CN105112053B - A kind of white fluorescent powder based near ultraviolet excitation and preparation method thereof - Google Patents
A kind of white fluorescent powder based near ultraviolet excitation and preparation method thereof Download PDFInfo
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- CN105112053B CN105112053B CN201510656174.8A CN201510656174A CN105112053B CN 105112053 B CN105112053 B CN 105112053B CN 201510656174 A CN201510656174 A CN 201510656174A CN 105112053 B CN105112053 B CN 105112053B
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Abstract
The present invention is a kind of white fluorescent powder based near ultraviolet excitation：Its chemical formula is (Ca1‑y Mg y )1‑x Dy x ZrO3,xFor Dy3+Molar percentage coefficient, 0.005≤x≤0.15；yFor Mg2+Molar percentage coefficient, 0.01≤y≤ 0.30, Dy3+For the centre of luminescence.The invention also discloses a kind of preparation method of the white fluorescent powder based near ultraviolet excitation：With analytically pure calcium carbonate CaCO3, magnesium carbonate MgCO3Or magnesia MgO, zirconium dioxide ZrO2And dysprosia Dy2O3For raw material, it is well mixed, is then placed in crucible and calcines, ground after taking-up and produce white fluorescent powder.The Mg of white fluorescent powder doping of the present invention2+Ion raw material is cheap and easily-available；Can effectively it be excited by black light；Luminous efficiency is high, performance is good.
Description
Technical field
The present invention relates to a kind of fluorescent material, particularly a kind of white fluorescent powder based near ultraviolet excitation；The present invention is also
It is related to the preparation method of the white fluorescent powder.
Background technology
Dy3+It is a kind of centre of luminescence that can produce white light, its luminous spectrum is mainly made up of two luminous components：In first,
Blue transmitting light of the cardiac wave length positioned at 480nm or so；Second, centre wavelength is located at 580nm or so yellow transmitting light, both are at synthesis
For white light.Alkaline earth zirconates has higher fusing point, good mechanical performance and chemically and thermally stability, has perovskite knot
Structure, CaZrO especially therein3Pass through [ZrO6] it is octahedral significantly rotation and inclination realize closs packing, distortion degree is big,
This structure can effectively obstruct the energy transmission between Doped ions, it is possible to reach it is larger concentration is quenched and produce compared with
Strong is luminous.
In recent years, people are attempted Dy3+Mix in alkaline earth zirconates, study it and launch the property of white light, and inquired into it
Potentially applied in WLEDs (white light LEDs).Have been reported that CaZrO3:Dy3+Possess in the case where 350-420nm is excited preferably luminous
Property, 482nm or so blue light, and 575nm or so gold-tinted can be launched under 351nm near ultraviolet excitations.But at present
Untill, it is seen in the CaZrO of report3:Dy3+Luminous intensity it is relatively low, its luminescent properties need further improve.
The content of the invention
The technical problems to be solved by the invention are in view of the shortcomings of the prior art, there is provided a kind of new based on black light
The white fluorescent powder excited, the white fluorescent powder can effectively be excited by black light, and luminous intensity is high.
Another technical problem to be solved by this invention there is provided the foregoing white fluorescent based near ultraviolet excitation
A kind of preparation method of powder.
Technical scheme to be solved by this invention is realized by following technical scheme.The present invention is that one kind is based on
The white fluorescent powder of near ultraviolet excitation, is characterized in：Its chemical formula is (Ca1-yMgy)1-xDyxZrO3, x Dy3+Moles hundred
Divide than coefficient, 0.005≤x≤0.15；Y is Mg2+Molar percentage coefficient, 0.01≤y≤0.30, Dy3+For the centre of luminescence.
A kind of white fluorescent powder based near ultraviolet excitation of the present invention, further preferred technical scheme are：
In chemical formula preferably：0.01≤x≤0.06；0.01≤y≤0.10.Further preferably：X=0.02；Y=0.03.
Technical problem to be solved by this invention can also further be realized by following technical scheme.The present invention
Also disclose a kind of preparation method of the white fluorescent powder based near ultraviolet excitation as described in above technical scheme, its feature
It is：Its step is as follows：With analytically pure calcium carbonate CaCO3, magnesium carbonate MgCO3Or magnesia MgO, zirconium dioxide ZrO2And oxygen
Change dysprosium Dy2O3For raw material, weigh appropriate raw material by chemical formula composition and remix uniformly, be then placed in crucible, in high temperature furnace
Middle calcining, sintering temperature be 1200 DEG C~1500 DEG C, maintain furnace cooling after this temperature 2-10 hours, ground after taking-up produce it is white
Color fluorescent material.
In invention described above preparation method, raw material can be well mixed using following methods：The original that will be weighed
Material is well mixed directly in alms bowl is ground.Also raw material is well mixed using following methods：Added into the raw material weighed appropriate
Alcohol, wet-mixing is carried out using magnetic agitation or ball mill, then utilizes oven for drying.It is of the present invention to be based near ultraviolet
Light activated white fluorescent powder is visually seen as white powder, can effectively be excited by black light.Compared with prior art, originally
The advantages of invention and technique effect are as follows：
1st, white fluorescent powder of the present invention is compared to CaZrO3:Dy3+Luminescent material, wherein the Mg adulterated2+Ion raw material is cheap
It is easy to get；The excitation wavelength of gained luminescenjt powder is located at 300-440nm scopes, and main excitation peak is located at 351nm, can be by black light
Effectively excite；Under near ultraviolet excitation, white fluorescent powder of the present invention can emission center wavelength respectively positioned at 483nm blue light and
575nm gold-tinted, both, which synthesize, produces white light.
2nd, the centre of luminescence Dy of white fluorescent powder of the present invention3+Luminous efficiency height under near ultraviolet excitation, performance are good.
3rd, preparation method of the present invention prepares luminescenjt powder in atmosphere using high temperature solid-state method, and the preparation technology operates letter
Single, practical, cost is low, it is possible to achieve large-scale industrial manufactures.
Brief description of the drawings
Fig. 1 is 6 hours, Dy of 1400 DEG C of sintering3+Content is 2mol%, Mg2+Content is 3mol% samples
(Ca0.97Mg0.03)0.98Dy0.02ZrO3The XRD spectrum of (being designated as (a))；
Fig. 2 is the excitation spectrum of sample (a)；
Fig. 3 is the excitation spectrum of sample (a)；
Fig. 4 is the emission spectrum of sample (a)；
Fig. 5 is the emission spectrum of sample (a) and sample (b).
Embodiment
Concrete technical scheme of the invention described further below, in order to which those skilled in the art is further understood that
The present invention, without forming the limitation to its right.
Embodiment 1, a kind of white fluorescent powder based near ultraviolet excitation：Its chemical formula is (Ca1-yMgy)1-xDyxZrO3,
X is Dy3+Molar percentage coefficient, x=0.005；Y is Mg2+Molar percentage coefficient, y=0.01, Dy3+In luminous
The heart.Prepared using conventional method.
Embodiment 2, a kind of white fluorescent powder based near ultraviolet excitation：Its chemical formula is (Ca1-yMgy)1-xDyxZrO3,
X is Dy3+Molar percentage coefficient, x=0.15；Y is Mg2+Molar percentage coefficient, y=0.30, Dy3+For the centre of luminescence.
Its preparation methods steps are as follows：With analytically pure calcium carbonate CaCO3, magnesium carbonate MgCO3Or magnesia MgO, titanium dioxide
Zirconium ZrO2And dysprosia Dy2O3For raw material, weigh appropriate raw material by chemical formula composition and remix uniformly, be then placed in earthenware
In crucible, calcined in high temperature furnace, sintering temperature be 1200 DEG C, maintain the furnace cooling after 10 hours of this temperature, after taking-up grinding be
Obtain white fluorescent powder.
Embodiment 3, a kind of white fluorescent powder based near ultraviolet excitation：Its chemical formula is (Ca1-yMgy)1-xDyxZrO3,
X is Dy3+Molar percentage coefficient, x=0.06；Y is Mg2+Molar percentage coefficient, y=0.10, Dy3+For the centre of luminescence.
Its preparation methods steps are as follows：With analytically pure calcium carbonate CaCO3, magnesium carbonate MgCO3Or magnesia MgO, titanium dioxide
Zirconium ZrO2And dysprosia Dy2O3For raw material, weigh appropriate raw material by chemical formula composition and remix uniformly, be then placed in earthenware
In crucible, calcined in high temperature furnace, sintering temperature is 1500 DEG C, maintains the furnace cooling after 2 hours of this temperature, grinds and produce after taking-up
White fluorescent powder.
Embodiment 4, a kind of white fluorescent powder based near ultraviolet excitation：Its chemical formula is (Ca1-yMgy)1-xDyxZrO3,
X is Dy3+Molar percentage coefficient, x=0.10；Y is Mg2+Molar percentage coefficient, y=0.20, Dy3+For the centre of luminescence.
Its preparation methods steps are as follows：With analytically pure calcium carbonate CaCO3, magnesium carbonate MgCO3Or magnesia MgO, titanium dioxide
Zirconium ZrO2And dysprosia Dy2O3For raw material, weigh appropriate raw material by chemical formula composition and remix uniformly, use with lower section
Raw material is well mixed by method：The raw material weighed is well mixed directly in alms bowl is ground；It is then placed in crucible, in high temperature furnace
Calcining, sintering temperature are 1350 DEG C, maintain the furnace cooling after 5 hours of this temperature, are ground after taking-up and produce white fluorescent powder.
Embodiment 5, a kind of white fluorescent powder based near ultraviolet excitation：Its chemical formula is (Ca1-yMgy)1-xDyxZrO3,
X is Dy3+Molar percentage coefficient, x=0.02；Y is Mg2+Molar percentage coefficient, y=0.03, Dy3+For the centre of luminescence.
Its preparation methods steps are as follows：With analytically pure calcium carbonate CaCO3, magnesium carbonate MgCO3Or magnesia MgO, titanium dioxide
Zirconium ZrO2And dysprosia Dy2O3For raw material, weigh appropriate raw material by chemical formula composition and remix uniformly, use with lower section
Raw material is well mixed by method：Suitable alcohols are added into the raw material raw material weighed, wet method is carried out using magnetic agitation or ball mill
Mixing, then utilizes oven for drying；It is then placed in crucible, is calcined in high temperature furnace, sintering temperature is 1400 DEG C, maintains this temperature
Degree furnace cooling after 6 hours, grinds after taking-up and produces white fluorescent powder.
With the crystal habit of PANalytical X ' pert Pro MPD X-ray diffractometers (XRD) analysis sample.Reference
Fig. 1, Fig. 1 are 6 hours, Dy of 1400 DEG C of sintering3+Content is 2mol%, Mg2+Content is 3mol% samples (Ca0.97Mg0.03)0.98Dy0.02ZrO3The XRD spectrum of (being designated as (a)), its structure are in single CaZrO3Phase, it is consistent with JCPDS35-0790, not
Appearance and Mg2+Or Dy3+Relevant dephasign, illustrate that these ions have fully taken up Ca2+Or Zr4+Case.Other sintering temperatures
The XRD of different or different Doped ions content samples is similar with the sample, and simply the intensity at peak is different.Therefore, can be true
Fixed gained sample is the CaZrO of perovskite structure3Sill.
Utilize the excitation spectrum and emission spectrum of HITACHI F-7000 type sepectrophotofluorometer test samples.Reference picture
2-5, Fig. 2 are the excitation spectrum of sample (a), and Fig. 3 is the excitation spectrum of sample (a), and excitation peak is distributed in 300-440nm scopes
Interior, it is that (emission spectra monitoring wavelength is λ to 351nm that master, which excites peak value,em=483nm), corresponding to Dy3+'s6H15/2→6P7/2Feature swashs
Hair.Fig. 4 is the emission spectrum of sample (a), and Fig. 5 is the emission spectrum of sample (a) and sample (b), including with 483nm blue light and
(PLE monitoring wavelength is λ to two strong emission peak centered on 575nm gold-tintedex=351nm), correspond respectively to Dy3+'s4F9/2→6H15/2With4F9/2→6H13/2Transition.It can be found that the emission peak of (a) sample is also far above (b) sample.
Claims (1)
- A kind of 1. white fluorescent powder based near ultraviolet excitation, it is characterised in that：Its chemical formula is (Ca1-y Mg y )1- x Dy x ZrO3,xFor Dy3+Molar percentage coefficient, x=0.02；yFor Mg2+Molar percentage coefficient, y=0.03, Dy3+For The centre of luminescence；Its preparation methods steps are as follows：With analytically pure calcium carbonate CaCO3, magnesium carbonate MgCO3Or magnesia MgO, zirconium dioxide ZrO2And dysprosia Dy2O3For raw material, weigh appropriate raw material by chemical formula composition and remix uniformly, using following methods Raw material is well mixed：Suitable alcohols are added into the raw material raw material weighed, carrying out wet method using magnetic agitation or ball mill mixes Close, then utilize oven for drying；It is then placed in crucible, is calcined in high temperature furnace, sintering temperature is 1400 DEG C, maintains this temperature Furnace cooling after 6 hours, ground after taking-up and produce white fluorescent powder.
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Citations (3)
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| US3959658A (en) * | 1974-06-13 | 1976-05-25 | Purdue Research Foundation | Microwave dosimeter utilizing thermoluminescent materials |
| CN102786303A (en) * | 2012-08-07 | 2012-11-21 | 内蒙古工业大学 | Ceramic nanometer composite material for heat barrier coating and preparation method of ceramic nanometer composite material |
| CN104831360A (en) * | 2015-05-14 | 2015-08-12 | 中国科学院合肥物质科学研究院 | Ca-Mg-Zr-doped rare earth-tanto-niobate crystal as well as melt-method crystal growth method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959658A (en) * | 1974-06-13 | 1976-05-25 | Purdue Research Foundation | Microwave dosimeter utilizing thermoluminescent materials |
| CN102786303A (en) * | 2012-08-07 | 2012-11-21 | 内蒙古工业大学 | Ceramic nanometer composite material for heat barrier coating and preparation method of ceramic nanometer composite material |
| CN104831360A (en) * | 2015-05-14 | 2015-08-12 | 中国科学院合肥物质科学研究院 | Ca-Mg-Zr-doped rare earth-tanto-niobate crystal as well as melt-method crystal growth method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| CaZrO3：Ln ( Ln = Pr3+，Sm3+，Tb3+，Dy3+，Tm3+)荧光粉的制备与光谱调控;董晓睿等;《发光学报》;20141130;第35卷(第11期);第1311-1316页 * |
| Tricolor luminescence in rare earth doped CaZrO3 perovskite oxides;Yuhei Shimizu等;《Materials Science and Engineering B》;20081215;第161卷;第100-103页 * |
| 稀土离子掺杂锆酸钙纳米晶的制备及发光性质;李玮等;《硅酸盐学报》;20111130;第39卷(第11期);第1729-1733页 * |
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