CN1702144A - Rare earth nano zincate red phosphor for semiconductor lighting device and its preparation method - Google Patents
Rare earth nano zincate red phosphor for semiconductor lighting device and its preparation method Download PDFInfo
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- CN1702144A CN1702144A CN 200510026705 CN200510026705A CN1702144A CN 1702144 A CN1702144 A CN 1702144A CN 200510026705 CN200510026705 CN 200510026705 CN 200510026705 A CN200510026705 A CN 200510026705A CN 1702144 A CN1702144 A CN 1702144A
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Abstract
The invention discloses a semiconductor-illuminating rare-earth zincate red fluorescent material and the method for preparation. LED using rare-earth red fluorescent material is composed of (M1)x (M2) yREzZnO2, M1 being Li, Na or K, and M2 being Mg, Ca or Ba, x=0-0.3, y=0.01-1, z=0-0.1, x+ y+ z= 1, RE being from Eu, Dy, Pr, Sm, and so on. The preparation condition is mild. It has strong absorption at 200-400 nm, counterchecking the outward of LED ultraviolet light, and improving energy efficiency, and has very strong excitative peak at 400-420 nm, main peak at 413 nm, and transmission peak at 600-620 nm, and main peak at 610, having strong luminous intensity, perfect color purity, and light-heat endurance, satisfying the requirement of LED-using fluorescent powder, and having potential application value in LED illumination material.
Description
Technical field
The present invention relates to a kind of rare earth luminescent material, relate to a kind of NUV (near ultraviolet) or purplish blue optical excitation LED (light emitting diode) rare-earth red fluorescent material and preparation method thereof specifically.
Background technology
Energy-conservation and environmental protection is the two principal themes of green illumination.Present widely used electricity-saving lamp light efficiency is about 70lm/w, and fluorescent material needs mercuryvapour as working gas, contaminate environment.
Therefore, research and develop novelly, eco-friendly LED white-light illuminating technology and corresponding luminescent material thereof have become main direction in recent years.White light LEDs has the advantage of energy-conserving and environment-protective, and light efficiency can reach 200lm/w in theory, be considered to extremely rising the 4th generation lighting source.Ri Ya chemical company took the lead in technical breakthrough of blue GaN LED and very fast industrialization in 1993, and then realized White-light LED illumination in 1996.Up to the present, the light efficiency of LED white-light illuminating only has 30lm/w, and except chip and encapsulation technology factor, luminescent material is the not high major reason of light efficiency.Wherein, the influence of red light-emitting material is particularly evident.
The ultimate principle of white light LEDs and scheme:
According to luminescence and colorimetry principle, realize that white light LEDs mainly contains three kinds of schemes: 1. the blue led chip with can be combined the composition white light LEDs by the gold-tinted fluorescent material that blue light effectively excites.Part blue light is absorbed by fluorescent material, excitated fluorescent powder emission gold-tinted; The white light that the gold-tinted of emission and remaining blue light can obtain corresponding colour temperature.2. as the trichromatic energy saving lamp, the led chip of emission NUV or royal purple light with can effectively be excited and launch the red, green, blue three primary colors fluorescent powder by NUV or royal purple light and organically combine and form white light LEDs.3. red, green, blue three-primary color LED chip or luminotron are assembled into a pixel (pixel), realize white light.
Because aspects such as luminous efficiency, purity of color, second kind of scheme has more using value and development potentiality.With in the luminescent material, red fluorescence powder mainly adopts Y at the LED that is studied in recent years
2O
2S:Eu
3+, because aspect, Y such as poor stability, luminous efficiency be low
2O
2S:Eu
3+There is significant disadvantages.And red fluorescence powder has become the bottleneck of LED with fluorescent material and even white light LEDs development.Researching and developing new and effective red fluorescence powder has become the important goal of LED lighting engineering.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of rare earth nano zincate red phosphor for semiconductor lighting device and preparation method thereof, to overcome the defective that prior art exists.
Rare-earth red fluorescent material of the present invention, its composition is represented by following general formula: (M1)
x(M2)
yRE
zZnO
2
Wherein:
M1 represents lithium, sodium or potassium;
M2 represents magnesium, calcium, strontium or barium;
RE represents Eu, Dy, Pr, Sm.
x＝0～0.3，y＝0.01～1，z＝0～0.03，x+y+z＝1；
Preferred L 1 is a lithium, and preferred L 2 is a strontium;
Preferred x=0.1～0.3, y=0.5～1, z=0.01～0.03;
Under above-mentioned preferred condition, rare-earth red fluorescent material of the present invention has better illumination effect.
Preparation method of the present invention comprises the steps:
Nitrate, Zn (NO with magnesium, calcium, strontium or barium
3)
2, luminescent activator, alkali-metal nitrate and citric acid dissolving mix, to neutral, heating evaporation moisture is 4～5 hours then with ammoniacal liquor regulator solution pH, obtain gel, oven dry obtains presoma, presoma 500～1000 ℃ of following thermal treatments 1～4 hour, is promptly obtained product.
Said luminescent activator is selected from the nitrate of Eu, Dy, Pr or Sm;
Said basic metal is selected from lithium, sodium or potassium;
The add-on of the nitrate of magnesium, calcium, strontium or barium is 89% of a benchmark with the zinc nitrate molar weight;
The add-on of luminescent activator is 1% of a benchmark with the zinc nitrate molar weight;
The add-on of alkali-metal nitrate is 10% of a benchmark with the zinc nitrate molar weight;
Citric acid is excessive to be good;
According to preparation method of the present invention, preferably add metal nitrate with stoichiometry.
In fluorescent material of the present invention, rare earth ion RE is as luminescent activator, and zincate is as matrix, and basic metal is as the charge compensation agent.The matrix zincate has very strong absorption in NUV district and purple blue light region, RE also has strong excitation peak in this zone, after the RE ion enters the case of zincate, the generation transmission ofenergy has increased the absorption about 400nm, cause this fluorescent material about 400nm, to have well and excite, thereby meet the requirement that excites that LED uses.
Among the present invention, mix alkalimetal ion after, fluorescence intensity has strengthened 3 times.
In preparation process of the present invention, add metal nitrate with stoichiometry, purpose can not introduced foreign ion.Metal nitrate is dissolved in water on the one hand, and nitrate ion can react with citric acid and decompose easily on the other hand, thereby can remove this ion easily.
What adopt in the present invention is the citric acid sol-gel method, and this kind method reaction conditions is relatively gentleer, and sintering temperature is lower than the high temperature solid-state method.In this method kind, the effect of citric acid may be as follows: one is the chelating of citric acid and reactant metal ion, and another is the redox reaction of citrate ion and nitrate ion.The implication of excessive citric acid is the good complexation of metal ions of adding of citric acid, and can be fully with system in the nitrate ion reaction, remove nitrate ion.
The present invention adopts citric acid-sol gel process, under comparatively gentle condition, has made superfine fluorescent powder, and this fluorescent material has very strong absorption at 200～400nm, can stop that the UV-light of LED leaks, and can improve energy efficiency on the other hand on the one hand.This luminescent material has very intensive excitation peak at the 400-420nm place, main peak is at 413nm, emission peak is 600-620nm, main peak is at 610nm, luminous intensity is good, and good purity of color is arranged, and very high photo and thermal stability is arranged, meet the requirement of LED, great potential using value is arranged in the LED an illuminating material with fluorescent material.
Description of drawings
Fig. 1 is the fluorescence spectrum figure of sample.
Fig. 2 is the XRD of sample.
Fig. 3 is the uv-visible absorption spectra figure of fluor.
Embodiment 1
With 10mL 0.5mol/LSr (NO
3)
2, 10mL 0.5mol/LZn (NO
3)
2, and 6.3042g citric acid stirring and dissolving be mixed, with ammoniacal liquor regulator solution pH to neutral.Be put in 80 ℃ of water-baths transpiring moisture then 4 hours, and made solution form gel, put into 110 ℃ of baking ovens subsequently 12 hours, form xerogel.Again presoma is put into retort furnace,, handled 2 hours in 1000 ℃ again, treat that temperature reduces to room temperature, promptly obtain product in 500 ℃ of pre-burnings 1 hour.
Embodiment 2
With 10mL 0.5mol/LMg (NO
3)
2, 10mL 0.5mol/LZn (NO
3)
2, and 6.3042g citric acid stirring and dissolving be mixed, with ammoniacal liquor regulator solution pH to neutral.Be put in 80 ℃ of water-baths transpiring moisture then 5 hours, and made solution form gel, put into 110 ℃ of baking ovens subsequently 12 hours, form xerogel.Again presoma is put into retort furnace,, handled 2 hours in 1000 ℃ again, treat that temperature reduces to room temperature, promptly obtain product in 500 ℃ of pre-burnings 1 hour.
Embodiment 3
With 10mL 0.5mol/LCa (NO
3)
2, 10mL 0.5mol/LZn (NO
3)
2, and 6.3042g citric acid stirring and dissolving be mixed, with ammoniacal liquor regulator solution pH to neutral.Be put in 80 ℃ of water-baths transpiring moisture then 4 hours, and made solution form gel, put into 110 ℃ of baking ovens subsequently 12 hours, form xerogel.Again presoma is put into retort furnace,, handled 2 hours in 1000 ℃ again, treat that temperature reduces to room temperature, promptly obtain product in 500 ℃ of pre-burnings 1 hour.
Embodiment 4
With 10mL 0.5mol/LBa (NO
3)
2, 10mL 0.5mol/LZn (NO
3)
2, and 6.3042g citric acid stirring and dissolving be mixed, with ammoniacal liquor regulator solution pH to neutral.Be put in 80 ℃ of water-baths transpiring moisture then 4 hours, and made solution form gel, put into 110 ℃ of baking ovens subsequently 12 hours, form xerogel.Again presoma is put into retort furnace,, handled 2 hours in 1000 ℃ again, treat that temperature reduces to room temperature, promptly obtain product in 500 ℃ of pre-burnings 1 hour.
Embodiment 5
With 9mL 0.5mol/LSr (NO
3)
2, 10mL 0.5mol/LZn (NO
3)
2, 1mL 0.05mol/LSm (NO
3)
3Be mixed with 6.3357g citric acid stirring and dissolving, extremely neutral with ammoniacal liquor regulator solution pH.Be put into then in 80 ℃ of water-baths and evaporated 4～5 hours, make solution form gel, put into 110 ℃ of baking ovens subsequently 12 hours, form xerogel.Again presoma is put into retort furnace,, handled 2 hours in 1000 ℃ again, treat that temperature reduces to room temperature, promptly obtain product in 500 ℃ of pre-burnings 1 hour.
Embodiment 6
With 9mL 0.5mol/LSr (NO
3)
2, 10mL 0.5mol/LZn (NO
3)
2, 1mL 0.05mol/LEu (NO
3)
3Be mixed with 6.3357g citric acid stirring and dissolving, extremely neutral with ammoniacal liquor regulator solution pH.Be put into then in 80 ℃ of water-baths and evaporated 4～5 hours, make solution form gel, put into 110 ℃ of baking ovens subsequently 12 hours, form xerogel.Again presoma is put into retort furnace,, handled 2 hours in 1000 ℃ again, treat that temperature reduces to room temperature, promptly obtain product in 500 ℃ of pre-burnings 1 hour.
Embodiment 7
With 9mL 0.5mol/LSr (NO
3)
2, 10mL 0.5mol/LZn (NO
3)
2, 1mL 0.05mol/LDy (NO
3)
3Be mixed with 6.3357g citric acid stirring and dissolving, extremely neutral with ammoniacal liquor regulator solution pH.Be put into then in 80 ℃ of water-baths and evaporated 4.5 hours, make solution form gel, put into 110 ℃ of baking ovens subsequently 12 hours, form xerogel.Again presoma is put into retort furnace,, handled 2 hours in 1000 ℃ again, treat that temperature reduces to room temperature, promptly obtain product in 500 ℃ of pre-burnings 1 hour.
Embodiment 8
With 9mL 0.5mol/LSr (NO
3)
2, 10mL 0.5mol/LZn (NO
3)
2, 1mL 0.05mol/LPr (NO
3)
3Be mixed with 6.3357g citric acid stirring and dissolving, extremely neutral with ammoniacal liquor regulator solution pH.Be put into then in 80 ℃ of water-baths and evaporated 4～5 hours, make solution form gel, put into 110 ℃ of baking ovens subsequently 12 hours, form xerogel.Again presoma is put into retort furnace,, handled 2 hours in 1000 ℃ again, treat that temperature reduces to room temperature, promptly obtain product in 500 ℃ of pre-burnings 1 hour.
Embodiment 9
With 9mL 0.5mol/LSr (NO
3)
2, 10mL 0.5mol/LZn (NO
3)
2, 1mL 0.05mol/LSm (NO
3)
3, 0.0425gNaNO
3Be mixed with 6.3357g citric acid stirring and dissolving, extremely neutral with ammoniacal liquor regulator solution pH.Be put into then in 80 ℃ of water-baths and evaporated 4 hours, make solution form gel, put into 110 ℃ of baking ovens subsequently 12 hours, form xerogel.Again presoma is put into retort furnace,, handled 2 hours in 1000 ℃ again, treat that temperature reduces to room temperature, promptly obtain product in 500 ℃ of pre-burnings 1 hour.
Embodiment 10
With 9mL 0.5mol/L Sr (NO
3)
2, 10mL 0.5mol/LZn (NO
3)
2, 1mL 0.05mol/LSm (NO
3)
3, 0.0506gKNO
3Be mixed with 6.6509g citric acid stirring and dissolving, extremely neutral with ammoniacal liquor regulator solution pH.Be put into then in 80 ℃ of water-baths and evaporated 4～5 hours, make solution form gel, put into 110 ℃ of baking ovens subsequently 12 hours, form xerogel.Again presoma is put into retort furnace,, handled 2 hours in 1000 ℃ again, treat that temperature reduces to room temperature, promptly obtain product in 500 ℃ of pre-burnings 1 hour.
Embodiment 11
With 9mL 0.5mol/L Sr (NO
3)
2, 10mL 0.5mol/LZn (NO
3)
2, 1mL 0.05mol/LSm (NO
3)
3, 0.0345gLiNO
3Be mixed with 6.6509g citric acid stirring and dissolving, extremely neutral with ammoniacal liquor regulator solution pH.Be put into then in 80 ℃ of water-baths and evaporated 5 hours, make solution form gel, put into 110 ℃ of baking ovens subsequently 12 hours, form xerogel.Again presoma is put into retort furnace,, handled 2 hours in 1000 ℃ again, treat that temperature reduces to room temperature, promptly obtain product in 500 ℃ of pre-burnings 1 hour.
The fluorescence spectrum figure of sample sees Fig. 1.The XRD of sample (X-ray diffractogram) sees among Fig. 2 figure: a:SrZnO
2, b:SrZnO
2: Sm, c:SrZnO
2: Sm, Li).The uv-visible absorption spectra figure of fluor sees Fig. 3.
Claims (7)
1. a rare earth nano zincate red phosphor for semiconductor lighting device is characterized in that, its composition is represented by following general formula:
(M1)
x(M2)
yRE
zZnO
2；
Wherein:
M1 represents lithium, sodium or potassium;
M2 represents magnesium, calcium, strontium or barium;
RE represents Eu, Dy, Pr, Sm.
x＝0～0.3，y＝0.01～1，z＝0～0.03，x+y+z＝1。
2. rare-earth red fluorescent material according to claim 1 is characterized in that, M1 is a lithium, and M2 is a strontium; RE is Sm.
x＝0.1～0.3，y＝0.5～1，z＝0.01～0.03。
3. the preparation method of rare-earth red fluorescent material according to claim 1 and 2 is characterized in that, comprises the steps:
Nitrate, Zn (NO with magnesium, calcium, strontium or barium
3)
2, luminescent activator, alkali-metal nitrate and citric acid dissolving mix, regulator solution pH is to neutral, heating evaporation moisture obtains gel then, oven dry obtains presoma, and presoma 500～1000 ℃ of following thermal treatments, is promptly obtained product;
Said luminescent activator is selected from the nitrate of Eu, Dy, Pr or Sm;
Said basic metal is selected from lithium, sodium or potassium;
The add-on of the nitrate of magnesium, calcium, strontium or barium is 89% of a benchmark with the zinc nitrate molar weight;
The add-on of luminescent activator is 1% of a benchmark with the zinc nitrate molar weight;
The add-on of alkali-metal nitrate is 10% of a benchmark with the zinc nitrate molar weight.
4. method according to claim 3 is characterized in that citric acid is excessive.
5. method according to claim 3 is characterized in that, adds each metal nitrate with stoichiometry.
6. method according to claim 3 is characterized in that, and is extremely neutral with ammoniacal liquor regulator solution pH.
7. method according to claim 3 is characterized in that, with presoma 500～1000 ℃ of following thermal treatments 1～4 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690654A (en) * | 2012-06-06 | 2012-09-26 | 大连海事大学 | High-efficiency up-conversion emission phosphor and preparation method thereof |
| CN106893583A (en) * | 2017-02-23 | 2017-06-27 | 中国计量大学 | A kind of zincate green emitting phosphor and preparation method thereof |
-
2005
- 2005-06-13 CN CN 200510026705 patent/CN1290965C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690654A (en) * | 2012-06-06 | 2012-09-26 | 大连海事大学 | High-efficiency up-conversion emission phosphor and preparation method thereof |
| CN106893583A (en) * | 2017-02-23 | 2017-06-27 | 中国计量大学 | A kind of zincate green emitting phosphor and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1290965C (en) | 2006-12-20 |
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Granted publication date: 20061220 Termination date: 20100613 |