CN102367381A - Lanthanide metal doped tungsten and molybdate phosphor composition - Google Patents
Lanthanide metal doped tungsten and molybdate phosphor composition Download PDFInfo
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- CN102367381A CN102367381A CN2011102602327A CN201110260232A CN102367381A CN 102367381 A CN102367381 A CN 102367381A CN 2011102602327 A CN2011102602327 A CN 2011102602327A CN 201110260232 A CN201110260232 A CN 201110260232A CN 102367381 A CN102367381 A CN 102367381A
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- doped tungsten
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Abstract
A lanthanide metal doped tungsten and molybdate phosphor composition disclosed in the invention, belonging to the field of scheelite structured luminescent material, relates to a study of a doped tungsten and molybdate phosphor composition. The lanthanide metal doped tungsten and molybdate phosphor composition is represented by the following general chemical formula: A(WO4)0.5(MoO4)0.5:RE<3+>0.01, wherein, A represents Ca, Sr, or Ba, RE<3+> represents Eu<3+>, Dy<3+>, Nd<3+>, or Ce<3+>. The phosphor composition is prepared by weighing alkaline earth oxides or carbonic acid materials, WO3, MoO3, and lanthanide metal oxides with corresponding qualities according to the required molar ratio of a certain amount of the target system, A(WO4)0.5(MoO4)0.5:RE<3+>0.01, carrying out ball milling for 5-15 h, then drying the uniformly mixed reactant, letting the dried mixture be subject to react for 2-4 h at the temperature of 600-1000 DEG C, and then naturally cooling to room temperature to obtain the phosphor composition of A(WO4)0.5(MoO4)0.5:RE<3+>0.01. The invention has the advantages of simple technology and low cost. The prepared phosphor composition appears a scheelite structure and the spherical particles have the particle size of about 1 mum. The prepared phosphor composition has narrow peak shape of the emission spectrum and pure fluorescent color and is beneficial to the practical applications.
Description
Technical field
The invention belongs to the scheelite-type structure luminescent material, relate to tungsten hydrochlorate Luminescence Study of Modified Porous, particularly relate to the research of lanthanide metal ion Doped Tungsten molybdate phosphor combination thing.
Background technology
[0002] scheelite type tungsten (molybdenum) hydrochlorate belongs to the self activation fluor, and its luminescence center is compound ion WO
4 2-(or MoO
4 2-), the emmission spectrum that its transition produces is wideband structural; And have higher quantum yield, can effectively absorb near-ultraviolet light, emitting fluorescence.Sheelite tungsten (molybdenum) hydrochlorate is widely used in photodiode, super large screen displaying etc., is the focus and emphasis of the research of field of photovoltaic materials.At present to tungsten; Following several respects are mainly concentrated in the research of (molybdenum) hydrochlorate fluorescent powder:
is unit tungsten; The preparation and the performance study of (molybdenum) hydrochlorate fluorescent powder.Adopt high temperature solid-state method to prepare AMoO like people such as Geun-Kyu Choi
4(A=Ca, Sr, Ba) fluorescent material, Titipun Thongtem seminar utilizes microwave assisting method to prepare SrMoO
4And SrWO
4Crystallite.People such as nearest P.S.Pizani have reported employing Hydrothermal Preparation BaMoO again
4Fluor.Unit tungsten (molybdenum) hydrochlorate fluorescent material emission peak broad, fluorescence color is impure, has limited them and has used widely.Though also just like Ca
xSr
1-xWO
4And Ba
xSr
1-xWO
4Etc. the research report of mixed alkaline earth tungsten (molybdenum) the hydrochlorate fluorescent material of type, but because the luminescence center of tungsten (molybdenum) hydrochlorate is WO
4 2-(or MoO
4 2-), thereby it is also not obvious to the regulation and control of tungsten (molybdenum) hydrochlorate luminescent properties only to change alkaline earth metal cation.2. be to adopt rare earth ion that unit tungsten (molybdenum) hydrochlorate is carried out doping vario-property, the acquisition type is AMO
4: RE
3+(A=Ca, Sr, Ba; M=W, Mo; Re
3+=Tb
3+, Eu
3+, Dy
3+Deng) fluorescent powder.Adopt solid phase method to prepare Eu like the document report
3+Adulterated CaMoO
4Red fluorescence powder, Hydrothermal Preparation Sm
3+Adulterated AMO
4(A=Ca, Sr, Ba) blue colour fluorescent powder, polymer precursor method (PPM) preparation Eu
3+Adulterated BaMoO
4Powder and utilize the Pechini legal system to be equipped with Eu
3+And Tb
3+The CaMoO of codoped
4Powder etc.Though through the rear-earth-doped emission peak that makes tungsten (molybdenum) hydrochlorate obtain narrower rare earth ion, adjustable its luminescent properties; But to the red shift change effect of the change of its excitation spectrum especially excitation wavelength and not obvious.Therefore, how can regulate and control the emmission spectrum of tungsten (molybdenum) hydrochlorate fluorescent material, can regulate and control its excitation spectrum again, make its excitation spectrum move (red shift) by ultraviolet and near ultraviolet region to visible region, expand the range of application of said material, be necessary.
Summary of the invention
The object of the present invention is to provide the adulterated tungsten hydrochlorate of lanthanide metal ion sosoloid phosphor combination thing, to solve the existing the problems referred to above of present unit tungsten (molybdenum) hydrochlorate fluorescent material.This novel compsns has been realized positively charged ion and anionic common regulation and control simultaneously, the luminescent properties that can obtain to enrich, and realization tungsten hydrochlorate base fluorescent powder is used widely.The general formula of lanthanide metal ion Doped Tungsten molybdate phosphor combination thing provided by the present invention can be expressed as: A (WO
4)
0.5(MoO
4)
0.5: RE
3+ 0.01(A=Ca, Sr, Ba; RE
3+=Eu
3+, Dy
3+Deng).The present invention is with the luminous crystallite A of tungsten hydrochlorate sosoloid (WO
4)
0.5(MoO
4)
0.5(A=Ca, Sr Ba) are matrix, through mixing lanthanide metal ion RE
3+Come the adjustable novel fluorescence powder of obtained performance.
The novel lanthanide metal ion Doped Tungsten of synthetic of the present invention molybdate phosphor combination thing adopts high temperature solid-state method to obtain.This method is easy and simple to handle, cost is low, and temperature of reaction is about 600 ℃ ~ 1000 ℃, can in production practice, use.The phosphor combination thing of preparation is scheelite-type structure, is the spheroidal particle of the about 1 μ m of size; The emmission spectrum peak shape of synthetizing phosphor powder is narrower, and fluorescence color is purer, helps the application in reality.In addition, tungsten hydrochlorate phosphor combination thing provided by the invention can also mix other like Tb
3+, Eu
2+, Sm
3+Deng lanthanide ion, even two or more lanthanide ion codopeds, obtain launching the phosphor combination thing of different colours.
Description of drawings
Fig. 1 is the A (WO of the method for the invention preparation
4)
0.5(MoO
4)
0.5: Dy
3+ 0.01(A=Ca
2+, Sr
2+, Ba
2+) X-ray diffractogram of the luminous crystallite of sosoloid.(a)?Ca(WO
4)
0.5(MoO
4)
0.5:Dy
3+ 0.01；(b)?Sr(WO
4)
0.5(MoO
4)
0.5:Dy
3+ 0.01；(c)?Ba(WO
4)
0.5(MoO
4)
0.5:Dy
3+ 0.01
Fig. 2 is the A (WO of the method for the invention preparation
4)
0.5(MoO
4)
0.5: Dy
3+ 0.01(A=Ca
2+, Sr
2+, Ba
2+) sem photograph of the luminous crystallite of sosoloid;
Fig. 3 is the A (WO of the method for the invention preparation
4)
0.5(MoO
4)
0.5: Dy
3+ 0.01(A=Ca
2+, Sr
2+, Ba
2+) the emmission spectrum figure of the luminous crystallite of sosoloid;
Fig. 4 is the A (WO of the method for the invention preparation
4)
0.5(MoO
4)
0.5: Eu
3+ 0.01(A=Ca
2+, Sr
2+, Ba
2+) the exciting light spectrogram of the luminous crystallite of sosoloid;
Fig. 5 is the A (WO of the method for the invention preparation
4)
0.5(MoO
4)
0.5: Eu
3+ 0.01(A=Ca
2+, Sr
2+, Ba
2+) the emmission spectrum figure of the luminous crystallite of sosoloid.
Embodiment
The present invention is with analytically pure WO
3, MoO
3, alkaline earth metal carbonate and lanthanide metal oxide etc. be raw material, prepares lanthanide metal ion Doped Tungsten molybdate phosphor combination thing through high temperature solid-state method.
The chemical general formula of the lanthanide metal ion Doped Tungsten molybdate phosphor combination thing of the present invention's preparation is:
A (WO
4)
0.5(MoO
4)
0.5: RE
3+ 0.01(A=Ca, Sr, Ba; RE
3+=Dy
3+, Eu
3+Deng)
Agents useful for same of the present invention has:
The CaO analytical pure, SrCO
3Analytical pure, BaCO
3Analytical pure, WO
3Analytical pure, MoO
3Analytical pure, Eu
2O
3Analytical pure, Dy
2O
3Analytical pure
Embodiment 1:A (WO
4
)
0.5
(MoO
4
)
0.5
: Dy
3+
0.01
(A=Ca, Sr, Ba) preparation of phosphor combination thing
By a certain amount of complex Ca (WO of preparation
4)
0.5(MoO
4)
0.5: Dy
3+ 0.01The mol ratio of the required various raw materials of phosphor combination thing takes by weighing CaO, the WO of certain mass
3, MoO
3, Dy
2O
3In ball grinder, add agate ball and 20-40 ml absolute ethyl alcohol ball milling 8-15 hour that quality is about 3 times of reactants then successively.The uniform reactant of thorough mixing is ground to certain fineness with product at last through 600 ℃-1000 ℃ after solid state reaction 2-4 hour, promptly obtains Ca (WO
4)
0.5(MoO
4)
0.5: Dy
3+ 0.01The phosphor combination thing.Use SrCO respectively
3, BaCO
3Substitute CaO, other condition is constant, can obtain Sr (WO
4)
0.5(MoO
4)
0.5: Dy
3+ 0.01And Ba (WO
4)
0.5(MoO
4)
0.5: Dy
3+ 0.01The phosphor combination thing.
The X-ray diffractogram of three types of phosphor combination things is as shown in Figure 1, and each compsn is sheelite four directions phase structure, shows that they have formed sosoloid.The ESEM of phosphor combination thing is as shown in Figure 2, and each compsn is spheroidal particle, about the about 1 μ m of median size, helps the application of fluorescent material in reality.Shown in Figure 3 is the emmission spectrum figure of phosphor combination thing, shows that compsn has not only presented Dy
3+Narrow emission peak and pure fluorescence color, and realized two kinds of anionic combinations, can realize the regulation and control of fluorescent powder emission wavelength.
Embodiment 2:A (WO
4
)
0.5
(MoO
4
)
0.5
: Eu
3+
0.01
(A=Ca, Sr, Ba) preparation of phosphor combination thing
Use Eu
2O
3Replacement Dy
2O
3, remaining presses embodiment 1 process implementing, preparation A (WO
4)
0.5(MoO
4)
0.5: Eu
3+ 0.01(A=Ca, Sr, Ba) phosphor combination thing.
Fig. 4 is the collection of illustrative plates that excites of three types of phosphor combination things, and Fig. 4 shows that the phosphor combination thing can well be complementary by near ultraviolet excitation and at present a lot of needed exciting light of optical material, has good actual application prospect.Shown in Figure 5 is the emmission spectrum figure of phosphor combination thing, shows the fellowship through two kinds of negatively charged ion and three types of luminescence center of lanthanide series metal europium, and compsn proposed by the invention presents typical pure red emission.
Claims (4)
1. the high-temperature solid phase preparation method of lanthanide metal ion Doped Tungsten molybdate phosphor combination thing is characterized in that this phosphor combination thing comprises A (WO
4)
0.5(MoO
4)
0.5: Dy
3+ 0.01And A (WO
4)
0.5(MoO
4)
0.5: Eu
3+ 0.01, compsn is with general formula A (WO
4)
0.5(MoO
4)
0.5: RE
3+ 0.01Represent A=Ca, Sr, Ba in the formula; RE
3+=Eu
3+, Dy
3+, Nd
3+, Ce
3+Deng.
2. require said lanthanide metal ion Doped Tungsten molybdate phosphor combination thing according to right 1, it is characterized in that said phosphor combination thing also contains one or more lanthanide metal ions, the general formula of compsn is A (WO
4)
0.5(MoO
4)
0.5: RE
3+ 0.01, RE representes lanthanide series metal in formula, it is selected from least a among Dy, Eu, Nd, the Ce.
3. require the high-temperature solid phase preparation method of said lanthanide metal ion Doped Tungsten molybdate phosphor combination thing according to right 1, it is characterized in that temperature of reaction is 600 ℃-1000 ℃, the reaction times is 2-4 hour.
4. require the high-temperature solid phase preparation method of said lanthanide metal ion Doped Tungsten molybdate phosphor combination thing according to right 1, it is characterized in that said alkaline earth metal cpds is that analytically pure MOX or carbonate are CaO, SrCO
3, BaCO
3WO
3, MoO
3Lanthanon is that analytically pure respective metal oxide compound is Eu
2O
3, Dy
2O
3, Nd
2O
3, Ce
2O
3Deng.
Priority Applications (1)
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|---|---|---|---|
| CN2011102602327A CN102367381A (en) | 2011-09-05 | 2011-09-05 | Lanthanide metal doped tungsten and molybdate phosphor composition |
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|---|---|---|---|
| CN2011102602327A CN102367381A (en) | 2011-09-05 | 2011-09-05 | Lanthanide metal doped tungsten and molybdate phosphor composition |
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|---|---|
| CN102367381A true CN102367381A (en) | 2012-03-07 |
Family
ID=45759974
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041931A (en) * | 2019-04-19 | 2019-07-23 | 中国计量大学 | A kind of near-infrared fluorescent film and preparation method thereof, near-infrared LED |
| CN110791287A (en) * | 2019-09-27 | 2020-02-14 | 合肥学院 | Rare earth doped tungsten molybdate and preparation method and application thereof |
| CN112646578A (en) * | 2020-12-25 | 2021-04-13 | 成都理工大学 | Dy (Dy)3+Doping with Na5Y(MoO4)4Warm white fluorescent powder and preparation method thereof |
| CN113322069A (en) * | 2021-06-10 | 2021-08-31 | 昆明理工大学 | Molybdate reversible multicolor photochromic up-conversion phosphor and preparation method thereof |
| CN113429960A (en) * | 2021-07-05 | 2021-09-24 | 四川师范大学 | Can be used for trace Cu2+Carbon quantum dot composite UiO-66 derivative for ion detection |
Citations (2)
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|---|---|---|---|---|
| CN101067081A (en) * | 2007-06-06 | 2007-11-07 | 厦门大学 | Phosphor for white light LED with adjustable emitting peak and its prepn process |
| CN101338194A (en) * | 2008-05-15 | 2009-01-07 | 沈阳化工学院 | Rare-earth red fluorescent material and method for preparing same |
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2011
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Patent Citations (2)
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|---|---|---|---|---|
| CN101067081A (en) * | 2007-06-06 | 2007-11-07 | 厦门大学 | Phosphor for white light LED with adjustable emitting peak and its prepn process |
| CN101338194A (en) * | 2008-05-15 | 2009-01-07 | 沈阳化工学院 | Rare-earth red fluorescent material and method for preparing same |
Non-Patent Citations (1)
| Title |
|---|
| 赖欣等: "Dy3+掺杂CaWO4荧光粉体的制备及发光性能", 《材料导报B: 研究篇》, vol. 25, no. 6, 30 June 2011 (2011-06-30) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041931A (en) * | 2019-04-19 | 2019-07-23 | 中国计量大学 | A kind of near-infrared fluorescent film and preparation method thereof, near-infrared LED |
| CN110041931B (en) * | 2019-04-19 | 2022-04-15 | 中国计量大学 | Near-infrared fluorescent film, preparation method thereof and near-infrared LED |
| CN110791287A (en) * | 2019-09-27 | 2020-02-14 | 合肥学院 | Rare earth doped tungsten molybdate and preparation method and application thereof |
| CN110791287B (en) * | 2019-09-27 | 2022-08-05 | 合肥学院 | Rare earth doped tungsten molybdate and preparation method and application thereof |
| CN112646578A (en) * | 2020-12-25 | 2021-04-13 | 成都理工大学 | Dy (Dy)3+Doping with Na5Y(MoO4)4Warm white fluorescent powder and preparation method thereof |
| CN112646578B (en) * | 2020-12-25 | 2022-07-08 | 成都理工大学 | Dy (Dy)3+Doping with Na5Y(MoO4)4Warm white fluorescent powder and preparation method thereof |
| CN113322069A (en) * | 2021-06-10 | 2021-08-31 | 昆明理工大学 | Molybdate reversible multicolor photochromic up-conversion phosphor and preparation method thereof |
| CN113429960A (en) * | 2021-07-05 | 2021-09-24 | 四川师范大学 | Can be used for trace Cu2+Carbon quantum dot composite UiO-66 derivative for ion detection |
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Application publication date: 20120307 |