CN102337125A - Borate fluorescent powder for warm white LED (light-emitting diode) - Google Patents

Borate fluorescent powder for warm white LED (light-emitting diode) Download PDF

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Publication number
CN102337125A
CN102337125A CN2011102043811A CN201110204381A CN102337125A CN 102337125 A CN102337125 A CN 102337125A CN 2011102043811 A CN2011102043811 A CN 2011102043811A CN 201110204381 A CN201110204381 A CN 201110204381A CN 102337125 A CN102337125 A CN 102337125A
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China
Prior art keywords
fluorescent powder
light
borate
white led
warm
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CN2011102043811A
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Chinese (zh)
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刘全生
张希艳
柏朝晖
卢利平
王晓春
米晓云
王能利
孙海鹰
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Changchun University of Science and Technology
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Changchun University of Science and Technology
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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

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Abstract

The invention relates to borate fluorescent powder for a warm white LED (light-emitting diode) and belongs to the technical field of a photoelectric functional material and the illumination of a solid semiconductor. Either the existing fluorescent powder for the white LED is short of a red light component, so that the light source color rendering index is lower and the warm colour tone cannot be generated, or the color tone of the existing fluorescent powder for the white LED is red, so that the light emitted by the produced white light LED is excessively warm. The formula of the borate fluorescent powder is one of the following formulas: M3B2O6:ER2+, A+; M2B2O5:RE2+, A+; M5B4O11:RE2+, A+; MB2O4:RE2+, A+; and MB4O7:RE2+, A+, wherein in the formula, M is selected from one or two of Ca, Sr, Ba, Ma, Pb and Zn, the RE is selected from one or two of Y, La, Pr, Nd, Eu, Gd, Tb, Ce, Dy, Yb, Er, Sc, Mn, Zn, Cu, Ni and Lu, the content of the RE is 0.01 to 10 atomicity percent of borate in the chemical formula, the A is selected from one or two of Li, Na, K, Rb and Cs, and the quantity of oxide or fluoride adopted for introducing the A is 0 to 20 percent of the material mass of the formula. The wavelength of a transmitted peak value is in the range of 560 to 575nm for generating warm light in the white light LED.

Description

Warm white LED is used borate fluorescent powder
Technical field
The present invention relates to a kind of warm white LED and use borate fluorescent powder; It is a kind of photoelectric functional material; This material can be directly and near ultraviolet chip or GaN base blue chip constitute white light LEDs; As the solid white-light illuminating, belong to the photoelectric functional material technical field, also belong to the solid semiconductor lighting technical field.
Background technology
Compare with the traditional lighting light source, white light LEDs has advantages such as low voltage, less energy-consumption, long lifetime, response are fast, high reliability, easy care, meets the requirement of energy-saving and environmental protection.One of approach that obtains white light LEDs is the fluorescent material conversion.The example that the compound generation white light of near ultraviolet chip or blue chip and polychrome or yellow fluorescent powder is a success.Existing phosphor for white light LED mainly contains two kinds, and a kind of is aluminate substrate, like YAG:Ce 2+, another kind is a silicate substrate, like Sr 2SiO 4: Eu 2+, Sr 3SiO 5: 0.07Eu 2+YAG:Ce 2+The emmission spectrum peak value of fluorescent material is positioned at 540nm, lacks the ruddiness composition, and the light source colour rendering index is lower, can not produce warm tones.And the emission peak wavelength of silicate substrate fluorescent material can produce warm tones, low colour temperature because of having reached 575nm, and still, silicate substrate fluorescent material emission peak wavelength is long, and tone is red partially, makes that the white light LEDs of made is luminous warm excessively; In addition, its synthesis temperature of this fluorescent material is high, poor chemical stability.
Also have one type of borate substrate luminescent material in the prior art, it have with low cost, synthesis temperature is low, good chemical stability.Existing borate substrate luminescent material has following several kinds.
The one Chinese patent application that application number is 01141945.8, name is called " a kind of borate red fluorescent powder for color plasma plate display and method of manufacture thereof " discloses a scheme, and wherein the chemical formula of borate red fluorescent powder is: (Y 1-x-y-zGd zM yEu x) BO 3, wherein M is La, Tb, Sm.Yet except borate, all the other materials are rare earth in this borate, cause the fluorescent material cost higher; Its exciting light is a deep ultraviolet, only is applicable to that plasma shows, with the near ultraviolet chip or the blue chip that use in the white light LEDs industry of present basic forming and do not match.
The one Chinese patent application that application number is 200810007451.2, name is called " borate fluorescent material and white light emitting device " discloses a scheme, and wherein the structural formula of borate fluorescent material is M a(M b) 1-xBO 3: (M c) x, M in the formula aBe Li, Na, K, Rb, Cs or above-mentioned combination, M bBe Mg, Ca, Sr, Ba, Zn or above-mentioned combination, M cBe Y, La, Pr, Nd, Eu, Gd, Tb, Ce, Dy, Yb, Er, Sc, Mn, Zn, Cu, Ni, Lu or above-mentioned combination; This borate fluorescent material by UV-light or blue-light excited after radiate visible light, constitute white light emitting device with other fluorescence material of all kinds.Yet the emission peak wavelength of this fluorescent material is the longest to be merely 507nm, can't obtain warm white.
Summary of the invention
In order to obtain a kind of borate substrate luminescent material; By near ultraviolet or blue-light excited; Broadband emission, emission peak wavelength is used for white light LEDs greater than 540nm, less than 575nm; Produce the warm white of colour rendering index height, optics high conformity, we have invented a kind of warm white LED and have used borate fluorescent powder.
It is one of following that the present invention's warm white LED uses its chemical formula of borate fluorescent powder: M 3B 2O 6: RE 2+, A +, M 2B 2O 5: RE 2+, A +, M 5B 4O 11: RE 2+, A +, MB 2O 4: RE 2+, A +, MB 4O 7: RE 2+, A +In the formula: M is a kind of of Ca, Sr, Ba, Mg, Pb, Zn or two kinds; RE is a kind of of Y, La, Pr, Nd, Eu, Gd, Tb, Ce, Dy, Yb, Er, Sc, Mn, Zn, Cu, Ni, Lu or two kinds, and the content of RE is 0.01～10at% of said chemical formula mesoboric acid salt; A is a kind of of Li, Na, K, Rb, Cs or two kinds, and introducing the oxide compound that A adopted or the amount of fluorochemical is 0～20% of said molecular formula material mass.
The present invention's warm white LED with borate fluorescent powder in, the M material is a divalent metal, combines to constitute the borate matrix of fluorescent material with borate, have with low cost, synthesis temperature is low, good chemical stability.The A material is introduced with oxide compound, fluorochemical or muriatic form, in fluorescent material, mainly plays the electric charge compensation and promotes lattice to grow.The RE material serves as activator in fluorescent material.This fluorescent material presents wide range and excites; Have near ultraviolet and blue-light excited characteristic; Present the wide range emission near ultraviolet and blue-light excited sample down, emission peak wavelength is used for the warm white that white light LEDs can produce colour rendering index height, optics high conformity in 560～575nm scope.
Description of drawings
Fig. 1 is the present invention's fluorescent powder product Sr 3B 2O 6: Eu 0.07 2+XRD figure.
Fig. 2 is the present invention's fluorescent powder product Sr 3B 2O 6: Eu 0.07 2+The exciting light spectrogram.
Fig. 3 is the present invention's fluorescent powder product Sr 3B 2O 6: Eu 0.07 2+Emmission spectrum figure.
Fig. 4 is the present invention's fluorescent powder product Sr 3B 2O 6: Eu 0.07 2+The combined light spectrogram, this figure double as is a Figure of abstract.
Fig. 5 is the present invention's fluorescent powder product Sr 3B 2O 6: Eu 0.07 2+Chromaticity coordinates.
Fig. 6 is the present invention's fluorescent powder product Sr 2B 2O 5: Eu 0.07 2+, Li +XRD figure.
Fig. 7 is the present invention's fluorescent powder product Sr 2B 2O 5: Eu 0.07 2+, Li +The exciting light spectrogram.
Fig. 8 is the present invention's fluorescent powder product Sr 2B 2O 5: Eu 0.07 2+, Li +Emmission spectrum figure.
Embodiment
Warm white LED through the present invention further specifies the present invention with the preparation of borate fluorescent powder below.
Embodiment 1:
Warm white LED uses the borate fluorescent powder chemical formula to be Sr 3B 2O 6: Eu 0.07 2+The preparation of employing high temperature solid-state method.Raw material comprises Eu 2O 3, H 3BO 3And SrCO 3, purity is 99.99%.The determined stoichiometric ratio of fluorescent material chemical formula according to prepared is confirmed proportioning raw materials; Accurately weigh each raw material and place agate mortar, porphyrize also mixes, and ground mixed powder is transferred to monkey; Put into high temperature box furnace; Under the reducing atmosphere of gac, calcination 2h under 1150 ℃ of temperature obtains required product.
Calcination process reaction mechanism is following: at high temperature gac is with Eu 3+Be reduced to Eu 2+Then, SrCO 3And H 3BO 3Reaction generates Sr 3B 2O 6Eu 2+Be entrained in Sr 3B 2O 6In the matrix, finally form Sr 3B 2O 6: Eu 2+Raw material H in reaction process 3BO 3Have two kinds of effects, the one, as reactant; The 2nd, as fusing assistant, reduce temperature of reaction, make the powder blended more even simultaneously.
The concrete reaction as follows:
C+Eu 2O 3→2EuO+CO
3SrCO 3+2H 3BO 3→Sr 3B 2O 6+H 2O
Sr 3B 2O 6+Eu 2+→Sr 3B 2O 6:Eu 2+
Fluorescent powder product has hexagonal system Sr 3B 2O 6Structure, see shown in Figure 1ly, have spacer R*c (167).Fluorescent powder product has wide excitation spectrum, sees shown in Figure 2ly, excites peak value to be positioned near the 460nm, and the monitoring wavelength is 566nm.Fluorescent powder product has wide emmission spectrum, sees shown in Figure 3ly, and emission peak is positioned near the 566nm, and excitation wavelength is 460nm.566nm gold-tinted that fluorescent powder product is sent and the combination of 460nm blue light form warm white, see shown in Figure 4.The fluorescent powder product chromaticity coordinates is (0.338,0.346,0.316), sees shown in Figure 5ly, can know that fluorescent powder product has white light output.
Embodiment 2:
Warm white LED uses the borate fluorescent powder chemical formula to be Sr 2B 2O 5: Eu 0.07 2+, Li +The preparation of employing high temperature solid-state method.Raw material comprises Eu 2O 3, H 3BO 3And SrCO 3, purity is 99.99%, also has Li in addition 2O (analytical pure), add-on is Sr 2B 2O 5: Eu 0.07 2+, Li +5% of quality.The determined stoichiometric ratio of fluorescent material chemical formula according to prepared is confirmed proportioning raw materials; Accurately weigh each raw material and place agate mortar, porphyrize also mixes, and ground mixed powder is transferred to monkey; Put into high temperature box furnace; Under the reducing atmosphere of gac, calcination 2h under 1050 ℃ of temperature obtains required product.
Fluorescent powder product has Sr 2B 2O 5Crystalline structure is seen shown in Figure 6.Fluorescent powder product has wide excitation spectrum, sees shown in Figure 7ly, and the monitoring wavelength is 570nm.Fluorescent powder product has wide emmission spectrum, sees shown in Figure 8ly, and emission peak is positioned near the 570nm.

Claims (2)

1. a warm white LED is used borate fluorescent powder, it is characterized in that, its chemical formula is one of following: M 3B 2O 6: RE 2+, A +, M 2B 2O 5: RE 2+, A +, M 5B 4O 11: RE 2+, A +, MB 2O 4: RE 2+, A +, MB 4O 7: RE 2+, A +In the formula: M is a kind of of Ca, Sr, Ba, Mg, Pb, Zn or two kinds; RE is a kind of of Y, La, Pr, Nd, Eu, Gd, Tb, Ce, Dy, Yb, Er, Sc, Mn, Zn, Cu, Ni, Lu or two kinds, and the content of RE is 0.01～10at% of said chemical formula mesoboric acid salt; A is a kind of of Li, Na, K, Rb, Cs or two kinds, and introducing the oxide compound that A adopted or the amount of fluorochemical is 0～20% of said molecular formula material mass.
2. warm white LED according to claim 1 is used borate fluorescent powder; It is characterized in that having near ultraviolet and blue-light excited characteristic, present the wide range emission near ultraviolet and blue-light excited sample down; Emission peak wavelength is used for white light LEDs in 560～575nm scope.
CN2011102043811A 2011-07-21 2011-07-21 Borate fluorescent powder for warm white LED (light-emitting diode) Pending CN102337125A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103094394A (en) * 2013-01-18 2013-05-08 厦门大学 Down-conversion crystalline silicon solar cell and preparation method thereof
CN103215035A (en) * 2012-12-21 2013-07-24 彩虹集团电子股份有限公司 Europium excited strontium magnesium borate ultraviolet phosphor and preparation method thereof
CN103865530A (en) * 2014-03-07 2014-06-18 厦门大学 Near ultraviolet exited red phosphor powder and preparation method thereof
CN109762563A (en) * 2019-01-28 2019-05-17 广东工业大学 It is a kind of with β-potassium carbonate structure orthoborate fluorescent powder and preparation method thereof
CN112505816A (en) * 2020-11-30 2021-03-16 中国科学院新疆理化技术研究所 Compound potassium barium borate, potassium barium borate birefringent crystal, preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
K. MACHIDA ET AL.: "LUMINESCENCE PROPERTIES OF Eu(Ⅱ)-BORATES AND Eu2+-ACTIVED Sr-BORATES", 《JOURNAL OF LUMINESCENCE》 *
WOO-SEUK SONG ET AL.: "Yellow-emitting phosphor of Sr3B2O6:Eu2+ for application to white light-emitting diodes", 《MATERIALS CHEMISTRY AND PHYSICS》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103215035A (en) * 2012-12-21 2013-07-24 彩虹集团电子股份有限公司 Europium excited strontium magnesium borate ultraviolet phosphor and preparation method thereof
CN103094394A (en) * 2013-01-18 2013-05-08 厦门大学 Down-conversion crystalline silicon solar cell and preparation method thereof
CN103865530A (en) * 2014-03-07 2014-06-18 厦门大学 Near ultraviolet exited red phosphor powder and preparation method thereof
CN103865530B (en) * 2014-03-07 2015-10-21 厦门大学 A kind of near ultraviolet excitated red fluorescence powder and preparation method thereof
CN109762563A (en) * 2019-01-28 2019-05-17 广东工业大学 It is a kind of with β-potassium carbonate structure orthoborate fluorescent powder and preparation method thereof
CN112505816A (en) * 2020-11-30 2021-03-16 中国科学院新疆理化技术研究所 Compound potassium barium borate, potassium barium borate birefringent crystal, preparation method and application

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