CN101210181B - Fluorescent material, white light luminescent device and false proof coating - Google Patents

Fluorescent material, white light luminescent device and false proof coating Download PDF

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CN101210181B
CN101210181B CN200610171786A CN200610171786A CN101210181B CN 101210181 B CN101210181 B CN 101210181B CN 200610171786 A CN200610171786 A CN 200610171786A CN 200610171786 A CN200610171786 A CN 200610171786A CN 101210181 B CN101210181 B CN 101210181B
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fluorescent material
white light
blue
wave band
emitting device
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CN101210181A (en
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黄天恒
叶耀宗
王丽萍
赵文轩
吴仁杰
王先知
董建岳
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Industrial Technology Research Institute ITRI
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    • 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 provides a fluorescent material, which comprises M9.33-x-ySi6O26:EuxBiy, wherein M is Y, La, Gd, Lu or combination thereof, x is not less than 0 and not larger than 3, y is not less than0 and not larger than 1, and the summation of x and y is not equal to 0. The material can be matched with other fluorescent material as a white light emitting device, and can also be used individually as fluorescent coating for anti-counterfeit pattern.

Description

Fluorescent material, white light emitting device and anti-counterfeit paint
Technical field
The present invention relates to a kind of fluorescent material, relate more specifically to of the application of this material at white light emitting device or anti-counterfeit paint.
Background technology
Photodiode (LED is used in the market at present, light emitting diode) white light emitting device will replace traditional tengsten lamp and fluorescent lamp lighting gradually, because of it has following properties: (1) volume is little, be applicable to the use of array package illumination, and visual its should be used as the combination of different colours kind; (2) life-span long, its life-span can reach more than 10,000 hours, exceeded more than 50 times than general traditional osram lamp; (3) durable, because it is encapsulated as transparent resin, therefore can be shatter-proof and shock-resistant; (4) environmental protection because its internal structure does not contain mercury, is not therefore polluted and the offal treatment problem; (5) economize the energy and low power consumption, its current consumption is 1/3 to 1/5 of general osram lamp approximately.
And so-called " white light " is often referred to a kind of mixed light of many colors, the being seen white light of human eye is formed by the coloured light that comprises wavelength more than two kinds at least, for example: blue light adds the white light that sodium yellow can obtain two wavelength, can obtain the white light of three-wavelength after blue light, green light, red light are mixed.
White light emitting diode can be made employed material and is divided into according to it: Organic Light Emitting Diode and inorganic light-emitting diode.Main in the market semi-conductor white light source mainly comprises following three kinds of modes.First kind is to form the white-light emitting module with red bluish-green Tricolor LED crystal grain, it has high-luminous-efficiency, high color rendering (color render), but simultaneously also because of different colours crystal grain (Chip) brilliant material difference of heap of stone, the related voltage characteristic that makes is also different thereupon.Therefore make that manufacturing cost is higher, complex circuit designs and mixed light be difficult for.
Second kind excites yellow YAG fluorescent material to produce the photodiode of white light for what day inferior chemistry proposed with blue light-emitting diode, is main flow mode in the market.The optical cement that is mixed with gold-tinted YAG fluorescent material is filled in periphery at blue LED chip, the wavelength of blue light that this blue LED chip sends is about 400-530nm, the blue-light excited gold-tinted fluorescent material that utilizes blue LED chip to send produces gold-tinted, all the other blue lights cooperate the gold-tinted that fluorescent material sent, and promptly form blue yellow blended two wavelength white lights.
Yet the restriction of this white light LEDs in general illumination is extremely many, and major cause is as follows: because blue light accounts for the major part of luminescent spectrum, therefore, have the higher and uneven phenomenon of colour temperature.For these reasons, must improve the chance of blue light and the effect of gold-tinted fluorescent material, to reduce the blue light strength or the intensity of raising gold-tinted.Moreover, change because of the blue light-emitting diode emission wavelength can increase with temperature, and then cause the control of white light source color to be difficult for.In addition, for want of ruddiness causes color rendering relatively poor.
The third is to excite to contain in the transparent optical cement with ultraviolet light-emitting diodes evenly to be mixed with a certain proportion of blueness, green, red fluorescence powder, can obtain the white light of three-wavelength after exciting.Three wavelengh white light light-emitting diode has the high color rendering advantage, but the insufficient shortcoming of luminous efficiency is arranged.But even so, this white light LEDs makes up after can making the three primary colors fluorescent material respectively again, reaches in processing procedure elasticity to have more advantage than preceding two kinds of white light LEDs in nature.Most red line emitting phosphors mostly is sulfide, nitride or other oxide compound.The light conversion efficiency height of sulphide phosphor, but shortcoming is a poor stability, is subject to aqueous vapor or oxygen deterioration.Nitride phosphor stable good, but its synthetic being difficult for often need the High Temperature High Pressure processing procedure, not only danger also raises the cost.As for the most handy in the oxide compound be silicates, lack at present the red light fluorescent powder that is suitable for.In sum, need a kind of new silicates red line emitting phosphors at present badly, further to be applied to white light LEDs.
On the other hand, along with the progress of printing technology, the crime gimmick of document forgery or banknote is also serious day by day, and therefore needing a kind of new fluorescent material at present badly is applied to anti-counterfeit paint.
Summary of the invention
Be difficult for or the stable inadequately shortcoming of performance for solving existing red light fluorescent powder preparation, the invention provides a kind of fluorescent material, comprise M 9.33-x-ySi 6O 26: Eu xBi y, wherein M is Y, La, Gd, Lu or aforesaid combination, 0≤x≤3; 0≤y≤1; And x+y ≠ 0.
The present invention also provides a kind of white light emitting device, comprises above-mentioned fluorescent material; Blue-light fluorescent material; The green glow fluorescent material; And excitation light source.
The present invention also provides a kind of anti-counterfeit paint, comprises above-mentioned fluorescent material.
Description of drawings
Fig. 1 is in the preferred embodiment of the present invention, Gd 7.33Si 6O 26: Eu 2The excitation-emission collection of illustrative plates;
Fig. 2 is in the preferred embodiment of the present invention, Gd 9.28Si 6O 26: Bi 0.05The excitation-emission collection of illustrative plates;
Fig. 3 is in the preferred embodiment of the present invention, Gd 8.68Si 6O 26: Eu 0.6Bi 0.05The excitation-emission collection of illustrative plates;
Fig. 4 is in the preferred embodiment of the present invention, Gd 8.68Si 6O 26: Eu 0.6Bi 0.05The X-ray diffracting spectrum;
Fig. 5 is in the preferred embodiment of the present invention, Gd 8.68Si 6O 26: Eu 0.6Bi 0.05Gd 2O 3The excitation-emission collection of illustrative plates of mixed phase;
Fig. 6 is in the preferred embodiment of the present invention, Gd 8.68Si 6O 26: Eu 0.6Bi 0.05Gd 2O 3The x-ray diffraction pattern of mixed phase.
Embodiment
The invention provides a kind of fluorescent material, comprise M 9.33-x-ySi 6O 26: Eu xBi y, wherein M is Y, La, Gd, Lu or aforesaid combination, 0≤x≤3; 0≤y≤1; And x+y ≠ 0.The negatively charged ion of this fluorescent material is silicates [Si 6O 26] 28-, with general silicate [SiO 4] 4-Deng comparing, has different composition structures.The positively charged ion that fluorescent material of the present invention adopts is trivalent or quadrivalent element, as Y 3+, La 3+, Gd 3+, Lu 3+, Eu 3+, Bi 3+, and Si 4+Eu 3+With Bi 3+Be activator, have different effects separately.For instance, has only Eu when activator 3+The time, its preferable excitation wavelength is 250nm, 350nm, reaches 393nm, and its luminous wave band is 610-650nm, and luminous main peak is the ruddiness of 610nm.When activator only has Bi 3+The time, its maximum excitation wavelength is 370nm, luminous wave band is 430-470nm, and luminous main peak is the blue light of 458nm.If activator contains Eu 3+With Bi 3+During two kinds of activators, what then have ruddiness and blue light simultaneously excites wave band and luminous wave band.On as anti-counterfeit paint, has multi-functional.For instance, coat at the first layer of banknote and have only Bi 3+Be the fluorescent material of activator, the second layer is coated has Eu 3+With Bi 3+Be the fluorescent material of activator, coat for the 3rd layer and have only Eu 3+Fluorescent material for activator.The first layer and the second layer are luminous after 370nm is ultraviolet ray excited to become specific blue light pattern, and the second layer luminously after 250nm, 350nm or 393nm are ultraviolet ray excited becomes specific ruddiness pattern with the 3rd layer.The first layer, the second layer, trilaminar formation order can arbitrarily be changed, and the design of view case is with easy to operate and decide.In addition, the first layer, the second layer, with the 3rd layer also can be separately as security pattern, or be combined into security pattern with other common anti-counterfeit paint.
The forming method of above-mentioned fluorescent material is a solid-state sintering, at first takes by weighing the Y of suitable mol ratio according to stoichiometry 2O 3, La 2O 3, Gd 2O 3, Lu 2O 3, Eu 2O 3, Bi 2O 3, and SiO 2After, grind behind the uniform mixing, insert High Temperature Furnaces Heating Apparatus after putting into crucible, after the 1200-1400 ℃ of about 3-8 of sintering hour, get final product above-mentioned fluorescent material.
Because the luminous main peak of fluorescent material of the present invention is positioned at the ruddiness of 613nm, therefore in the application of white light LEDs based on as red light flourescent material.The UV-light of selecting 250nm, 350nm or 393nm for use is during as the excitation light source of fluorescent material of the present invention, the blue-light fluorescent material such as the BaMgAl of the co-wavelength excitation light source of also can arranging in pairs or groups 10O 17: Eu 2+, ZnS:Ag, fluorescent materials such as Cl, and green glow fluorescent material such as BaMg 2Al 10O 17: Eu 2+, Mn 2+, ZnS:Cu, fluorescent material mixed distribution such as Al behind optical cement, with ultraviolet ray excited it.Red blue green light through ultraviolet ray excited generation is mixed into white light.But it should be noted that if do excitation light source, in the white light emitting device outermost uv filter should be set and user's eyes be damaged avoiding with UV-light.Above-mentioned excitation light source can come from photodiode, laser diode or other suitable light-emitting device.
After it should be noted that fluorescent material stimulated luminescence for some time, can produce heat and accumulate on transparent optical cement.Fluorescent material is after being heated, and it excites wave band will produce change.If excite wave band narrow (＜5nm), then launching efficiency will significantly reduce and cause brightness to descend.But in the present invention,, can generate a little M of blending by the sintering process adjustment 2O 3The M of phase 9.33-x-ySi 6O 26: Eu xBi yReactant.Resultant with mixed phase is than only having pure phase M 9.33-x-ySi 6O 26: Eu xBi yResultant excite wide waveband, and stability is also preferable.
For making the clearer feature of the present invention of those skilled in the art, especially exemplified by following preferred embodiment.
Embodiment 1
Get Gd 2O 3(FW=362.5,650mg, 1.79mmol ProChem Inc 99.9%), Eu 2O 3(FW=352,172mg, 0.49mmol Seedchem 99.99%), SiO 2(FW=60.08,176mg, 2.92mmol SHOWA 99%) grinds behind the uniform mixing, inserts High Temperature Furnaces Heating Apparatus after putting into crucible, after 1400 ℃ of about 3-8 of following sintering hours, promptly gets 1g Gd 7.33Si 6O 26: Eu 2The exciting and launch collection of illustrative plates as shown in Figure 1 of above-mentioned product, maximum excitation wavelength is positioned at 250nm and 393nm, and luminous wave band is between 610-650nm, and its main peak is positioned at 610nm, and it is luminous to take on a red color.
Embodiment 2
Get Gd 2O 3(FW=362.5,818mg, 2.25mmol, ProChem Inc 99.9%), Bi 2O 3(FW=465.96,5mg, 0.01mmol,
Figure G2006101717869D00041
99.5%) SiO, 2(FW=60.08,175mg 2.91mmol), grind behind the uniform mixing, insert High Temperature Furnaces Heating Apparatus after putting into crucible, after 1400 ℃ of about 3-8 of following sintering hours, promptly get 1g Gd 9.28Si 6O 26: Bi 0.05The excitation-emission collection of illustrative plates of above-mentioned product as shown in Figure 2, it is 370nm that its best excites wave band, luminous wave band is 430-470nm, its main peak is 458nm, is blue-light-emitting.
Embodiment 3
Get Gd 2O 3(FW=362.5,767mg, 2.12mmol), Eu 2O 3(FW=352,51mg, 0.14mmol), Bi 2O 3(FW=495.96,5.7mg, 0.01mmol), SiO 2(FW=60.08,176mg 2.93mmol), grind behind the uniform mixing, insert High Temperature Furnaces Heating Apparatus after putting into crucible, after 1400 ℃ of about 3-8 of following sintering hours, promptly get 1g Gd 8.68Si 6O 26: Eu 0.6Bi 0.05The excitation-emission collection of illustrative plates of above-mentioned product when its excitation wavelength is 370nm, sends blue light as shown in Figure 3, and luminous wave band is 430-470nm, and main peak is 458nm; When excitation wavelength is 250nm, 350nm, and during 393nm, sends ruddiness, luminous wave band is 610-650nm, and main peak is 610nm.The X-ray diffractogram of above-mentioned product as shown in Figure 4.
Embodiment 4
Get Gd 2O 3(FW=362.5,767mg, 2.12mmol), Eu 2O 3(FW=352,51mg, 0.14mmol), Bi 2O 3(FW=495.96,5.7g, 0.01mmol), SiO 2(FW=60.08,176mg 2.93mmol), grind behind the uniform mixing, insert High Temperature Furnaces Heating Apparatus after putting into crucible, after about 4 hours, promptly get 1g Gd at 1300 ℃ of following sintering 9.33Si 6O 26: EuBi and Gd 2O 3: the mixed phase of EuBi, its excitation-emission collection of illustrative plates is as shown in Figure 5.In Fig. 5, excite a wider range of wave band, can effectively avoid exciting wave band not meet the problem of excitation light source wave band after the photodiode heating in the LED application.Fig. 6 then is the X-ray diffractogram of above-mentioned product.Has a little Gd by learning among the figure 2O 3Phase, but by diffracted intensity Gd 9.33Si 6O 26Still account for the overwhelming majority mutually.
Though the present invention discloses as above with several preferred embodiments, so it is not in order to limit the present invention.Any the technical staff in the technical field of the invention, without departing from the spirit and scope of the present invention, Ying Kezuo changes arbitrarily and retouching.Therefore, protection scope of the present invention should be as the criterion with appended claims institute restricted portion.

Claims (14)

1. fluorescent material, it is made up of silicate and oxide compound, and the structural formula of described silicate is as follows:
M 9.33-x-ySi 6O 26:Eu x，Bi y；
Described oxide compound is M 2O 3
Wherein M is Y, La, Gd, Lu or aforesaid combination;
0≤x≤3；
0≤y≤1；
x+y≠0。
2. fluorescent material as claimed in claim 1, y=0 wherein, its excitation light source is 250nm, 350nm or 393nm, and luminous wave band is the ruddiness of 610-650nm.
3. fluorescent material as claimed in claim 1, wherein during x=0, its excitation light source is 370nm, and luminous wave band is the blue light of 430-470nm.
4. fluorescent material as claimed in claim 1, x wherein, y ≠ 0 o'clock, its excitation light source is 250nm, 350nm, 370nm or 393nm, and luminous wave band comprises the ruddiness of 610-650nm and the blue light of 430-470nm.
5. fluorescent material as claimed in claim 1, its excitation light source comprises photodiode or laser diode.
6. fluorescent material as claimed in claim 1, wherein the blending ratio of this oxide compound and this silicate is between 1: 99-99: 1.
7. fluorescent material as claimed in claim 1, its sintering temperature are between 1200-1400 ℃, and its sintering time was between 3-8 hour.
8. white light emitting device comprises:
Fluorescent material as claimed in claim 1;
Blue-light fluorescent material;
The green glow fluorescent material; And
Excitation light source.
9. white light emitting device as claimed in claim 8, wherein the luminous wave band of this blue-light fluorescent material is between 450-490nm.
10. white light emitting device as claimed in claim 9, wherein this blue-light fluorescent material comprises BaMgAl 10O 17: Eu 2+Or ZnS:Ag, Cl.
11. white light emitting device as claimed in claim 8, wherein the luminous wave band of this green glow fluorescent material is between 520-570nm.
12. white light emitting device as claimed in claim 11, wherein this green glow fluorescent material comprises BaMgAl 10O 17: Eu 2+, Mn 2+Or ZnS:Cu, Al.
13. white light emitting device as claimed in claim 8, its excitation light source are photodiode or laser diode.
14. an anti-counterfeit paint comprises the described fluorescent material of claim 1.
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JP5770298B2 (en) * 2010-10-22 2015-08-26 コーニンクレッカ フィリップス エヌ ヴェ Luminescent substance and light emitting device having the luminescent substance
CN103178210A (en) * 2013-03-04 2013-06-26 中国科学院长春光学精密机械与物理研究所 Organic thin-film transistor based transparent color-variable multiple-anti-counterfeiting flash memory device and manufacturing method and application thereof
CN108659840A (en) * 2018-07-25 2018-10-16 淮阴师范学院 Eu3+Red fluorescence powder of activation and preparation method thereof
CN112980443A (en) * 2021-03-01 2021-06-18 松山湖材料实验室 Eu (Eu)3+Activated silicate red-light fluorescent powder and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1597841A (en) * 2004-08-25 2005-03-23 南京工业大学 White light fluorescence powder excitated by blue light and its application mfg. technology and mfg. apparatus
WO2006022792A2 (en) * 2004-08-04 2006-03-02 Intematix Corporation Novel silicate-based yellow-green phosphors
US20060086311A1 (en) * 2003-11-04 2006-04-27 Zagumennyi Alexander I Scintillation substances (variants)
CN1844303A (en) * 2006-05-12 2006-10-11 中山大学 Orange yellow fluorescent powder for white light LED and method for production thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060086311A1 (en) * 2003-11-04 2006-04-27 Zagumennyi Alexander I Scintillation substances (variants)
WO2006022792A2 (en) * 2004-08-04 2006-03-02 Intematix Corporation Novel silicate-based yellow-green phosphors
CN1597841A (en) * 2004-08-25 2005-03-23 南京工业大学 White light fluorescence powder excitated by blue light and its application mfg. technology and mfg. apparatus
CN1844303A (en) * 2006-05-12 2006-10-11 中山大学 Orange yellow fluorescent powder for white light LED and method for production thereof

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