CN108893113A - A kind of adjustable high thermal stability fluorescent powder of coloration - Google Patents

A kind of adjustable high thermal stability fluorescent powder of coloration Download PDF

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Publication number
CN108893113A
CN108893113A CN201810861643.3A CN201810861643A CN108893113A CN 108893113 A CN108893113 A CN 108893113A CN 201810861643 A CN201810861643 A CN 201810861643A CN 108893113 A CN108893113 A CN 108893113A
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fluorescent powder
energy level
coloration
ion
xtb
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CN108893113B (en
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苟婧
陈雅利
俞斌勋
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Shaanxi Normal University
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Shaanxi Normal University
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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
    • C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
    • C09K11/7752—Phosphates
    • C09K11/7753—Phosphates with alkaline earth metals

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a kind of adjustable high thermal stability fluorescent powder of coloration, the molecular formula of the fluorescent powder is Sr8Zn1‑xSc(PO4)7:xTb3+, 0.02≤x≤0.14 in formula.The present invention passes through in Sr8ZnSc(PO4)7Tb is adulterated in matrix3+Ion, generation and Tb3+Ion5D3The defect cluster that energy level matches and the energy level depth is different.Under 370nm near ultraviolet excitation, the shallow defect cluster of energy level captures electronics as trap, by electronics transfer to Tb under room temperature thermal agitation3+Ion5D3Energy level, to compensate for caused by x increase5D3→7FJEmission peak is decayed rapidly, in blue emission5D3→7FJAnd green emitted5D4→7FJSynergistic effect under Sr8ZnSc(PO4)7:xTb3+The coloration of series phosphor powder is moved to bright green from sapphirine with the increase of x.And at high temperature due to Tb3+Ion5D3Energy level can obtain the energy transmitted from deep trap, compensate for Sr8ZnSc(PO4)7:xTb3+The thermal quenching behavior of series phosphor powder at high temperature, makes its behavior when operating temperature is up to 150 DEG C with zero thermal quenching.

Description

A kind of adjustable high thermal stability fluorescent powder of coloration
Technical field
The invention belongs to fluorescent material technical fields, and in particular to a kind of adjustable high thermal stability fluorescent powder of coloration.
Background technique
For high-power WLED (white-light-emitting diodes), develop excellent under elevated operating temperature The fluorescent powder of good thermal stability is the bottleneck of current commercialization high power WLED.Commercial fluorescent powder at present, in elevated operating temperature Under Quenching of fluorescence phenomenon can occur, 120 DEG C of operating temperature has been that high power WLED can be realized efficient delivery efficiency Temperature extremes.Therefore how to design and develop novel high thermal stability fluorescent powder is one for the commercialization for realizing high power WLED A huge challenge.
Summary of the invention
The object of the present invention is to provide one kind under the near ultraviolet excitation adjustable high thermal stability fluorescent powder of coloration.
For above-mentioned purpose, the molecular formula of the adjustable high thermal stability fluorescent powder of coloration of the present invention is Sr8Zn1-xSc (PO4)7:xTb3+, 0.02≤x≤0.14, preferably 0.12≤x≤0.14 in formula.
The preparation method of the above-mentioned adjustable high thermal stability fluorescent powder of coloration is：According to Sr8Zn1-xSc(PO4)7:xTb3+'s Stoichiometric ratio, by reaction raw materials Sr (NO3)2(99.9%), ZnO (99.99%), (NH4)2HPO4(98.5%), Sc2O3 (99.99%) and Tb4O7(99.99%) uniformly mixing, keeps the temperature 4 hours at 900 DEG C, then after keeping the temperature 11 hours at 1250 DEG C Cooled to room temperature obtains Sr8Zn1-xSc(PO4)7:xTb3+Fluorescent powder.
The present invention passes through in Sr8ZnSc(PO4)7Tb is adulterated in matrix3+Ion, generation and Tb3+Ion5D3Energy level matches And the defect cluster that the energy level depth is different.Under the excitation of black light 370nm, defect cluster captures electronics as trap, certain Thermal agitation under by electronics transfer to Tb3+Ion5D3Energy level, to realize Sr8ZnSc(PO4)7:Tb3+The coloration of fluorescent powder can Thermal stability under tune and elevated operating temperature.
At room temperature, work as Sr8ZnSc(PO4)7:Tb3+Fluorescent powder is excited by 370nm, and the shallower trap of energy level is under thermal agitation The electronics transfer that will be captured is to Tb3+Ion5D3Energy level, to compensate for Tb3+When ion doping concentration increases,5D3 →5D4Nonradiative transition caused by5D3→7FJEmission peak is decayed rapidly, to realize as the continuous increase of doping concentration makes5D3→7FJEmission peak luminous intensity is not in significantly to decay, and makes Sr8ZnSc(PO4)7:xTb3+The photism of series phosphor powder It can be by blue emission5D3→7FJAnd green emitted5D4→7FJTwo groups of joint effects, coloration is with Tb3+The increasing of ions dosage Add from sapphirine (0.205,0.186) and be moved to bright green (0.245,0.411), final realize passes through Tb3+Ions dosage Variation obtains Sr8ZnSc(PO4)7:xTb3+The coloration of fluorescent powder is adjustable.
When operating temperature is up to 150 DEG C, as near ultraviolet excitation Sr8ZnSc(PO4)7:Tb3+When fluorescent powder, energy level is deeper The electronics transfer that will be captured under thermal agitation of trap to Tb3+Ion5D3Energy level, to compensate at high temperature5D3→7FJ With5D4→7FJThe thermal quenching phenomenon of emission peak, realizes Sr8ZnSc(PO4)7:xTb3+Series phosphor powder zero thermal quenching at high temperature Behavior.
Detailed description of the invention
Fig. 1 is emission spectrum of the sample of Examples 1 to 4 preparation under 370nm near ultraviolet excitation.
Fig. 2 is the sample of Examples 1 to 4 preparation under 370nm near ultraviolet excitation5D3→7F5With5D4→7F5Emit peak intensity Degree and Tb3+Adulterate the curved line relation between molar concentration.
Fig. 3 be marked in CIE chromaticity diagram Examples 1 to 4 preparation sample under 370nm near ultraviolet excitation its send out The chromaticity coordinates at peak is penetrated, point a, b, c and d successively represent 1,2,3,4 sample of embodiment.
Fig. 4 is the sample of Examples 1 to 4 preparation as temperature increases emission peak5D3→7FJThe pass of integral area and temperature It is curve.
Fig. 5 is the sample of Examples 1 to 4 preparation as temperature increases emission peak5D4→7FJThe pass of integral area and temperature It is curve.
Fig. 6 be embodiment 3 prepare sample under 370nm near ultraviolet excitation with the raised luminous thermal quenching light of temperature Spectrum.
Fig. 7 be embodiment 4 prepare sample under 370nm near ultraviolet excitation with the raised luminous thermal quenching light of temperature Spectrum.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to These embodiments.
Embodiment 1
According to Sr8Zn0.98Sc(PO4)7:0.02Tb3+Stoichiometric ratio, by 1.6930g (8mmol) Sr (NO3)2 (99.9%), 0.0800g (0.98mmol) ZnO (99.99%), 0.9244g (7mmol) (NH4)2HPO4(98.5%), 0.0690g(0.5mmol)Sc2O3(99.99%) and 0.0037g (0.005mmol) Tb4O7(99.99%) uniformly mixing, 900 4 hours are kept the temperature at DEG C, then cooled to room temperature after keeping the temperature 11 hours at 1250 DEG C, obtains Sr8Zn0.98Sc(PO4)7: 0.02Tb3+Fluorescent powder.
Embodiment 2
According to Sr8Zn0.90Sc(PO4)7:0.10Tb3+Stoichiometric ratio, by 1.6930g (8mmol) Sr (NO3)2 (99.9%), 0.0733g (0.9mmol) ZnO (99.99%), 0.9244g (7mmol) (NH4)2HPO4(98.5%), 0.0690g (0.5mmol)Sc2O3(99.99%) and 0.0187g (0.025mmol) Tb4O7(99.99%) uniformly mixing, is protected at 900 DEG C Temperature 4 hours, then cooled to room temperature after keeping the temperature 11 hours at 1250 DEG C, obtain Sr8Zn0.90Sc(PO4)7:0.10Tb3+It is glimmering Light powder.
Embodiment 3
According to Sr8Zn0.88Sc(PO4)7:0.12Tb3+Stoichiometric ratio, by 1.6930g (8mmol) Sr (NO3)2 (99.9%), 0.0716g (0.88mmol) ZnO (99.99%), 0.9244g (7mmol) (NH4)2HPO4(98.5%), 0.0690g(0.5mmol)Sc2O3(99.99%) and 0.0243g (0.03mmol) Tb4O7(99.99%) uniformly mixing, 900 4 hours are kept the temperature at DEG C, then cooled to room temperature after keeping the temperature 11 hours at 1250 DEG C, obtains Sr8Zn0.88Sc(PO4)7: 0.12Tb3+Fluorescent powder.
Embodiment 4
According to Sr8Zn0.86Sc(PO4)7:0.14Tb3+Stoichiometric ratio, by 1.6930g (8mmol) Sr (NO3)2 (99.9%), 0.0700g (0.86mmol) ZnO (99.99%), 0.9244g (7mmol) (NH4)2HPO4(98.5%), 0.0690g(0.5mmol)Sc2O3(99.99%) and 0.0262g (0.035mol) Tb4O7(99.99%) uniformly mixing, 900 4 hours are kept the temperature at DEG C, then cooled to room temperature after keeping the temperature 11 hours at 1250 DEG C, obtains Sr8Zn0.86Sc(PO4)7: 0.14Tb3+Fluorescent powder.
Inventor has carried out luminescent properties to sample prepared by Examples 1 to 4 and thermal stability is tested, the result is shown in Figure 1 ~7.
As seen from Figure 1, with the increase of x, gained sample5D4→7FJSeries emissions peak enhances, and5D3→7FJSeries Emission peak, which first enhances, then fainter reduction.From Figure 2 it can be seen that gained sample5D4→7F5Emission peak intensity is always with x Increase and enhance, and5D3→7F5Emission peak intensity then has fainter reduction with the increase first enhancing of x, but it is strong Degree is without occurring significantly decaying.It has been reported that mix Tb3+Fluorescent powder in, due to5D3→5D4Nonradiative transition,5D3 →7FJIt is easy to quench, is difficult to observe5D3→7FJBlue emission peak.Therefore it has been reported that mix Tb3+Fluorescent powder in It can only observe5D4→7FJGreen emitted peak.But for Sr8ZnSc(PO4)7:Tb3+Fluorescent powder, when its at room temperature by 370nm excitation, the electronics transfer that the shallower trap of energy level will be captured under thermal agitation is to Tb3+Ion5D3Energy level, thus more It has mended with Tb3+Ion doping concentration increases a large amount of5D3→5D4Caused by nonradiative transition5D3→7FJEmission peak is decayed rapidly, To realize that the continuous increase with doping concentration makes5D3→7FJEmission peak luminous intensity is not in significantly to decay.Fig. 3 Show the increase with x, blue emission peak in fluorescent powder5D3→7FJWith green emitted peak5D4→7FJJoint effect fluorescent powder is whole Luminescent behavior, therefore, the increase of x make the coloration of fluorescent powder from sapphirine (0.205,0.186) change to bright green (0.245, 0.411).Therefore in Sr8Zn1-xSc(PO4)7:xTb3+The light-emitting phosphor face that can be needed by adjusting x in fluorescent powder Color.
By Fig. 4~7 as it can be seen that as temperature increases, the sample of Examples 1 to 4 preparation5D3→7FJWith5D4→7FJEmission peak Intensity is all enhanced, the sample that when temperature is up to 150 DEG C prepared by Examples 1 to 45D3→7FJIt is sudden that emission peak all has zero heat It goes out behavior, the sample that when temperature is up to 250 DEG C prepared by Examples 1 to 45D4→7FJEmission peak still has zero thermal quenching row For.Wherein, the sample of x=0.02,0.12 and 0.14 is when temperature is up to 225 DEG C5D3→7FJEmission peak still has zero heat sudden It going out behavior, the sample of x=0.12 shows most excellent thermal stability, in 75 DEG C and 175 DEG C,5D3→7FJEmission peak Luminous intensity is increased to its 1.28 and 1.19 times at room temperature respectively,5D4→7FJThe luminous intensity of emission peak is increased to respectively Its at room temperature 1.19 and 1.18 times.

Claims (3)

1. a kind of adjustable high thermal stability fluorescent powder of coloration, it is characterised in that：The molecular formula of the fluorescent powder is Sr8Zn1-xSc (PO4)7:xTb3+, 0.02≤x≤0.14 in formula, the behavior when operating temperature is up to 150 DEG C with zero thermal quenching.
2. the adjustable high thermal stability fluorescent powder of coloration according to claim 1, it is characterised in that：In the molecular formula, 0.12≤x≤0.14。
3. the adjustable high thermal stability fluorescent powder of coloration according to claim 1, it is characterised in that：The fluorescent powder exists Under 370nm near ultraviolet excitation, coloration is with Tb3+The increase of ions dosage is moved to bright from sapphirine (0.205,0.186) Green (0.245,0.411).
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Cited By (1)

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CN110760308A (en) * 2019-09-02 2020-02-07 陕西师范大学 High-thermal-stability fluorescent powder

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Publication number Priority date Publication date Assignee Title
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