CN1919968A - Erbium activated alkaline-earth rare-earth sulfide red luminescent material - Google Patents

Erbium activated alkaline-earth rare-earth sulfide red luminescent material Download PDF

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CN1919968A
CN1919968A CNA2006100322693A CN200610032269A CN1919968A CN 1919968 A CN1919968 A CN 1919968A CN A2006100322693 A CNA2006100322693 A CN A2006100322693A CN 200610032269 A CN200610032269 A CN 200610032269A CN 1919968 A CN1919968 A CN 1919968A
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earth
rare
luminescent material
solution
illuminating material
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廉世勋
田科明
尹笃林
李承志
朱爱玲
刘利民
曾立华
张华京
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Hunan Normal University
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Hunan Normal University
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Abstract

The invention relates the red luminescent material and preparing method. The component general formula is as follows: M1-xM'xY2S4: Er3+(M, M'=Ca, Sr, Ba):yEr, zRE', where RE' is La, Ce, Pr, Nd, Sm, Eu, Gd Tb, Dy, Ho, Tm, Yb, or Lu. The maximum excitation wave length is between 250-400nm, the maximum emission wavelength is 672nm. The method is back titrating method at room temperature, dipping the cation solution into precipitant solution. Dry the precipitum below 80Deg.C, grind them, and get precursor body. Calcine the precursor body with CS2 carried by nitrogen or argon gas at 1050Deg.C, and get the product. The red luminescent material has high color purity, and it can be used to make displaying and illuminating devices.

Description

Erbium activated alkaline-earth rare-earth sulfide red luminescent material
Technical field the invention belongs to the luminescent material technical field, is alkaline-earth rare-earth sulfide red luminescent material and manufacture method and application about the rare earth erbium ion doping.
Background technology is present, has been found that multiple red illuminating material.Eu 2+Activated alkaline earth sulfide CaS is the broadband emission red light fluorescent powder of a kind of main peak at 645nm; Eu 2+Activated strontium aluminium composite sulfur oxide compound is the broadband emission red fluorescence powder of a kind of main peak at nm; Eu 3+Or Sm 3+Rare earth oxide (the Y of ion doping 2O 3), oxysulfide (Y 2O 2S), system such as vanadate and phosphoric acid salt has the narrowband emission red fluorescence powder of main peak at 618nm; The titanates of alkali-earth metals system.Pr 3+Activated titanates of alkali-earth metals MTiO 3(M=Ca, Sr, Ba) is a kind of red illuminating material of stable performance.Though first three luminescent material of planting system all has good red long-afterglow character, perishable and emit foul smell in malaria because of sulphurous materials, application is restricted.Eu 2+, Mn 2+Deng activated alkaline-earth rare-earth ternary sulfide MB 2S 4(M=Ca, Sr, Ba; B=La Y) also is a class red fluorescence powder.These red fluorescence powders have been applied to fields such as trichromoscope, LED, material of infrared window.
But the red fluorescence powder research field is useless so far to be addressed the problem: the emission main peak is good greater than 660nm and monochromaticity.Eu 2+, Mn 2+Though adulterated fluorescent material emission wavelength grows (emission wavelength is generally greater than 630nm) but bands of a spectrum are wide, monochromaticity is poor; Eu 3+, Sm 3+, Pr 3+Though activated fluorescent material bands of a spectrum are narrow, monochromaticity good but emissive wavelength bands (emission wavelength is generally less than 620nm).So bands of a spectrum are narrow, monochromaticity good but the red fluorescence powder of emission wavelength long (emission wavelength is generally greater than 630nm) is to have using value.Document did not appear in the newspapers in the past.
Alkaline-earth rare-earth ternary sulfide MB 2S 4Have broad the forbidden band energy gap (23～3.6eV), be a kind of suitable luminescent material matrix.The present invention finds Er 2+Activated alkaline-earth rare-earth ternary sulfide (MB 2S 4) be that a kind of bands of a spectrum are narrow, monochromaticity good, the long red fluorescence powder of transmitted wave.MY 2S 4: Er 2+Fluorescent material has potential to be worth in field emission display (Field Emission Display is called for short FED).
Adopt traditional high temperature solid-state method at H 2Synthetic alkaline earth rare-earth ternary sulfide (MB under the S atmospheric condition 2S 4) need react 3～4 days down at 1000～1100 ℃, the actual application value of this synthetic method is little.Synthetic method with application prospect should possess two basic conditions: one, and synthesis temperature is lower; Its two, the reaction times is shorter.Select softening method can synthesize size of particles sub-micro or nano-phosphor, widen its range of application.The present invention adopts novel method to synthesize submicron Er 2+Activated alkaline-earth rare-earth ternary sulfide (MB 2S 4) fluorescent material.
Summary of the invention technical problem to be solved by this invention is at above-mentioned weak point of the prior art, and a kind of round-the-clock stable alkaline-earth rare-earth ternary sulfide red illuminating material and synthetic method and methods for using them thereof are provided; This class luminescent material has the character that absorbs UV-light zone red-emitting at 250～4000nm.
The technical scheme that solution the technology of the present invention problem is adopted is that the raw materials used composition general formula of this red illuminating material is:
M 1-xM′ xY 2S 4:Er 3+(M，M′＝Ca，Sr，Ba):yEr，zRE′
Wherein: RE '=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, one or both among the Lu.
0≤x≤1，0＜y≤0.005，0＜z≤0.005
Its maximum excitation wavelength is at 250～400nm and 420～550nm, and maximum emission wavelength is in the 672nm zone.
The present invention has following characteristics:
1, the present invention is a kind of rare earth Er 3+Ion-activated alkaline-earth rare-earth ternary sulfide red illuminating material.
2, the red illuminating material chemical constitution characteristics of indication of the present invention are that alkaline-earth rare-earth sulfide is matrix, Er 3+Be activator, other rare earth ion is a coactivator.
3, the red illuminating material of indication of the present invention has significant characteristic: near the ultraviolet region of excitation wavelength 330nm and the blue green light district of 560nm annex, excitation spectrum has very strong emission at scarlet zone 672nm.
The red illuminating material synthetic method of indication of the present invention is:
One, batching
Press M 1-xM ' xY 2S 4: Er 3+(M, M '=Ca, Sr, Ba): yEr, zRE ' metering is than taking by weighing Y 2O 3, Er 2O 3With Y 2O 3, Er 2O 3Be dissolved in excessive a little dense HNO 3In deionized water, and the heating suspension liquid is to improve the dissolution rate of oxide compound.The HNO of evaporating surplus on electric furnace 3, remix CaCO 3, Sr (NO 3) 2, Ba (NO 3) 2, be made into the cationic solution of the mixed nitrate of different concns, with Y (NO 3) 3Calculating concentration is 0.5mol/L.At room temperature use the back titration method, with (the NH of desired concn 4) 2CO 3Solution precipitator is put into three-necked flask, under the magnetic agitation effect, the cationic solution that is contained in the separating funnel is splashed into the speed of 2.5～3.0ml/min, and observes the adularescent precipitation and generate.Titration is used the B decompress filter after finishing.With pure water washing 2 times to remove byproduct of reaction, again with absolute ethanol washing 2 times to prevent in drying course, producing serious reunion.Dry being lower than under 80 ℃ the temperature, grind evenly a little.
Two, synthetic
With the presoma numbering, place porcelain boat, put into the electric tube furnace that is rapidly heated.Earlier logical nitrogen is warmed up to 800 ℃ so that catch up with most air, feeds the CS that carries do carrier gas with nitrogen then 2, the flow velocity of nitrogen is 8～10ml/min, at 1050 ℃ of calcining 4h, is cooled to 600 ℃ and stops logical CS 2, but keeping logical nitrogen to 400 ℃, normal temperature takes out a little down and grinds evenly, promptly gets sample.
Description of drawings
Fig. 1 SrY 1.8S 4: the excitation spectrum of 0.2Er and emmission spectrum
Fig. 2 BaY 1.8S 4: the excitation spectrum of 0.2Er and emmission spectrum
Fig. 3 Sr 0.997Ca 0.003Y 1.8S 4: the emmission spectrum of 0.2Er
Fig. 4 Ba 0.999Y 1.9S 4: 0.1Er, the excitation spectrum of 0.001Eu and emmission spectrum
Embodiment
Example 1 SrY 1.8S 4: 0.2Er red fluorescence powder (A)
Press SrY 1.8S 4: 20%Er measures than taking by weighing 203.22gY 2O 3, 38.25gEr 2O 3With Y 2O 3, Er 2O 3Be dissolved in excessive a little dense HNO 3In deionized water, and the heating suspension liquid is to improve the dissolution rate of oxide compound.The HNO of evaporating surplus on electric furnace 3, remix 211.6gSr (NO 3) 2, with Y (NO 3) 3Calculating concentration is the cationic solution that 0.5mol/L is made into mixed nitrate.Will be as the 333.75gNH of precipitation agent 2CH 2COOH is made into 2mol/l solution.NH 2CH 2COOH solution is put into three-necked flask, under the magnetic agitation effect, the cationic solution that is contained in the separating funnel is splashed into the speed of 2.5～3.0ml/min.Titration is used the B decompress filter after finishing.With pure water washing 2 times, absolute ethanol washing 2 times.Dry being lower than under 80 ℃ the temperature, grind evenly, obtain presoma.
With the presoma numbering, place porcelain boat, put into the electric tube furnace that is rapidly heated.Earlier logical nitrogen is warmed up to 800 ℃ so that catch up with most air, feeds the CS that carries do carrier gas with nitrogen then 2, the flow velocity of nitrogen is 8～10ml/min, at 1050 ℃ of calcining 4h, is cooled to 600 ℃ and stops logical CS 2, but keeping logical nitrogen to 400 ℃, normal temperature takes out a little down and grinds evenly, promptly gets fluorescent material SrY 1.8S 4: 0.2Er.Excitation spectrum and emmission spectrum are as shown in Figure 1.
Example 2 BaY 1.8S 4: 0.2Er red fluorescence powder (B)
Press SrY 1.8S 4: 20%Er measures than taking by weighing 203.22g Y 2O 3, 38.25g Er 2O 3With Y 2O 3, Er 2O 3Be dissolved in excessive a little dense HNO 3In deionized water, and the heating suspension liquid is to improve the dissolution rate of oxide compound.The HNO of evaporating surplus on electric furnace 3, remix 261g Ba (NO 3) 2, with Y (NO 3) 3Calculating concentration is the cationic solution that 0.5mol/L is made into mixed nitrate.Will be as the 333.75gNH of precipitation agent 2CH 2COOH is made into 2mol/l solution.NH 2CH 2COOH solution is put into three-necked flask, under the magnetic agitation effect, the cationic solution that is contained in the separating funnel is splashed into the speed of 2.5～3.0ml/min.Titration is used the B decompress filter after finishing.With pure water washing 2 times, absolute ethanol washing 2 times.Dry being lower than under 80 ℃ the temperature, grind evenly, obtain presoma.
With the presoma numbering, place porcelain boat, put into the electric tube furnace that is rapidly heated.Earlier logical nitrogen is warmed up to 800 ℃ so that catch up with most air, feeds the CS that carries do carrier gas with nitrogen then 2, the flow velocity of nitrogen is 8～10ml/min, at 1050 ℃ of calcining 4h, is cooled to 600 ℃ and stops logical CS 2, but keeping logical nitrogen to 400 ℃, normal temperature takes out a little down and grinds evenly, promptly gets fluorescent material BaY 1.8S 4: 0.2Er.Excitation spectrum and emmission spectrum are as shown in Figure 2.
Example 3 Sr 0.997Ca 0.003Y 1.8S 4: 0.2Er red fluorescence powder (C)
Press Sr 0.997Ca 0.003Y 1.8S 4: 0.2Er measures than taking by weighing 203.22g Y 2O 3, 38.25g Er 2O 3, 0.3gCaCO 3With Y 2O 3, Er 2O 3And CaCO 3Be dissolved in excessive a little dense HNO 3In deionized water, and the heating suspension liquid is to improve the dissolution rate of oxide compound.The HNO of evaporating surplus on electric furnace 3, remix 211g б Ba (NO 3) 2, with Y (NO 3) 3Calculating concentration is the cationic solution that 0.5mol/L is made into mixed nitrate.Will be as the 333.75g NH of precipitation agent 2CH 2COOH is made into 2mol/L solution.NH 2CH 2COOH solution is put into three-necked flask, under the magnetic agitation effect, the cationic solution that is contained in the separating funnel is splashed into the speed of 2.5～3.0ml/min.Titration is used the B decompress filter after finishing.With pure water washing 2 times, absolute ethanol washing 2 times.Dry being lower than under 80 ℃ the temperature, grind evenly, obtain presoma.With the presoma numbering, place porcelain boat, put into the electric tube furnace that is rapidly heated.Earlier logical nitrogen is warmed up to 800 ℃ so that catch up with most air, feeds the CS that carries do carrier gas with nitrogen then 2, the flow velocity of nitrogen is 8～10ml/min, at 1050 ℃ of calcining 4h, is cooled to 600 ℃ and stops logical CS 2, but keeping logical nitrogen to 400 ℃, normal temperature takes out a little down and grinds evenly, promptly gets fluorescent material Sr 0.997Ca 0.003Y 1.8S 4: 0.2Er.Excitation spectrum and emmission spectrum are as shown in Figure 3.
Example 4 Ba 0.999Y 1.9S 4: 0.1Er, 0.001Eu red fluorescence powder
Press Sr 0.997Ca 0.003Y 1.9S 4: 0.1Er, 0.001Eu measures than taking by weighing 214.51gY 2O 3, 19.13gEr 2O 3, 0.176g Eu 2O 3With Y 2O 3, Er 2O 3And Eu 2O 3Be dissolved in excessive a little dense HNO 3In deionized water, and the heating suspension liquid is to improve the dissolution rate of oxide compound.The HNO of evaporating surplus on electric furnace 3, remix 260.7g Ba (NO 3) 2, with Y (NO 3) 3Calculating concentration is the cationic solution that 0.5mol/L is made into mixed nitrate.Will be as the 333.75g NH of precipitation agent 2CH 2COOH is made into 2mol/L solution.NH 2CH 2COOH solution is put into three-necked flask, under the magnetic agitation effect, the cationic solution that is contained in the separating funnel is splashed into the speed of 2.5～3.0ml/min.Titration is used the B decompress filter after finishing.With pure water washing 2 times, absolute ethanol washing 2 times.Dry being lower than under 80 ℃ the temperature, grind evenly, obtain presoma.With the presoma numbering, place porcelain boat, put into the electric tube furnace that is rapidly heated.Earlier logical nitrogen is warmed up to 800 ℃ so that catch up with most air, feeds the CS that carries do carrier gas with nitrogen then 2, the flow velocity of nitrogen is 8～10ml/min, at 1050 ℃ of calcining 4h, is cooled to 600 ℃ and stops logical CS 2, but keeping logical nitrogen to 400 ℃, normal temperature takes out a little down and grinds evenly, promptly gets fluorescent material Ba 0.999Y 1.9S 4: 0.1Er, 0.001Eu.Excitation spectrum and emmission spectrum are as shown in Figure 4.

Claims (4)

1, a kind of red illuminating material is characterized in that being is matrix, rare earth ion Er with the alkaline-earth rare-earth ternary sulfide 3+With other metal ions be coactivator, it is formed general formula and is:
M 1-xM′ xY 2S 4:Er 3+(M，M′＝Ca，Sr，Ba):yEr，zRE′
Wherein: RE '=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, one or both among the Lu.
0≤x≤1，0＜y≤0.005，0＜z≤0.005
2, red illuminating material according to claim 1 is characterized in that its maximum excitation wavelength at 250～400nm and 420～550nm, and maximum emission wavelength is at 672nm.
3, a kind ofly be used to make the described red illuminating material method of claim 1, it is characterized in that at room temperature using the back titration method, the precipitation agent (NH of desired concn 4) 2CO 3Solution is put into flask, under continuous stirring action, the speed of cationic solution with 2.5～3.0ml/min is splashed into, until precipitation fully.After titration finished, decompress filter with pure water washing 2 times, was used absolute ethanol washing 2 times again.Throw out is dried being lower than under 80 ℃ the temperature, grinds and evenly obtains presoma.Presoma is placed porcelain boat, put into the electric tube furnace that is rapidly heated.The CS that carries do carrier gas with nitrogen or argon gas 2At 1050 ℃ of calcining 4h, be cooled to normal temperature, take out and grind, promptly get product.
4, a kind of application rights requires the method for 1 described red illuminating material, it is characterized in that being used for making showing and illuminating device.
CNA2006100322693A 2006-09-19 2006-09-19 Erbium activated alkaline-earth rare-earth sulfide red luminescent material Pending CN1919968A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108998028A (en) * 2018-08-29 2018-12-14 东台市天源光电科技有限公司 A kind of sulfide green emitting phosphor and preparation method thereof and light emitting device using the fluorescent powder
WO2022052279A1 (en) 2020-09-14 2022-03-17 大连民族大学 Polysulfide up-conversion luminescent material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108998028A (en) * 2018-08-29 2018-12-14 东台市天源光电科技有限公司 A kind of sulfide green emitting phosphor and preparation method thereof and light emitting device using the fluorescent powder
WO2022052279A1 (en) 2020-09-14 2022-03-17 大连民族大学 Polysulfide up-conversion luminescent material

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Open date: 20070228