CN102516984B - A kind of orange red phosphor crystal material and its production and use - Google Patents
A kind of orange red phosphor crystal material and its production and use Download PDFInfo
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- CN102516984B CN102516984B CN201110353636.0A CN201110353636A CN102516984B CN 102516984 B CN102516984 B CN 102516984B CN 201110353636 A CN201110353636 A CN 201110353636A CN 102516984 B CN102516984 B CN 102516984B
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Abstract
The invention provides a kind of orange red phosphor crystal material and preparation method thereof.The chemical formula of this material is { Cu
6[3,5-bis-(4-pyridine)-1,2,4-triazoles]
3br
3n.Utilize 2,5-bis-(4-pyridine)-1,3,4-oxadiazoles as bridgingligand, prepare stable and that luminous efficiency is higher orange red phosphorescence { Cu by the solvent thermal of gentleness or hydrothermal method
6[3,5-bis-(4-pyridine)-1,2,4-triazoles]
3br
3n crystalline material.The crystalline material obtained can send bright fluorescent red-orange under ultra violet lamp, Heat stability is good, and luminous efficiency is high.
Description
Technical field
The present invention relates to High Efficiency Luminescence crystalline material and its preparation method and application, especially triazole copper complex crystallo-luminescence material 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, realization is mixed with the phosphorescent emissions of 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 triazole copper complex mentioned in this patent book is exactly this kind of have good thermal stability and light stability ligand polymer, it is prepare under the condition of low-temperature solvent heat or hydro-thermal rare, efficient orange phosphor material.
Summary of the invention
The present invention proposes orange red phosphor crystal material of a kind of three novel nitrogen copper complexes and preparation method thereof
The chemical formula of the strong phosphor crystal material adopting the present invention to prepare is: { Cu
6[3,5-bis-(4-pyridine)-1,2,4-triazoles]
3br
3}
n, molecular weight is 1287.67, and spacer is Fdd2, and unit cell parameters is
z=8, R1=0.066.The luminescent lifetime of this material is τ
1=2.26 μ s, 30.58%, τ
2=78.84 μ s, 44.44%, and τ
3=0.47 μ s, 24.98%.
The present invention adopts following preparation technology: strong phosphor crystal material { Cu
6[3,5-bis-(4-pyridine)-1,2,4-triazoles]
3br
3}
npreparation.By CuI, 2,5-bis-(4-pyridine)-1,3,4-oxadiazoles and water or ethanol, be uniformly mixed, be heated to seal to 80-220 degree, cool to room temperature, filters and obtain solid, and washing, just obtains described yellow phosphorescence crystalline 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.1,2, the 4-triazole organic group utilizing infrared absorption spectrum to demonstrate to exist in structure.Prove that this material can keep stable within the scope of temperature 30-400 DEG C by thermogravimetric analysis, there is the value applied in wide temperature range.Under portable ultraviolet lamp BJRY26-4W irradiates, this crystal prototype sends bright orange red light, 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 (280 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 orange red phosphor crystal material of triazole 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 asymmetric cell structural representation of this crystalline material;
Accompanying drawing 2: the excitation spectrum of this crystalline material, the luminous photo under emission spectrum and portable ultraviolet lamp BJRY26-4W irradiate.
Accompanying drawing 3: the thermogravimetric curve of this crystalline material.
Embodiment
Example 1:(1) take 25.0mg CuBr or CuBr
2, 2,5-bis-(4-pyridine)-1,3,4-oxadiazoles of 10.0mg, join in the autoclave of 30mL in 5mL25% ammoniacal liquor and 15mL deionized water, and at room temperature stir 7h and obtain the solution that mixes.This mixing solutions is heated 35h at 220 DEG C, then with 2 DEG C of h
-1rate of temperature fall under cool to room temperature.Reaction product washes with water repeatedly, obtains red bulk crystals.Calculating its productive rate according to the CuI used is 55%.Bright fluorescent red-orange can be seen under portable ultraviolet lamp BJRY26-4W irradiates.
(2) CuBr or CuBr of 55.0mg is taken
2, join in the autoclave of 40mL in 2,5-bis-(4-pyridine)-1,3, the 4-oxadiazoles of 20.0mg and 18mL second cyanogen, and at room temperature stir 5h and obtain the solution that mixes.This mixing solutions is heated 27h at 160 DEG C, then with 40 DEG C of h
-1rate of temperature fall under cool to room temperature.Reaction product washes with water repeatedly, obtains red bulk crystals.Calculating its productive rate according to the CuI used is 39%.Bright fluorescent red-orange can be seen under irradiating with portable ultraviolet lamp BJRY26-4W.
(3) CuBr or CuBr of 110.0mg is taken
2, join in the autoclave of 25mL in 2,5-bis-(4-pyridine)-1,3, the 4-oxadiazoles of 35.0mg and 10mL ethanol, and at room temperature stir 5h and obtain the solution that mixes.This mixing solutions is heated 72h at 80 DEG C, then cool to room temperature.Reaction product washes with water repeatedly, obtains red bulk crystals.Calculating its productive rate according to the CuI used is 71%.Bright fluorescent red-orange can be seen under irradiating with portable ultraviolet lamp BJRY26-4W.
(4) CuBr or CuBr of 220.0mg is taken
2, join in the autoclave of 50mL in 2,5-bis-(4-pyridine)-1,3, the 4-oxadiazoles of 70.0mg and 30mL deionized water, and at room temperature stir 5h and obtain the solution that mixes.This mixing solutions is heated 120h at 120 DEG C, then with 2 DEG C of h
-1rate of temperature fall under cool to room temperature.Reaction product washes with water repeatedly, obtains red bulk crystals.Calculating its productive rate according to the CuI used is 43%.Fluorescent red-orange can be seen under irradiating with portable ultraviolet lamp BJRY26-4W.
Claims (3)
1. an orange red phosphor crystal material, this materials chemistry formula is { Cu
6[3,5-bis-(4-pyridine)-1,2,4-triazoles]
3br
3}
n, molecular weight is 1287.67, and spacer is Fdd2, and unit cell parameters is
z=8, R1=0.066.
2. the preparation method of an orange 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 water or ethanol, be uniformly mixed, be heated to seal to 80-220 DEG C, cool to room temperature, filtration obtains solid, and washing, obtains described orange red phosphor crystal material.
3. a purposes for orange red phosphor crystal material according to claim 1, is characterized in that: described orange red phosphor crystal material is in order to prepare photoluminescence powder.
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| CN103406147B (en) * | 2013-07-31 | 2015-05-06 | 山西师范大学 | Preparation method and application of nanometer tubular cuprous bromide photocatalysis material |
| CN107011367A (en) * | 2017-04-05 | 2017-08-04 | 江南大学 | A kind of preparation for the luminescent crystal material that there is selectivity to detect dichromate ion |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999528A (en) * | 2006-12-29 | 2007-07-18 | 中国科学院长春应用化学研究所 | Copper (1) compound with imidazole derivate as compounding body |
| CN101024651A (en) * | 2007-02-14 | 2007-08-29 | 南开大学 | Silver coordination polymer containing azacylo-ligand, its preparing method and use |
| WO2009003700A1 (en) * | 2007-07-05 | 2009-01-08 | Merck Patent Gmbh | Luminescent metal complexes for organic electronic devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999528A (en) * | 2006-12-29 | 2007-07-18 | 中国科学院长春应用化学研究所 | Copper (1) compound with imidazole derivate as compounding body |
| CN101024651A (en) * | 2007-02-14 | 2007-08-29 | 南开大学 | Silver coordination polymer containing azacylo-ligand, its preparing method and use |
| WO2009003700A1 (en) * | 2007-07-05 | 2009-01-08 | Merck Patent Gmbh | Luminescent metal complexes for organic electronic devices |
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