CN103013500A - Method for preparing Zn/ZnO composite luminescent material - Google Patents
Method for preparing Zn/ZnO composite luminescent material Download PDFInfo
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- CN103013500A CN103013500A CN201210538938XA CN201210538938A CN103013500A CN 103013500 A CN103013500 A CN 103013500A CN 201210538938X A CN201210538938X A CN 201210538938XA CN 201210538938 A CN201210538938 A CN 201210538938A CN 103013500 A CN103013500 A CN 103013500A
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Abstract
The invention discloses a method for preparing a composite hollow structure material, and in particular relates to a method for preparing an inorganic material zinc/zinc oxide luminescent material. A hot-filament chemical gas-phase deposition method is adopted in the invention, and comprises the following steps of: putting a certain amount of ZnO powder serving as a source material into a quartz boat to ensure that the quartz boat is positioned at a certain distance away from the lower part of a tungsten filament; placing a gold-plating substrate at a certain distance away from the lower part of the source material; vacuumizing and then heating at a high temperature; introducing hydrogen and preserving temperature; and reducing the temperature to obtain the Zn/ZnO composite luminescent material. The method has the advantages of high process controllability, low cost and high purity of the manufactured product, and is easy to operate. The product prepared by the preparation method has wide application in industries such as semiconductors and illumination.
Description
Technical field
The present invention relates to a kind of preparation method of micro/nano material, specifically refer to a kind of preparation method of inorganic materials zinc/zinc oxide luminescent material.
Technical background
ZnO is a kind of broad stopband metal oxide semiconductor material, and its energy gap is 3.37eV, and exciton bind energy is 60meV, and huge potentiality are arranged aspect photovoltaic applications.Photodiode, photocatalyst, sensor and solar cell take zinc oxide as base successfully prepares in the laboratory even has been applied in the industrial production.The method of making ZnO nano material mainly contains template, chemical Vapor deposition process, liquid phase method, solid phase method etc. at present.Chemical Vapor deposition process is to utilize gaseous substance to carry out chemical reaction at solid surface, generates the process of solid-state deposit.Chemical gas-phase method has that device is simple, and raw materials used cost is low, realizes easily the superiority such as large-scale industrial production.The most tempting characteristic of ZnO is the exciton bind energy that has up to 60meV, so high bound energy is so that it is at room temperature difficult by thermal excitation (molecular thermalmotion under the room temperature can be 26meV), thereby greatly improved the excitation-emission mechanism of ZnO material, reduced the sharp threshold values of penetrating under the room temperature.Because the existence of zinc oxide native defect, compound luminous with band-to-band transition except exciton, it is luminous to obtain several intraband transitions.
Along with people to the going deep into of ZnO research, had been found that multiple different luminous mechanism, obtained a plurality of glow peaks under different wave length.This provides good selection to the multiple application of satisfying under the different situations.People are just making great efforts the luminescence phenomenon of different-energy position in the ZnO material is studied fully, wish to choose as required technology of preparing, control preparation condition, strengthen the glow peak of required energy position, suppress other glow peaks, thereby greatly strengthen the using value of ZnO luminescent material aspect.At present, utilizing hot filament CVD to prepare the Zn/ZnO composite luminescent material does not also report.
Summary of the invention
The present invention is directed to deficiency of the prior art, proposed a kind of convenience, effective preparation method.
The present invention is achieved by following technical proposals:
A kind of preparation method of Zn/ZnO composite luminescent material is characterized in that comprising the steps:
(1) take the ZnO powder as source material, place quartz boat, quartz boat is positioned at 1cm place, tungsten filament below, places gold-plated silicon substrate at 2cm place below source material, as shown in Figure 1.Then quartz boat is placed stove, and stove is sealed, sealing wherein generally is to adopt refractory brick to carry out shutoff;
(2) to vacuumizing in the stove, until the stove internal gas pressure reaches-0.1MPa, close vacuum extractor, pass into the rare gas element argon gas, when furnace pressure reaches a normal atmosphere, open vacuum extractor, again the stove internal gas pressure is evacuated to-0.1MPa;
At least repetitive operation 4 times of above-mentioned vacuum;
(3) completing steps (2), exhaust vacuum after, stove is heated, until be warming up to 950～1050 ° of C, pass into 100sccm hydrogen, be incubated 5～10 minutes; Sccm wherein is volumetric flow rate unit, English full name: standard-state cubic centimeter per minute, and meaning is: mark condition milliliter per minute;
(4) then stove is cooled to room temperature naturally, take out substrate, products therefrom is the Zn/ZnO composite luminescent material on the substrate.
As preferably, the stove described in above-mentioned preparation method's the step (1) is the hot-wire chemical gas-phase deposition stove.
Said process of the present invention is to adopt hot filament CVD, taking by weighing a certain amount of ZnO powder with electronic balance is that source material places quartz boat, quartz boat is positioned at 1cm place, tungsten filament below, place gold-plated silicon substrate at 2cm place below source material, as shown in Figure 1, then quartz boat is placed stove, the air inlet air outlet respectively adds a refractory brick, capping.Start mechanical pump, intraductal atmospheric pressure is reached-0.1MPa, close valve, pass into an amount of argon gas, when overpressure reaches a normal atmosphere, drive valve and be communicated with atmosphere, again start the oxygen in four eliminating tube furnace furnace chambers of the above operation of mechanical pump repetition.Start stove, be warming up to 950～1050 ° of C, pass into 100sccm hydrogen, be incubated 5～10 minutes.Stove cools to room temperature naturally, closes gas, takes out substrate, and products therefrom is the Zn/ZnO composite luminescent material on the substrate.
Beneficial effect: in the preparation process of the present invention, agents useful for same is commerical prod, need not loaded down with trivial details preparation; Process controllability is strong, and is easy to operate, and cost is low, and the product purity that makes is high.
Description of drawings
Fig. 1 is the inventive method hot filament chemical vapor deposition reactor device synoptic diagram;
Fig. 2 is scanning electron microscope (SEM) photo of the Zn/ZnO composite luminescent material that makes with 1000 ° of C of the present invention;
Fig. 3 is scanning electron microscope (SEM) photo of the Zn/ZnO composite luminescent material that makes with 1000 ° of C of the present invention;
Fig. 4 is X-ray diffraction (XRD) spectrogram of the Zn/ZnO composite luminescent material that makes with 1000 ° of C of the present invention;
Fig. 5 is luminescent spectrum (PL) figure of the Zn/ZnO composite luminescent material that makes with 1000 ° of C of the present invention;
Embodiment
Further specify the present invention below in conjunction with example.
Embodiment 1
Taking by weighing a certain amount of ZnO powder with electronic balance is that source material places quartz boat, and quartz boat is positioned at 1cm place, tungsten filament below, places gold-plated silicon substrate at 2cm place below source material, as shown in Figure 1, then quartz boat is placed stove, the air inlet air outlet respectively adds a refractory brick, capping.Start mechanical pump, intraductal atmospheric pressure is reached-0.1MPa, close valve, pass into an amount of argon gas, when overpressure reaches a normal atmosphere, drive valve and be communicated with atmosphere, again start the oxygen in four eliminating tube furnace furnace chambers of the above operation of mechanical pump repetition.Start stove, be warming up to 1000 ° of C, pass into 100sccm hydrogen, be incubated 5 minutes.Stove cools to room temperature naturally, closes gas, takes out substrate, and products therefrom is the Zn/ZnO composite luminescent material on the substrate.Products therefrom is directly observed under scanning electron microscope, as shown in Figure 2, can be found that a large amount of diameters generate at 4 to 5 microns spherical particle.Fig. 3 can find out that this spherical particle is hollow structure.The XRD analysis of Fig. 4 shows that the structure of product is comprised of hexagonal system ZnO and hexagonal system Zn, has formed composite structure.Fig. 5 is the PL figure of product, wherein the broad peak at 530nm place be since generation cause the red shift of defect luminescence peak.Exist relatively strong green luminescence peak to show the defective that has a large amount of oxygen room and Zn space in this hollow compound structural among Fig. 5, improved the luminescent properties of single oxide.
Embodiment 2
As embodiment 1, taking by weighing a certain amount of ZnO powder with electronic balance is that source material places quartz boat, quartz boat is positioned at 1cm place, tungsten filament below, place gold-plated silicon substrate at 2cm place below source material, as shown in Figure 1, then quartz boat is placed stove, the air inlet air outlet respectively adds a refractory brick, capping.Start mechanical pump, intraductal atmospheric pressure is reached-0.1MPa, close valve, pass into an amount of argon gas, when overpressure reaches a normal atmosphere, drive valve and be communicated with atmosphere, again start the oxygen in four eliminating tube furnace furnace chambers of the above operation of mechanical pump repetition.Start stove, be warming up to 950 ° of C, pass into 100sccm hydrogen, be incubated 10 minutes.Stove cools to room temperature naturally, closes gas, takes out substrate, and products therefrom is the Zn/ZnO composite luminescent material on the substrate.The pattern of product, structure, composition and luminescent properties are all identical with embodiment 1.
Embodiment 3
As embodiment 1, taking by weighing a certain amount of ZnO powder with electronic balance is that source material places quartz boat, quartz boat is positioned at 1cm place, tungsten filament below, place gold-plated silicon substrate at 2cm place below source material, as shown in Figure 1, then quartz boat is placed stove, the air inlet air outlet respectively adds a refractory brick, capping.Start mechanical pump, intraductal atmospheric pressure is reached-0.1MPa, close valve, pass into an amount of argon gas, when overpressure reaches a normal atmosphere, drive valve and be communicated with atmosphere, again start the oxygen in four eliminating tube furnace furnace chambers of the above operation of mechanical pump repetition.Start stove, be warming up to 985 ° of C, pass into 100sccm hydrogen, be incubated 10 minutes.Stove cools to room temperature naturally, closes gas, takes out substrate, and products therefrom is the Zn/ZnO composite luminescent material on the substrate.The pattern of product, structure, composition and luminescent properties are all identical with embodiment 1.
Embodiment 4
As embodiment 1, taking by weighing a certain amount of ZnO powder with electronic balance is that source material places quartz boat, quartz boat is positioned at 1cm place, tungsten filament below, place gold-plated silicon substrate at 2cm place below source material, as shown in Figure 1, then quartz boat is placed stove, the air inlet air outlet respectively adds a refractory brick, capping.Start mechanical pump, intraductal atmospheric pressure is reached-0.1MPa, close valve, pass into an amount of argon gas, when overpressure reaches a normal atmosphere, drive valve and be communicated with atmosphere, again start the oxygen in four eliminating tube furnace furnace chambers of the above operation of mechanical pump repetition.Start stove, be warming up to 1015 ° of C, pass into 100sccm hydrogen, be incubated 5 minutes.Stove cools to room temperature naturally, closes gas, takes out substrate, and products therefrom is the Zn/ZnO composite luminescent material on the substrate.The pattern of product, structure, composition and luminescent properties are all identical with embodiment 1.
Embodiment 5
As embodiment 1, taking by weighing a certain amount of ZnO powder with electronic balance is that source material places quartz boat, quartz boat is positioned at 1cm place, tungsten filament below, place gold-plated silicon substrate at 2cm place below source material, as shown in Figure 1, then quartz boat is placed stove, the air inlet air outlet respectively adds a refractory brick, capping.Start mechanical pump, intraductal atmospheric pressure is reached-0.1MPa, close valve, pass into an amount of argon gas, when overpressure reaches a normal atmosphere, drive valve and be communicated with atmosphere, again start the oxygen in four eliminating tube furnace furnace chambers of the above operation of mechanical pump repetition.Start stove, be warming up to 1050 ° of C, pass into 100sccm hydrogen, be incubated 8 minutes.Stove cools to room temperature naturally, closes gas, takes out substrate, and products therefrom is the Zn/ZnO composite luminescent material on the substrate.The pattern of product, structure, composition and luminescent properties are all identical with embodiment 1.
Claims (2)
1. the preparation method of a Zn/ZnO composite luminescent material is characterized in that comprising the steps:
(1) take the ZnO powder as source material, place quartz boat, quartz boat is positioned at 1cm place, tungsten filament below, places gold-plated silicon substrate at 2cm place below source material; Then quartz boat is placed stove, and stove is sealed;
(2) to vacuumizing in the stove, until the stove internal gas pressure reaches-0.1MPa, close vacuum extractor, pass into the rare gas element argon gas, when furnace pressure reaches a normal atmosphere, open vacuum extractor, again the stove internal gas pressure is evacuated to-0.1MPa;
At least repetitive operation 4 times of above-mentioned vacuum;
(3) completing steps (2), exhaust vacuum after, stove is heated, until be warming up to 950～1050 ° of C, pass into 100sccm hydrogen, be incubated 5～10 minutes;
(4) then stove is cooled to room temperature naturally, take out substrate, products therefrom is the Zn/ZnO composite luminescent material on the substrate.
2. preparation method according to claim 1 is characterized in that the stove described in the step (1) is the hot-wire chemical gas-phase deposition stove.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108620054A (en) * | 2018-05-04 | 2018-10-09 | 长春理工大学 | A kind of coralliform Zn-ZnO composite material and preparation methods |
| CN115739121A (en) * | 2022-11-14 | 2023-03-07 | 中国科学院福建物质结构研究所 | Metal-coated composite semiconductor material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618269A (en) * | 2012-03-13 | 2012-08-01 | 浙江理工大学 | Method for preparing nano luminescent material with CdS/Sn alloplasmic structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618269A (en) * | 2012-03-13 | 2012-08-01 | 浙江理工大学 | Method for preparing nano luminescent material with CdS/Sn alloplasmic structure |
Non-Patent Citations (1)
| Title |
|---|
| 丛亮 等: "ZnO：Zn的光致发光和电致发光性能", 《功能材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108620054A (en) * | 2018-05-04 | 2018-10-09 | 长春理工大学 | A kind of coralliform Zn-ZnO composite material and preparation methods |
| CN115739121A (en) * | 2022-11-14 | 2023-03-07 | 中国科学院福建物质结构研究所 | Metal-coated composite semiconductor material and preparation method and application thereof |
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