, difficulty is caused to catalyticing research；In addition, metal organic vapor growth method (MOVPE) is although behaviour
Make simply, but AsH used3, PH3Toxicity it is extremely strong and growth rate is slow.Therefore, it is at low cost to prepare one kind, it is easy to operate,
The easily controllable nano zine oxide of growth course has certain economic value.
Bibliography：
[1] new development [J] material Leaders of Jia Xiaolin, Zhang Haijun, Tan Wei zinc-oxide films research, in September, 2003, the
The albums of volume 17：The of page 207~208
[2]A.Janotti,C.G.V.d.Walle,Fundamentals of zinc oxide as a
semiconductor,Rep.Prog.Phys.,72(2009)126501.
[3]Y.I.Alivov,C.Liu,A.Teke,M.A.Reshchikov,S.
V.Avrutin,S.-J.Cho,H.A comprehensive review of ZnO materials and
devices,J.Appl.Phys.,98(2005)041301.
[4]T.Minami and T.Miyata,Thin Solid Films 517,1474(2008).
[5]J.H.Lee,D.G.Lim,K.J.Yang,and W.S.Choi,J.Cryst.Growth 326,50(2011).
Invention content
It is an object of the invention to be directed to the above-mentioned problems in the prior art, provide it is a kind of it is simple for process, at low cost,
It is nontoxic, deposition rate is fast, purity is high, the controllable growth zinc oxide nano on doped zinc oxide aluminium electro-conductive glass without adding catalyst
The method of rice structure.
The present invention includes the following steps：
1) substrate is cleaned, removes surface contaminant；
2) substrate after cleaning is put into the corundum boat for filling zinc powder, is then placed in chemical vapor deposition (CVD) stove
Centralised temperature area simultaneously starts to vacuumize；
3) it when the vacuum degree in chemical vapor deposition (CVD) stove reaches 8.6mbar, starts to warm up, for three-temperature-zone
Vapor deposition (CVD) stove is learned, stove both sides temperature is raised to 250 DEG C respectively, and center temperature is raised to 650 DEG C；It is passed through oxygen and argon again
The mixed gas gas of gas；
4) after step 3) completion, system cools down, you can obtains uniform nano structure of zinc oxide.
In step 1), AZO substrates can be used in the substrate, and AZO electro-conductive glass, the AZO can be used in the AZO substrates
The AZO conduction glass that the specification that the production of Hefei Ke Jing Materials Technology Ltd. can be used in electro-conductive glass is 20mm × 20mm × 2mm
Glass；The cleaning can pass sequentially through ethyl alcohol and acetone is cleaned by ultrasonic.
In step 2), the zinc powder that purity is 99.99% can be used in the zinc powder；The spacing of the zinc powder and substrate can be
3~5cm.
In step 3), the rate of the heating can be 10 DEG C/min；The throughput of the argon gas can be 50sccm, oxygen
Throughput can be 4~8sccm；The time of the mixed gas gas for being passed through oxygen and argon gas can be 15min.
The present invention prepares nano structure of zinc oxide sample using CVD equipment on AZO substrates, creatively proposes and passes through
Corresponding growth parameter(s) is controlled, is of moderate size, size uniform and along the nano structure of zinc oxide of c-axis preferential growth, it can
To apply to ultra-violet light-emitting and piezoelectric sensing etc., before especially having prodigious application in the efficiency for improving solar cell
Scape.In addition, this method have many advantages, such as operating procedure it is simple, it is at low cost, reproducible, can grow in batches, not generate pollution, it is excellent
The preparation method of nano zine oxide complicated now is changed, there is certain economic value.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) figure of the nano structure of zinc oxide obtained by embodiment 1.
Fig. 2 is (SEM) figure of the nano structure of zinc oxide obtained by embodiment 3.
Fig. 3 is X-ray diffraction (XRD) figure of the nano structure of zinc oxide obtained by embodiment.It can be seen from the figure that, nanometer
Structure is along c-axis oriented growth.
Specific implementation mode
Embodiment 1
(1) the AZO substrates of purchase alcohol is cleaned by ultrasonic 10min, then 1min is cleaned with deionized water, then with third
Ketone is cleaned by ultrasonic 10min, Ion Cleaning 1min is finally spent, to obtain the cleaner substrate in surface.
(2) AZO for being put into high-purity zinc powder (purity reaches 99.99%) in the corundum boat that overall length is 10cm and cleaning up
Substrate is placed on zinc powder the position of 2cm, and AZO substrates are placed on the position of 5cm, and the control of the distance between zinc source and substrate is made to exist
3cm, and corundum boat is sent into CVD stoves middle position, wherein zinc powder is located at the pipeline opening end of ventilation, is taken out therewith to stove true
It is empty.
(3) it when vacuum degree reaches 8.6mbar in pipeline, starts setting up parameter and gives stove liter with the speed of 10 DEG C/min
Temperature, for three-temperature-zone stove, both sides temperature is raised to 250 DEG C respectively, and center temperature is raised to 650 DEG C.
(4) start the mixed gas gas that oxygen and inert gas argon gas are passed through to stove on the basis of step (3), argon gas
Throughput remains 50sccm, and the throughput of oxygen is 4.0sccm, and duration of ventilation is set as 15min, can obtain after cooling
To nano structure of zinc oxide.
Scanning electron microscope (SEM) figure of nano structure of zinc oxide obtained by embodiment 1 is referring to figure.
Embodiment 2
(1) the AZO substrates of purchase alcohol is cleaned by ultrasonic 10min, then 1min is cleaned with deionized water, then with third
Ketone is cleaned by ultrasonic 10min, Ion Cleaning 1min is finally spent, to obtain the cleaner substrate in surface.
(2) AZO for being put into high-purity zinc powder (purity reaches 99.99%) in the corundum boat that overall length is 10cm and cleaning up
Substrate is placed on zinc powder the position of 2cm, and AZO substrates are placed on the position of 7cm, and the control of the distance between zinc source and substrate is made to exist
5cm, and corundum boat is sent into CVD stoves middle position, wherein zinc powder is located at the pipeline opening end of ventilation, is taken out therewith to stove true
It is empty.
(3) it when vacuum degree reaches 8.6mbar in pipeline, starts setting up parameter and gives stove liter with the speed of 10 DEG C/min
Temperature, for three-temperature-zone stove, both sides temperature is raised to 250 DEG C respectively, and center temperature is raised to 650 DEG C.
(4) start the mixed gas gas that oxygen and inert gas argon gas are passed through to stove on the basis of step (3), argon gas
Throughput remains 50sccm, and the throughput of oxygen is 4.0sccm, and duration of ventilation is set as 15min, can obtain after cooling
To nano structure of zinc oxide.
Embodiment 3
(1) the AZO substrates of purchase alcohol is cleaned by ultrasonic 10min, then 1min is cleaned with deionized water, then with third
Ketone is cleaned by ultrasonic 10min, Ion Cleaning 1min is finally spent, to obtain the cleaner substrate in surface.
(2) AZO for being put into high-purity zinc powder (purity reaches 99.99%) in the corundum boat that overall length is 10cm and cleaning up
Substrate is placed on zinc powder the position of 2cm, and AZO substrates are placed on the position of 7cm, and the control of the distance between zinc source and substrate is made to exist
5cm, and corundum boat is sent into CVD stoves middle position, wherein zinc powder is located at the pipeline opening end of ventilation, is taken out therewith to stove true
It is empty.
(3) it when vacuum degree reaches 8.6mbar in pipeline, starts setting up parameter and gives stove liter with the speed of 10 DEG C/min
Temperature, for three-temperature-zone stove, both sides temperature is raised to 250 DEG C respectively, and center temperature is raised to 650 DEG C.
(4) start the mixed gas gas that oxygen and inert gas argon gas are passed through to stove on the basis of step (3), argon gas
Throughput remains 50sccm, and the throughput of oxygen is 8.0sccm, and duration of ventilation is set as 15min, can obtain after cooling
To nano structure of zinc oxide.
(SEM) figure of nano structure of zinc oxide obtained by embodiment 3 is referring to Fig. 2.
X-ray diffraction (XRD) figure of nano structure of zinc oxide obtained by embodiment is referring to Fig. 3.
It can be seen from the figure that, nanostructure is along c-axis oriented growth.
In conclusion different nanostructures can be prepared by controlling growth parameter(s), it is raw that the foregoing is merely the present invention
Long preferably nanostructure.
Claims (7)
1. the method for controllable growth nano structure of zinc oxide on doped zinc oxide aluminium electro-conductive glass, it is characterised in that including following step
Suddenly：
1) doped zinc oxide aluminium electro-conductive glass is cleaned, removes surface contaminant；
2) the doped zinc oxide aluminium electro-conductive glass after cleaning is put into the corundum boat for filling zinc powder, is then placed in chemical vapor deposition
Lu Nei centralised temperatures area simultaneously starts to vacuumize；
3) it when the vacuum degree in chemical vapor deposition stove reaches 8.6mbar, starts to warm up, for three-temperature-zone chemical vapor deposition
Stove, stove both sides temperature are raised to 250 DEG C respectively, and center temperature is raised to 650 DEG C；It is passed through the mixed gas gas of oxygen and argon gas, institute again
The time for stating the mixed gas gas for being passed through oxygen and argon gas is 15min；
4) after step 3) completion, system cools down to get to uniform nano structure of zinc oxide.
2. as described in claim 1 on doped zinc oxide aluminium electro-conductive glass controllable growth nano structure of zinc oxide method, it is special
Sign is the doped zinc oxide aluminium electro-conductive glass that the doped zinc oxide aluminium electro-conductive glass uses specification as 20mm × 20mm × 2mm.
3. as described in claim 1 on doped zinc oxide aluminium electro-conductive glass controllable growth nano structure of zinc oxide method, it is special
Sign is that in step 1), the cleaning is to pass sequentially through ethyl alcohol and acetone ultrasonic cleaning.
4. as described in claim 1 on doped zinc oxide aluminium electro-conductive glass controllable growth nano structure of zinc oxide method, it is special
Sign be in step 2), the zinc powder use purity for 99.99% zinc powder.
5. as described in claim 1 on doped zinc oxide aluminium electro-conductive glass controllable growth nano structure of zinc oxide method, it is special
Sign is that in step 2), the spacing of the zinc powder and doped zinc oxide aluminium electro-conductive glass is 3~5cm.
6. as described in claim 1 on doped zinc oxide aluminium electro-conductive glass controllable growth nano structure of zinc oxide method, it is special
Sign is that in step 3), the rate of the heating is 10 DEG C/min.
7. as described in claim 1 on doped zinc oxide aluminium electro-conductive glass controllable growth nano structure of zinc oxide method, it is special
Sign is that in step 3), the throughput of the argon gas is 50sccm, and the throughput of oxygen is 4~8sccm.
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| 掺铝氧化锌透明导电薄膜上无催化剂生长ZnO纳米棒阵列及其光学特性研究;林算治;《中国优秀硕士学位论文全文数据库》;20140228;正文第20页第1段-第26页第2段 * |
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