CN103602334B - A kind of all-sulphide phosphor and preparation method thereof - Google Patents
A kind of all-sulphide phosphor and preparation method thereof Download PDFInfo
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- CN103602334B CN103602334B CN201310337350.2A CN201310337350A CN103602334B CN 103602334 B CN103602334 B CN 103602334B CN 201310337350 A CN201310337350 A CN 201310337350A CN 103602334 B CN103602334 B CN 103602334B
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Abstract
The present invention relates to fluorescent material, refer in particular to a kind of all-sulphide phosphor and preparation method thereof.The present invention is with analytically pure C
4h
6cdO
4× 4H
2o, C
4h
6coO
4× 4H
2o, CrCl
3× 6H
2o is raw material, thiocarbamide be precipitation agent, dehydrated alcohol as solvent, prepare sulfide Cd by hydrothermal method
1-xco
xcrS, x=0.85; Cd prepared by hydrothermal method
1-xco
xcrS presents simple cubic structure, and particle is tiny, size-grade distribution is comparatively even, has good fluorescence property, is expected to obtain application in LED component, vacuum uv phosphor and vacuum ultraviolet (VUV) quantum-cutting.
Description
Technical field
The present invention relates to fluorescent material, refer in particular to a kind of all-sulphide phosphor and preparation method thereof.
Background technology
Since 20 century 70 rare earth doping fluorescent powder commercializations, people enter a brand-new stage to probing into of fluorescent material; The preparation method of traditional rare earth doping fluorescent powder is high temperature solid-state method, and the method is simple to operate, is easy to suitability for industrialized production, and the material emission brightness of preparation is high; But high temperature solid state reaction needs high temperature, the long reaction time of about 1300 DEG C, the product morphology irregularity of preparation, size-grade distribution be uneven, it is uneven to form, easily carry dephasign secretly, and after being processed to form fluorescent material, luminescent properties also can decline; Water heat transfer phosphor is method emerging in recent years, the method production cost is lower, high, the degree of crystallinity of powder purity of preparation better, good dispersity and granularity is controlled, the powder of preparation is without the need to subsequent heat treatment, avoid the shortcomings such as particle growth in high-temperature heat treatment process and impurity are mixed into, weak point is that the fluorescent material luminous intensity of preparation is more weak.
The nineties in 20th century blue-ray LED and long wave ultraviolet laser diode (LD) technical breakthrough and industrialization promoted the development of white light emitting diode (white light-emitting diode, WLED) greatly; The series of advantages such as volume is little owing to having for white light LEDs, life-span length, energy-saving and environmental protection, become forth generation solid light source; The objectionable impuritiess such as LED light source itself is not mercurous, plumbous, pollute without infrared rays and ultraviolet, can not produce pollution in production with in using; Realizing one of approach of LED solid state light emitter is utilize fluorescent material transformation approach, and this LED component is only containing a kind of chip (being generally ultraviolet or blue light), and fluorescent material converts chip emission to visible ray, and multi-wavelength is mixed to form white light; At present, exploitation can be become the focus of various countries scientist research by the special phosphor that blue light, purple light and ultraviolet high efficiency rate excite.
The cost of solar cell costliness and low transformation efficiency make the mankind there is huge spread between the exploitation of sun power and the actual reserves of sun power; The photon energy of incident sunlight and solar cell bandwidth E
gbetween spectral mismatch, cause the power loss more than 70% in sun power to be fallen; In order to solve spectral mismatch problem, can by upper conversion and lower conversion two kinds of methods; Lower conversion (also referred to as quantum-cutting) is luminescence process photon high for energy being divided into two or more energy photons, this process can reduce absorb high-energy photon after the power loss that causes of current carrier thermalization; If excite in theory vacuum ultraviolet photon (vacuumultraviolet, VUV) two light photons can effectively be produced, its quantum yield can, more than 100%, therefore descend conversion can apply in plasma flat-panel display, solar cell and efficient non-mercury florescent lamp.
The Cd that the present invention is dispersed better by simple hydrothermal method technique preparation, granularity is thinner
1-xco
xcrS powder, avoid the high-temperature calcination of solid state reaction and the problem of long reaction time, the method can be prepared without the need to subsequent heat treatment and has simple cubic structure, powder body material that fluorescence property is good, is expected to obtain application in LED component, vacuum uv phosphor and vacuum ultraviolet (VUV) quantum-cutting.
Summary of the invention
The present invention take inorganic salt as raw material, thiocarbamide is precipitation agent, dehydrated alcohol as solvent, prepare sulfide Cd by hydrothermal method
1-xco
xcrS powder, main contents comprise:
With analytically pure C
4h
6cdO
4× 4H
2o, C
4h
6coO
4× 4H
2o, CrCl
3× 6H
2o is raw material, CH
4n
2s is precipitation agent, with dehydrated alcohol as solvent, prepares sulfide Cd by hydrothermal method
1-xco
xcrS.
Take above-mentioned four kinds of raw materials according to stoichiometric ratio, dissolve in dehydrated alcohol, be transferred in hydrothermal reaction kettle and mix.
Water heating kettle is slowly warming up to 150-170 DEG C from room temperature, and hydro-thermal reaction occurs insulation 7.5-12.5h.
After hydro-thermal reaction terminates, take out reaction product after water heating kettle being cooled to room temperature, washing, centrifugal, dry, grinding, obtain Cd
1-xco
xcrS powder.
The consumption of described dehydrated alcohol should be able to dissolve C
4h
6cdO
4× 4H
2o, C
4h
6coO
4× 4H
2o, CrCl
3× 6H
2o, CH
4n
2s, is transferred in hydrothermal reaction kettle and mixes, and mixing solutions accounts for 80% of water heating kettle volume.
Accompanying drawing explanation
Cd prepared by Fig. 1 hydrothermal method
1-xco
xcrS(x=0.85) XRD figure of powder;
Cd prepared by Fig. 2 (a) hydrothermal method
1-xco
xcrS(x=0.85) the SEM figure of powder;
Cd prepared by Fig. 2 (b) hydrothermal method
1-xco
xcrS(x=0.85) the TEM selected area electron diffraction figure of powder;
Cd prepared by Fig. 3 hydrothermal method
1-xco
xcrS(x=0.85) excitation spectrum of powder and emmission spectrum;
Cd prepared by table 1 hydrothermal method
1-xco
xcrS(x=0.85) the EDS power spectrum ultimate analysis of powder.
Embodiment
In order to for a more detailed description to the present invention, existing in conjunction with the embodiments as follows with figure brief introduction: to weigh analytically pure C according to stoichiometric ratio
4h
6cdO
4× 4H
2o, C
4h
6coO
4× 4H
2o, CrCl
3× 6H
2o, CH
4n
2s(excessive 50%), mixing is dissolved in the dehydrated alcohol of 30ml, and be transferred in hydrothermal reaction kettle and mix, mixing solutions accounts for 80% of water heating kettle volume, and water heating kettle is slowly warming up to 160 DEG C from room temperature, in this temperature 10h, hydro-thermal reaction occurs; After hydro-thermal reaction terminates, be cooled to after room temperature take out reaction product until water heating kettle, repeatedly centrifugal with absolute ethanol washing, supercentrifuge, washing, centrifugal product vacuum drying oven, in 80 DEG C of dry 36h, are taken out grinding and are obtained Cd after cooling
1-xco
xcrS(x=0.85) powder.
Cd prepared by hydrothermal method
1-xco
xthe crystalline structure of CrS powder measures with Rigaku D/max-2500/PC X-ray Diffractionmeter (XRD, Rigaku Corporation, Japan), and XRD diffraction curve is shown in Fig. 1; Cd prepared by hydrothermal method
1-xco
xcrS presents purer simple cubic structure, and XRD diffraction peak is narrower and sharp-pointed, shows Cd prepared by hydrothermal method
1-xco
xcrS well-crystallized.
Cd prepared by hydrothermal method
1-xco
xthe pattern JEOL JSM6360LA scanning electron microscopy(SEM of CrS powder, JEOL Ltd., and JEOL JEM-2100 transmission electron microscope(TEM Japan), JEOL Ltd., Japan) observe, SEM image is shown in Fig. 2 (a), and TEM image is shown in Fig. 2 (b); Cd prepared by hydrothermal method
1-xco
xcrS powder granule is comparatively thin, presents the particle that size is hundreds of nanometer, subglobular, there is certain agglomeration; Fig. 2 (b) provides Cd
1-xco
xthe TEM selected area electron diffraction figure of CrS [111] tape spool, the feature of SAED image shows that the nano material of observing is the monocrystalline presenting simple cubic structure.The unit cell parameters that tem observation obtains is consistent with the unit cell parameters that XRD measuring result calculates.
Cd prepared by hydrothermal method
1-xco
xthe excitation spectrum of CrS powder and emmission spectrum Cary Eclipse fluorescence spectrophotometer(Cary Eclipse, Agilent Technologies Inc., USA) measure, Fig. 3 is Cd
1-xco
xthe PL spectrum of CrS powder; Cd
1-xco
xthe excitation spectrum of CrS powder covers the spectral range of 200-300nm ultraviolet band, and its excitation peak is positioned at 229nm, is the excitons excite band of matrix; Under 229nm excitation wavelength excites, Cd
1-xco
xcrS transmits a strong and wide emission band in blue region, and emission peak is positioned at 458nm, relevant with the compound of the electronic defects be correlated with in sulphur room; Cd prepared by hydrothermal method
1-xco
xcrS has good fluorescence property, is expected in LED component, obtains application without in mercury vacuum uv phosphor and vacuum ultraviolet (VUV) quantum-cutting.
Table 1
Claims (4)
1. a preparation method for all-sulphide phosphor, the molecular formula of described all-sulphide phosphor is Cd
1-xco
xcrS, x=0.85,
for simple cubic structure; Its excitation spectrum covers the spectral range of 200-300nm ultraviolet band, and its excitation peak is positioned at 229nm, is the excitons excite band of matrix; Under 229nm excitation wavelength excites, Cd
1-xco
xcrS forms emission band in blue region, and emission peak is positioned at 458nm, it is characterized in that comprising the steps: with analytically pure C
4h
6cdO
4× 4H
2o, C
4h
6coO
4× 4H
2o, CrCl
3× 6H
2o is raw material, CH
4n
2s is precipitation agent, with dehydrated alcohol as solvent, prepares sulfide Cd by hydrothermal method
1-xco
xcrS, be specially: take above-mentioned four kinds of raw materials according to stoichiometric ratio, dissolve in dehydrated alcohol, be transferred in hydrothermal reaction kettle and mix, water heating kettle is slowly warming up to 150-170 DEG C from room temperature, and hydro-thermal reaction occurs insulation 7.5-12.5h, after hydro-thermal reaction terminates, take out reaction product after water heating kettle being cooled to room temperature, washing, centrifugal, dry, grinding, obtain Cd
1-xco
xcrS powder.
2. the preparation method of a kind of all-sulphide phosphor as claimed in claim 1, is characterized in that: the consumption of described dehydrated alcohol should be able to dissolve C
4h
6cdO
4× 4H
2o, C
4h
6coO
4× 4H
2o, CrCl
3× 6H
2o, CH
4n
2s, is transferred in hydrothermal reaction kettle and mixes, and mixing solutions accounts for 80% of water heating kettle volume.
3. the preparation method of a kind of all-sulphide phosphor as claimed in claim 1, is characterized in that: described CH
4n
2s is according to stoichiometric ratio excessive 50%.
4. the preparation method of a kind of all-sulphide phosphor as claimed in claim 1, is characterized in that: the condition of described drying is: with vacuum drying oven in 80 DEG C of dry 36h.
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| CN103602334B true CN103602334B (en) | 2015-10-28 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000019205A (en) * | 1998-09-09 | 2000-04-06 | 김충섭 | Method for producing hydrogen using cadmium sulfide grouped photo catalyst for generating hydrogen |
| CN101994156A (en) * | 2010-12-09 | 2011-03-30 | 东北林业大学 | Preparation method of magnetic element-doped CdS nanorods |
| CN102161500A (en) * | 2011-02-24 | 2011-08-24 | 西北工业大学 | Preparation method of cobalt-doped zinc oxide nano-material |
-
2013
- 2013-08-06 CN CN201310337350.2A patent/CN103602334B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000019205A (en) * | 1998-09-09 | 2000-04-06 | 김충섭 | Method for producing hydrogen using cadmium sulfide grouped photo catalyst for generating hydrogen |
| CN101994156A (en) * | 2010-12-09 | 2011-03-30 | 东北林业大学 | Preparation method of magnetic element-doped CdS nanorods |
| CN102161500A (en) * | 2011-02-24 | 2011-08-24 | 西北工业大学 | Preparation method of cobalt-doped zinc oxide nano-material |
Non-Patent Citations (2)
| Title |
|---|
| First principles density functional calculations of half-metallic ferromagnetism in Zn1-xCrxS and Cd1-xCrxS;S. Nazir等;《Current Opinion in Solid State and Materials Science》;20100215;第14卷(第1期);第1-6页 * |
| Structural, optical and magnetic properties of Co doped CdS nanoparticles;G. Giribabu等;《Journal of Alloys and Compounds》;20130721;第581卷;第363-368页 * |
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Effective date of registration: 20201123 Address after: No. 159, Chengjiang Middle Road, Jiangyin City, Wuxi City, Jiangsu Province Patentee after: Jiangyin Intellectual Property Operation Co., Ltd Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |
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