CN1271169C - Vacuum ultraviolet energized red fluorescent material and process for preparation - Google Patents

Vacuum ultraviolet energized red fluorescent material and process for preparation Download PDF

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CN1271169C
CN1271169C CN 200410073337 CN200410073337A CN1271169C CN 1271169 C CN1271169 C CN 1271169C CN 200410073337 CN200410073337 CN 200410073337 CN 200410073337 A CN200410073337 A CN 200410073337A CN 1271169 C CN1271169 C CN 1271169C
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vacuum ultraviolet
excited
present
insulations
fluorescent material
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CN1635049A (en
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王育华
王灵利
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Lanzhou University
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Lanzhou University
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Abstract

The present invention discloses a novel red borate luminescent material excited by vacuum ultraviolet light and a synthesis method thereof. The novel red borate luminescent material conforms to the following molecule general formulas: Y<0.95-x>M<x>B<1-y>N<y>O3: Eu<3+> and (Y, Gd)M<x>B<1-y>N<y>O3: Eu<3+>, wherein M=Ca, Sr, Ba, Zn, the x is at most 0.1, N=Al, Si, P, and the y is at most 0.1. Compared with the existing (Y, Gd)BO3: Eu<3+>, the material has better luminescence property under the excitation of ultraviolet light or vacuum ultraviolet light, and has better color purity when the luminous intensity is improved. The novel red borate luminescent material of the present invention is synthesized by a solid phase method and a hydrothermal method.

Description

A kind of vacuum ultraviolet-excited red fluorescence material and preparation method
Technical field
The present invention relates to new vacuum ultraviolet-excited novel red borate fluorescent material of a class and preparation method thereof.
Background technology
Plasma display (PDP) is a kind of emerging display device, compare with CRT monitor, LCD display commonly used, so numerous advantages such as the PDP indicating meter has that the visual angle is wide, big area, in light weight, good contrast, response are fast, undistorted, vibration and shock resistant are PDP indicating meter great prospect.The two big key components that PDP shows are device and luminescent material, and perfect day by day along with designs, luminescent material select the technology that becomes PDP demonstration most critical for use.In PDP, vacuum ultraviolet (VUV) the excited inorganic luminescent material that sends with plasma gas (Xe) sends red, green, primary colors, thus form video.Because borate has good optical property and highly stable physicochemical property, so red illuminating material is with (Y, Gd) BO 3As substrate material.The red illuminating material general molecular formula of widespread use is (Y, Gd) BO in PDP at present 3: Eu, its luminous efficiency is higher.Yet, at (Y, Gd) BO 3: in the Eu luminescent material, its luminescence peak 591nm ( 5D 0→ 7F 1Transition).This is because at (Y, Gd) BO 3: in the Eu crystalline structure, the trivalent europium is in the reason of height centrosymmetry position.Compare (Y, Gd) BO with CIE (the commission internationaldeclared standards) 3: the luminous generation Huang of Eu moves, and purity of color is relatively poor, and according to detection, its blood orange is 0.45 than only, therefore has influence on the display effect of PDP.Also, superseded (Y, Gd) BO are arranged just because of this reason 3: the Eu material is as the cry of red illuminating material.
For the PDP fluorescent material, luminous efficiency and purity of color are of equal importance, but only the pattern etc. from synthetic method (coprecipitation method, ultrasonic heat solution, sol-gel method and flux method etc.), control product can only exert an influence to luminous intensity, is very limited to the improvement of the purity of color of luminescent material.
Summary of the invention
First purpose of the present invention provides a class at the vacuum ultraviolet-excited boric acid alkali fluorescent material that can send comparatively pure ruddiness down, and second purpose of the present invention provides described Preparation of Fluorescent Material method.
The general molecular formula of fluorescent material of the present invention is Y 0.95-xM xB 1-yN yO 3: Eu 3+(M=Ca, Sr, Ba, Zn, 0≤x≤0.1; N=Al, Si, P, 0≤y≤0.1).
By other ion that in matrix, mixes, break YBO among the present invention 3: Eu 3+The high symmetry of crystalline structure middle-weight rare earths element surrounding environment almost is in this essential reason of centrosymmetry position thereby change the trivalent europium, has realized keeping or improve the purpose of its luminous intensity simultaneously to improve the purity of color of material.
As improvement of the present invention, can in material, introduce the Gd ion, this moment, the general molecular formula of fluorescent material was (Y, Gd) M xB 1-yN yO 3: Eu 3+(M=Ca, Sr, Ba, Zn, 0≤x≤0.1; N=Al, Si, P, 0≤y≤0.1).Owing to added gadolinium ion as sensitizing agent in the material, the luminescent properties of material is further improved.
The present invention has synthesized novel red borate fluorescent material Y with solid phase method and hydrothermal method 0.95-xM xB 1-yN yO 3: Eu 3+(M=Ca, Sr, Ba, Zn, 0≤x≤0.1; N=Al, Si, P, 0≤y≤0.1) and improve product (Y, Gd) M xB 1-yN yO 3: Eu 3+(M=Ca, Sr, Ba, Zn, 0≤x≤0.1; N=Al, Si, P, 0≤y≤0.1).After tested, they are than existing luminescent material (Y, Gd) BO 3: Eu 3+Better purity of color is arranged, and luminous intensity increases also.
Behind the doping N element, the improved effective order of purity of color is aluminium, silicon, phosphorus in the luminescent material of the present invention; Behind the doping M element, the improved effective order of purity of color is calcium, zinc, strontium, barium in the luminescent material of the present invention.
Method one of the present invention is the oxide compound with Y, Gd, Eu, Si, Al, the carbonate of Ca, Sr, Ba, Zn, Secondary ammonium phosphate and boric acid are by being incubated 2.5 hours at 500 ℃ earlier behind the stoichiometric ratio uniform mixing, and take out the cooling back, in 1100 ℃ of insulations 2 hours, obtain purpose product Y behind the regrinding 1-xM xB 1-yN yO 3: Eu 3+
Method two of the present invention is a hydrothermal method, be about to the oxide compound of Y, Gd, Eu, the soluble salt of Al, Ca, Sr, Ba, Zn, silicic acid, Secondary ammonium phosphate and boric acid are dissolved in the salpeter solution by stoichiometric ratio, and oven dry is transferred in the reactor then, adding distil water, react at 250 ℃～300 ℃, after reaction finishes, the product that obtains is centrifugal, washing, separate, oven dry can obtain the purpose product.
What need special instruction is in the material of the present invention, when doping M element, should use the Li compensation charge.
The purity of color of products therefrom of the present invention is better than the fluorescent material of prior art, and its preparation method is also fairly simple.
Replace the cost that the part rare earth element can reduce luminescent material with calcium, strontium, barium or zinc among the present invention.
Description of drawings
Accompanying drawing 1 is the X-ray diffractogram of the fluorescent material of different aluminum content, and wherein: the aluminium content among curve a, b, c, d, the e is respectively 10%, 8%, 6%, 4%, 2%.
Accompanying drawing 2 be the fluorescent material of different aluminum content in the emmission spectrum of vacuum ultraviolet-excited down (147nm) and the comparison of blood orange ratio thereof, wherein: the aluminium content among curve a, b, c, d, the e is respectively 10%, 8%, 6%, 4%, 2%, curve f is (Y, Gd) BO 3: Eu 3+Emmission spectrum.
Accompanying drawing 3 is that 10% fluorescent material is at the vacuum ultraviolet-excited emmission spectrum and the blood orange ratio of (147nm) down for silicone content of the present invention.
Accompanying drawing 4 is that 10% fluorescent material is at the vacuum ultraviolet-excited emmission spectrum and the blood orange ratio of (147nm) down for calcium contents of the present invention.
Embodiment
Below provide relevant embodiment of the present invention and relevant Comparative Examples.
Embodiment one
Initial feed: yttrium oxide, europium sesquioxide, aluminum oxide, boric acid
Raw material is pressed stoichiometric ratio Y 0.95B 1-xAl xO 3: Eu 3+(0≤x≤0.1) accurately weighing, its mesoboric acid excessive 10% to be replenishing evaporable loss under the high temperature, with the raw material ground and mixed evenly after, prior to 500 ℃ of insulations 2.5 hours, in 1100 ℃ of insulations 2 hours down, obtain product Y again 0.95B 1-xAl xO 3: Eu 3+(0≤x≤0.1).
Embodiment two
Initial feed: yttrium oxide, europium sesquioxide, silicon-dioxide, boric acid
Raw material is pressed stoichiometric ratio Y 0.95B 1-xSi xO 3: Eu 3+(0≤x≤0.1) accurately weighing, its mesoboric acid excessive 10% to be replenishing evaporable loss under the high temperature, with the raw material ground and mixed evenly after, prior to 500 ℃ of insulations 2.5 hours, in 1100 ℃ of insulations 2 hours down, obtain product Y again 0.95B 1-xSi xO 3: Eu 3+(0≤x≤0.1).
Embodiment three
Initial feed: yttrium oxide, europium sesquioxide, lime carbonate, Quilonum Retard, boric acid
Raw material is pressed stoichiometric ratio Y 0.95-xCa xBO 3: Eu 3+(0≤x≤0.1) accurately weighing, its mesoboric acid excessive 10% is to replenish evaporable loss under the high temperature, and lithium is used for compensating in the position of Y and mixes the charge differences that Ca causes.With the raw material ground and mixed evenly after, prior to 500 ℃ of insulations 2.5 hours, in 1100 ℃ of insulations 2 hours down, obtain product Y again 0.95-xCa xBO 3: Eu 3+(0≤x≤0.1).
Embodiment four
Initial feed: yttrium oxide, gadolinium sesquioxide, europium sesquioxide, aluminum oxide, boric acid
Raw material is pressed stoichiometric ratio (Y, Gd) B 1-xAl xO 3: Eu 3+(0≤x≤0.1) accurately weighing, its mesoboric acid excessive 10% to be replenishing evaporable loss under the high temperature, with the raw material ground and mixed evenly after, prior to 500 ℃ of insulations 2.5 hours, in 1100 ℃ of insulations 2 hours down, obtain product (Y, Gd) B again 1-xAl xO 3: Eu 3+(0≤x≤0.1).
Comparative Examples
Initial feed: yttrium oxide, gadolinium sesquioxide, europium sesquioxide, boric acid
As with contrast of the present invention, prepared prior art product (Y with solid phase method 0.65Gd 0.3Eu 0.05) BO 3Its technology is: by each component of the accurate weighing of stoichiometric ratio, its mesoboric acid excessive 10% to be replenishing evaporable loss under the high temperature, with the raw material ground and mixed evenly after, prior to 500 ℃ of insulations 2.5 hours, in 1100 ℃ of insulations 2 hours down, obtain product (Y again 0.65Gd 0.3Eu 0.05) BO 3
The also available hydrothermal method of above all samples is prepared.
Aforesaid embodiment and Comparative Examples are used X-ray powder diffractometer (XRD respectively; ModelD/max-2400, Rigaku Co.Ltd.Japan) working sample thing phase; Sample adopts spectrophotofluorometer (Model RF-4500, Shimadzu Corporation.Japan) to measure exciting with emmission spectrum of UV wave band; The vacuum ultraviolet-excited characteristics of luminescence is measured with ARC Model VM-502 type vacuum monochromator, and proofreaies and correct with sodium salicylate (Sodium Benzoate).
Experimental result shows that prepared sample is white powder, and through X-ray diffraction analysis, all samples is single-phase.As an example, accompanying drawing 1 has provided the X-ray diffractogram with the different aluminum content sample of high temperature solid-state method preparation, and is that 10% sample has carried out indexing to aluminium content.Accompanying drawing 2 (a～e) provided the emmission spectrum of mixing the aluminium series of samples, as can be seen from the figure aluminium content increases at 10% o'clock by 2%, and the blood orange of its emmission spectrum increases to 1.250 than (R/O) by 0.380.In mixing the series of samples of silicon, silicone content increases to 10% by 5%, and its blood orange increases to 0.76 than (R/O) by 0.65, and accompanying drawing 3 is that silicone content is the emmission spectrum of 10% sample, and its blood orange is 0.76 than (R/O).In mixing the series of samples of phosphorus, phosphorus content increases to 10% by 5%, and its blood orange increases to 0.65 than (R/O) by 0.61.In mixing the series of samples of calcium, calcium contents increases to 10% by 5%, and its blood orange increases to 0.68 than (R/O) by 0.61, and it is the emmission spectrum of 10% sample that accompanying drawing 4 has provided calcium contents, and its blood orange is 0.68 than (R/O).In mixing the series of samples of zinc, zinc content increases to 10% by 5%, and its blood orange increases to 0.65 than (R/O) by 0.61.In mixing the series of samples of barium, barium content increases to 10% by 5%, and its blood orange increases to 0.65 than (R/O) by 0.58.In mixing the series of samples of strontium, content of strontium increases to 10% by 5%, and its blood orange increases to 0.66 than (R/O) by 0.65.
As with contrast of the present invention, to the prior art product (Y of solid phase method preparation 0.65Gd 0.3Eu 0.05) BO 3, detecting with preceding method, accompanying drawing 2 (f) has provided its emmission spectrum, and its blood orange is 0.45 than only.The blood orange ratio of the commodity red fluorescence powder that market is buied (KX-504, Japan change into company and produce) is 0.55.
It can also be seen that the novel fluorescent material Y after the doping from the emmission spectrum of sample 1-xM xB 1-yN yO 3: Eu 3+(M=Ca, Sr, Ba, Zn, 0≤x≤0.1; N=Al, Si, P, 0≤y≤0.1) luminous intensity and prior art product (Y, Gd) BO 3: Eu 3+Substantially be consistent, also strengthen to some extent individually.
Under ultraviolet excitation, the emmission spectrum of sample has identical rule.
Above experimental result shows, as material (Y, Gd) BO 3: Eu 3+In when mixing element such as part element of second, third main group and Si, Zn, can effectively improve the purity of material emitting red light.Particularly adopt aluminium, and when aluminium content is higher than 8%, its luminous purity of color best.

Claims (3)

1, a kind of vacuum ultraviolet-excited red illuminating material is characterized in that its molecular formula general formula is (Y, Gd) M xB 1-yN yO 3: Eu 3+, wherein: M is Ca or Sr or Ba or Zn, 0＜x≤0.1; N is Al or Si or P, 0＜y≤0.1.
2, vacuum ultraviolet-excited method for preparing red luminescence material according to claim 1, it is characterized in that oxide compound with Y, Gd, Eu, Si, Al, the carbonate of Ca, Sr, Ba, Zn, Secondary ammonium phosphate and boric acid are by behind the stoichiometric ratio thorough mixing, earlier 500 ℃ of insulations 2.5 hours, take out the cooling back, in 1100 ℃ of insulations 2 hours, obtains the purpose product behind the regrinding.
3, vacuum ultraviolet-excited method for preparing red luminescence material according to claim 1, it is characterized in that oxide compound with Y, Gd, Eu, the soluble salt of Al, Ca, Sr, Ba, Zn, silicic acid, Secondary ammonium phosphate and boric acid are dissolved in the salpeter solution by stoichiometric ratio, and oven dry is transferred in the reactor then, adding distil water, react at 250 ℃～300 ℃, after reaction finishes, the product that obtains is centrifugal, washing, separate, oven dry can obtain the purpose product.
CN 200410073337 2004-11-26 2004-11-26 Vacuum ultraviolet energized red fluorescent material and process for preparation Expired - Fee Related CN1271169C (en)

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CN100575454C (en) * 2008-01-10 2009-12-30 同济大学 Adulterated zinc ammonium phosphate orange red luminescent powder material of a kind of europium and preparation method thereof
CN101775286B (en) * 2010-01-11 2013-11-06 中国地质大学（武汉） Preparation method of orange red fluorescent powder for white LED
CN102382645B (en) * 2011-09-16 2013-02-13 中国石油大学(华东) Color-adjustable borate luminescent material and synthesis method thereof
CN107354420B (en) * 2017-06-28 2020-05-19 中国航发北京航空材料研究院 Preparation method of graphene modified thermal spraying powder for preparing residual stress coating

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