CN101113332A - Nitride luminescent material and method for making same - Google Patents

Nitride luminescent material and method for making same Download PDF

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CN101113332A
CN101113332A CNA2007101197746A CN200710119774A CN101113332A CN 101113332 A CN101113332 A CN 101113332A CN A2007101197746 A CNA2007101197746 A CN A2007101197746A CN 200710119774 A CN200710119774 A CN 200710119774A CN 101113332 A CN101113332 A CN 101113332A
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luminescent material
alloy
molar ratio
nitride luminescent
furnace
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CN100554370C (en
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刘泉林
魏小丹
蔡丽艳
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Abstract

The invention relates to a nitride luminescent material and a preparation method thereof and pertains to the technical field of luminescent materials. A general chemical formula of the material is Y1-xMxy+Si3N5-3x+xyO3x-xy, wherein, M is Ce or Eu, y is equal to 3 or 2, X is more than 0 and less than 1, My+ is a luminescence center. The rare earth My+ luminescence center is incorporated in YSi3 (N, O) 5 in matrix. Alloy YaSib and CecSid are smelted by an electric arc furnace and grinded; proper YaSib, Si3N4 and CecSid or YaSib, Si3N4 and Eu2O3 are taken according to ratio and fully and evenly mixed; after squashing, the squashed mixture is put into a high temperature solid phase reaction furnace to be sintered under 1600-1800 DEG C for 1-10h and protected under N2 atmosphere of 1to 10 atmospheric pressure, and the nitride material that has specific luminescence center My+ and X value are prepared. The invention has the advantages that the invention has excellent fluorescence properties in visible light wave range and 400-600nm emission wavelength can be obtained when the invention is stimulated by light with wavelength being 350-510nm.

Description

A kind of nitride luminescent material and preparation method thereof
Technical field
The present invention relates to the luminescent material technical field, a kind of nitride luminescent material and preparation method thereof particularly is provided, with high purity Ln (Ln is La or Y), Si, Ce, Eu 2O 3With Si 3N 4Be raw material,, prepare nitride material with good luminescent properties by arc melting and high temperature solid-phase sintering.
Background technology
Up to now, multiple luminescent material has appearred, fields of society performance vital role.But great majority are with oxide compound, and sulfide or oxysulfide are matrix, and mix in these matrix a spot of transition metal ion or rare earth ion are luminescence center.The poor chemical stability of these compounds, after particularly comprehensive luminous efficiency and the temperature quenching characteristic, really material that can be practical is also few.Along with the development of society, they more and more are difficult to adapt to white light-emitting diodes illumination and the requirement of development such as modern plasma and Field Emission Display technology to material.
When with Ce 3+Or Eu 2+During as activator, it absorbs and emission band is by 4f n4f N-1 5d 1Transition causes.Because the 5d track exposes at skin, influenced greatly by residing crystalline environment on every side.Studies show that 4f n4f N-1 5d 1Excite and emission band position that transition causes depend primarily on 5d energy level position of centre of gravity and crystal field splitting.Mainly by the decision of chemical bond character, the 5d engery level cracking depends on crystal field intensity to 5d energy level position of centre of gravity.Along with rare earth activation ion and coordination anion covalent linkage composition increase on every side, the center of gravity of 5d energy level reduces, and excites accordingly with the emission band position and moves to the long wave direction.
Existing research points out that in all compounds, nitride has the strongest covalent linkage.And at present international and domestic research about nitride phosphor is reported seldom.Therefore, exploring novel long emission wavelength material in the nitride system of the prevailing stable chemical performance of covalent linkage is a kind of new research tendency.At present, also do not have about at LnSi 3(N, O) 5Doped Ce in the matrix 3+Or Eu 2+The report of luminescent properties.
Summary of the invention
The object of the present invention is to provide a kind of nitride luminescent material and preparation method thereof, obtained to have the nitride luminescent material of good luminescent properties.
Nitride luminescent material chemical general formula of the present invention is: Ln 1-xM x Y+Si 3N 5-3x+xyO 3x-xy, wherein, Ln is La or Y, M is Ce or Eu, y=3 or 2,0＜X＜1.Its excitation wavelength is positioned between 350 ~ 510nm, and emission wavelength is positioned between 400 ~ 600nm.
The present invention selects Ce for use 3+With Eu 2+Be luminescence center, with LnSi 3(N, O) 5 is matrix, with highly purified Ln, Si, Ce, Eu 2O 3And Si 3N 4Be raw material, utilize arc melting and high temperature solid-phase sintering prepared to go out a kind of Ce of containing 3+Or Eu 2+Nitride luminescent material Ln 1-xM x Y+Si 3N 5-3x+xyO 3x-xy(Ln is La or Y, and M is Ce or Eu, y=3 or 2).
The present invention is with chemical general formula Ln 1-xM x Y+Si 3N 5-3x+xyO 3x-xyIn X, i.e. rare-earth luminescent center Ce 3+Or Eu 2+Different percentage compositions, be to select the parameter batching of parameter point, wherein 0＜X＜1.
The objective of the invention is to implement by following method.With Ce 3+Or Eu 2+Be luminescence center, utilize purity to be higher than 99.5% metal Ln, simple substance Si, nanometer Si 3N 4Powder, metal Ce and Eu 2O 3Powder is a raw material, by arc melting, grind, compressing tablet, technologies such as high temperature solid-phase sintering, the nitride luminescent material that obtains the luminescent properties excellence with and preparation method thereof.
When luminescence center M is Ce, during y=3, concrete processing step is:
(1) be 5: 3 with molar ratio, 5: 4,1: 1,2: 3, the Ln and the Si of 3: 5 or 1: 2 placed electric arc furnace, carried out melting, the alloy Ln that makes when galvanic current is 70A ~ 120A aSi bFully grind to form powder subsequently, wherein, a and b are alloy Ln aSi bThe variable of middle element Ln and Si.
(2) be 5: 3 with molar ratio, 3: 2,5: 4,1: 1, the Ce and the Si of 3: 5 or 1: 2 placed electric arc furnace, carried out melting, the alloy Ce that makes when galvanic current is 70A～120A cSi dFully grind to form powder subsequently, wherein, c and d are alloy Ce cSi dThe variable of middle Elements C e and Si.
(3) according to general formula Ln 1-xM x Y+Si 3N 5-3x+xyO 3x-xy, with Ln aSi b, Ce cSi dAnd Si 3N 4According to molar ratio Place mortar; With alcohol is dispersion agent, fully grinds, to be mixed evenly after, oven dry, compressing tablet; Then the sheet sample is loaded in the graphite furnace, in 1～10 atmospheric N 2Protection down, with 1600 ~ 1800 ℃ of sintering 1～10 hour, furnace cooling.
When luminescence center M is Eu, during y=2, concrete processing step is:
(1) be 5: 3 with molar ratio, 5: 4,1: 1,2: 3, the Ln and the Si of 3: 5 or 1: 2 placed electric arc furnace, carried out melting, the alloy Ln that makes when galvanic current is 70A～120A aSi bFully grind to form powder subsequently, wherein, a and b are alloy Ln aSi bThe variable of middle element Ln and Si.
(2) according to general formula Ln 1-xM x Y+Si 3N 5-3x+xyO 3x-xy, with Ln aSi b, Eu 2O 3And Si 3N 4According to molar ratio 1 - X a : X 2 : [ 1 - b 3 a ( 1 - X ) ] Place mortar; With alcohol is dispersion agent, fully grinds, to be mixed evenly after, oven dry, compressing tablet; Then the sheet sample is loaded in the graphite furnace, in 1～10 atmospheric N 2Protection down, with 1600～1800 ℃ of sintering 1～10 hour, furnace cooling.
Advantage of the present invention is:
1, prepares with LnSi first 3(N, O) 5Luminescent material Ln for matrix 1-xM x Y+Si 3N 5-3x+xyO 3x-xy(Ln is La or Y; M is Ce or Eu, y=3 or 2,0＜X＜1), it has good luminescent properties, and excitation wavelength is positioned between 350 ~ 510nm, and emission wavelength is positioned between 400 ~ 600nm, is Ce 3+Or Eu 2+Wide emission peak.
2, utilize arc melting to make the raw material of LnSi and the final nitride material of CeSi alloy conduct.
3, adopt nano-powder Si 3N 4, increase speed of reaction, reduce the experimental installation requirement.
4, this nitride stable chemical performance, long service life.
Description of drawings
The nitride luminescent material that Fig. 1 obtains for embodiment 1 provided by the invention, the excitation spectrum when emission wavelength is 555nm.
The nitride luminescent material that Fig. 2 obtains for embodiment 1 provided by the invention, the emission spectrum when excitation wavelength is 420nm.
The nitride luminescent material that Fig. 3 obtains for embodiment 1 provided by the invention, the emission spectrum when excitation wavelength is 470nm.
The nitride luminescent material that Fig. 4 obtains for embodiment 2 provided by the invention, the excitation spectrum when emission wavelength is 555nm.
The nitride luminescent material that Fig. 5 obtains for embodiment 2 provided by the invention, the emission spectrum when excitation wavelength is 397nm.
The nitride luminescent material that Fig. 6 obtains for embodiment 3 provided by the invention, the excitation spectrum when emission wavelength is 510nm.
The nitride luminescent material that Fig. 7 obtains for embodiment 3 provided by the invention, the emission spectrum when excitation wavelength is 360nm.
The nitride luminescent material that Fig. 8 obtains for embodiment 4 provided by the invention, the excitation spectrum when emission wavelength is 550nm.
The nitride luminescent material that Fig. 9 obtains for embodiment 4 provided by the invention, the emission spectrum when excitation wavelength is 397nm.
Embodiment
Embodiment 1
Purity is higher than 99.5% Y and Si places electric arc furnace by 1: 1 molar ratio, melting under the electric current of 100A, (a=1 b=1), grinds to obtain alloy Y Si; Purity is higher than 99.5% Ce and Si, and the molar ratio by 1: 1 places electric arc furnace, melting under the electric current of 80A, and (c=1 d=1), grinds to obtain alloy CeSi.Select batching point X=0.05, with YSi, CeSi, Si 3N 4Powder 57: 3: 40 in molar ratio places mortar, is dispersion medium with the dehydrated alcohol, fully is ground to evenly oven dry, compressing tablet.Be loaded into then in the graphite furnace, at 1 atmospheric N 2Under the atmosphere protection, 1800 ℃ of sintering of high temperature 2 hours, back furnace cooling.It is Y that the nitride that obtains finally embodies formula 0.95Ce 0.05Si 3N 5(wherein, Ln is Y, and M is Ce, y=3, X=0.05).Obtained nitride material has good luminescent properties.Its excite with emission spectrum shown in Fig. 1～3.
Embodiment 2
Purity is higher than 99.5% Y and Si places electric arc furnace by 1: 1 molar ratio, melting under the electric current of 100A, (a=1 b=1), grinds to obtain alloy Y Si.Select batching point X=0.1, with YSi, Eu 2O 3, Si 3N 4Powder was loaded in the mortar in 54: 3: 40 in molar ratio, was dispersion medium with the dehydrated alcohol, fully was ground to evenly oven dry, compressing tablet.Be loaded into then in the graphite furnace, at 1 atmospheric N 2Under the atmosphere protection, 1800 ℃ of sintering of high temperature 2 hours, it is Y that back furnace cooling, the nitride that obtains embody formula 0.9Eu 0.1Si 3N 4.9O 0.1(wherein, Ln is Y, and M is Eu, y=2, X=0.1).Obtained nitride material has good luminescent properties.Its excite with emission spectrum shown in Fig. 4,5.
Embodiment 3
Purity is higher than 99.5% La and Si places electric arc furnace by 1: 1 molar ratio, melting under the electric current of 80A, (a=1 b=1), grinds to obtain alloy LaSi; Purity is higher than 99.5% Ce and Si, and the molar ratio by 1: 1 places electric arc furnace, melting under the electric current of 80A, and (c=1 d=1), grinds to obtain alloy CeSi.Select batching point X=0.02, with LaSi, CeSi, Si 3N 4Powder 147: 3: 100 in molar ratio places mortar, is dispersion medium with the dehydrated alcohol, fully is ground to evenly oven dry, compressing tablet.Be loaded into then in the graphite furnace, at 1 atmospheric N 2Under the atmosphere protection, 1700 ℃ of sintering of high temperature 2 hours, it is La that back furnace cooling, the nitride that obtains embody formula 0.98Ce 0.02Si 3N 5(wherein, Ln is La, and M is Ce, y=3, X=0.02).Obtained nitride material has good luminescent properties.Its excite with emission spectrum shown in Fig. 6,7.
Embodiment 4
Purity is higher than 99.5% La and Si, places electric arc furnace by 1: 1 molar ratio, melting under the electric current of 80A, (a=1 b=1), grinds to obtain alloy Y Si.Select batching point X=0.05, with LaSi, Eu 2O 3, Si 3N 4The powder material was loaded in the mortar in 114: 3: 82 in molar ratio, was dispersion medium with the dehydrated alcohol, fully was ground to evenly oven dry, compressing tablet.Be loaded into then in the graphite furnace, at 1 atmospheric N 2Under the atmosphere protection, 1700 ℃ of sintering of high temperature 2 hours, it is La that back furnace cooling, the nitride that obtains embody formula 0.95Eu 0.05Si 3N 4.95O 0.05(wherein, Ln is La, and M is Eu, y=2, X=0.05).Obtained nitride material has good luminescent properties.Its excite with emission spectrum shown in Fig. 8,9.

Claims (6)

1. nitride luminescent material, it is characterized in that: chemical general formula is Ln 1-xM x Y+Si 3N 5-3x+xyO 3x-xy, wherein, Ln is La or Y, M is Ce or Eu, y=3 or 2,0＜X＜1.
2. by the described nitride luminescent material of claim 1, it is characterized in that: excitation wavelength is positioned between 350 ~ 510nm, and emission wavelength is positioned between 400 ~ 600nm; Concrete wavelength location and parameter X, i.e. the percentage composition of luminescence center, selection relevant.
3. method for preparing right 1 described nitride luminescent material is characterized in that: when luminescence center M is Ce, during y=3, technology is:
(1) be 5: 3 with molar ratio, 5: 4,1: 1,2: 3, the Ln and the Si of 3: 5 or 1: 2 placed electric arc furnace, carried out melting, the alloy Ln that makes when galvanic current is 70A ~ 120A aSi bFully grind to form powder subsequently, wherein, a and b are alloy Ln aSi bThe variable of middle element Ln and Si.
(2) be 5: 3 with molar ratio, 3: 2,5: 4,1: 1, the Ce and the Si of 3: 5 or 1: 2 placed electric arc furnace, carried out melting, the alloy Ce that makes when galvanic current is 70A～120A cSi dFully grind to form powder subsequently, wherein, c and d are alloy Ce cSi dThe variable of middle Elements C e and Si.
(3) according to general formula Ln 1-xM x Y+Si 3N 5-3x+xyO 3x-xy, with Ln aSi b, Ce cSi dAnd Si 3N 4According to molar ratio 1 - X a : X c : [ 1 - b 3 a ( 1 - X ) - d 3 c X ] Place mortar; With alcohol is dispersion agent, fully grinds, to be mixed evenly after, oven dry, compressing tablet; Then the sheet sample is loaded in the graphite furnace, at 1～10 atmospheric N 2Protection down, with 1600 ~ 1800 ℃ of sintering 1～10 hour, furnace cooling.
4. by right 3 described nitride luminescent material preparation methods, it is characterized in that: raw material Ln, Si, Ce is with nanometer Si aN 4Powder, purity is not less than 99.5%.
5. method for preparing right 1 described nitride luminescent material is characterized in that: when luminescence center M is Eu, during y=2, technology is:
(1) be 5: 3 with molar ratio, 5: 4,1: 1,2: 3, the Ln and the Si of 3: 5 or 1: 2 placed electric arc furnace, carried out melting, the alloy Ln that makes when galvanic current is 70A～120A aSi bFully grind to form powder subsequently, wherein, a and b are alloy Ln aSi bThe variable of middle element Ln and Si.
(2) according to general formula Ln 1-xM x Y+Si 3N 5-3x+xyO 3x-xy, with Ln aSi b, Eu 2O 3And Si 3N 4According to molar ratio 1 - X a : X 2 : [ 1 - b 3 a ( 1 - X ) ] Place mortar; With alcohol is dispersion agent, fully grinds, to be mixed evenly after, oven dry, compressing tablet; Then the sheet sample is loaded in the graphite furnace, at 1～10 atmospheric N 2Protection down, with 1600～1800 ℃ of sintering 1～10 hour, furnace cooling.
6. by right 5 described nitride luminescent material preparation methods, it is characterized in that: raw material Ln, Si, Eu 2O 3With nanometer Si 3N 4Powder, purity is not less than 99.5%.
CNB2007101197746A 2007-07-31 2007-07-31 A kind of nitride luminescent material and preparation method thereof Expired - Fee Related CN100554370C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102660268A (en) * 2012-05-11 2012-09-12 北京晶创达科技有限公司 Method for preparing nitride phosphor by using oxides as raw materials, and nitride phosphor
CN104119906A (en) * 2013-04-26 2014-10-29 海洋王照明科技股份有限公司 Antimony terbium co-doped silicon nitride luminescent material and preparation method and application thereof
CN104140816A (en) * 2013-05-06 2014-11-12 海洋王照明科技股份有限公司 Samarium-doped rare-earth silicon nitride luminescent material and preparation method and application thereof
CN105647533A (en) * 2016-04-06 2016-06-08 江苏罗化新材料有限公司 Novel nitric oxide red phosphor and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102660268A (en) * 2012-05-11 2012-09-12 北京晶创达科技有限公司 Method for preparing nitride phosphor by using oxides as raw materials, and nitride phosphor
CN102660268B (en) * 2012-05-11 2014-11-19 北京晶创达科技有限公司 Method for preparing nitride phosphor by using oxides as raw materials, and nitride phosphor
CN104119906A (en) * 2013-04-26 2014-10-29 海洋王照明科技股份有限公司 Antimony terbium co-doped silicon nitride luminescent material and preparation method and application thereof
CN104140816A (en) * 2013-05-06 2014-11-12 海洋王照明科技股份有限公司 Samarium-doped rare-earth silicon nitride luminescent material and preparation method and application thereof
CN105647533A (en) * 2016-04-06 2016-06-08 江苏罗化新材料有限公司 Novel nitric oxide red phosphor and preparation method thereof
CN105647533B (en) * 2016-04-06 2017-09-29 江苏罗化新材料有限公司 A kind of nitrogen oxides red fluorescence powder and preparation method thereof

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