CN107722980A - A kind of red gadolinium molydbate calcium analysis samarium bicone luminescent material and preparation method thereof - Google Patents
A kind of red gadolinium molydbate calcium analysis samarium bicone luminescent material and preparation method thereof Download PDFInfo
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- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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Abstract
The invention discloses a kind of red gadolinium molydbate calcium analysis samarium bicone luminescent material and preparation method thereof.Samarium oxide is first configured to samarium nitrate solution by it, while gadolinium nitrate, calcium nitrate and sodium molybdate solid are dissolved in into deionized water and are configured to corresponding nitrate solution respectively；Gadolinium nitrate solution, calcium nitrate solution, samarium nitrate solution are mixed；Then appropriate complexing agent EDTA is added in the mixed solution of gained, and stirred at normal temperatures；Sodium molybdate solution is added in mixed solution above, is stirred to obtain milky turbid, be transferred to hydrothermal reaction kettle and carry out hydro-thermal reaction；After hydro-thermal reaction terminates, cooling, centrifugation, washing and drying, you can obtain gadolinium molydbate calcium and mix the luminous bicone sample of samarium.The preparation method reaction temperature of the present invention is low, low for equipment requirements, and operation is fairly simple, and a kind of obtained gadolinium molydbate calcium mixes the luminous bicone luminescent material of samarium, and pattern is regular, uniform in size, and luminescent properties are good.
Description
Technical field
The invention belongs to rare earth luminescent material technical field, is related to a kind of emitting red light bicone, specifically a kind of
Red gadolinium molydbate calcium analysis samarium bicone luminescent material and preparation method thereof.
Background technology
White light LEDs have the advantages that small volume, luminous efficiency height, long lifespan, response are fast, safe to use, environment friendly and pollution-free,
So as to be widely used in the numerous areas such as room lighting, LCD backlight, information display screen, traffic sign lamp, and gradually start
Substitute incandescent lamp, three-color fluorescent lamp and high-voltage gas discharging light and turn into noticeable forth generation lighting source.But by
Lack red color light component in white light, causing White-light LED illumination light source to occur, luminous efficiency is relatively low, colour rendering is poor and the color of light source
The problems such as reproducibility is poor.Therefore, luminescent properties and rush of the rare earth red light fluorescent powder of synthesizing efficient to raising white light LEDs
The extensive use for entering white light LEDs has great importance.
Alkali earth molybdates are due to good physico-chemical property and efficient the advantages of absorbing ultraviolet light, being increasingly becoming
A kind of excellent host material.In addition, rare earth ion has excellent luminescent properties due to 4f-4f and 4f-5d transition.Its
In, rare-earth Sm3+Because in 646nm, (transition regime is4G5/2→6H9/2) there is very strong blood orange light transmitting at place and is often used as red
Photoactivation agent.In recent years, reaction condition is gentle, energy consumption is low because having for hydro-thermal method；The pattern and particle size of sample are easily controlled；
Technique is simple, it is not necessary to the advantages that high-temperature calcination is handled, is increasingly becoming a kind of effective ways for preparing rare earth luminescent material.To now
Untill, although having there is the alkali earth molybdates red light fluorescent powder that scholar has synthesized rare earth doped Eu ions, mesh
The preceding CaGd for also preparing doping Sm ions with hydro-thermal method without document report2(MoO4)4:Sm3+Red fluorescence powder.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of red gadolinium molydbate calcium to mix samarium bicone hair
Luminescent material and preparation method thereof.The present invention uses hydrothermal synthesis method, solves the luminous bipyramid bodily form of method of the prior art
Looks are uneven, have a strong impact on the technical problem of luminescent powder intensity.
The present invention is using corresponding rare earth nitrades as rare earth source, and complexing is used as using disodium ethylene diamine tetraacetate (EDTA)
Agent, stirring forms mixed solution in aqueous first, and then above-mentioned mixed solution is transferred in hydrothermal reaction kettle and enters water-filling
Thermal response obtains a kind of red gadolinium molydbate calcium and mixes the luminous bicone fluorescent material of samarium.
Technical scheme is specifically described as follows.
The present invention provides the preparation method that a kind of red gadolinium molydbate calcium mixes samarium bicone luminescent material, comprises the following steps：
(1) samarium nitrate solution, gadolinium nitrate solution and calcium nitrate solution are mixed；In mixed solution, calcium nitrate, gadolinium nitrate and
The mol ratio of samaric nitrate is (1.00~1.05)：(1.85~1.90)：(0.15~0.20)；
(2) complexing agent is added in the mixed solution obtained by step (1), and stirred at a temperature of 25 ± 1 DEG C；It is used
Complexing agent is EDTA, and the mol ratio of calcium nitrate is 0.34 in itself and step (1):1.05~1.70:1；
(3) it is 4 according to the mol ratio of calcium nitrate in sodium molybdate and step (1):1.05~4.05:1, by sodium molybdate solution plus
Enter into the mixed solution obtained by step (2), be stirred to obtain milky turbidity liquid, being transferred to hydrothermal reaction kettle after stirring enters water-filling
Thermal response；After hydro-thermal reaction terminates, obtained reaction solution is naturally cooled into room temperature in atmosphere, then uses deionization successively
Water, absolute ethyl alcohol centrifuge respectively, wash 2~3 times after be dried, that is, obtain red CaGd1.85(MoO4)4:0.15Sm3+Bipyramid
Body luminescent material.
In the present invention, in step (1), the concentration of samarium nitrate solution is 0.05 ± 0.001mol/L, gadolinium nitrate solution it is dense
Spend for 1.00 ± 0.001mol/L, the concentration of calcium nitrate solution is 1.00 ± 0.001mol/L, and the concentration of sodium molybdate solution is
1.00±0.001mol/L。
In the present invention, the mol ratio of complexing agent and calcium nitrate is 0.68：1~1.36：1.It is further preferred that complexing agent and
The mol ratio of calcium nitrate is 0.68：1.
In the present invention, in step (3), hydrothermal reaction kettle is transferred to after stirring 2~3h, the compactedness of hydrothermal reaction kettle for 40~
60%.
In the present invention, in step (3), hydrothermal temperature is 175~185 DEG C, and the hydro-thermal reaction time is 18~22h.
The present invention also provides the red gadolinium molydbate calcium that a kind of above-mentioned preparation method obtains and mixes samarium bicone luminescent material.
The luminescent material that the present invention obtains is the three-dimensional CaGd assembled by nano particle1.85(MoO4)4:0.15Sm3+Gadolinium molydbate
Calcium mixes the luminous bicone of samarium, its very close standard red spot (0.67,0.33) of luminous chromaticity coordinates.
A kind of CaGd of the present invention1.85(MoO4)4:0.15Sm3+Gadolinium molydbate calcium mixes the luminous bicone of samarium, leads in preparation process
The amount for changing EDTA is crossed, the pattern and particle diameter distribution of bicone structure can be adjusted, therefore, the preparation method can be controlled effectively
CaGd processed1.85(MoO4)4:0.15Sm3+The granular size and pattern of rare earth luminescent material.
The present invention compares with prior art, and its technological progress is significant.The preparation method reaction temperature of the present invention is low, right
Equipment requirement is low, and operation is fairly simple, is adapted to large-scale production.Obtained CaGd1.85(MoO4)4:0.15Sm3+Luminous bicone
Morphology controllable, it is uniform in size, and luminescent properties are good.
Brief description of the drawings
Fig. 1 is that the chemical formula of embodiment 1, embodiment 2, embodiment 3, embodiment 4 and the gained of embodiment 5 is CaGd1.85
(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium light bicone X-ray powder diffraction pattern.
Fig. 2 is that the chemical formula of the gained of embodiment 1 is CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium and light
The scanning electron microscope (SEM) photograph of bicone.
Fig. 3 is that the chemical formula of the gained of embodiment 2 is CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium and light
The scanning electron microscope (SEM) photograph of bicone.
Fig. 4 is that the chemical formula of the gained of embodiment 3 is CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium and light
The scanning electron microscope (SEM) photograph of bicone.
Fig. 5 is that the chemical formula of the gained of embodiment 4 is CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium and light
The scanning electron microscope (SEM) photograph of bicone.
Fig. 6 is that the chemical formula of the gained of embodiment 5 is CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium and light
The scanning electron microscope (SEM) photograph of bicone.
Fig. 7 is that the chemical formula of the gained of embodiment 2 is CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium and light
The exciting light spectrogram of bicone.
Fig. 8 is that the chemical formula of the gained of embodiment 2 is CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium and light
The launching light spectrogram of bicone.
Fig. 9 is that the chemical formula of the gained of embodiment 2 is CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium and light
The CIE chromaticity diagram of bicone.
Figure 10 is the CaGd synthesized by embodiment 21.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mixes the luminous bicone of samarium
Fluorescence decay curve.
Embodiment
The present invention is expanded on further below by specific embodiment and with reference to accompanying drawing, but is not intended to limit the present invention.
Using PANalytical X ' Pert PRO x-ray powder diffraction instruments (Cu-K α radiate,) measure institute
The red CaGd of preparation1.85(MoO4)4:0.15Sm3+Gadolinium molydbate calcium mixes the structure of the luminous bicone of samarium.
Prepared CaGd is characterized using Hitachi S-3400N ESEMs1.85(MoO4)4:0.15Sm3+Red molybdic acid
Gadolinium calcium mixes the pattern and particle size of the luminous bicone of samarium.
Using the prepared red CaGd of Edinburgh FS5 XRFs test1.85(MoO4)4:0.15Sm3+Molybdic acid
Gadolinium calcium mixes the fluorescent emission performance of the luminous bicone material of samarium.
Embodiment 1
A kind of red gadolinium molydbate calcium mixes the luminous bicone of samarium, and its chemical formula is CaGd1.85(MoO4)4:0.15Sm3+。
A kind of above-mentioned red gadolinium molydbate calcium mixes the preparation method of the luminous bicone of samarium, specifically comprises the following steps：
Samarium oxide is added in the salpeter solution that concentration is 5~40%, stirs and dissolve under the conditions of 40~60 DEG C, match somebody with somebody
Into the samarium nitrate solution that concentration is 0.05 ± 0.001mol/L；Gadolinium nitrate, calcium nitrate and sodium molybdate are dissolved in deionized water, respectively
Be made into concentration be 1.00 ± 0.001mol/L gadolinium nitrate solution, 1.00 ± 0.001mol/L calcium nitrate solution and 1.00 ±
0.001mol/L sodium molybdate solution.
1.85 ± 0.01ml gadolinium nitrates, 1.00 ± 0.01ml calcium nitrate and 3.00 ± 0.01ml samarium nitrate solutions are measured in burning
In cup, mixed solution is obtained after being thoroughly mixed；
Take 0.1g EDTA to be added in the mixed solution of above-mentioned gained, stir 1h；
4.00 ± 0.01ml sodium molybdate solutions are measured, are added to above-mentioned mixed solution.Under normal temperature, continue after stirring 3h, will
Reacted milky turbid is transferred in 100ml polytetrafluoroethyllining lining autoclave, autoclave is sealed, then 180
DEG C incubation water heating reaction 20h, then will be cooled to room temperature in obtained reaction solution air；
By obtained reaction solution successively with deionized water and absolute ethyl alcohol centrifuge washing 3~4 times, the sample that then will have been centrifuged
Product, which are placed in 80 DEG C of baking ovens, dries 12h, that is, it is CaGd to obtain chemical formula1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium
Luminous bicone.
Embodiment 2
A kind of red gadolinium molydbate calcium mixes the luminous bicone of samarium, and its chemical formula is CaGd1.85(MoO4)4:0.15Sm3+。
A kind of above-mentioned red gadolinium molydbate calcium mixes the preparation method of the luminous bicone of samarium, specifically comprises the following steps：
Samarium oxide is added in the salpeter solution that concentration is 5~40%, stirs and dissolve under the conditions of 40~60 DEG C, match somebody with somebody
Into the samarium nitrate solution that concentration is 0.05 ± 0.001mol/L；Gadolinium nitrate, calcium nitrate and sodium molybdate are dissolved in deionized water, respectively
Be made into concentration be 1.00 ± 0.001mol/L gadolinium nitrate solution, 1.00 ± 0.001mol/L calcium nitrate solution and 1.00 ±
0.001mol/L sodium molybdate solution.
1.85 ± 0.01ml gadolinium nitrates, 1.00 ± 0.01ml calcium nitrate and 3.00 ± 0.01ml samarium nitrate solutions are measured in burning
In cup, mixed solution is obtained after being thoroughly mixed；
Take 0.2g EDTA to be added in the mixed solution of above-mentioned gained, stir 1h；
4.00 ± 0.01ml sodium molybdate solutions are measured, are added to above-mentioned mixed solution.Under normal temperature, continue after stirring 3h, will
Reacted milky turbid is transferred in 100ml polytetrafluoroethyllining lining autoclave, autoclave is sealed, then 180
DEG C incubation water heating reaction 20h, then will be cooled to room temperature in obtained reaction solution air；
By obtained reaction solution successively with deionized water and absolute ethyl alcohol centrifuge washing 3~4 times, the sample that then will have been centrifuged
Product, which are placed in 80 DEG C of baking ovens, dries 12h, that is, it is CaGd to obtain chemical formula1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium
Luminous bicone.
Embodiment 3
A kind of red gadolinium molydbate calcium mixes the luminous bicone of samarium, and its chemical formula is CaGd1.85(MoO4)4:0.15Sm3+。
A kind of above-mentioned red gadolinium molydbate calcium mixes the preparation method of the luminous bicone of samarium, specifically comprises the following steps：
Samarium oxide is added in the salpeter solution that concentration is 5~40%, stirs and dissolve under the conditions of 40~60 DEG C, match somebody with somebody
Into the samarium nitrate solution that concentration is 0.05 ± 0.001mol/L；Gadolinium nitrate, calcium nitrate and sodium molybdate are dissolved in deionized water, respectively
Be made into concentration be 1.00 ± 0.001mol/L gadolinium nitrate solution, 1.00 ± 0.001mol/L calcium nitrate solution and 1.00 ±
0.001mol/L sodium molybdate solution.
1.85 ± 0.01ml gadolinium nitrates, 1.00 ± 0.01ml calcium nitrate and 3.00 ± 0.01ml samarium nitrate solutions are measured in burning
In cup, mixed solution is obtained after being thoroughly mixed；
Take 0.3g EDTA to be added in the mixed solution of above-mentioned gained, stir 1h；
4.00 ± 0.01ml sodium molybdate solutions are measured, are added to above-mentioned mixed solution.Under normal temperature, continue after stirring 3h, will
Reacted milky turbid is transferred in 100ml polytetrafluoroethyllining lining autoclave, autoclave is sealed, then 180
DEG C incubation water heating reaction 20h, then will be cooled to room temperature in obtained reaction solution air；
By obtained reaction solution successively with deionized water and absolute ethyl alcohol centrifuge washing 3~4 times, the sample that then will have been centrifuged
Product, which are placed in 80 DEG C of baking ovens, dries 12h, that is, it is CaGd to obtain chemical formula1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium
Luminous bicone.
Embodiment 4
A kind of red gadolinium molydbate calcium mixes the luminous bicone of samarium, and its chemical formula is CaGd1.85(MoO4)4:0.15Sm3+。
A kind of above-mentioned red gadolinium molydbate calcium mixes the preparation method of the luminous bicone of samarium, specifically comprises the following steps：
Samarium oxide is added in the salpeter solution that concentration is 5~40%, stirs and dissolve under the conditions of 40~60 DEG C, match somebody with somebody
Into the samarium nitrate solution that concentration is 0.05 ± 0.001mol/L；Gadolinium nitrate, calcium nitrate and sodium molybdate are dissolved in deionized water, respectively
Be made into concentration be 1.00 ± 0.001mol/L gadolinium nitrate solution, 1.00 ± 0.001mol/L calcium nitrate solution and 1.00 ±
0.001mol/L sodium molybdate solution.
1.85 ± 0.01ml gadolinium nitrates, 1.00 ± 0.01ml calcium nitrate and 3.00 ± 0.01ml samarium nitrate solutions are measured in burning
In cup, mixed solution is obtained after being thoroughly mixed；
Take 0.4g EDTA (1.3) to be added in the mixed solution of above-mentioned gained, stir 1h；
4.00 ± 0.01ml sodium molybdate solutions are measured, are added to above-mentioned mixed solution.Under normal temperature, continue after stirring 3h, will
Reacted milky turbid is transferred in 100ml polytetrafluoroethyllining lining autoclave, autoclave is sealed, then 180
DEG C incubation water heating reaction 20h, then will be cooled to room temperature in obtained reaction solution air；
By obtained reaction solution successively with deionized water and absolute ethyl alcohol centrifuge washing 3~4 times, the sample that then will have been centrifuged
Product, which are placed in 80 DEG C of baking ovens, dries 12h, that is, it is CaGd to obtain chemical formula1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium
Luminous bicone.
Embodiment 5
A kind of red gadolinium molydbate calcium mixes the luminous bicone of samarium, and its chemical formula is CaGd1.85(MoO4)4:0.15Sm3+。
A kind of above-mentioned red gadolinium molydbate calcium mixes the preparation method of the luminous bicone of samarium, specifically comprises the following steps：
Samarium oxide is added in the salpeter solution that concentration is 5~40%, stirs and dissolve under the conditions of 40~60 DEG C, match somebody with somebody
Into the samarium nitrate solution that concentration is 0.05 ± 0.001mol/L；Gadolinium nitrate, calcium nitrate and sodium molybdate are dissolved in deionized water, respectively
Be made into concentration be 1.00 ± 0.001mol/L gadolinium nitrate solution, 1.00 ± 0.001mol/L calcium nitrate solution and 1.00 ±
0.001mol/L sodium molybdate solution.
Measure 1.85 ± 0.01ml gadolinium nitrates (1.85), 1.00 ± 0.01ml calcium nitrate (1) and 3.00 ± 0.01ml
(0.15) samarium nitrate solution obtains mixed solution in beaker after being thoroughly mixed；
Take 0.5g EDTA (1.7) to be added in the mixed solution of above-mentioned gained, stir 1h；
4.00 ± 0.01ml sodium molybdate solutions are measured, are added to above-mentioned mixed solution.Under normal temperature, continue after stirring 3h, will
Reacted milky turbid is transferred in 100ml polytetrafluoroethyllining lining autoclave, autoclave is sealed, then 180
DEG C incubation water heating reaction 20h, then will be cooled to room temperature in obtained reaction solution air；
By obtained reaction solution successively with deionized water and absolute ethyl alcohol centrifuge washing 3~4 times, the sample that then will have been centrifuged
Product, which are placed in 80 DEG C of baking ovens, dries 12h, that is, it is CaGd to obtain chemical formula1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix samarium
Luminous bicone.
Red gadolinium molydbate calcium obtained by above-described embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5 mixes samarium hair
Light bicone sample is characterized through X-ray diffractometer and Hitachi S-3400N ESEMs respectively, and its result is shown in respectively
Fig. 1 and Fig. 2~6.
Fig. 1 gives embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5 in surfactant EDTA content
Respectively 0.1g, 0.2g, 0.3g, 0.4g and 0.5g X ray diffracting spectrum.From Fig. 1, it can be seen that although EDTA's adds
Dosage is different, but prepared CaGd1.85(MoO4)4:0.15Sm3+The characteristic diffraction peak of fluorescent material and the CaMoO of pure phase4(mark
Quasi- card numbering is PDF#29-0351) characteristic diffraction peak keep basically identical, and without the miscellaneous peak of other materials.Therefore,
The addition of surfactant EDTA, will not be to sample CaGd2(MoO4)4:Sm3+Crystal structure cause to change.
Fig. 2 gives the scanning electron microscope (SEM) photograph of embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5.Fig. 2 is
The scanning electron microscope (SEM) photograph of embodiment 1, as can be seen from the figure embodiment 1 under conditions of 0.1EDTA gained chemical formula be
CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix and start sharp-featured bicone structure occur in samarium sample, but
Be these bicone patterns surface also there is some particulates, performance it is very coarse, it is rough.These bicone structures simultaneously
Granular size and uneven, some has greatly small.Fig. 3 is the scanning electron microscope (SEM) photograph of embodiment 2, as can be seen from the figure embodiment
2 chemical formula obtained by under 0.2g EDTA is CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix the microcosmic of samarium sample
Structure all has changed into pattern rule, the bicone shape pattern of uniform particle diameter, and the length of bicone structure is about 5.5 μm.Also,
Bicone body structure surface does not have accumulating particulate, very smooth.Fig. 4, Fig. 5 and Fig. 6 are embodiment 3, embodiment 4 and embodiment 5 respectively
Surface sweeping scanning electron microscope (SEM) photograph.From these three it can be seen from the figure thats, when continuing to increase EDTA addition to 0.3g, 0.4g and 0.5g
When, the bicone shape pattern and grain size of the struc-ture of prepared sample start to become not of uniform size.Meanwhile these are not advised
Also occurs the phenomenon for being mutually gathered into block structure between bicone structure then.
In summary, in reaction EDTA addition difference can the pattern last to sample have a huge impact.This says
Bright surfactant EDT has tremendous influence effect during crystalline growth, to the microstructure of sample, while this also illustrates
EDTA is a kind of good pattern dressing agent, can play the effect of regulation and control pattern and particle diameter distribution.Work as surfactant EDTA
Addition when being 0.2g, red gadolinium molydbate calcium mix samarium light bicone pattern it is most regular and particle diameter is most homogeneous.
Above-described embodiment 1, embodiment 2 and the gained of embodiment 5 are tested using Edinburgh FS5 XRFs respectively
CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mix the fluorescent emission performance of samarium bicone, concrete outcome is shown in Fig. 7, Fig. 8
And Fig. 9.
Fig. 7 is that the red gadolinium molydbate calcium of the gained of embodiment 2 mixes the excitation spectrum of samarium bicone, as can be seen from the figure sample
CaGd1.85(MoO4)4:0.15Sm3+Excitation spectrum, be mainly made up of a wider excitation band and many sharp excitation peaks.
Wherein, this wider excitation band is predominantly located between 255-340nm, and wavelength corresponding to peak is 297nm.The broadband peak comes
From in O2-_Mo6+And O2-_Eu3+Charge transfer band (Charge transfer band, referred to as CTB).In addition, excitation spectrum
In these sharp excitation peaks come from rare earth luminous ion Sm3+Transition transmitting between internal configuration 4f-4f tracks.
Between 340nm and 450nm, rare-earth luminescent center Sm3+Excitation peak respectively positioned at 344nm (6H5/2→4K17/2)、362nm(6H5/2
→4D5/2)、376nm(6H5/2→6P7/2)、405nm(6H5/2→6G11/2) and 420nm (6H5/2→6P5/2).In these excitation peaks
Face, the most strong peak of intensity is 405nm, illustrates fluorescent material CaGd1.85(MoO4)4:0.15Sm3+At 405nm there is highest to absorb
Intensity.Fig. 8 is that the red gadolinium molydbate calcium of the gained of embodiment 2 mixes the emission spectrum of samarium bicone, as can be seen from the figure sample
CaGd0.85(MoO4)4:0.15Sm3+Emission spectrum, four very sharp hairs be present between the scope from 500nm to 750nm
Penetrate peak.These emission peaks in emission spectrum belong to rare earth luminous ion Sm3+Characteristic emission peak, respectively positioned at 563nm,
605nm, 646nm and 705nm, its transition regime correspond to respectively4G5/2→6H5/2、4G5/2→6H7/2、4G5/2→6H9/2With4G5/2→6H11/2.In these emission peaks, the most strong emission peak of emissive porwer is located at 646nm, belongs to red emission.This explanation
CaGd1.85(MoO4)4:0.15Sm3+It is a kind of good red emitting material that gadolinium molydbate calcium, which mixes samarium bicone fluorescent material,.
Fig. 9 gives CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mixes samarium bicone and the CIE of standard red spot
Chromatic diagram.It can be seen that the red light fluorescent powder CaGd that the present invention is prepared with hydro-thermal method1.85(MoO4)4:0.15Sm3+Color
Coordinate is (0.63,0.36), very close to standard red spot (0.67,0.33).So CaGd1.85(MoO4)4:0.15Sm3+
It is a kind of efficient red light fluorescent powder that red gadolinium molydbate calcium, which mixes samarium bicone, can be matched well with blue-light LED chip.
Figure 10 is CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mixes the fluorescence decay curve of samarium bicone.From upper
Figure is as can be seen that the attenuation curve of the fluorescent material can use double-exponential function：I (t)=A1exp(-t/τ1)+A2exp(-t/τ1)
It is fitted.It can be seen from the result after fitting, CaGd1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mixes samarium bicone
Fluorescence lifetime is 600.58 μ s.Therefore, CaGd of the invention1.85(MoO4)4:0.15Sm3+Red gadolinium molydbate calcium mixes samarium bicone
The high efficiency red phosphor powder that a kind of pattern is fairly regular, size is very uniform and fluorescence lifetime is longer.
The above is only the basic explanation under present inventive concept, and is made according to technical scheme any etc.
Effect conversion, all should belong to protection scope of the present invention.
Claims (7)
1. a kind of preparation method of red gadolinium molydbate calcium analysis samarium bicone luminescent material, it is characterised in that comprise the following steps：
(1) samarium nitrate solution, gadolinium nitrate solution and calcium nitrate solution are mixed；In mixed solution, calcium nitrate, gadolinium nitrate and nitric acid
The mol ratio of samarium is (1.00~1.05)：(1.85~1.90)：(0.15~0.20)；
(2) complexing agent is added in the mixed solution obtained by step (1), and stirred at a temperature of 25 ± 1 DEG C；Complexing used
Agent is EDTA, and the mol ratio of calcium nitrate is 0.34 in itself and step (1):1.05~1.70:1；
(3) it is 4 according to the mol ratio of calcium nitrate in sodium molybdate and step (1):1.05~4.05:1, sodium molybdate solution is added to
In mixed solution obtained by step (2), milky turbidity liquid is stirred to obtain, it is anti-that hydrothermal reaction kettle progress hydro-thermal is transferred to after stirring
Should；After hydro-thermal reaction terminates, obtained reaction solution is naturally cooled into room temperature in atmosphere, then successively with deionized water, nothing
Water-ethanol centrifuges respectively, wash 2~3 times after be dried, that is, obtain red CaGd1.85(MoO4)4:0.15Sm3+Bicone lights
Material.
2. preparation method as claimed in claim 1, it is characterised in that in step (1), the concentration of samarium nitrate solution for 0.05 ±
0.001mol/L, the concentration of gadolinium nitrate solution are 1.00 ± 0.001mol/L, the concentration of calcium nitrate solution for 1.00 ±
0.001mol/L, the concentration of sodium molybdate solution is 1.00 ± 0.001mol/L.
3. preparation method as claimed in claim 1, it is characterised in that the mol ratio of complexing agent and calcium nitrate is 0.68：1~
1.36：1.
4. preparation method as claimed in claim 1, it is characterised in that the mol ratio of complexing agent and calcium nitrate is 0.68:1.
5. preparation method as claimed in claim 1, it is characterised in that in step (3), hydro-thermal reaction is transferred to after stirring 2~3h
Kettle, the compactedness of hydrothermal reaction kettle is 40~60%.
6. preparation method as claimed in claim 1, it is characterised in that in step (3), hydrothermal temperature is 175~185
DEG C, the hydro-thermal reaction time is 18~22h.
A kind of 7. red gadolinium molydbate calcium analysis samarium bicone luminescent material that preparation method as claimed in claim 1 obtains.
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Non-Patent Citations (2)
| Title |
|---|
| X.-J. GENG等: "Luminescence properties and energy transfer process of Sm3+–Eu3+ co-doped molybdate red-emitting phosphors by hydrothermal method", 《APPLIED PHYSICS B》 * |
| YAOMIN DENG等: "Synthesis and photoluminescence characteristics of Ln3+ (Ln = Sm, Er and Dy)-doped BaGd2(MoO4)4 phosphors", 《OPTICAL MATERIALS》 * |
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