CN101775287B - CaTiO3:Eu<3+> fluorescent powder and preparation method thereof - Google Patents
CaTiO3:Eu<3+> fluorescent powder and preparation method thereof Download PDFInfo
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Abstract
The invention relates to CaTiO3:Eu<3+> fluorescent powder and a preparation method thereof. The CaTiO3:Eu<3+> fluorescent powder is characterized in that the stoichiometric ratio of Ca:Ti:Eu is (1-18):(32-49):50. The preparation method comprises the steps of: (1) weighing and grinding europium oxide, calcium carbonate and titanium dioxide and mixing uniformly at room temperature; and (2) calcining the mixture for 2-8h at 1200-1600 DEG C, and thus, obtaining the fluorescent powder. The fluorescent powder has the advantages of high chemical stability, small crystallite size, pure crystalline phase, excellent stability, extremely high luminous intensity, simple preparation method, low calcining temperature and easy production equipment obtaining and is suitable to industrialized production.
Description
Technical field
The invention belongs to fluorescent material and preparation field thereof, particularly relate to a kind of CaTiO
3: Eu
3+Fluorescent material and preparation method thereof.
Background technology
The White-light LED illumination light source is compared with luminescent lamp with traditional incandescent light, and very large advantage is arranged.At first the white light LEDs volume is little, and the life-span reaches tens thousand of hours, and close structure can be realized the big area array; Moreover white light LEDs do not contain harmful lead and mercury, avoided the pollution to environment; White light LEDs uses the direct supply lower than 5V to drive, and does not therefore have the 50Hz stroboscopic of traditional lighting light source; Traditional head light radiation zone, mainly at infrared region, can produce a large amount of heat, and the radiation zone of white light LEDs mainly concentrates on visible region, produces hardly heat, is a kind of cold light source, and is therefore not only energy-conservation but also eliminated hertzian wave beyond visible light to the harm of human body; White-light LED encapsulation is rear anti-vibration well, and security is good, can be applied under various rugged environments; The white light LEDs time of response is also very little, and is degradation failure.So significant advantage is arranged just, and semiconductor lighting will become the new and high technology that 21 century has development prospect most.
Fluorescent material as the core material of white light LEDs is all the hot research problem of lighting field all the time, and the performance of fluorescent material also directly affects the development of white light LEDs.The preparation method of fluorescent material is a lot, and main synthetic method has at present: high-temperature solid phase reaction method, sol-gel method, homogeneous coprecipitation method, low-temperature combustion synthesis, hydrothermal synthesis method, Microwave Radiation Synthesis Method, polymer-network gel method, surface diffusion method etc.Yttrium aluminum garnet (yttrium aluminum garnet, the YAG) fluorescent material that at first Japan Ri Ya chemical company developed in 1996 with gold-tinted series coordinates blue-ray LED to obtain high efficiency white light source.In recent years, the scientific research personnel has carried out large quantity research to preparation, the luminescent properties of yttrium aluminum garnet series phosphor powder.This fluorescent material relies on satisfactory stability and with the matched well of corresponding LED chip, has obtained application very widely, and commercialization.But the design of this class blue-light LED chip collocation gold-tinted fluorescent material exists very large defect, and at first this fluorescent material is by the high-temperature solid phase reaction method preparation, although high-temperature solid phase reaction method be the synthetizing phosphor powder application the earliest, a kind of maximum method.But that a major defect of this method is preparation temperature is high, reaction not exclusively, contain a small amount of original solid material in product.Secondly, along with the increase of duration of service, the problem of aging of chip will cause the light blue shift that sends, and the hybrid light source that finally makes the light that its and fluorescent material sends is indigo plant partially, and colour rendering index is reduced greatly.Zhou etc. are at Alloys and Compounds.2004, and 375 (1): reported a kind of Y for preparing by wet chemistry method in 93
3Al
5O
12: RE
3+(RE:Eu, Dy) fluorescent material, can effectively simplify synthesis technique, but still can't solve the aging series of problems that causes of chip.And the research of the high efficiency red phosphor powder that can effectively be excited by UV and nearly UV light can solve luminous colder this problem.The red fluorescence powder aspect, Zhuan Weidong etc. are at China rare earth journal 2004,22 (6): 854 have reported that a kind of divalent europium activates the red fluorescence powder of alkaline earth transition metal complex sulfide.Divalent europium activates sulfide (Sr, Ca) S:Eu
2+Excite the long 600nm of being of lower emission spike at 460nm.But this fluorescent material poor stability, easy deliquescence, must coat processing.As seen, still there is at present the problem of many sternnesses in the fluorescent material research field, such as, the fluorescent material that light conversion efficiency and thermal stability are good, particularly can extremely be lacked by the high efficiency red phosphor powder that nearly UV light effectively excites, and extremely need.Because the luminous efficiency of the present red fluorescent powder for white radiation LED of developing is low, can not meet the demands, this just needs us to find new and effective red fluorescent powder for white radiation LED.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of CaTiO
3: Eu
3+Fluorescent material and preparation method thereof, this CaTiO
3: Eu
3+Fluorescent material, chemical stability is high, grain-size is little, crystalline phase is pure; Have satisfactory stability and high luminous intensity, method is simple, and calcining temperature is low, and production unit is easy to get, and is suitable for suitability for industrialized production.
A kind of CaTiO of the present invention
3: Eu
3+Fluorescent material, is characterized in that, calcium: titanium: the stoichiometric ratio of europium is (1～18): (32～49): 50.
Described CaTiO
3: Eu
3+Fluorescent material, wherein calcium: titanium: the stoichiometric ratio of europium is 0.92: 1: 0.08.
Described CaTiO
3: Eu
3+Fluorescent material, wherein calcium: titanium: the stoichiometric ratio of europium is 0.88: 1: 0.12.
Described CaTiO
3: Eu
3+Fluorescent material, wherein calcium: titanium: the stoichiometric ratio of europium is 0.86: 1: 0.14.
Described CaTiO
3: Eu
3+Fluorescent material, wherein calcium: titanium: the stoichiometric ratio of europium is 0.94: 1: 0.06.
A kind of CaTiO of the present invention
3: Eu
3+The preparation method of fluorescent material comprises:
(1) at room temperature, press Eu
3+, Ca
2+And Ti
4+Mole ratio be (1～18): (32～49): 50 take europium sesquioxide, calcium carbonate and titanium dioxide grinds and mixes;
(2) with said mixture at 1200～1600 ℃ of temperature lower calcination 2～8h, obtain CaTiO
3: Eu
3+Fluorescent material.
Described step (1) Eu
3+, Ca
2+And Ti
4+Mole ratio be 18: 32: 50.
Described step (1) Eu
3+, Ca
2+And Ti
4+Mole ratio be 1: 49: 50.
Described step (2) CaTiO
3: Eu
3+The particle diameter of fluorescent material is 8～15 μ m.
The ratio of the oxide compound by regulating calcium, europium, obtain the different CaTiO that form
3: Eu
3+Fluorescent material.
High temperature solid-state method is the most traditional method maximum with application of synthesizing rare-earth fluorescent material.This method be will contain the compound of product element and some fusing assistants fully mix after pulverizing, through high-temperature roasting, pulverize and sieve and aftertreatment namely obtains fluorescent material.It burns till and generally includes following steps: the diffusion that strides across interface of (1) atom or ion; (2) chemical reaction of atom scale; (3) cenotype nucleation; (4) by transporting of solid and growing up of cenotype.Two important factors that determine solid state reaction are nucleation and velocity of diffusion.If have structural similarity between product and reactant, nucleation is easily carried out.Diffusion is relevant with size and the spread coefficient thereof of defect, interface topography, atom or the ion of solid phase inside.
Therefore in solid state reaction, reach matrix and activator composition are uniformly distributed, the lattice uniformity, must, first through the diffusing step between activator composition and Matrix Composition, then generate crystal.Diffusion process is obeyed Fick's law:
The quantity of n-material diffusion in formula; T-diffusion time;
The velocity of diffusion of-material; The D-spread coefficient; The sectional area that passes through during the diffusion of A-material; The c-material concentration; X-diffusion length velocity of diffusion
Be directly proportional to diffusion coefficient D, x is inversely proportional to diffusion length.Diffusion coefficient D can
Be expressed as: D=D
oExp (E
d/ RT)
Do-constant in formula; E
d-Diffusion Activation Energy; The R-gas law constant; The T-temperature.
Diffusion coefficient D and temperature T exponent function relation.The diffusion coefficient D of solid state reaction is than the diffusion coefficient D in liquid phase reaction much smaller (generally wanting little several orders of magnitude), in solid state reaction, intergranular diffusion length x is more much bigger than liquid reactive diffusion length x, thus the velocity of diffusion of solid state reaction just than liquid reactive velocity of diffusion slowly many.Complete diffusing step, the synthetizing phosphor powder product, must improve calcining temperature to 1200～1400 ℃, extends calcination time and reach a few hours.
In addition, at rhombic system CaTiO
3In lattice, Ca
2+And Eu
3+Be the eight-coordinate number.Ca
2+Ionic radius be 126pm, this numerical value and Eu
3+Ionic radius 120.6pm ten minutes approach.And the ionic radius that both approaches will produce less lattice distortion energy.So Eu
3+Replacing CaTiO
3In Ca
2+In time,, ratio was easier to, and then obtained the higher fluorescent material of luminous intensity.
Beneficial effect
(1) the present invention prepares CaTiO by solid phase method
3: Eu
3+Fluorescent material, chemical stability is high, grain-size is little, crystalline phase is pure; Have satisfactory stability and high luminous intensity, in fields such as LEDphosphor for LED illumination, white light emitting diode, scintillator, laser and radiological monitors, gather around and have broad application prospects;
(2) the inventive method is simple, and calcining temperature is low, and production unit is easy to get, and the rare earth doped chemical stability that can guarantee fluorescent material, be easy to scale operation take calcium titanate as matrix.
Description of drawings
Fig. 1 .CaTiO
3: Eu
3+The X-ray diffractogram of fluorescent material;
Fig. 2 .CaTiO
3: Eu
3+The stereoscan photograph of fluorescent material;
Fig. 3 .CaTiO
3: Eu
3+The fluorescence spectrum of fluorescent material.
Embodiment
, below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for explanation the present invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Take 4.600g calcium carbonate (0.046mol), 0.703g europium sesquioxide (0.002mol) and 3.990g titanium dioxide (0.05mol) add mortar.Said mixture is ground 10min form uniform mixture; Then the mixture that obtains is calcined 2h under 1400 ℃, namely obtain Ca
0.92TiO
3: Eu
3+ 0.08Fluorescent material.Fig. 1 is the X-ray diffractogram of the synthetic fluorescent material of the present embodiment, can find out: diffraction peak is consistent with the diffraction peak of the calcium titanate of Emission in Cubic, discovery belongs to the diffraction peak of other oxide compound of calcium, illustrate and do not contain impurity phase, analyse and compare by XRD data analysis software (JADE 5.0), result shows the CaTiO that has synthesized Emission in Cubic
3: Eu
3+Fluorescent material.Fig. 2 is CaTiO
3: Eu
3+The stereoscan photograph of fluorescent material, can find out that this fluorescent material powder grain diameter is at 8～15 μ m.Fig. 3 is excitation spectrum and the emmission spectrum of fluorescent material, can find out: synthetic fluorescent material has higher emissive porwer under near ultraviolet excitation.
Take 4.400g calcium carbonate (0.042mol), 1.054g europium sesquioxide (0.003mol) and 3.990g titanium dioxide (0.05mol) add mortar.Said mixture is ground 15min form uniform mixture; Then the mixture that obtains is calcined 4h under 1300 ℃, namely obtain Ca
0.88TiO
3: Eu
3+ 0.12Fluorescent material.The X ray test result shows: diffraction peak is consistent with the diffraction peak of the calcium titanate of Emission in Cubic, discovery belongs to the diffraction peak of other oxide compound of calcium, illustrate and do not contain impurity phase, analyse and compare by XRD data analysis software (JADE 5.0), result shows the CaTiO that has synthesized Emission in Cubic
3: Eu
3+Fluorescent material.Scanning electron microscopic observation shows: this fluorescent material powder grain diameter is at 8～15 μ m.Adopt the 400nm wavelength light to excite the fluorescence spectrum test of test fluorescent material to show: synthetic fluorescent material has higher emissive porwer under near ultraviolet excitation.
Embodiment 3
Take 4.300g calcium carbonate (0.043mol), 1.230g europium sesquioxide (0.0035mol) and 3.990g titanium dioxide (0.05mol) add ball grinder, and add 200ml ethanol as dispersion agent.Said mixture ball milling 120min is formed uniform mixture; Then the mixture that obtains dry 6h under 100 ℃, the drying composite that will obtain is finally calcined 6h under 1400 ℃, namely obtain Ca
0.86TiO
3: Eu
3+ 0.14Fluorescent material.The X ray test result shows: diffraction peak is consistent with the diffraction peak of the calcium titanate of Emission in Cubic, discovery belongs to the diffraction peak of other oxide compound of calcium, illustrate and do not contain impurity phase, analyse and compare by XRD data analysis software (JADE 5.0), result shows the CaTiO that has synthesized Emission in Cubic
3: Eu
3+Fluorescent material.Scanning electron microscopic observation shows: this fluorescent material powder grain diameter is at 8～15 μ m.Adopt the 400nm wavelength light to excite the fluorescence spectrum test of test fluorescent material to show: synthetic fluorescent material has higher emissive porwer under near ultraviolet excitation.
Take 4.700g calcium carbonate (0.047mol), 0.527g europium sesquioxide (0.0015mol) and 3.990g titanium dioxide (0.05mol) add mortar.Said mixture is ground 20min form uniform mixture; Then the mixture that obtains is calcined 2h under 1500 ℃, namely obtain Ca
0.94TiO
3: Eu
3+ 0.06Fluorescent material.The X ray test result shows: diffraction peak is consistent with the diffraction peak of the calcium titanate of Emission in Cubic, discovery belongs to the diffraction peak of other oxide compound of calcium, illustrate and do not contain impurity phase, analyse and compare by XRD data analysis software (JADE 5.0), result shows the CaTiO that has synthesized Emission in Cubic
3: Eu
3+Fluorescent material.Scanning electron microscopic observation shows: this fluorescent material powder grain diameter is at 8～15 μ m.Adopt the 400nm wavelength light to excite the fluorescence spectrum test of test fluorescent material to show: synthetic fluorescent material has higher emissive porwer under near ultraviolet excitation.
Claims (1)
1. CaTiO
3: Eu
3+The preparation method of fluorescent material comprises:
Take 4.300g calcium carbonate, 1.230g europium sesquioxide and 3.990g titanium dioxide add ball grinder, and add 200ml ethanol as dispersion agent; Said mixture ball milling 120min is formed uniform mixture; Then the mixture that obtains dry 6h under 100 ℃, the drying composite that will obtain is finally calcined 6h under 1400 ℃, namely obtain Ca
0.86TiO
3: Eu
3+ 0.14Fluorescent material.
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| CN104830330B (en) * | 2015-04-20 | 2016-08-24 | 陕西科技大学 | A kind of submicron order Sm3+: β-Li2tiO3reddish orange emitting phosphor and preparation method |
| CN104746176B (en) * | 2015-04-20 | 2017-01-04 | 黑龙江大学 | CaTiO3: Eu3+/ TiO2the preparation method of composite fibre |
| CN106010520B (en) * | 2016-05-20 | 2018-10-23 | 福建农林大学 | A kind of near ultraviolet excitated red fluorescence powder and its preparation method and application |
| CN108707456B (en) * | 2018-05-20 | 2021-02-12 | 河南城建学院 | Preparation method of red-light fluorescent powder |
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|---|---|---|---|---|
| CN101376523A (en) * | 2008-09-24 | 2009-03-04 | 东华大学 | Preparation of doped calcium titanate (CaTiO3: Eu3+) fluorescent powder |
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Non-Patent Citations (2)
| Title |
|---|
| "Preparation and photoluminescence characteristics of a new promising red NUV phosphor CaTiO3:Eu3+";jiapeng fu 等;《Journal of Alloys and Compounds》;20091019;418-421 * |
| jiapeng fu 等."Preparation and photoluminescence characteristics of a new promising red NUV phosphor CaTiO3:Eu3+".《Journal of Alloys and Compounds》.2009,418-421. |
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