CN106554777A - A kind of colourity is with adjustable luminescent material of temperature and preparation method and application - Google Patents
A kind of colourity is with adjustable luminescent material of temperature and preparation method and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 229910019792 NbO4 Inorganic materials 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 27
- 150000002500 ions Chemical class 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 21
- 229910052593 corundum Inorganic materials 0.000 claims description 21
- 239000010431 corundum Substances 0.000 claims description 21
- 239000004570 mortar (masonry) Substances 0.000 claims description 21
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 21
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 1
- 238000010791 quenching Methods 0.000 abstract description 4
- 230000000171 quenching effect Effects 0.000 abstract description 4
- -1 rare earth ion Chemical class 0.000 abstract description 4
- 230000000630 rising effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 28
- 229910002637 Pr6O11 Inorganic materials 0.000 description 19
- 229910003443 lutetium oxide Inorganic materials 0.000 description 19
- 230000009467 reduction Effects 0.000 description 19
- 230000005284 excitation Effects 0.000 description 14
- 230000009102 absorption Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000010955 niobium Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910002338 LaNbO4 Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a kind of colourity is with adjustable luminescent material of temperature and preparation method and application.Chemical composition expression is：Lu(1‑x)PrxNbO4, in formula, x is active ions Pr3+With respect to matrix rare earth ion Lu3+The molar content for accounting for, span：0.001≤x≤0.10.Present invention utilizes LuNbO4NbO in matrix4 3‑The effective of group lights, and degree of crystallinity is high, and luminous mass is good.Due to containing rare earth ion Lu in host material3+, be conducive to Pr3+The doping of ion.LuNbO4Host emission blue light, Pr3+In LuNbO4Main transmitting ruddiness in matrix.With the rising of temperature, matrix is to Pr3+The energy transfer efficiency of ion gradually increases, Pr3+Red emission in higher temperature not yet occurrence temperature quenching, cause blue emission gradually to weaken, red emission gradually strengthens.The luminescent material raises the controllability with luminescent chromaticity with temperature, the luminescent material mixing of various different colourities need not be used when light-sensitive device is prepared, it is to avoid the light absorbs between different luminescent materials.Synthesis step is simple, it is easy to operate.
Description
Technical field
The invention belongs to embedded photoluminescent material and lighting display technology field.More particularly, to a kind of colourity with temperature
Adjustable luminescent material and preparation method and application.
Background technology
Luminescent material it is of many uses, realize that the luminous excitation energy form of luminescent material has various, such as ultraviolet-visible
Light, gas discharge, electric field, X-ray, cathode-ray etc..With high-quality illumination and the extensive application of display device, preparation method
Simply, luminous efficiency is high, long service life rare earth luminescent material is more and more important.
Luminous is the process that interior of articles is converted into light radiation in some way after energy absorption.When object is subject to such as light
Irradiation, after extra electric field or beam bombardment, the energy that material absorbs is discharged by the form of light.It is topmost luminous
Form has two kinds, and one kind is that host material absorbs excitation energy and is converted into light emitting species release.Another kind is that matrix will absorb
Energy transmission to active ions, realized by the radiation transistion between active ions difference energy level luminous.Such as luminescent material
YNbO4:Eu3+/Tb3+, LaNbO4:Eu3+/Tb3+, matrix YNbO4And LaNbO4Black light can be absorbed and launch blue light, base
Matter transfers energy to the rare earth ion Eu for adulterating3+And Tb3+Afterwards so as to send bright ruddiness and green glow respectively.Refering to document
1：X.M Liu, Y. Lu, C. Chen, et al., J. Phys. Chem. C, 2014,118,27516-27524. join
Read document 2：K. Li, Y. Zhang, X.J. Li, et al. , Phys. Chem. Chem. Phys., 2015, 17,
4283-4292.
Rare earth niobates（LnNbO4）Due to good chemical stability, high heat endurance and emission conversion efficiency, from
The centre of luminescence NbO of activation4 3-, and the advantages of be easy to rare earth ion doped and it is widely used in field of light emitting materials.Near ultraviolet
Light is excited down, Pr3+Ion has the blue green light of feature（3P0→3H4）And ruddiness（1D2→3H4）Transmitting, in closed shell transition metal niobium
Hydrochlorate LuNbO4In matrix, charge migration Pr between valency3+ + Nb5+↔ Pr4+ + Nb4+State makes3P0Excitation state is effectively quenched,1D2Send out
Enhancing is penetrated, so that Pr3+In LuNbO4Main transmitting ruddiness in matrix.High-temperature is risen, matrix is to Pr3+The energy transmission effect of ion
Rate strengthens, and causes blue light and the transmitting ratio of ruddiness to change, it is possible to achieve luminescent chromaticity is with temperature continuously adjustabe.
The content of the invention
It is an object of the invention to provide a kind of degree of crystallinity is high, luminous mass is good, and preparation method is simple, pollution-free and illuminant colour
Degree can be with the continuously adjustable Pr of temperature3+The colourity of activation is with the continuously adjustable luminescent material of temperature.
It is a further object to provide the preparation method of above-mentioned luminescent material.
The colourity of the present invention has following chemical composition expression with the continuously adjustable luminescent material of temperature：Lu(1-x)
PrxNbO4, in formula, x is active ions Pr3+With respect to matrix rare earth ion Lu3+The molar content for accounting for, span：0.001
≤x≤0.10。
Host material selected by the present invention is LuNbO4, active ions are trivalent rare earth praseodymium ion Pr3+.Swash in black light
Give, host emission blue light, Pr3+The main transmitting ruddiness in the matrix.500 Ks are increased to from 300 K with temperature, blue light and red
Light transmitting ratio changes, and luminescent chromaticity is from continuously adjustabe in purple-purple pink colour-peach scope.
In room temperature（300 K）Under Shi Bochang is for the near ultraviolet excitation of 240 ~ 290 nm, work as Pr3+The Mole percent of doping
Content be 0.001≤x≤0.10, its luminous chromaticity coordinate value be x=0.191 ~ 0.242, y=0.073 ~ 0.143
Purple.
Described luminescent chromaticity is adjustable with temperature, with Lu(1-x)PrxNbO4As a example by (x=0.005) sample, in wavelength it is
Under the near ultraviolet excitation of 240 ~ 290 nm, when temperature T be 300 K≤T≤375 K, its luminous chromaticity coordinate value be x=
The purple of 0.225 ~ 0.324, y=0.091 ~ 0.151；When temperature T is 375 K<T≤450 K, its luminous colourity sit
Scale value be x=0.324 ~ 0.446, the opera pink of y=0.151 ~ 0.230；When temperature T is 450 K<T≤500 K,
Its luminous chromaticity coordinate value be x=0.446 ~ 0.474, the pink of y=0.230 ~ 0.255.
Above-mentioned colourity comprises the steps with the preparation method of the adjustable luminescent material of temperature：
S1. according to the chemical composition embodied in chemical composition expression formula described in claim 1, raw material is accurately weighed, is fully ground
Mill is well mixed, and obtains mixture；
S2. by mixture compressing tablet, it is then placed in reaction vessel, in reducing atmosphere, is placed in resistance furnace Program and heats up and roast
Burn, naturally cool to room temperature；
S3. step S2 products therefrom is taken out and is ground, that is, obtain product.
Wherein, the raw material described in step S1 is：Luteium oxide, praseodymium oxide and niobium oxide.
Preferably, it is that absolute ethyl alcohol is added in agate mortar as medium that being fully ground described in step S1 is well mixed
It is ground and is well mixed.
Preferably, the compressing tablet described in step S2 is that compressing tablet is carried out in cold isostatic press, and mixture obtained by step S1 is existed
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure.
Furthermore it is preferred that reaction vessel described in step S2 is corundum crucible.
Preferably, reducing atmosphere described in step S2 is referred to by heating the carbon monoxide atmosphere that carbon block is produced.
Preferably, the heating-up time described in step S2 is 2-5 h.
It is highly preferred that the heating-up time described in step S2 is 4 h.
Preferably, the condition of roasting described in step S2 is 1200 ~ 1300 DEG C, roasting 4-10 h.
It is highly preferred that the condition of roasting described in step S2 is 1220 ~ 1260 DEG C, 5 h of roasting.
Most preferably, the condition of roasting described in step S2 is 1250 DEG C, 5 h of roasting.
Compared with prior art, the present invention has the advantages that：
1. present invention utilizes LuNbO4NbO in matrix4 3-The effective of group lights, and degree of crystallinity is high, and luminous mass is good.
2. due to containing rare earth ion Lu in host material3+, be conducive to Pr3+The doping of ion.
3. LuNbO4Host emission blue light, Pr3+In LuNbO4Main transmitting ruddiness in matrix.
4. with Pr3+The rising of doping content, matrix is to Pr3+The energy transfer efficiency of ion gradually increases, Pr3+It is red
Light is launched（1D2→3H4Transition）In doping x=0.005, generation concentration quenching, causes blue emission gradually to weaken, and ruddiness is sent out
Penetrate first to strengthen and weaken afterwards.Work as Pr3+Doping be 0.001≤x≤0.10 when, LuNbO4:xPr3+In 261nm near ultraviolet excitations
Under luminescent chromaticity coordinate be respectively positioned on purple light area.
5., with the rising of temperature, matrix is to Pr3+The energy transfer efficiency of ion gradually increases, Pr3+Red emission
（1D2→3H4Transition）In higher temperature（450-500 K）When not yet occurrence temperature quenching, cause blue emission gradually to weaken, it is red
Light transmitting gradually strengthens.Therefore, the luminescent material raises the controllability with luminescent chromaticity with temperature, is preparing light-sensitive device
When need not be mixed with the luminescent material of various different colourities, it is to avoid the light absorbs between different luminescent materials.
6. the luminescent material synthesis step of the present invention is simple, it is easy to operate.
Description of the drawings
In Fig. 1, a is the present invention（Embodiment 5）Luminescent material monitor 613 nm when excitation spectrum, b for the present invention
（Embodiment 5）Emission spectrum of the luminescent material under 261 nm near ultraviolet excitations.
Fig. 2 is the present invention（Embodiment 1,3,5,10,11,14 and 19）Luminescent material in 261 nm black lights
Emission spectrum under exciting, is host emission (blue light, 390 nm) and Pr in interior illustration3+Ion1D2→3H4Transition transmitting is (red
Light, 613 nm) relative intensity with Pr3+The elevated changing trend diagram of doping content.
Fig. 3 is the present invention（Embodiment 1,3,5,10,11,14 and 19）Luminescent material in 261 nm black lights
Position view of the chromaticity coordinates under exciting in 1931 chromatic diagrams of CIE.
Launching lights of the Fig. 4 for 5 luminescent material of embodiment temperature K from 300 K to 500 under 261 nm near ultraviolet excitations
Spectrum, is matrix blue emission and Pr in interior illustration3+Ion1D2→3H4The integrated intensity of transition red emission is with the elevated change of temperature
Change tendency chart.
Chromaticity coordinates of the Fig. 5 for 5 luminescent material of embodiment temperature K from 300 K to 500 under 261 nm near ultraviolet excitations
Position view in 1931 chromatic diagrams of CIE.
Specific embodiment：
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not appointed to the present invention
The restriction of what form.Unless stated otherwise, the reagent for adopting of the invention, method and apparatus are for the art conventional reagent, side
Method and equipment.
Unless stated otherwise, following examples agents useful for same and material are commercial.
Embodiment 1：
Weigh luteium oxide（Lu2O3）0.5963 g, praseodymium oxide（Pr6O11）0.0005 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.999Pr0.001NbO4。
Embodiment 2：
Weigh luteium oxide（Lu2O3）0.5957 g, praseodymium oxide（Pr6O11）0.0010 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.998Pr0.002NbO4。
Embodiment 3：
Weigh luteium oxide（Lu2O3）0.5951 g, praseodymium oxide（Pr6O11）0.0015 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.997Pr0.003NbO4。
Embodiment 4：
Weigh luteium oxide（Lu2O3）0.5945 g, praseodymium oxide（Pr6O11）0.0020 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.996Pr0.004NbO4。
Embodiment 5：
Weigh luteium oxide（Lu2O3）0.5939g, praseodymium oxide（Pr6O11）0.0026 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.995Pr0.005NbO4。
Embodiment 6：
Weigh luteium oxide（Lu2O3）0.5933 g, praseodymium oxide（Pr6O11）0.0031 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.994Pr0.006NbO4。
Embodiment 7：
Weigh luteium oxide（Lu2O3）0.5927 g, praseodymium oxide（Pr6O11）0.0036 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.993Pr0.007NbO4。
Embodiment 8：
Weigh luteium oxide（Lu2O3）0.5921 g, praseodymium oxide（Pr6O11）0.0041 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.992Pr0.008NbO4。
Embodiment 9：
Weigh luteium oxide（Lu2O3）0.5915 g, praseodymium oxide（Pr6O11）0.0046 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.991Pr0.009NbO4。
Embodiment 10：
Weigh luteium oxide（Lu2O3）0.5909 g, praseodymium oxide（Pr6O11）0.0051 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.99Pr0.01NbO4。
Embodiment 11：
Weigh luteium oxide（Lu2O3）0.5850 g, praseodymium oxide（Pr6O11）0.0102 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.98Pr0.02NbO4。
Embodiment 12：
Weigh luteium oxide（Lu2O3）0.5790 g, praseodymium oxide（Pr6O11）0.0153 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.97Pr0.03NbO4。
Embodiment 13：
Weigh luteium oxide（Lu2O3）0.5730 g, praseodymium oxide（Pr6O11）0.0204 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.96Pr0.04NbO4。
Embodiment 14：
Weigh luteium oxide（Lu2O3）0.5671 g, praseodymium oxide（Pr6O11）0.0255 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.95Pr0.05NbO4。
Embodiment 15：
Weigh luteium oxide（Lu2O3）0.5611 g, praseodymium oxide（Pr6O11）0.0306 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.94Pr0.06NbO4。
Embodiment 16：
Weigh luteium oxide（Lu2O3）0.5551 g, praseodymium oxide（Pr6O11）0.0358 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, in Program intensification 4h to 1250 DEG C of resistance furnace, 5 h are sintered, room temperature is naturally cooled to；By sample
Grinding is taken out, product is finally given, its chemical composition expression formula is：Lu0.93Pr0.07NbO4。
Embodiment 17：
Weigh luteium oxide（Lu2O3）0.5491 g, praseodymium oxide（Pr6O11）0.0409 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.92Pr0.08NbO4。
Embodiment 18：
Weigh luteium oxide（Lu2O3）0.5432 g, praseodymium oxide（Pr6O11）0.0460 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.91Pr0.09NbO4。
Embodiment 19：
Weigh luteium oxide（Lu2O3）0.5372 g, praseodymium oxide（Pr6O11）0.0511 g, niobium oxide（Nb2O5）0.3987 g, Yu Ma
In Nao mortars, add absolute ethyl alcohol as medium, be fully ground and be well mixed；Mixture is placed in cold isostatic press
The slice of cylinder of a diameter of 12.5 mm and high about 5 mm is pressed under 150 MPa pressure；Material piece is placed in corundum crucible,
In Carbon monoxide reduction atmosphere, heat up 4 h to 1250 DEG C in resistance furnace Program, sinter 5 h, naturally cool to room temperature；By sample
Product take out grinding, finally give product, and its chemical composition expression formula is：Lu0.90Pr0.10NbO4。
According to a series of with different active ions of preparation method of the present invention acquisition（Active ions refer to that trivalent is dilute
Native ion Pr3+）Concentration（As molar content x, and span 0.001≤x≤0.10）LuNbO4: xPr3+It is luminous
Material is in monitoring Pr3+The excitation spectrum that measures during main 613 nm of emission peak and at 261 nm (peak of Host lattice absorption band)
Emission spectrum under near ultraviolet excitation is shown in Figure 1 to represent with embodiment 5.It is observed that：Lu(1-x)PrxNbO4
(0.001≤x≤0.10) serial emission material has very strong wide band absorption, the excitation spectrum of sample in ultra-violet (UV) band（A institutes in Fig. 1
Show）Display Host lattice absorption band is 240 ~ 290 nm, and the acromion positioned at Host lattice absorption band low energy direction belongs to Pr3+ + Nb5+
↔ Pr4+ + Nb4+Electric charge transfer between valency（IVCT）Band, the absworption peak in the range of 440-500 nm is then from Pr3+Ion
From3H4Ground state is arrived3P0,1,2, 1I6The f-f transition absorptions of excitation state.In Host lattice absorption band（261 nm）Excite down, the transmitting of sample
Spectrum（In Fig. 1 shown in b）Show the blue light of matrix（~ 390 nm）Transmitting and Pr3+Ruddiness（~ 613 nm）1D2→3H4Transition
Transmitting.
Lu(1-x)PrxNbO4Transmitting of (0.001≤x≤0.10) the serial emission material under 261 nm near ultraviolet excitations
Spectrum is shown in Figure 2 to represent with embodiment 1,3,5,10,11,14 and 19.It is observed that：With Pr3+Doping content
Rising, matrix is to Pr3+The energy transfer efficiency of ion gradually increases, and causes matrix blue emission to weaken, Pr3+Ruddiness send out
Penetrate after enhancing reaches maximum at x=0.005 and gradually weaken because generation concentration is quenched so that the transmitting ratio of blue light and ruddiness
Example is not with Pr3+There is big change in the increase of doping content.
By the chromaticity coordinate figure in Fig. 3 it is observed that Lu(1-x)PrxNbO4(0.001≤x≤0.10) serial emission material
Chromaticity coordinates of the material under 261 nm near ultraviolet excitations is x=0.191 ~ 0.242, y=0.073 ~ 0.143, positioned at purple
Light area.
Representative sample Lu0.995Pr0.005NbO4（Embodiment 5）Under 261 nm near ultraviolet excitations, temperature is from 300 K to 500
The emission spectrum of K is shown in Figure 4.It is observed that：Raise with temperature, matrix is to Pr3+Energy transfer efficiency gradually strengthen and
The possible occurrence temperature quenching of matrix, and Pr3+Red emission in LuNbO4There is in matrix good heat endurance, cause blue light
Raise with temperature with the ratio of ruddiness and be gradually reduced.
By representative sample Lu in Fig. 50.995Pr0.005NbO4（Embodiment 5）The different temperatures under 261 nm near ultraviolet excitations
When position of the chromaticity coordinate in 1931 CIE chromaticity diagrams it is observed that when temperature is increased to 500 K from 300 K, lighting
Colourity continuously adjustabe in the scope of purple light-purple powder light-pink light.
Claims (10)
1. a kind of colourity is with the adjustable luminescent material of temperature, it is characterised in that：
Chemical composition expression is：Lu(1-x)PrxNbO4, in formula, x is active ions Pr3+With respect to matrix rare earth ion Lu3+Account for
Molar content, span：0.001≤x≤0.10.
2. the preparation method of luminescent material described in claim 1, it is characterised in that comprise the steps：
S1. according to the chemical composition embodied in above-mentioned chemical composition expression formula, raw material is accurately weighed, is fully ground mixing equal
It is even, obtain mixture；
S2. by mixture compressing tablet, it is then placed in reaction vessel, in reducing atmosphere, is placed in resistance furnace Program and heats up and roast
Burn, naturally cool to room temperature；
S3. step S2 products therefrom is taken out and is ground, that is, obtain product.
3. preparation method according to claim 2, it is characterised in that the raw material described in step S1 is：Luteium oxide, praseodymium oxide
And niobium oxide.
4. preparation method according to claim 2, it is characterised in that being fully ground described in step S1 be well mixed be in
Add absolute ethyl alcohol to be ground as medium to be well mixed in agate mortar.
5. preparation method according to claim 2, it is characterised in that the compressing tablet described in step S2 is in cold isostatic press
Compressing tablet is carried out, mixture obtained by step S1 is pressed into into the cylinder of a diameter of 12.5 mm and high about 5 mm under 150 MPa pressure
Piece.
6. preparation method according to claim 2, it is characterised in that reaction vessel described in step S2 is corundum crucible.
7. preparation method according to claim 2, it is characterised in that reducing atmosphere described in step S2 is referred to by heating charcoal
The carbon monoxide atmosphere that block is produced.
8. preparation method according to claim 2, it is characterised in that the heating-up time described in step S2 is 3-6 h.
9. preparation method according to claim 2, it is characterised in that the condition of roasting described in step S2 is 1200 ~
1300 DEG C, roasting 5-10 h.
10. the colourity described in claim 1 with the adjustable luminescent material of temperature in the various illuminations with black light as excitaton source
Application in terms of display or luminescence generated by light.
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| CN107099281A (en) * | 2017-05-11 | 2017-08-29 | 中山大学 | One kind has highly sensitive optics temperature-measurement material and preparation method thereof |
| CN109181697A (en) * | 2018-10-29 | 2019-01-11 | 江苏师范大学 | A kind of niobates fluorescent powder of strong red emission and preparation method thereof |
| CN111170742A (en) * | 2020-01-21 | 2020-05-19 | 徐州凹凸光电科技有限公司 | Full spectrum Y3NbO7Cryolite-based fluorescent material and preparation method thereof |
| CN116023942A (en) * | 2022-09-20 | 2023-04-28 | 宝鸡文理学院 | Visual mechanical sensing material based on mechanoluminescence intensity ratio and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099281A (en) * | 2017-05-11 | 2017-08-29 | 中山大学 | One kind has highly sensitive optics temperature-measurement material and preparation method thereof |
| CN109181697A (en) * | 2018-10-29 | 2019-01-11 | 江苏师范大学 | A kind of niobates fluorescent powder of strong red emission and preparation method thereof |
| CN111170742A (en) * | 2020-01-21 | 2020-05-19 | 徐州凹凸光电科技有限公司 | Full spectrum Y3NbO7Cryolite-based fluorescent material and preparation method thereof |
| CN111170742B (en) * | 2020-01-21 | 2022-02-01 | 徐州凹凸光电科技有限公司 | Full spectrum Y3NbO7Cryolite-based fluorescent material and preparation method thereof |
| CN116023942A (en) * | 2022-09-20 | 2023-04-28 | 宝鸡文理学院 | Visual mechanical sensing material based on mechanoluminescence intensity ratio and preparation method thereof |
| CN116023942B (en) * | 2022-09-20 | 2023-11-10 | 宝鸡文理学院 | Visual mechanical sensing material based on mechanoluminescence intensity ratio and preparation method thereof |
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