CN102690659B - Orange red fluorescent powder for LED (Light Emitting Diode) and preparation method thereof - Google Patents
Orange red fluorescent powder for LED (Light Emitting Diode) and preparation method thereof Download PDFInfo
- Publication number
- CN102690659B CN102690659B CN2012101856458A CN201210185645A CN102690659B CN 102690659 B CN102690659 B CN 102690659B CN 2012101856458 A CN2012101856458 A CN 2012101856458A CN 201210185645 A CN201210185645 A CN 201210185645A CN 102690659 B CN102690659 B CN 102690659B
- Authority
- CN
- China
- Prior art keywords
- led
- fluorescent powder
- orange red
- red fluorescent
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention discloses orange red fluorescent powder for an LED (Light Emitting Diode), which is tervalent samarium activated tellurate fluorescent powder and has a chemical formula of (Ma-2xSmxAx)TebOc, wherein M is at least one of Ca, Sr and Ba; A is at least one of Li, Na and K; a is more than or equal to 1 but less than or equal to 3; b is more than or equal to 1 but less than or equal to 4; c is more than or equal to 3 but less than or equal to 11; and x is more than 0 but less than 0.1. The invention also discloses a preparation method for the compound, which comprises the following steps of: uniformly milling and mixing monomers, compounds or corresponding salts of M, Te and Sm and the compounds or corresponding salts of A; roasting at high temperature; and smashing, cleaning, removing impurities, and drying, and then processing, thereby obtaining the orange red fluorescent powder for the LED. The orange red fluorescent powder has the characteristics of wide excitation wavelength range, high efficiency, stability, and the like; the preparation method is simple; no pollution is caused; the cost is low; and the orange red fluorescent powder can be used for manufacturing a white light LED by using a purple light or ultraviolet light LED chip.
Description
Technical field
The present invention relates to a kind of orange red fluorescent powder and preparation method thereof, be particularly useful for orange red fluorescent powder of LED and preparation method thereof, belong to rare earth luminescent material technical field.
Background technology
20th century the nineties, along with high brightness GaN blue led makes a breakthrough technically, within 1996, occurred with blue led and YAG fluorescent material ((Y, Gd)
3al
5o
12: Ce
3+) white light LEDs that combines, this is considered to mankind's leap again after incandescent light, luminescent lamp on history of throwing light on, and is one of the high-tech sector of tool development prospect of 21 century.Adopt fluorescent material to produce white light and have three kinds of modes: blue-light LED chip coordinates yellow fluorescent powder; Blue-light LED chip coordinates red, green emitting phosphor; The UV-LED chip coordinates the red, green, blue three primary colors fluorescent powder.At present commercial is mainly the single-chip type high-brightness white-light LED that the gold-tinted of blue led chip and YAG fluorescent material combines, but this product application himself inherent defect occurs in general illuminated field credit union: because lacking ruddiness, cause color developing bad, can add therein red fluorescence powder to obtain high colour rendering index.Another trend is that purple light or ultraviolet leds chip coordinate red, green, blue three primary colors fluorescent powder mode, and it has more vast potential for future development, and this is that colour temperature is mated arbitrarily in 2500～10000K scope because the color developing of this mode is better.But, in prior art, for some shortage ruddiness composition of fluorescent material of white light LEDs, or red light emitting phosphor efficiency is not high, or unstable, as several sulfide red fluorescent material of U.S. Pat 6252254 reports.The white light LEDs colour rendering index that prior art encapsulates out is not high or efficiency is not high or unstable properties.Therefore the LED of development of new becomes the focus of domestic and international research with redness or orange red fluorescent powder.
Summary of the invention
The purpose of this invention is to provide a kind of can being excited by purple light or ultraviolet leds, there is good luminous characteristic and physical and chemical performance, orange red fluorescent powder for LED that manufacturing process is simple, pollution-free, cost is low and preparation method thereof, to overcome problems of the prior art.
For achieving the above object, the present invention takes following technical scheme:
Orange red fluorescent powder for LED of the present invention is the tellurate fluorescent material that samaric activates, and its chemical expression is (M
a-2xsm
xa
x) Te
bo
c.Wherein M is at least one in Ca, Sr, Ba, and A is at least one in Li, Na, K; 1≤a≤3; 1≤b≤4; 3≤c≤11; 0<x<0.1.
The preparation method of the orange red fluorescent powder for LED of the present invention comprises the following steps:
(1) with metal or compound or salt containing M, containing metal or compound or the salt of Te, containing metal or compound or the salt of Sm, compound or salt containing A are that raw material is raw material, and a mole proportioning of expressing requirement by above-mentioned chemical formula takes corresponding described raw material, and porphyrize, mix;
(2) by the mixture of step (1) in air in 600 ~ 800 ℃ of lower roastings once or twice, each cooling rear mill of roasting is mixed even, then carries out roasting next time; Each roasting time is 0.5 ~ 15 hour;
(3) removal of impurities, oven dry are pulverized, cleaned to product of roasting step (2) obtained, must be for the LED orange red fluorescent powder.
In the present invention, said compound or salt containing M, can be oxide compound, carbonate, nitrate or the organic acid salt containing M.Said compound or salt containing Te can be oxide compound, carbonate, nitrate or the organic acid salts containing Te.Said compound or salt containing A can be carbonate, nitrate or the organic acid salts containing A.Said compound or salt containing Sm can be oxide compound, carbonate, nitrate or the organic acid salts containing Sm.
In above-mentioned steps (1), grinding can be carried out in the solution such as ethanol, acetone.
In above-mentioned steps (3), said pulverizing can adopt physics fragmentation or comminution by gas stream, cleans and comprises one or more in pickling, alkali cleaning and washing.
Characteristics of the present invention are:
Fluorescent material prepared by the present invention can send the orange red light of main emission peak more than 590 nm under 340 nm ~ 420 nm optical excitation, with blue, green emitting phosphor, be used in conjunction with, be coated in purple light or ultraviolet leds, can prepare novel white light LEDs, as orange red emitting phosphor, partly for the preparation of white light LEDs, effciency of energy transfer is high; Also can coordinate with purple light or ultraviolet leds, or other type fluorescent material of remix, prepare bright color LED.Fluorescent material physical and chemical performance of the present invention is stable.And the fluorescent material synthetic method the present invention relates to is simple, easy handling, pollution-free, cost is low.
The accompanying drawing explanation
Fig. 1 is 405 nm optical excitation Ca
0.98li
0.01teO
3: 0.01Sm
3+the utilizing emitted light spectrogram obtained.
Fig. 2 is 375 nm optical excitation Ca
0.98li
0.01teO
3: 0.01Sm
3+the utilizing emitted light spectrogram obtained.
Fig. 3 is monitoring Ca
0.98li
0.01teO
3: 0.01Sm
3+the orange red photoemissive exciting light spectrogram of 602 nm.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further described, but be not limited to these embodiment.
Embodiment 1: take CaCO
34.5321g, TeO
27.3736g, Li
2cO
30.0171, Sm
2o
30.0806g above raw material is analytical pure, by the raw material mix grinding that takes evenly after, the alumina crucible roasting in air of packing into, 650 ℃ of insulations 3 hours.Cooling rear taking-up is pulverized, grinds, is washed removal of impurities, oven dry, and obtaining chemical constitution is Ca
0.98li
0.01teO
3: 0.01Sm
3+the orange red fluorescent powder for LED.Its 405 nm, the emmission spectrum under 375 nm optical excitation is shown in Fig. 1 and Fig. 2, main emission peak 602 nm.Monitor the excitation spectrum that 602 nm emissions obtain and see Fig. 3.As seen from the figure, this fluorescent material can effectively be excited by ultraviolet or the purple light in 340 nm ~ 420 nm scopes, has purposes widely.
Embodiment 2: take CaC
2o
411.0646g, TeO
24.7867g, Na
2c
2o
40.1206g, Sm
2o
30.3138g above raw material is analytical pure, by the raw material mix grinding that takes evenly after, the alumina crucible roasting in air of packing into, 700 ℃ of insulations 1 hour.Cooling rear taking-up is pulverized, grinds, is washed removal of impurities, oven dry, and obtaining chemical constitution is Ca
2.88na
0.06teO
6: 0.06Sm
3+the orange red fluorescent powder for LED.
Embodiment 3: take Sr (NO
3)
27.5711g, TeO
26.0758g, Li
2cO
30.0423g, Sm (NO
3)
30.3841g above raw material is analytical pure, by the raw material mix grinding that takes evenly after, the alumina crucible roasting in air of packing into, 700 ℃ of insulations 3 hours.Cooling rear taking-up is pulverized, grinds, is washed removal of impurities, oven dry, and obtaining chemical constitution is Sr
0.94li
0.03teO
4: 0.03Sm
3+the orange red fluorescent powder for LED.
Embodiment 4: take BaCO
36.0869g, TeO
25.1281g, K
2cO
30.0444g, Sm
2o
30.112g above raw material is analytical pure, by the raw material mix grinding that takes evenly after, the alumina crucible roasting in air of packing into, 700 ℃ of insulations 2 hours.Cooling rear taking-up is pulverized, grinds, is washed removal of impurities, oven dry, and obtaining chemical constitution is Ba
0.96k
0.02teO
4: 0.02Sm
3+the orange red fluorescent powder for LED.
Embodiment 5: take Ba (NO
3)
29.5857g, TeO
24.1529g, Li
2cO
30.0433g, Sm (NO
3)
30.3939g above raw material is analytical pure, by the raw material mix grinding that takes evenly after, the alumina crucible roasting in air of packing into, 750 ℃ of insulations 5 hours.Cooling rear taking-up is pulverized, grinds, is washed removal of impurities, oven dry, and obtaining chemical constitution is Ba
2.82li
0.09te
2o
9: 0.09Sm
3+the orange red fluorescent powder for LED.
Embodiment 6: take BaCO
35.1156g, TeO
25.8686g, Li
2cO
30.0307g, Sm
2o
30.1443g above raw material is analytical pure, by the raw material mix grinding that takes evenly after, the alumina crucible roasting in air of packing into, 750 ℃ of insulations 3 hours.Cooling rear taking-up is pulverized, grinds, is washed removal of impurities, oven dry, and obtaining chemical constitution is Ba
2.82li
0.09te
4o
11: 0.09Sm
3+the orange red fluorescent powder for LED.
Shown in the above and figure is only the preferred embodiment of the present invention.It should be pointed out that for the person of ordinary skill of the art, under the premise without departing from the principles of the invention, can also make some modification and improvement, these also should be considered as belonging to protection scope of the present invention.
Claims (13)
1. the orange red fluorescent powder for LED is characterized in that: this fluorescent material is the tellurate fluorescent material that samaric activates, and its chemical expression is (M
a-2xsm
xa
x) Te
bo
c, wherein M is at least one in Ca, Sr, Ba, A is at least one in Li, Na, K; 1≤a≤3; 1≤b≤4; 3≤c≤11; 0<x<0.1.
2. the preparation method of the orange red fluorescent powder for LED as claimed in claim 1 comprises the following steps:
(1), with metal or compound containing M, containing metal or the compound of Te, containing metal or the compound of Sm, the compound that contains A is raw material, and takes corresponding described raw material by mole proportioning of described chemical expression, grinds, and mixes;
(2) by the mixture of step (1) in air in 600 ~ 800 ℃ of lower roastings once or twice, each cooling rear mill of roasting is mixed even, then carries out roasting next time; Each roasting time is 0.5 ~ 15 hour;
(3) removal of impurities, oven dry are pulverized, cleaned to product of roasting step (2) obtained, must be for the orange red fluorescent powder of LED.
3. the preparation method of the orange red fluorescent powder for LED as claimed in claim 2 is characterized in that: the described compound containing M is the salt containing M, containing the compound of Te, is the salt containing Te, containing the compound of Sm, is the salt containing Sm, containing the compound of A, is the salt containing A.
4. the preparation method of the orange red fluorescent powder for LED as claimed in claim 2, it is characterized in that: in described step (1), described grinding can be carried out in ethanol or acetone soln.
5. the preparation method of the orange red fluorescent powder for LED as claimed in claim 2, it is characterized in that: can adopt the physics fragmentation in the pulverizing described in described step (3), described cleaning comprises one or more in pickling, alkali cleaning and washing.
6. the preparation method of the orange red fluorescent powder for LED as claimed in claim 5, it is characterized in that: described physics is broken for comminution by gas stream.
7. the preparation method of the orange red fluorescent powder for LED as claimed in claim 2 is characterized in that: the described compound containing M is the oxide compound containing M.
8. the preparation method of the orange red fluorescent powder for LED as claimed in claim 3 is characterized in that: the described salt containing M is carbonate, nitrate or the organic acid salt containing M.
9. the preparation method of the orange red fluorescent powder for LED as claimed in claim 2 is characterized in that: the described compound containing Te is the oxide compound containing Te.
10. the preparation method of the orange red fluorescent powder for LED as claimed in claim 3 is characterized in that: the described salt containing Te is carbonate, nitrate or the organic acid salt containing Te.
11. the preparation method of the orange red fluorescent powder for LED as claimed in claim 3 is characterized in that: the described salt containing A is carbonate, nitrate or the organic acid salt containing A.
12. the preparation method of the orange red fluorescent powder for LED as claimed in claim 2 is characterized in that: the described compound containing Sm is the oxide compound containing Sm.
13. the preparation method of the orange red fluorescent powder for LED as claimed in claim 3 is characterized in that: the described salt containing Sm is carbonate, nitrate or the organic acid salt containing Sm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101856458A CN102690659B (en) | 2012-06-07 | 2012-06-07 | Orange red fluorescent powder for LED (Light Emitting Diode) and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101856458A CN102690659B (en) | 2012-06-07 | 2012-06-07 | Orange red fluorescent powder for LED (Light Emitting Diode) and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102690659A CN102690659A (en) | 2012-09-26 |
| CN102690659B true CN102690659B (en) | 2013-12-11 |
Family
ID=46856399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101856458A Active CN102690659B (en) | 2012-06-07 | 2012-06-07 | Orange red fluorescent powder for LED (Light Emitting Diode) and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102690659B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587627B (en) * | 2018-06-01 | 2020-03-17 | 苏州大学 | Eu3+Ion-activated bismuth fluorochlorotelluroate and preparation method and application thereof |
| CN113717724B (en) * | 2021-09-28 | 2023-03-17 | 常州工程职业技术学院 | Eu (Eu) 3+ Doped transition metal tellurium oxide fluorescent powder and preparation method and application thereof |
| CN115710507B (en) * | 2022-11-17 | 2023-10-31 | 广东工业大学 | Tellurate near infrared fluorescent material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051172B (en) * | 2011-01-17 | 2013-05-01 | 中国计量学院 | Red fluorescent powder used for LED (light-emitting diode) and preparation method thereof |
-
2012
- 2012-06-07 CN CN2012101856458A patent/CN102690659B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102690659A (en) | 2012-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103627392B (en) | A kind of stibnate base red fluorescent powder and its preparation method and application | |
| CN102533266A (en) | Europium-activated tungsten molybdate red fluorescent powder for white LED (Light Emitting Diode) and preparation method of europium-activated tungsten molybdate red fluorescent powder | |
| CN101851508A (en) | Europium activated silicate green fluorescent powder and application thereof in white light emitting diode | |
| CN105694870B (en) | A kind of Eu3+The positive sodium magnesium silicate red fluorescence powder and its preparation method and application of activation | |
| CN102051172B (en) | Red fluorescent powder used for LED (light-emitting diode) and preparation method thereof | |
| CN102559179A (en) | Single-matrix white light fluorescent powder for white light light-emitting diode (LED) and preparation method thereof | |
| CN103305216B (en) | Borate red fluorescent powder and preparation method and application thereof | |
| CN102690659B (en) | Orange red fluorescent powder for LED (Light Emitting Diode) and preparation method thereof | |
| CN101412911A (en) | Aluminosilicate blue fluorescent powder and preparation thereof | |
| CN102071021B (en) | Orange red fluorescent powder for LED and preparation method thereof | |
| CN103289698B (en) | A kind of europium ion Eu 3+the phosphate base red fluorescence powder activated, preparation method and application | |
| CN102690660B (en) | Red fluorescent powder for light-emitting diode (LED) and preparation method for red fluorescent powder | |
| CN103468251B (en) | A kind of LED silicate green fluorescent powder and preparation method thereof | |
| CN102703066A (en) | Fluorosilicate fluorescent powder and preparation method thereof | |
| CN102433119A (en) | Tungsten molybdate red fluorescent powder for white light-emitting diode (LED) and preparation method of tungsten molybdate red fluorescent powder | |
| CN101781555A (en) | Deep red phosphor powder suitable to be excited by blue LED, preparation method thereof, and electric light source made by same | |
| CN105062472B (en) | A kind of preparation method and application of the blue colour fluorescent powder for warm white LED | |
| CN103725284B (en) | Single-substrate white-light fluorescent powder for white light and preparation method thereof | |
| CN104910914A (en) | Lanthanum boron vanadate-based red fluorescent material and preparation method thereof | |
| CN103602335B (en) | Blue fluorescent powder for white light LED and preparation method thereof | |
| CN102433118B (en) | Niobate red fluorescent powder as well as preparation method and application thereof | |
| CN103450898A (en) | Titanate base red fluorescent powder for white LED (Light Emitting Diode) and preparation method thereof | |
| CN103992795A (en) | Red phosphor for LED, and preparation method thereof | |
| CN103468261B (en) | White light phosphor taking titanate as single substrate and preparation method of white light phosphor | |
| CN106085421A (en) | A kind of Eu3+positive magnesium silicate potassium fluorescent material activated and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |