CN100428502C - Method for preparation of a-b orientated ZnO nanometer linear array - Google Patents

Method for preparation of a-b orientated ZnO nanometer linear array Download PDF

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CN100428502C
CN100428502C CNB2006100226709A CN200610022670A CN100428502C CN 100428502 C CN100428502 C CN 100428502C CN B2006100226709 A CNB2006100226709 A CN B2006100226709A CN 200610022670 A CN200610022670 A CN 200610022670A CN 100428502 C CN100428502 C CN 100428502C
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zno nano
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CN101038943A (en
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邓宏
韦敏
陈金菊
戴丽萍
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University of Electronic Science and Technology of China
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Abstract

The invention provides a method for preparing ZnO nano line array in a-b orientation which belongs to electronic material technical field, relates to wide bond gap semiconductor ZnO luminescent material, especially relates to a method for preparing ZnO nano line array. The invention uses chemical vapor deposition technique, and employs pure ZnO powder as evaporation source and sapphire Al2O3 (1120) as substrate, and controls the temperature of the evaporation source to be no less than the thermal decomposition temperature of the ZnO powder and the temperature of the substrate to be no less than 750 DEG C. and vacuum degree at 200 to 300 torr, and employs Ar gas as transmission gas with gas flow rate of 35 sccm. In this manner, the ZnO powder is heated to decompose into Zn and O, and then by Ar gas transmission, the ZnO nano line array in a-b orientation is deposited on the substrate. The invention employs current chemical vapor deposition technique, and can easily prepare the ZnO nano line array in a-b orientation which has excellent uv sensitive character and quick light response speed.

Description

A kind of preparation method of a-b oriented ZnO nano linear array
Technical field
The invention belongs to technical field of electronic materials, relate to wide bandgap semiconductor ZnO luminescent material, particularly the preparation method of ZnO nano-wire array.
Technical background
ZnO is because of exciton bind energy big (60mev) in recent years, can obtain ultra-violet light-emitting efficiently and become another research focus behind the GaN material in room temperature.Wherein ZnO nano-wire array system is expected as nano photoelectric device of future generation.What at first receive publicity is to have height-oriented ZnO nano-wire array as natural laserresonator, can produce Ultra-Violet Laser when being excited, and the ZnO nano wire has extremely low optical excitation threshold value 40kW/cm 2(thin-film material is 300kW/cm 2～4MW/cm 2), chemism and one-dimensional nano structure, make the ZnO nano wire become one of ideal material of making the ultraviolet nanometer laser; Simultaneously, the ZnO nano-wire array has high brightness and good stability of photoluminescence, and its electronic field emission performance can satisfy the requirement of flat-panel display device brightness, is a kind of flat-panel monitor luminescent material of being potential very much; The ZnO nano-wire array has good ultraviolet sensitivity characteristic, so the ZnO nano-wire array can be used for making high-sensitivity ultraviolet detector and optical switch; The ZnO nano-wire array also can be used for making transducer and memory device in addition, nanometer resonance tunnel device, and field-effect transistors etc. have broad application prospects in fields such as Aero-Space, information communications.
At present existing many methods all can prepare the ZnO nano wire, as vapor transportation method, chemical vapor deposition (CVD) method, pulse laser high temperature evaporation method, electrodeposition process, sol-gel process, hydro thermal method, template lambda limiting process and microemulsion method etc.
In the preparation of ZnO nano-material, one of most critical issue is the ZnO nano wire of preparation oriented growth.The great majority that the preparation method who has reported obtains are c axle preferrel orientation ZnO nano-arrays; And the ZnO nano-wire array with obvious a-b orientation, promptly the C axle is parallel to the ZnO nano-wire array of substrate growth, does not also appear in the newspapers as yet.And after the photoelectric properties test, find this a-b oriented ZnO nano linear array, have the responsive characteristic of very strong ultraviolet light (the ZnO nano-array that is better than c axle orientation), particularly its speed of photoresponse fast (less than 50 μ s) is very favorable factor as photoelectric device.
Summary of the invention
The ZnO nano-wire array that the present invention adopts the chemical vapour deposition technique preparation to have the a-b orientation.Vapour deposition process utilizes the gas-phase reaction of high-temperature physics evaporation or organo-metallic compound, by the gas transmission, makes reactant deposit on the low-temperature substrate and is grown to one-dimentional structure.The direction of growth of ZnO nano-wire array of the present invention and size have reasonable controllability, chemical vapour deposition technique deposition height, and chemical constituent is controlled easily, and the crystal defect of formation is less, and has the hot properties of suitable nanowire growth.
The present invention adopts chemical vapour deposition technique, as shown in Figure 1, is evaporation source with pure ZnO powder, adopts sapphire Al 2O 3As substrate, the temperature of control evaporation source is not less than the heat decomposition temperature of ZnO powder, the control underlayer temperature is not less than 750 ℃, and vacuum degree is held in the palm at 200-300, and transport gas adopts Ar gas, throughput is 35sccm, making the ZnO powder decomposes is Zn and O, again by argon gas transmission, deposition growing a-b oriented ZnO nano linear array on substrate, it is characterized in that described sapphire Al 2O 3Substrate is Al 2O 3(1120).
Need to prove about technical solution of the present invention:
1, key of the present invention
The present invention adopts sapphire Al 2O 3(1120) substrate preparation ZnO nano-wire array (as sample 1 among Fig. 2 (a)) as a comparison, adopts sapphire Al 2O 3(0001) the ZnO nano-wire array of substrate acquisition (as sample 2 among Fig. 2 (a)).The pattern of two kinds of samples and structure are as Fig. 2 (b) with (c).As Fig. 2 (a), when using sapphire Al 2O 3(0001) during substrate, 2 appearance of sample (002) peak; And use sapphire Al 2O 3(1120) during substrate, the ZnO of sample 1 (002) peak is very little, almost disappear, and (100) peak and (110) peak are all very strong, show the selection of substrate, and be an of paramount importance influencing factor to the oriented growth of nano wire.
2, technical conditions of the present invention
The temperature in better controlled source is very important, and the speed that decompose in necessary assurance source is suitable, and source temperature is too high or low excessively, and is all unfavorable to the growth of ZnO nano wire.
Also must guarantee certain substrate temperature during growing ZnO nano-wire, when other condition (as reactor volume, oxygen partial pressure etc.) was identical, substrate temperature was high more, and vapour pressure is big more, and the yardstick of the ZnO nano wire of preparation is just big more, arrangement is also intensive more.The yardstick of ZnO nano wire increases with the rising of substrate temperature.
Under the certain situation of raw material and temperature, the gaseous phase partial pressure in the reactor directly has influence on the product pattern.Container size, raw material consumption, gas flow rate and kind all have influence on the gas phase saturation in the reactor.
Feed argon gas in the reaction system, control throughput and sedimentation time also are The key factor very.Throughput is too small or sedimentation time is too short, can not get nano wire, and excessive then nano wire is grown uneven.Suitable throughput and sedimentation time can obtain well-grown nano wire.
3, performance characteristic of the present invention
Fig. 3 is the I-V curve that adopts the prepared ZnO nano-wire array typical sample with a-b orientation of the present invention.Au interdigital electrode and ZnO nano-wire array form ohmic contact.Its dark current is 8 μ A when voltage is 5V, and when with the 256nm UV-irradiation, its bright electric current is 248.2 μ A, and wherein photogenerated current is 240.2 μ A, illustrates that the ZnO nano-wire array of a-b orientation has good ultraviolet sensitivity performance.
Add a constant 5V voltage to sample, adopt same 256nm ultra violet lamp sample, the electric current of sample changes by the automatic record of XY recorder, Fig. 4 has shown the ultraviolet light response that it is stable, can see in time of 50 μ s and rise to 217.3 μ A from 8 μ A, when uviol lamp was closed, electric current dropped to 23.7 μ A from 248 μ A in the time of 20 μ s, illustrated that the ZnO nano-wire array of the a-b axle orientation of growing on sapphire has response fast to ultraviolet light.
Adopt spectrophotometer as the light source irradiation sample, the optical responsivity of specimen.Fig. 5 is the optical responsivity curve of typical sample, and illustration wherein is the SEM figure of ZnO nano wire.In the 250nm-354nm scope, the optical responsivity of nano wire becomes greatly with the increase of optical source wavelength, and the optical responsivity maximum of ZnO nano wire is 0.56A/W when wavelength is 354nm.The responsiveness of sample begins to descend subsequently, and when wavelength during greater than 450nm, responsiveness drops to 0.14A/W.Fig. 4 can see that there is more obviously " blue shift " phenomenon in the typical ZnO film sample of the absorption band of ZnO nano wire.
The invention has the beneficial effects as follows:
The present invention utilizes existing chemical vapour deposition technique, and the employing ZnO powder is an evaporation source, adopts sapphire Al 2O 3(1120) as substrate, prepare ZnO nano-wire array easily with a-b orientation, the ZnO nano-wire array of resulting a-b orientation has responsive characteristic of good ultraviolet light and fast speed of photoresponse.
Description of drawings
Fig. 1 is preparation method's the schematic flow sheet of the ZnO nano-wire array of a kind of a-b orientation of the present invention.
Fig. 2 (a) is the XRD figure spectrum of two kinds of samples, and wherein: sample 1 is to adopt sapphire Al 2O 3(1120) substrate preparation ZnO nano-wire array (promptly adopting the ZnO nano-wire array of the prepared a kind of a-b orientation of the present invention), sample 2 is to adopt sapphire Al 2O 3(0001) the ZnO nano-wire array of substrate acquisition (being the ZnO nano-wire array of existing c-axle orientation); (b) be the ZnO nano-wire array SEM figure that on sapphire (1120) substrate, grows; (c) be the ZnO nano-wire array SEM figure that on sapphire (0001) substrate, grows.
Fig. 3 is the ZnO nano-wire array that adopts the prepared a kind of a-b orientation of the present invention at the-5V I-V curve under the 5V bias voltage.
Fig. 4 is the ultraviolet light response collection of illustrative plates of ZnO nano-wire array under 5V bias voltage, 256nm UV-irradiation that adopts the prepared a kind of a-b orientation of the present invention.
Fig. 5 is the photoresponse collection of illustrative plates that adopts the ZnO nano-wire array of the prepared a kind of a-b orientation of the present invention.
Embodiment
The ZnO nano wire is to utilize two warm area CVD systems produce among the present invention.Whole system can be divided into air path part, growth room and control section.
Concrete implementation step is as follows:
1. the preparation of evaporation source
The pure ZnO powder of analysis that adopts Tianjin City Chemical Agent Research Institute production among the present invention is as evaporation source.
2. sapphire Al 2O 3(1120) cleaning step of substrate base:
1) cleans;
2) soak: use potassium bichromate solution, use washed with de-ionized water then;
3) ultrasonic cleaning 1: in the deionized water, and 5～10 minutes, twice;
4) ultrasonic cleaning 2: in the acetone, and 5～10 minutes, twice;
5) ultrasonic cleaning 3: in the absolute ethyl alcohol, and 5～10 minutes, twice;
6) drying;
7) stand-by.
3. the CVD of zinc oxide nanowire is synthetic
Utilize the elevated temperature heat decomposition reaction of chemical vapour deposition (CVD), reaction equation is as follows:
Figure C20061002267000061
Zn(Vapor)+O→ZnO(nanowire)
The concrete operations step is as follows:
1) evaporation source and substrate are put into CVD system response chamber.ZnO powder is placed in the aluminium oxide boat sapphire Al 2O 3(1120) substrate is positioned over the 10-15cm place, gas circuit downstream in ZnO source.
2) open vacuum pump, system is vacuumized, make the vacuum that keeps the 200-300 holder in the aluminium oxide boiler tube;
3) regulate temperature controller, the boiler tube heating rate is 20 ℃/min, and ZnO powder is decomposed under 1350 ℃ of temperature, makes underlayer temperature be stabilized in 750 ℃ of the growth temperatures of setting;
4) be carrier gas with high-purity Ar (99.99%), open air-transmitting main valve, open gas flowmeter, setting its flow value is 35sccm.Open the valve that links to each other with boiler tube simultaneously, make transport gas enter boiler tube;
5) sedimentation time is 30 minutes, after the end, stops heating earlier, closes air valve again, the adjustments of gas flowmeter, and making its flow is zero, closes the boiler tube valve, closes vacuum pump; Treat to take out sample after furnace tube temperature is reduced to room temperature, promptly obtain the ZnO nano-wire array of a kind of a-b orientation of the present invention after the drying.

Claims (1)

1, a kind of preparation method with ZnO nano-wire array of a-b orientation adopts chemical vapour deposition technique, and concrete chemical vapor deposition conditions is: with pure ZnO powder is evaporation source, adopts sapphire Al 2O 3As substrate, the temperature of control evaporation source is not less than the heat decomposition temperature of ZnO powder, and the control underlayer temperature is not less than 750 ℃, and vacuum degree is held in the palm at 200-300, and transport gas adopts Ar gas, and throughput is 35sccm; Concrete deposition process is: making the ZnO powder decomposes is Zn and O, and by the argon gas transmission, deposition growing a-b oriented ZnO nano linear array is characterized in that on substrate, described sapphire Al again 2O 3Substrate is Al 2O 3(1120).
CNB2006100226709A 2006-12-27 2006-12-27 Method for preparation of a-b orientated ZnO nanometer linear array Expired - Fee Related CN100428502C (en)

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CN101552203B (en) * 2008-04-02 2010-07-21 中国科学院微电子研究所 Method for realizing ZnO nanowire fixation in preparation of ZnO nanowire field effect tube
CN101552205B (en) * 2008-04-02 2010-12-15 中国科学院微电子研究所 Method for realizing positioning of ZnO nanowire to field effect tube substrate
CN101552206B (en) * 2008-04-02 2010-12-15 中国科学院微电子研究所 Method for realizing ZnO nanowire fixation in preparation of ZnO nanowire field effect tube
CN102107852B (en) * 2009-12-24 2013-05-22 中国科学院微电子研究所 Semiconductor nano structure and manufacturing method and application thereof
CN101805012A (en) * 2010-04-02 2010-08-18 北京化工大学 Preparation method of ZnO one-dimensional nanometer material
CN104386647B (en) * 2014-10-27 2016-04-13 暨南大学 A kind of orientation arrangement method of halloysite nanotubes and coating thereof and application
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