CN102492418A - Green emitting phosphor applicable to near ultraviolet light excitation and preparation method thereof - Google Patents
Green emitting phosphor applicable to near ultraviolet light excitation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses green emitting phosphor applicable to near ultraviolet light excitation and a preparation method thereof. A chemical formula of the green emitting phosphor is Ca7-7x-7yMII7yEu7xMg(SiO4)4, wherein MII is alkaline-earth metal Sr 2+, Ba 2+ and transition metal Zn 2+, x is mixed molar weight of Eu 2+, 0.00001<=x<=0.3, y is the molar weight of the MII replacing Ca 2+, and 0<=y<=0.4. The green emitting phosphor emits green light under excitation of ultraviolet-near ultraviolet, has the advantages of being high in emitting quality, wide in exciting wavelength and the like, and can be used as phosphor powder for a white light light-emitting diode (LED) excited by the near ultraviolet light. A solid phase sintering method is adopted and includes sintering for 1 to 15 hours at the temperature from 1,000 to 1,500 DEG C under reducing atmosphere and cooling to obtain the green emitting phosphor for the white light LED. The preparation method is simple and free of pollution.
Description
Technical field
the present invention relates to a kind of fluorescence luminescent material and preparation method thereof; Be particularly related to a kind of fluorescent material that is suitable for transmitting green fluorescence under near ultraviolet excitation and preparation method thereof; It can be applicable to belong to the fluorescent material technical field in ultraviolet or the near ultraviolet white light LEDs.
Background technology
are at global energy crisis, to environmental requirement under the strict form; In the product that uses the illumination class; Long service life, energy-conservation, safety, environmental protection, rich color, microminiaturized semiconductor LED light source can be provided, by universally acknowledged for being one of main path of energy-conserving and environment-protective.White light LEDs is as a kind of novel solid-state illumination technology, and it is described as the lighting source of new generation of mercury lamp that 21 century must replace incandescent light and the easy contaminate environment of high energy consumption, more and more receives people's attention in energy-conservation green illumination field.
are since first white light LEDs in 1996 comes out; Its technology of preparing has obtained developing rapidly; The luminous efficiency of product improves constantly; Be expected to replace traditional lighting sources such as incandescent light, luminescent lamp and high voltage mercury lamp, become the green illumination light source of tool development prospect of 21st century.At present, the technology of preparing of white light LEDs mainly contains 3 kinds: the one, and the combination of red, green, blue three-color LED, this method can arbitrarily be adjusted color, but power supply is complicated, and cost is higher.The 2nd, blue-ray LED and YAG (Y
3
Al
5
O
12
): Ce
3+
The yellow fluorescent powder combination, this method relative cost is lower, and efficient is higher; But owing to lack red composition, colour rendering index is relatively poor, simultaneously; Also because the absorption peak of the light-converting material of blue-light LED chip requires to be positioned at wavelength 420～470nm, and the fluorescent material that can satisfy this requirement is considerably less, absorption intensity neither be very big; Seek this type fluorescent material suitable difficulty is arranged; So the wavelength of led chip along with the development of ME, more and more moves toward the shortwave direction, make " near ultraviolet (360-410nm) type white light LEDs (NUV-LED) " become the most active system of present research.The 3rd, the combination of ultraviolet or near ultraviolet LED and three primary colors fluorescent powder, its advantage is that color developing is best, but present product luminous efficiency is lower.Therefore, development of new efficiently, redness, green and the blue colour fluorescent powder of Heat stability is good be the key that improves the white light LEDs luminous mass.
<b >At present, research near ultraviolet type white light-LED with green emitting phosphor maximum be orthosilicate system M</b><sub ><b >2</b></sub><b >SiO</b><sub ><b >4</b></sub><b >: Eu</b><sup ><b >2+</b></sup><b >(M=Ca, Sr Ba), wherein, mainly are to fluorescent material Ba</b><sub ><b >2</b></sub><b >SiO</b><sub ><b >4</b></sub><b >: Eu</b><sup ><b >2+</b></sup><b >Carried out a series of research work; The result shows: this fluorescent material emission peak under near ultraviolet excitation is positioned at 505 nm wideband spectrum; And its excitation spectrum is very wide; Fine with near-ultraviolet light chip coupling just in time, the chromaticity coordinates of the green light LED that obtains with the NUV-LED chips incorporate is x=0.1904, y=0.4751.For example, Chinese invention patent " a kind of preparation method of silicate green fluorescent powder " (CN1664056A), it is Zn that a kind of chemical constitution is provided</b><sub ><b >2-2x</b></sub><b >Mn</b><sub ><b >2x</b></sub><b >SiO</b><sub ><b >4</b></sub><b >, the silicate green fluorescent powder of 0.0025≤x≤0.08 wherein; Chinese invention patent (CN102020986A) discloses Mn</b><sup ><b >2+</b></sup><b >A kind of silicate green fluorescent powder of activated and preparation method thereof, its chemical constitution are M</b><sup ><b >1</b></sup><sub ><b >x</b></sub><b >Zn</b><sub ><b >2-2x-y</b></sub><b >M</b><sup ><b >2</b></sup><sub ><b >x</b></sub><b >SiO</b><sub ><b >4</b></sub><b >: Mn</b><sub ><b >y</b></sub><b >, M wherein</b><sup ><b >1</b></sup><b >Be Li, Na, the one or more combination among the K, M</b><sup ><b >2</b></sup><b >Be Al, Ga, Y, Sc, Gd, La, the one or more combination among the Lu, 0.001≤x≤0.5,0.005≤y≤0.2; Chinese invention patent " a kind of method of optimizing silicate green fluorescent powder material crystalline form " (CN102191057A) in, the chemical general formula of silicate green fluorescent powder be (Ba, A)</b><sub ><b >1-x</b></sub><b >SiO</b><sub ><b >4</b></sub><b >: xEu, wherein 0<X<1.0 A is Ca or Sr element; Chinese invention patent " low-temperature synthetic method of silicate green-light fluorescent powder " (CN101805607A) in, adopt reducing atmosphere 800～1000 ℃ of following sintering 2～4 hours, having synthesized main crystalline phase is Ca</b><sub ><b >2</b></sub><b >MgSi</b><sub ><b >2</b></sub><b >O</b><sub ><b >7</b></sub><b >: Eu</b><sup ><b >2+</b></sup><b >Green emitting phosphor; Chinese invention patent " a kind of alkaline-earth metal silicate fluorescent powder " (CN1827735A) in, the chemical constitution of the silicate fluorescent powder that provides is Sr</b><sub ><b >x</b></sub><b >Ba</b><sub ><b >2-x-y</b></sub><b >Eu</b><sub ><b >y</b></sub><b >Si</b><sub ><b >z</b></sub><b >O</b><sub ><b >2+2z</b></sub><b >, 1< wherein; X<2,0.02≤y≤0.2,0.7≤z≤1.5.</b>
The divalent europium activated in the prior art, is adopted in sum in
, and the green emitting phosphor that can be complementary with the near ultraviolet white light LEDs, does not appear in the newspapers.
Summary of the invention
the objective of the invention is to overcome the deficiency that prior art exists; Provide a kind of percent crystallinity high; Luminous mass is good; With low cost, and preparation technology is simple, pollution-free green fluorescent material and preparation method thereof, and the green fluorescence powder material limited for kind adds a kind of novel product.
For reaching above purpose, the technical scheme that the present invention adopts provides a kind of green emitting phosphor that is suitable near ultraviolet excitation, and it is a kind of divalent europium Eu
2+
Activated Magnesium Silicate q-agent calcium salt, its chemical formula are Ca
7-7x-7y
M
II
7y
Eu
7x
Mg (SiO
4
)
4
, in the formula, M
II
Be earth alkali metal barium ion Ba
2+
, strontium ion Sr
2+
And transition metal zine ion Zn
2+
In a kind of, or their arbitrary combination; X is divalent europium Eu
2+
The doping molar weight, the span of x is 0.00001≤x≤0.3, y is alkaline earth metal cation M
II
Replace calcium ion Ca
2+
Molar weight, the span of y is 0≤y≤0.4.
A kind of preparation method of green emitting phosphor that is suitable near ultraviolet excitation comprises the steps:
1, to contain calcium ion Ca
2+
, contain alkaline earth metal cation M
II
Compound, mg ion Mg
2+
Compound, contain anion silicon Si
4+
Compound, contain europium ion Eu
3+
Compound be raw material, press chemical formula Ca
7-7x-7y
M
II
7y
Eu
7x
Mg (SiO
4
)
4
The mol ratio of middle element takes by weighing raw material, after grinding and mixing, and calcining under air atmosphere, calcining temperature is 150～800 ℃, calcination time is 3～8 hours; Said M
II
Be earth alkali metal barium ion Ba
2+
, strontium ion Sr
2+
And transition metal zine ion Zn
2+
In a kind of, or their arbitrary combination; X is divalent europium Eu
2+
The doping molar weight, the span of x is 0.00001≤x≤0.3, y is alkaline earth metal cation M
II
Replace calcium ion Ca
2+
Molar weight, the span of y is 0≤y≤0.4;
2, thorough mixing grinds evenly behind the naturally cooling, in reducing atmosphere, carries out sintering once more, and sintering temperature is 1000～1500 ℃, and sintering time is 1～15 hour, obtains the rare earth doped europium ion Eu of powder shaped
2+
The calcium magnesium silicate green luminescent material.
The described calcium ion Ca that contains
2+
Compound be a kind of in quicklime, calcium hydroxide, nitrocalcite, lime carbonate, the calcium sulfate, or their arbitrary combination.
The described compound that contains mg ion is Natural manganese dioxide, five scale formula magnesiumcarbonate C
4
Mg
4
O
12
-H
2
MgO
2
-5H
2
O, Marinco H, magnesiumcarbonate, magnesium nitrate, a kind of in magnesium oxalate, the sal epsom, or their arbitrary combination.
The described alkaline earth metal cation M that contains
II
Compound comprise alkaline earth metal oxide, alkaline earth metal carbonate, alkaline earth metal hydroxides, alkine earth metal nitrate, earth alkali metal oxalate, alkaline earth metal sulphate, and a kind of in the earth alkali metal organic complex, or their arbitrary combination.
The described anion silicon Si that contains
4+
Compound be a kind of in silicon-dioxide, the tetraethoxy, or their combination.
The described europium ion Eu that contains
3+
Compound be a kind of in europium sesquioxide, oxalic acid europium, the europium nitrate, or their arbitrary combination.
Reducing atmosphere described in preparing method's step 2 is a kind of in following three kinds of atmosphere, or their arbitrary combination:
(1) hydrogen atmosphere, or the volume ratio of hydrogen and nitrogen is the mixed-gas atmosphere of 1:0.2～0.85;
(2) CO gas atmosphere;
The gas atmosphere that
(3) carbon granules or gac burn and produced in air.
Compared with prior art, the advantage of technical scheme of the present invention is:
The substrate material that
1, technical scheme of the present invention provide can be realized the reduction of bivalent rare earth ionic easily on technology, and the bivalent rare earth ion can stable existence in this matrix.Green emitting phosphor ZnS:Cu with present commercialization + , Al 3+ Compare, the preparation process of substrate material of the present invention is simple, the product easily collecting, and no waste water and gas discharging, environmental friendliness especially is fit to serialization production.
2, this green fluorescent material have the excitation area than broad, and quite identical with the near ultraviolet type white light LEDs excitation area 360～410nm of present use; Through composition that changes the matrix element and the ratio of regulating each element, can obtain the green emitting phosphor that halfwidth changes, and consider that to the influence of its emissive porwer therefore earth alkali metal forms solid solution structure, is applicable near ultraviolet type white light LEDs.
The fluor that
3, the present invention obtain is in ultraviolet or the near ultraviolet excitated very strong green light of emission down, and it can be satisfied with the application of near ultraviolet type white light LEDs preferably.Simultaneously, the invention provides the preparation method of this fluorescent material, its step is simple, easy handling.
Description of drawings
Fig. 1 is by the X-ray powder diffraction collection of illustrative plates of the material sample of embodiment of the invention technical scheme preparation and the comparison of standard card PDF#27-1060;
Fig. 2 is the exciting light spectrogram in ultraviolet and near ultraviolet region that material sample monitoring emission light 510 nm by the preparation of embodiment of the invention technical scheme are obtained;
Fig. 3 excites the luminescent spectrum that obtains down by the material sample that embodiment of the invention technical scheme prepares at near-ultraviolet light 378 nm.
Embodiment
further describe the present invention below in conjunction with accompanying drawing and embodiment.
Embodiment 1
Ca
6.86
Eu
0.14
Mg (SiO
4
)
4
Preparation
Take by weighing lime carbonate CaCO
3
: 2.2867 grams, five scale formula magnesiumcarbonate C
4
Mg
4
O
12
-H
2
MgO
2
-5H
2
The O:0.324 gram, silicon-dioxide SiO
2
: 0.8012 gram, europium sesquioxide Eu
2
O
3
: 0.0821 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, optimum calcinating temperature is 500-700 ℃, best calcination time 5-6 hour, be cooled to room temperature then, take out sample.The thorough mixing grinding is even once more for the incinerating raw material for the first time; Among reducing atmospheres such as nitrogen (interpolation gac), CO gas, hydrogen or nitrogen and hydrogen mixture, carry out sintering once more; 1200～1300 ℃ of optimal sintering temperatures; Calcination time 8～10 hours is chilled to room temperature then, takes out sample.Promptly obtain the rare earth doped europium ion Eu of powder shaped
2+
The calcium magnesium silicate green luminescent material.
Referring to accompanying drawing 1, it is that the XRD test result shows that prepared material is calcium magnesium silicate (Ca by the X-ray powder diffraction collection of illustrative plates of the material sample of present embodiment technical scheme preparation and the comparison of standard card PDF#27-1060
7
Mg (SiO
4
)
4
) monophase materials.
are referring to accompanying drawing 2; Can find out the exciting light spectrogram of near ultraviolet region from what material sample monitoring emission light 510 nm by the preparation of the present invention's technology were obtained; This material green emitting excite main near ultraviolet (NUV) zone between 350～400 nm, source, can mate the near ultraviolet LED chip well.
are referring to accompanying drawing 3; It is to excite the luminescent spectrum that obtains down at near-ultraviolet light 378 nm by the material sample that the present embodiment technical scheme prepares; Can find out that by Fig. 3 the main center emission wavelength of this material is the green light band at 510 nm.
Embodiment 2
Ca
6.93
Eu
0.07
Mg (SiO
4
)
4
Preparation
Take by weighing lime carbonate CaCO
3
: 2.31 grams, magnesium basic carbonate C
4
Mg
4
O
12
-H
2
The MgO:0.324 gram, silicon-dioxide SiO
2
: 0.8012 gram, europium sesquioxide Eu
2
O
3
: 0.041 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, optimum calcinating temperature is 600～750 ℃, calcination time 6～7 hours is cooled to room temperature then, takes out sample.The thorough mixing grinding is even once more for the incinerating raw material for the first time; Among reducing atmospheres such as nitrogen (interpolation gac), CO gas, hydrogen or nitrogen and hydrogen mixture, carry out sintering once more; 1100～1200 ℃ of optimal sintering temperatures; Best sintering time 10～12 hours is chilled to room temperature then, takes out sample.Promptly obtain the rare earth doped europium ion Eu of powder shaped
2+
The calcium magnesium silicate green luminescent material, its main structure properties, excitation spectrum and luminescent spectrum are similar with embodiment 1.
Embodiment 3
Ca
6.79
Eu
0.21
Mg (SiO
4
)
4
Preparation
Take by weighing lime carbonate CaCO
3
: 2.263 grams, magnesium basic carbonate C
4
Mg
4
O
12
-H
2
The MgO:0.324 gram, silicon-dioxide SiO
2
: 0.8012 gram, europium sesquioxide Eu
2
O
3
: 0.1232 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, optimum calcinating temperature is 650～700 ℃, calcination time 5～7 hours is cooled to room temperature then, takes out sample.The thorough mixing grinding is even once more for the incinerating raw material for the first time; Among reducing atmospheres such as nitrogen (interpolation gac), CO gas, hydrogen or nitrogen and hydrogen mixture, carry out sintering once more; 1250～1350 ℃ of optimal sintering temperatures; Best sintering time 10～12 hours is chilled to room temperature then, takes out sample.Promptly obtain the rare earth doped europium ion Eu of powder shaped
2+
The calcium magnesium silicate green luminescent material, its main structure properties, excitation spectrum and luminescent spectrum are similar with embodiment 1.
Embodiment 4
Ca
6.65
Eu
0.35
Mg (SiO
4
)
4
Preparation
Take by weighing lime carbonate CaCO
3
: 2.217 grams, magnesium basic carbonate C
4
Mg
4
O
12
-H
2
The MgO:0.324 gram, silicon-dioxide SiO
2
: 0.8012 gram, europium sesquioxide Eu
2
O
3
: 0.2053 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, optimum calcinating temperature is 600～750 ℃, calcination time 5～7 hours is cooled to room temperature then, takes out sample.The thorough mixing grinding is even once more for the incinerating raw material for the first time; Among reducing atmospheres such as nitrogen (interpolation gac), CO gas, hydrogen or nitrogen and hydrogen mixture, carry out sintering once more, 1200～1300 ℃ of temperature, calcination time 12～13 hours; Be chilled to room temperature then, take out sample.Promptly obtain the rare earth doped europium ion Eu of powder shaped
2+
The calcium magnesium silicate green luminescent material, its main structure properties, excitation spectrum and luminescent spectrum are similar with embodiment 1.
Embodiment 5
Ca
6.51
Eu
0.49
Mg (SiO
4
)
4
Preparation
Take by weighing lime carbonate CaCO
3
: 2.17 grams, magnesium basic carbonate C
4
Mg
4
O
12
-H
2
The MgO:0.324 gram, silicon-dioxide SiO
2
: 0.8012 gram, europium sesquioxide Eu
2
O
3
: 0.2874 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, optimum calcinating temperature is 650～750 ℃, calcination time 5～7 hours is cooled to room temperature then, takes out sample.The thorough mixing grinding is even once more for the incinerating raw material for the first time; Among reducing atmospheres such as nitrogen (interpolation gac), CO gas, hydrogen or nitrogen and hydrogen mixture, carry out sintering once more, 1300～1400 ℃ of temperature, calcination time 11～12 hours; Be chilled to room temperature then, take out sample.Promptly obtain the rare earth doped europium ion Eu of powder shaped
2+
The calcium magnesium silicate green luminescent material, its main structure properties, excitation spectrum and luminescent spectrum are similar with embodiment 1.
Embodiment 6
Ca
6.3
Eu
0.7
Mg (SiO
4
)
4
Preparation
Take by weighing lime carbonate CaCO
3
: 2.1 grams, magnesium basic carbonate C
4
Mg
4
O
12
-H
2
The MgO:0.324 gram, silicon-dioxide SiO
2
: 0.8012 gram, europium sesquioxide Eu
2
O
3
: 0.41 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, optimum calcinating temperature is 580～700 ℃, calcination time 6～7 hours is cooled to room temperature then, takes out sample.The thorough mixing grinding is even once more for the incinerating raw material for the first time; Among reducing atmospheres such as nitrogen (interpolation gac), CO gas, hydrogen or nitrogen and hydrogen mixture, carry out sintering once more, 1150～1250 ℃ of temperature, calcination time 11～12 hours; Be chilled to room temperature then, take out sample.Promptly obtain the rare earth doped europium ion Eu of powder shaped
2+
The calcium magnesium silicate green luminescent material, its main structure properties, excitation spectrum and luminescent spectrum are similar with embodiment 1.
Embodiment 7
Ca
6.86
Sr
0.07
Eu
0.07
Mg (SiO
4
)
4
Preparation
Take by weighing lime carbonate CaCO
3
: 2.2867 grams, magnesium basic carbonate C
4
Mg
4
O
12
-H
2
The MgO:0.324 gram, silicon-dioxide SiO
2
: 0.8012 gram, europium sesquioxide Eu
2
O
3
: 0.041 gram, Strontium carbonate powder SrCO
3
: 0.0344 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, optimum calcinating temperature is 600～700 ℃, calcination time 5～7 hours is cooled to room temperature then, takes out sample.The thorough mixing grinding is even once more for the incinerating raw material for the first time; Among reducing atmospheres such as nitrogen (interpolation gac), CO gas, hydrogen or nitrogen and hydrogen mixture, carry out sintering once more, 1200～1350 ℃ of temperature, calcination time 8～10 hours; Be chilled to room temperature then, take out sample.Promptly obtain the rare earth doped europium ion Eu of powder shaped
2+
The calcium magnesium silicate green luminescent material, its main structure properties, excitation spectrum and luminescent spectrum are similar with embodiment 1.
Embodiment 8
Ca
6.51
Ba
0.35
Eu
0.14
Mg (SiO
4
)
4
Preparation
Take by weighing lime carbonate CaCO
3
: 2.17 grams, magnesium basic carbonate C
4
Mg
4
O
12
-H
2
The MgO:0.324 gram, silicon-dioxide SiO
2
: 0.8012 gram, europium sesquioxide Eu
2
O
3
: 0.0821 gram, barium carbonate BaCO
3
: 0.23 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, optimum calcinating temperature is 650～700 ℃, calcination time 6～7 hours is cooled to room temperature then, takes out sample.The thorough mixing grinding is even once more for the incinerating raw material for the first time; Among reducing atmospheres such as nitrogen (interpolation gac), CO gas, hydrogen or nitrogen and hydrogen mixture, carry out sintering once more, 1300～1400 ℃ of temperature, calcination time 10～12 hours; Be chilled to room temperature then, take out sample.Promptly obtain the rare earth doped europium ion Eu of powder shaped
2+
The calcium magnesium silicate green luminescent material, its main structure properties, excitation spectrum and luminescent spectrum are similar with embodiment 1.
Embodiment 9
Ca
6.16
Zn
0.7
Eu
0.14
Mg (SiO
4
)
4
Preparation
Take by weighing lime carbonate CaCO
3
: 2.053 grams, magnesium basic carbonate C
4
Mg
4
O
12
-H
2
The MgO:0.324 gram, silicon-dioxide SiO
2
: 0.8012 gram, europium sesquioxide Eu
2
O
3
: 0.0821 gram, zinc carbonate ZnCO
3
: 0.2926 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 680～750 ℃, calcination time 6～7 hours is cooled to room temperature then, takes out sample.The thorough mixing grinding is even once more for the incinerating raw material for the first time; Among reducing atmospheres such as nitrogen (interpolation gac), CO gas, hydrogen or nitrogen and hydrogen mixture, carry out sintering once more, 1200～1300 ℃ of temperature, calcination time 10～12 hours; Be chilled to room temperature then, take out sample.Promptly obtain the rare earth doped europium ion Eu of powder shaped
2+
The calcium magnesium silicate green luminescent material, its main structure properties, excitation spectrum and luminescent spectrum are similar with embodiment 1.
Claims (8)
1. green emitting phosphor that is suitable near ultraviolet excitation, it is characterized in that: it is a kind of divalent europium Eu
2+Activated Magnesium Silicate q-agent calcium salt, its chemical formula are Ca
7-7x-7yM
II 7yEu
7xMg (SiO
4)
4, in the formula, M
IIBe earth alkali metal barium ion Ba
2+, strontium ion Sr
2+And transition metal zine ion Zn
2+In a kind of, or their arbitrary combination; X is divalent europium Eu
2+The doping molar weight, the span of x is 0.00001≤x≤0.3, y is alkaline earth metal cation M
IIReplace calcium ion Ca
2+Molar weight, the span of y is 0≤y≤0.4.
2. a kind of preparation method of green emitting phosphor that is suitable near ultraviolet excitation as claimed in claim 1 is characterized in that comprising the steps:
(1) to contain calcium ion Ca
2+, contain alkaline earth metal cation M
IICompound, mg ion Mg
2+Compound, contain anion silicon Si
4+Compound, contain europium ion Eu
3+Compound be raw material, press chemical formula Ca
7-7x-7yM
II 7yEu
7xMg (SiO
4)
4The mol ratio of middle element takes by weighing raw material, after grinding and mixing, and calcining under air atmosphere, calcining temperature is 150～800 ℃, calcination time is 3～8 hours; Said M
IIBe earth alkali metal barium ion Ba
2+, strontium ion Sr
2+And transition metal zine ion Zn
2+In a kind of, or their arbitrary combination; X is divalent europium Eu
2+The doping molar weight, the span of x is 0.00001≤x≤0.3, y is alkaline earth metal cation M
IIReplace calcium ion Ca
2+Molar weight, the span of y is 0≤y≤0.4;
(2) thorough mixing grinds evenly behind the naturally cooling, in reducing atmosphere, carries out sintering once more, and sintering temperature is 1000～1500 ℃, and sintering time is 1～15 hour, obtains the rare earth doped europium ion Eu of powder shaped
2+The calcium magnesium silicate green luminescent material.
3. a kind of preparation method of green emitting phosphor that is suitable near ultraviolet excitation according to claim 2 is characterized in that: the described calcium ion Ca that contains
2+Compound be a kind of in quicklime, calcium hydroxide, nitrocalcite, lime carbonate, the calcium sulfate, or their arbitrary combination.
4. a kind of preparation method of green emitting phosphor that is suitable near ultraviolet excitation according to claim 2 is characterized in that: the described compound that contains mg ion is Natural manganese dioxide, five scale formula magnesiumcarbonate C
4Mg
4O
12-H
2MgO
2-5H
2O, Marinco H, magnesiumcarbonate, magnesium nitrate, a kind of in magnesium oxalate, the sal epsom, or their arbitrary combination.
5. a kind of preparation method of green emitting phosphor that is suitable near ultraviolet excitation according to claim 2 is characterized in that: the described alkaline earth metal cation M that contains
IICompound comprise alkaline earth metal oxide, alkaline earth metal carbonate, alkaline earth metal hydroxides, alkine earth metal nitrate, earth alkali metal oxalate, alkaline earth metal sulphate, and a kind of in the earth alkali metal organic complex, or their arbitrary combination.
6. a kind of preparation method of green emitting phosphor that is suitable near ultraviolet excitation according to claim 2 is characterized in that: the described anion silicon Si that contains
4+Compound be a kind of in silicon-dioxide, the tetraethoxy, or their combination.
7. a kind of preparation method of green emitting phosphor that is suitable near ultraviolet excitation according to claim 2 is characterized in that: the described europium ion Eu that contains
3+Compound be a kind of in europium sesquioxide, oxalic acid europium, the europium nitrate, or their arbitrary combination.
8. a kind of preparation method of green emitting phosphor that is suitable near ultraviolet excitation according to claim 2 is characterized in that: described reducing atmosphere is a kind of in following three kinds of atmosphere, or their arbitrary combination:
(1) hydrogen atmosphere, or the volume ratio of hydrogen and nitrogen is the mixed-gas atmosphere of 1:0.2～0.85;
(2) CO gas atmosphere;
(3) carbon granules or the gac gas atmosphere that in air, burns and produced.
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| US20080020236A1 (en) * | 2006-07-21 | 2008-01-24 | Samsung Electronics Co., Ltd. | Phosphor for white light-emitting device and white light-emitting device including the same |
| CN101475804A (en) * | 2008-12-02 | 2009-07-08 | 罗维鸿 | Orthosilicate green phosphor for light emitting diode and preparation thereof |
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| US20070125982A1 (en) * | 2005-12-02 | 2007-06-07 | Sarnoff Corporation | Metal silicate halide phosphors and LED lighting devices using the same |
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Application publication date: 20120613 |