CN103059049B - A kind of pure red phosphor crystal material and its production and use - Google Patents
A kind of pure red phosphor crystal material and its production and use Download PDFInfo
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- CN103059049B CN103059049B CN201110326238.XA CN201110326238A CN103059049B CN 103059049 B CN103059049 B CN 103059049B CN 201110326238 A CN201110326238 A CN 201110326238A CN 103059049 B CN103059049 B CN 103059049B
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Abstract
The invention provides a kind of pure red phosphor crystal material and preparation method thereof.The chemical formula of this material is [Cu
i 3(3,5-bis-(4-pyridine)-1,2,4-oxadiazoles)) I
3]
n.Utilize 2,5-bis-(4-pyridine)-1,3,4-oxadiazoles as bridgingligand, prepare stable and that luminous efficiency is higher red phosphorescent [Cu by the solvent thermal of gentleness or hydrothermal method
i 3(3,5-bis-(4-pyridine)-1,2,4-oxadiazoles)) I
3]
ncrystalline material.The crystalline material obtained can send bright pure ruddiness under ultra violet lamp, and Heat stability is good, luminous efficiency is high.
Description
Technical field
The present invention relates to High Efficiency Luminescence crystalline material and preparation method thereof, Qi Shi oxadiazole copper complex crystallo-luminescence material of You and preparation method thereof.
Background technology
Along with the exhaustion of fossil energy, the step of energy dilemma closes on day by day.While exploitation renewable energy source, the utilization ratio improving the energy causes showing great attention to of countries in the world equally.At present, the electric energy that illumination consumes account for the last 50% of whole world generating total amount.In order to effectively put forward high-octane utilising efficiency, there is higher energy conversion efficiency and effectively can avoid the high efficient luminous material of the higher-energy loss existed in conventional luminescent material, receiving scientific circles and business circles pay close attention to more and more widely.Phosphor material can pass through intersystem crossing, realize the phosphorescent emissions being mixed with singlet state and triplet state luminescence. in theory, the internal quantum efficiency of the OLED luminescent layer utilizing phosphor material to make can reach 100%, its luminous efficiency improves three times than fluorescent material, and therefore phosphor material receives and pays close attention to more and more widely.In addition, the higher quantum yield of luminescent material be realized, necessarily require optical material can maximum possible be photon by the Conversion of energy of absorption, but not be converted into heat energy by non-radiative relaxation.And reduce the non-radiative relaxation of material, just need material to have less phonon energy, good degree of crystallinity, and larger light transmission rate etc.Therefore, optical crystal material, due to its good crystallization property and larger light transmission rate and less phonon energy (< 1000cm
-1), the non-radiative relaxation effect existed in non-crystalline material can be avoided, therefore there is higher luminous efficiency usually.In addition because they have compared with light stable physics and photochemical character, can in wider temperature, humidity, keeps features such as stablizing in pressure range, the emitting components under multiple extreme condition can be used in, therefore just become a study hotspot of high efficient luminous material.But because most crystallo-luminescence material is all prepared by high temperature crystal pulling method or molten-salt growth method, so its preparation condition requires harsher, and cost is higher, also causes certain pollution to environment.Therefore, the comparatively easy preparation method of utilization and relatively gentle experiment condition prepare the extensive concern that stable and efficient crystal phosphorescence luminescent material receives everybody.And mentioned oxadiazole copper complex is exactly this kind of have good thermal stability and light stability ligand polymer in this patent book, it is prepare under the condition of low-temperature solvent heat or hydro-thermal rare, efficient pure red phosphor material.
Summary of the invention
The present invention proposes efficient pure red phosphor crystal material of a kind of novel oxadiazole copper complex and preparation method thereof
The chemical formula of the strong phosphor crystal material adopting the present invention to prepare is: [Cu
i 3(3,5-bis-(4-pyridine)-1,2,4-oxadiazoles)) I
3]
n, spacer is P21/n, and unit cell parameters is
β (deg)=96.073 (5),
the luminescent lifetime of this material is for being (τ
1=0.05 μ s, 46.74%, τ
2=0.13 μ s, 42.59%, and τ
3=0.01 μ s, 10.48%), in addition, its corresponding cie color coordinate (0.66,0.31), is wherein positioned at pure red region.
The present invention adopts following preparation technology:
Strong phosphor crystal material [Cu
i 3(3,5-bis-(4-pyridine)-1,2,4-oxadiazoles)) I
3]
npreparation.By CuI, 2,5-bis-(4-pyridine)-1,3,4-oxadiazoles and ammoniacal liquor, ethanol or water, be uniformly mixed, be heated to seal to 80-220 degree, cool to room temperature, filters and obtain solid, and washing, obtains described efficient pure red phosphor crystal material.
Obtained the single crystal structure of this sample by the experiment of X-ray single crystal diffraction, demonstrate this sample obtained is the crystalline material of highly crystalline simultaneously.1,3, the 4-oxadiazole organic group utilizing infrared absorption spectrum to demonstrate to exist in structure.Prove that this material can keep stable within the scope of temperature 30-450 DEG C by thermogravimetric analysis, there is the value applied in wide temperature range.Under utilizing commercial portable ultraviolet lamp (5W) to irradiate, this crystal prototype sends bright ruddiness, when this crystal prototype is placed after ten hours at refrigerator freezing district (-18 DEG C), or after a few hours placed by High Temperature Furnaces Heating Apparatus (300 DEG C), the performance of its luminescence does not observe any change.Thus illustrate this crystalline material can be used as photoluminescence powder to make luminous printing ink, luminous paint, luminescent plastics, luminous printing paste etc. ideal material.The luminous printing ink utilizing this crystalline material to make not only is applicable to the pattern and character of the various illumination effect of wire mark, as label, toy, calligraphy and painting, glass picture, non-setting adhesive etc., and because of it, there is the features such as transparency is high, good film-forming property, coating are thin, can spray or wire mark on the artworks such as all kinds of embossment, circular engravure (figure of buddha, vitrotype, plaster statue, tri-coloured glazed pottery), polymer picture, lamp decoration, under the prerequisite not affecting its original decorations coloured silk or lines, greatly improve its added value.This crystalline material also can be used as fire exit cue mark, withdraws mark, biological labled material etc.Using the light-converting agent of this luminescent material as sunlight, join in agricultural plastic film and make plastic sheeting for farm use or booth, make agricultural light conversion film to improve photosynthetic light quality, improve the efficiency of light energy utilization, promote farm crop, the precocity mainly making vegetables and volume increase.This crystalline material can make the three-color phosphor of various types of flat panel display as plasma panel display (PDP), Field Emission Display (FED) and LCD backlight.This luminescent material can make all kinds of compact fluorescent lamp (electricity-saving lamp) and fluorescent material thereof, becomes the main force in " Green Lighting Project ".In addition, this material can be used for storing the X-ray pickup system calculated.And the X-ray intensifying screen utilizing this embedded photoluminescent material to make, for diagnosing human disease, ensure that people's medical treatment & health plays an important role.Therefore, this luminescent material has good application prospect potential.
The efficient pure red phosphor crystal material of efficient red phosphorus luminescent material oxadiazole copper complex prepared by the present invention has technique simply, and cost is low, reproducible, and luminous efficiency is high, can carry out the advantage such as producing in enormous quantities.The present invention is compared with the luminescent crystal material prepared both at home and abroad, and have thermostability high, good light stability, luminous efficiency is high, is a kind of excellent new and effective luminescent crystal material.
Accompanying drawing explanation
Accompanying drawing 1: the laminate structure schematic diagram of the 2-dimension of this crystalline material;
Accompanying drawing 2: the excitation spectrum of this crystalline material, the luminous photo under emission spectrum and ultra violet lamp.
Accompanying drawing 3: the thermogravimetric curve of this crystalline material.
Embodiment
Example 1:(1) take 200.0mgCuI, 40.0mg2,5-bis-(4-pyridine)-1,3,4-oxadiazoles, ammoniacal liquor 1mL, and to join in the autoclave of 20mL in 10mL ethanol water, and at room temperature stir the solution that 5h obtains mixing.This mixing solutions is heated 72h at 180 DEG C, then with 3 DEG C of h
-1rate of temperature fall under cool to room temperature.The precipitation obtained washes with water repeatedly, obtains red needle-like crystal.Calculating its productive rate according to the CuI used is 52.5%.Irradiate with the portable fluorescence of 4W and can see bright emitting red light.
(2) take 300.0mgCuI, 20.0mg2,5-bis-joins in the autoclave of 50mL in (4-pyridine)-1,3,4-oxadiazoles and 24mL deionized water, and at room temperature stirs the solution that 15h obtains mixing.This mixing solutions is heated 120h at 80 DEG C, then with 2 DEG C of h
-1rate of temperature fall under cool to room temperature.The precipitation obtained washes with water repeatedly, obtains red needle-like crystal.Calculating its productive rate according to the CuI used is 25.5%.Irradiate with the portable fluorescence of 4W and can see bright emitting red light.
(3) take 100.0mgCuI, 50.0mg2,5-bis-joins in the autoclave of 40mL in (4-pyridine)-1,3,4-oxadiazoles and 18mL deionized water, and at room temperature stirs the solution that 5h obtains mixing.This mixing solutions is heated 27h at 210 DEG C, then with 40 DEG C of h
-1rate of temperature fall under cool to room temperature.The precipitation obtained washes with water repeatedly, obtains red needle-like crystal.Calculating its productive rate according to the CuI used is 59%.Irradiate with the portable fluorescence of 4W and can see bright emitting red light.
(4) take 50.0mgCuI, 150.0mg2,5-bis-(4-pyridine)-1,3,4-oxadiazoles, join in the autoclave of 20mL in 8mL25% ammoniacal liquor and 6mL deionized water, and at room temperature stir 7h and obtain the solution that mixes.This mixing solutions is heated 26h at 100 DEG C, then with 6 DEG C of h
-1rate of temperature fall under cool to room temperature.The precipitation obtained washes with water repeatedly, obtains red needle-like crystal.Calculating its productive rate according to the CuI used is 35%.Irradiate with the portable fluorescence of 4W and can see bright emitting red light.
Claims (3)
1. a pure red phosphor crystal material, this materials chemistry formula is [Cu
i 3(3,5-bis-(4-pyridine)-1,2,4-oxadiazoles)) I
3]
n, spacer is P21/n, and unit cell parameters is
β=96.073 (5) °,
2. the preparation method of a pure red phosphor crystal material according to claim 1, it is characterized in that: by CuI, 2,5-bis-(4-pyridine)-1,3,4-oxadiazole and ammoniacal liquor, ethanol or water, be uniformly mixed, be heated to seal to 80-220 DEG C, cool to room temperature, filtration obtains solid, and washing, obtains described pure red phosphor crystal material.
3. a purposes for pure red phosphor crystal material according to claim 1, is characterized in that: described pure red phosphor crystal material is in order to prepare photoluminescence powder.
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| CN201110326238.XA CN103059049B (en) | 2011-10-21 | 2011-10-21 | A kind of pure red phosphor crystal material and its production and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103588795A (en) * | 2013-11-27 | 2014-02-19 | 中国科学院福建物质结构研究所 | Ionic cuprous luminous complexes and use thereof |
| CN108774324A (en) * | 2018-06-07 | 2018-11-09 | 南京工业大学 | A kind of achievable feux rouges and the photoemissive Cu-MOF crystalline materials of near-infrared and preparation method |
| CN108558915A (en) * | 2018-06-07 | 2018-09-21 | 南京工业大学 | Orange photoemissive Cu-MOF luminescent crystals material and preparation method can be achieved in one kind |
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Non-Patent Citations (3)
| Title |
|---|
| Coordination Assemblies of CoII/CuII/ZnII/CdII with 2,5-Bipyridyl-1,3,4-Oxadiazole and Dicyanamide Anion: Structural Diversification and Properties;Miao Du et al.;《Crystal Growth&Design》;20100526;第10卷(第7期);3285-3296 * |
| Microporous Metal-Organic Frameworks: Structures, in Situ Formation of Ligand, and Crystal-to-Crystal Transformations;Zhen-Lan Fang et al.;《Crystal Growth&Design》;20110420;第11卷;2546-2552 * |
| Synthesis, structure and luminescent properties of Cu(I)-cyanide frameworks based on bent dipyridyl-oxadiazole ligands;Hui Wang et al.;《Journal of Molecular Structure》;20080205;第889卷;154-159 * |
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