CN105543958B - A kind of luminescence generated by light crystalline material boric acid europium potassium and its preparation method and application - Google Patents
A kind of luminescence generated by light crystalline material boric acid europium potassium and its preparation method and application Download PDFInfo
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- CN105543958B CN105543958B CN201510948891.8A CN201510948891A CN105543958B CN 105543958 B CN105543958 B CN 105543958B CN 201510948891 A CN201510948891 A CN 201510948891A CN 105543958 B CN105543958 B CN 105543958B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/774—Borates
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
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Abstract
The invention discloses a kind of luminescence generated by light crystalline material boric acid europium potassium and its preparation method and application, belong to rare earth luminescent material technical field.Technical scheme main points are：A kind of luminescence generated by light crystalline material boric acid europium potassium, its chemical formula are K5/2Eu5/6(B5O10), belong to trigonal system, chiral space groupR32, cell parameter isa=b=1.326nm,c=1.538nm,α=β=90o,γ=120º.Metaboric acid europium potassium monocrystalline is synthesized using o, uniform mixed material will be fully ground and be placed in platinum crucible, is put into batch-type furnace and heats synthesis, in maximum temperature constant temperature, then Slow cooling, is down to after room temperature and the monocrystal of the compound is made.The crystalline material can be excited by 390nm light and launch bright red fluorescence, available for fluorescence luminescent material and device, meet the demands such as electronics industry, public place are shown and household electrical appliance are shown.
Description
Technical field
The invention belongs to rare earth luminescent material technical field, and in particular to a kind of luminescence generated by light crystalline material boric acid europium potassium and
Its preparation method and application.
Background technology
Luminescent material is indispensable material in people's daily life, and the engineering such as decoration, advertising sign energy-conservation is to fluorescence
The application of material is especially prominent, and new requirement is it is also proposed to all technical of fluorescent material.Therefore, increasingly compel to be essential
Find the advanced luminescent material having the characteristics that efficiently, stable and high excitation.In the development of luminescent material and luminescence
During, rare earth luminescent material plays the role of milestone, and rare earth element is also played than other elements and more importantly acted on.
Rare earth luminescent material mainly has rear-earth-doped alkaline earth sulfide, rear-earth-doped alkaline earth metal fluorohalide, rare earth to mix
Several big systems such as miscellaneous tantalates and rear-earth-doped oxide.In optical storage, radiation dose measurement, infrared sensing, image
Enhancing, near-infrared-visible ray conversion etc. have wide practical use.Rare earth ion has the 4 of underfillfElectron shell,
Therefore with abundant electron energy level and long-life excitation state, up to more than 20 ten thousand, energy level transition passage, can produce a variety of more
The radiation absorption of sample and transmitting.Rare earth atom or the observable spectral line of ion about more than 30,000 bars, they can launch from
Ultraviolet light, visible ray to infrared light district various wavelength electromagnetic radiation.With entering for Rare Earth Separation, purification and correlation technique
Step, the research and application of rare earth luminescent material have obtained significant development.Rare earth luminescent material has the characteristics of many excellent, such as
Light absorpting ability is strong, launch wavelength distributed area field width and emission band are narrow etc., simultaneously because rare earth ion electron configuration is
4f n5s 25p 6（0≤n≤14）, electronics is shielded, so 4 when in doped matrix latticefElectronics is affected by the ambient
It is very weak.Exactly these excellent characteristics, rare earth compound is set to turn into the main study subject for seeking new and high technology material.At present,
The fields such as rare earth luminescent material is widely used in illuminating, shows, images, the detection of medical radiology image, radiation field and record,
Form very big industrial production and consumption market scale.In recent years, with PDP, Field Electron Emission display（FED）And have
Electromechanical laser display（OLED）Deng the appearance of FPD, the research of rare earth luminescent material also has become luminescent material research
Emphasis and forward position, competition both domestic and external are very fierce.China possesses development rare earth and applies advantageous resources advantage, and the world is dilute
In soil resource, 30% rare earth resources are in China, and great variety of goods.China's rare earth resources are on the one hand to go out using feature at present
Mouth raw material and crude product；On the other hand but in import finished product and highly finished product.China is in rare earth deep processing and Rare Earth Functional Materials
Do not stand in world forefront in development and application field.Therefore, carrying out rare earth fine processing and the research of Rare Earth Functional Materials has
Important meaning, and the research of rare earth luminescent material is also one of Main way.
Rare earth luminescent material using borate as matrix is a branch in luminescent material.Borate is due to sintering temperature
Low, low in raw material price, species is various, and synthesis technique is simple, it is considered to be luminous host of great practical value.Boric acid alkali
The difference of B-O coordination modes in the diversity and structure of matter structure composition, it is set to be applied to the host material of different light source activations.
The research of current rare earth borate luminescent material obtains the seldom of practical application mainly also in laboratory stage.How to develop
New light emitting borate material, the value of sassolite salt mineral is lifted, be the problem of researcher needs thinking.In addition,
In terms of the research of light emitting borate material is concentrated mainly on preparation method, performance characterization and structure prediction, show for material emission
The research of the mechanism and influence factor of elephant is also relatively weak, not yet forms perfect theoretical system, it is necessary to further strengthen reason
By research.
The content of the invention
Present invention solves the technical problem that a kind of luminescence generated by light crystalline material boric acid europium potassium and preparation method thereof is there is provided,
The preparation technology and the doping of rare earth ion that the crystalline material boric acid europium potassium need not be complicated, its material body just containing rare earth from
Sub- Eu3+, and strong Eu can be launched under excitation light3+Characteristic emission light feux rouges（611nm）, to meet practical application need
Will, obtained luminescence generated by light crystalline material boric acid europium potassium can be applied in fluorescence luminescent material or electronic device.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, a kind of luminescence generated by light crystalline material boric acid europium
Potassium, it is characterised in that：The chemical formula of the crystalline material boric acid europium potassium is K5/2Eu5/6(B5O10), belong to trigonal system, chiral space
GroupR32, cell parameter isa=b=1.326nm,c=1.538nm,α=β=90o,γ=120o, Z=9, V=2.343nm3。
The preparation method of luminescence generated by light crystalline material boric acid europium potassium of the present invention, it is characterised in that concretely comprise the following steps：
Using pyrosol synthetic method, with the K of excess2O-B2O3System is fluxing agent, by raw material K2CO3、Eu2O3And B2O3According to mole
Than for 10:1:20 ratio is mixed and fully milled uniformly, is fitted into 20mL platinum crucible after being compacted and is placed in Muffle furnace, first
Reactant is stood into 24h in 1000 DEG C of fully meltings, then chilling is cooled to 850 DEG C of constant temperature 24h, then with 5 DEG C/h cooling speed
Rate is cooled to 650 DEG C, and last chilling is cooled to the strip boric acid europium potassium monocrystal that water white transparency is made in room temperature.
Application of the luminescence generated by light crystalline material boric acid europium potassium of the present invention in fluorescence luminescent material or electronic device.
Fluorescence spectrum, which is tested, to be shown, compound K provided by the invention5/2Eu5/6(B5O10) strong red light can be launched, it can use
Make the field of light emitting materials such as public arena, station terminal navigation light.And the synthetic method of synthesizing luminescent material is simple, raw material
It is cheap and easy to get, product nontoxic pollution-free, good luminescence property.
Brief description of the drawings
Fig. 1 is K produced by the present invention5/2Eu5/6(B5O10) crystal space structure chart；
Fig. 2 is K produced by the present invention5/2Eu5/6(B5O10) crystal powder diffraction and single crystal data simulation comparison diagram；
Fig. 3 is K produced by the present invention5/2Eu5/6(B5O10) crystal excites fluorogram；
Fig. 4 is K produced by the present invention5/2Eu5/6(B5O10) crystal transmitting fluorogram.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment
Boric acid europium potassium K5/2Eu5/6(B5O10) crystal preparation：The method of present invention growth crystal is referred to as o, again
Referred to as flux growth metrhod, this method are that crystalline component is dissolved in the fluxing agent less than its fusing point at high temperature, are formed uniform
Saturated solution, forming supersaturated solution by slow cooling or other methods afterwards separates out crystal.This experiment using crystal into
Part K beyond point2O-B2O3System, because fusing point is relatively low equivalent to having done from fluxing agent, such raw material be both target crystal again
Make fluxing agent, there is very big flexibility, while avoid into other impurity.Concrete operation step is as follows：By raw material K2CO3、
Eu2O3And B2O3It is 10 according to mol ratio:1:20 ratio accurately weighs on electronic balance, because the fusing of carbonic acid can discharge
Go out CO2Gas, it is well mixed so first raw material is put into agate mortar, is then charged into Platinum crucible, is placed in 1000 DEG C
To being completely melt it in heating furnace, take out, slowly waved solution cooled and solidified in crucible internal walls after gas all effusion,
Constant temperature 24h in heating furnace is placed in after capping again, then is cooled to 850 DEG C of constant temperature 24 rapidly, it is slow with 2 DEG C/h rate of temperature fall afterwards
650 DEG C are cooled to, power supply is directly closed after the completion of cooling, temperature is dropped to room temperature rapidly, avoids other cenotypes from generating or send out
Raw phase transformation.After crucible is cooled to room temperature, it is soaked in water, washes away fluxing agent, the crystalline substance of water white transparency is obtained after drying
Body, its physicochemical properties is stable, and deliquescence, not non-efflorescing cementitious, is not easily decomposed.
Ray crystallographic analysis：Select a transparent intact small crystals under an optical microscope to be bonded on glass fiber, in room
In the CCD surface detector diffractometers of Brooker Smart Apex 2 under temperature（Molybdenum target λ=0.71073）Upper peak-seeking, indexing, with true
Determine cell parameter and orientation matrix.Initial data with ω scan modes collect after the completion of, by data convert, absorption correction it
Afterwards, it is possible to obtain the data such as diffraction index, diffracted intensity and background intensity.Obtaining cell parameter and diffracted intensity data
Afterwards, select correct space group, the position of heavy atom obtained with direct method, remaining atom site by difference Fourier synthesis come
It is determined that then whole atomic coordinates and discomposition parameter etc. are carried out to be based on F2Complete matrix least square method refine to receive
Hold back.Above structure elucidation and refine are completed using Shelx-2013 programs.Finally, its space group is entered by Platon programs
Row is checked and its structure checked on website, no crystallography mistake.The powder diagram and examination that mono-crystalline structures fit
The powder diagram for testing to obtain is contrasted（See accompanying drawing 2）, verify the correctness of structure elucidation.The parameter of single crystal structure determination is such as
Shown in following table：
Products therefrom is analyzed with FLS980 XRFs, 611nm transmitting light monitoring under test its excite it is glimmering
Light, it was observed that there is maximum excitation fluorescence peak in 390nm right positions（See accompanying drawing 3）, this can be attributed to Eu3+Ion7F0
→5L6Electron transition.Crystal K5/2Eu5/6(B5O10) transmitting fluorescence Spectra as shown in Figure 4, under the exciting of 390nm wavelength lights,
Material sends Eu3+Three characteristic fluorescence peaks of ion, occur respectively at 590nm, 611nm, 705nm, be respectively belonging to Eu3+
Ion5D0→7F1、5D0→7F2、5D0→7F2Electron transition.Due to5D0→7F1Transition correspond to dipole moment transition, and5D0
→7F2Transition correspond to electric dipole moment transition, due in K5/2Eu5/6(B5O10) in crystal structure, Eu3+During ion is in non-
The symmetrical lattice position of the heart, so should be based on electric dipole moment transition, i.e., based on red emission, this is consistent with experimental result.
Embodiment above describes the general principle of the present invention, main features and advantages, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (3)
- A kind of 1. luminescence generated by light crystalline material boric acid europium potassium, it is characterised in that：The chemical formula of the crystalline material boric acid europium potassium is K5/ 2Eu5/6(B5O10), belong to trigonal system, chiral space groupR32, cell parameter isa=b=1.326nm,c=1.538nm,α=β=90 O,γ=120o, Z=9, V=2.343nm3。
- A kind of 2. preparation method of the luminescence generated by light crystalline material boric acid europium potassium described in claim 1, it is characterised in that specific step Suddenly it is：Using high temperature solution synthetic method, with the K of excess2O-B2O3System is fluxing agent, by raw material K2CO3、Eu2O3And B2O3Press It is 10 according to mol ratio:1:20 ratio is mixed and fully milled uniformly, is fitted into 20mL platinum crucible after being compacted and is placed in Muffle In stove, reactant is first stood into 24h in 1000 DEG C of fully meltings, then chilling is cooled to 850 DEG C of constant temperature 24h, then with 5 DEG C/h's Rate of temperature fall is cooled to 650 DEG C, and last chilling is cooled to the strip boric acid europium potassium monocrystal that water white transparency is made in room temperature.
- 3. the answering in fluorescence luminescent material or electronic device of the luminescence generated by light crystalline material boric acid europium potassium described in claim 1 With.
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| CN106319624A (en) * | 2016-09-20 | 2017-01-11 | 河南理工大学 | Photoluminescent crystalline material sodium samarium borate and preparation method and application thereof |
| CN106479496B (en) * | 2016-09-23 | 2018-08-17 | 河南理工大学 | A kind of emitting red light crystalline material boric acid europium sodium and its preparation method and application |
| CN106480500B (en) * | 2016-10-08 | 2019-04-23 | 河南理工大学 | A kind of luminescence generated by light crystalline material boric acid praseodymium potassium and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004123764A (en) * | 2002-08-07 | 2004-04-22 | Nec Lighting Ltd | Red light-emitting phosphor and light-emitting element using the same |
| JP2004124049A (en) * | 2002-08-07 | 2004-04-22 | Nec Lighting Ltd | Red light-emitting phosphor, light-emitting element and fluorescent lamp |
| JP3792665B2 (en) * | 2002-08-07 | 2006-07-05 | Ｎｅｃライティング株式会社 | Red light emitting phosphor, light emitting element and fluorescent lamp |
| CN102010709A (en) * | 2010-12-03 | 2011-04-13 | 山东宏艺科技股份有限公司 | Yellow-light type fluorescent powder |
| CN102199426A (en) * | 2011-04-02 | 2011-09-28 | 北京工商大学 | Stable red fluorescent material, its preparation method and method for enhancing luminescent efficiency |
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| JP2004123764A (en) * | 2002-08-07 | 2004-04-22 | Nec Lighting Ltd | Red light-emitting phosphor and light-emitting element using the same |
| JP2004124049A (en) * | 2002-08-07 | 2004-04-22 | Nec Lighting Ltd | Red light-emitting phosphor, light-emitting element and fluorescent lamp |
| JP3792665B2 (en) * | 2002-08-07 | 2006-07-05 | Ｎｅｃライティング株式会社 | Red light emitting phosphor, light emitting element and fluorescent lamp |
| CN102010709A (en) * | 2010-12-03 | 2011-04-13 | 山东宏艺科技股份有限公司 | Yellow-light type fluorescent powder |
| CN102199426A (en) * | 2011-04-02 | 2011-09-28 | 北京工商大学 | Stable red fluorescent material, its preparation method and method for enhancing luminescent efficiency |
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