CN1331982C - Phosphor powder of composite oxide in use for white light LED and fabricated electric light source - Google Patents
Phosphor powder of composite oxide in use for white light LED and fabricated electric light source Download PDFInfo
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- CN1331982C CN1331982C CNB2004100804837A CN200410080483A CN1331982C CN 1331982 C CN1331982 C CN 1331982C CN B2004100804837 A CNB2004100804837 A CN B2004100804837A CN 200410080483 A CN200410080483 A CN 200410080483A CN 1331982 C CN1331982 C CN 1331982C
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- composite oxide
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- 239000000843 powder Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 22
- 239000000126 substance Substances 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 32
- 241001025261 Neoraja caerulea Species 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 230000004907 flux Effects 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000013467 fragmentation Methods 0.000 claims description 2
- 238000006062 fragmentation reaction Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 230000005284 excitation Effects 0.000 abstract description 2
- 229910052692 Dysprosium Inorganic materials 0.000 abstract 1
- 229910052771 Terbium Inorganic materials 0.000 abstract 1
- 229910052793 cadmium Inorganic materials 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910052735 hafnium Inorganic materials 0.000 abstract 1
- 229910052709 silver Inorganic materials 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 15
- 238000005303 weighing Methods 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 9
- 238000000695 excitation spectrum Methods 0.000 description 8
- 238000011161 development Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- -1 halogenide Chemical compound 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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
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- Luminescent Compositions (AREA)
Abstract
The present invention discloses composite oxide fluorescent powder which can be effectively excited by an ultraviolet LED, a violet light LED or a blue light LED, and a manufacturing method for producing the composite oxide fluorescent powder as well as an electric light source made by the composite oxide fluorescent powder. The fluorescent powder has the chemical formula of AaMO4: Ry, wherein A is one kind or a plurality of kinds of Y, La, Gd, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, Cd and Ag; M is one kind or a plurality of kinds of Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf; R is one kind or a plurality of kinds of Pr, Sm, Tb and Dy; a is bigger than or equal to 0.1 and is smaller than or equal to 2, and X is bigger than or equal to 0.0001 and is smaller than or equal to 0.5. The manufacturing method comprises the following steps that single substances, compounds or relevant salt classes of A, M and R in the chemical formula and a proper quantity of fluxing agents are uniformly mixed and ground, and after synthesized through high temperature, the fluorescent powder is obtained by post treatment. The fluorescent powder of the present invention has the characteristics of wide range of excitation wavelength, high efficiency, stability, simple manufacturing method, no pollution, low cost, etc. The fluorescent powder of the present invention can be matched with an ultraviolet LED, a violet light LED or a blue light LED to form a novel electric light source.
Description
Technical field
The present invention relates to a kind of phosphor powder of composite oxide that can effectively be excited by ultraviolet, purple light or blue-ray LED and made electric light source thereof.
Background technology
As far back as eighties of last century sixties, the scientific worker utilizes the luminous principle of semiconductor PN, be developed into LED (Light Emitting Diode), LED of all kinds during this time is developed successively, but after the GaInN blue-ray LED of greater efficiency in 1993 was successfully developed, full-colorization LED product just was achieved.After GaInN and green LED exploitation were finished, white light LEDs just became the target that industry is pursued.Through nearly 40 years development, LED is as light source, because it has numerous advantages such as power saving, pollution-free, stable performance, time of response weak point, life-span length, shock resistance, vibration resistance and cost are low, has been the main development trend of throwing light in the modern times.
The generation of white light LEDs has two kinds of approach: first method is exactly with three kinds of LED combination results of red, green, blue white light; Second method is exactly to mix with other luminescent material of LED de-excitation to form white light, the fluorescent material that promptly cooperates jaundice light with blue-ray LED, perhaps cooperate glow green and two kinds of fluorescent material of burn red, perhaps with purple light or three kinds of fluorescent material of ultraviolet LED de-excitation red, green, blue etc. with blue-ray LED.
From present development trend, at aspects such as feasibility, practicality and commercializations, second method all is far superior to first method, and it is quite crucial therefore to synthesize the special fluorescent material with good luminous characteristic.At present, utilize blue led to cooperate the technology of YAG yellow fluorescent powder generation white light ripe relatively, but the technology of utilizing LED to excite multiple fluorescent material to obtain white light still only rests on theory stage, its reason be the LED three-color phosphor that can be employed at present be not efficient low be exactly the character instability, so the LED of development of new becomes the focus of domestic and international research with three-color phosphor.
The present invention relates to a kind of phosphor powder of composite oxide that can effectively be excited by ultraviolet, purple light or blue-ray LED, such fluorescent material has characteristics such as excitation wavelength range is wide, efficient, stable, can be widely used in white light LEDs.In application for a patent for invention 200310101629.7, we disclose a kind of composition and preparation method thereof and made electric light source of composite oxides red fluorescence powder.Patent of the present invention is 1 with the difference of patent application 200310101629.7) the activator kind is different, do not contain europium in the activator of fluorescent material of the present invention; 2) glow color difference, the glow color of fluorescent material of the present invention can be red, also can be that green or yellow wait other color; 3) excitation spectrum of the fluorescent material that relates in the excitation spectrum of fluorescent material of the present invention and the application for a patent for invention 200310101629.7 is different and be applicable to different led chips.
Summary of the invention
The purpose of this invention is to provide a kind of good luminous performance, can be stablized phosphor powder of composite oxide by the chemical property that ultraviolet, purple light or blue-ray LED effectively excite.
Another object of the present invention provides a kind of method of making this fluorescent material, this fluorescent material manufacture method is simple, easy handling, pollution-free, cost is low.
A further object of the present invention provides a kind of by the made electric light source of this fluorescent material.
For achieving the above object, the present invention takes following technical scheme:
A class LED of the present invention with the chemical formula of phosphor powder of composite oxide is: A
aMO
4: R
x
Wherein, A is Y, La, Gd, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, one or more among Cd and the Ag;
M is one or more among Cr, Mo, W, V, Nb, Ta, Ti, Zr and the Hf;
R is Pr, Sm, one or more among Tb and the Dy;
0.1≤a≤2，0.0001≤x＜0.5。
The method that the present invention relates to prepare this fluorescent material is as follows:
(1), metal or compound or the salt to contain A, the metal or compound or the salt that contain M, the compound or the salt that contain R are raw material, express the mole proportioning of requirement by above-mentioned chemical formula, converse the weight of pairing above-mentioned raw materials respectively, and take by weighing described raw material, add an amount of reaction flux, porphyrize mixes;
(2), the mixture that step (1) is obtained carries out high-temperature roasting in air;
(3), step (2) is obtained product of roasting again through last handling process, promptly make phosphor powder of composite oxide of the present invention.
In described step (1), described compound and salt comprise A, M, the pairing oxide compound of R, sulfide, halogenide, carbonate, nitrate or organic acid salt etc.;
In described step (1), be reaction flux with at least a in halogenide, ammonium chloride, boric acid, boron trioxide, sodium sulfate and the potassium primary phosphate of the halogenide that contains A, M.
In described step (1), with respect to the gross weight of the fluorescent material that will make, the addition of fusing assistant is 0.001-10wt%.
In described step (1), grinding can be in solution such as ethanol, acetone or directly dry method carry out;
In described step (2), high-temperature roasting can be once, or several times, each high-temperature roasting time is 0.5～15 hour
In described step (2), each high-temperature roasting temperature is 500～1500 ℃.
In described step (3), last handling process comprises fragmentation, comminution by gas stream, removal of impurities, oven dry, classification.
In described step (3), the removal of impurities process comprises pickling or/and washing in the aftertreatment.
In described step (3), classification process can adopt one or more in the methods such as settling process, method of sieving, hydraulic classification and air classification in the aftertreatment.
Synthetic phosphor powder of composite oxide of the present invention can effectively be excited by 280nm～490nm light, thereby can be coated in and prepare novel white light LEDs on the blue-light LED chip; Also can be complementary, be used for the preparation of white light LEDs, the energy conversion rate height with purple light or ultraviolet leds; Also can be complementary with blue light, purple light or ultraviolet leds, or the fluorescent material of other type of remix, prepare bright color LED.And the fluorescent material synthetic method that the present invention relates to is simple, easy handling, and pollution-free, cost is low.Therefore, adopt fluorescent material of the present invention can make following electric light source.
A kind of electric light source contains UV-light or purple light or blue-ray LED and phosphor powder of composite oxide A of the present invention
aMO
4: R
x
Wherein, A is Y, La, Gd, Li, N a, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, one or more among Cd and the Ag;
M is one or more among Cr, Mo, W, V, Nb, Ta, Ti, Zr and the Hf;
R is Pr, Sm, one or more among Tb and the Dy;
0.1≤a≤2，0.0001≤x＜0.5。
Characteristics of the present invention are:
1, material property of the present invention is highly stable, processing such as its process bubble, alkali soak, heat, and the performance of fluorescent material does not change substantially.
2, the excitation spectrum scope of material of the present invention is very wide, and is all very good from the stimulation effect of 280-490nm.
3, simple, pollution-free, the easy handling of this fluorescent material manufacture method.
Description of drawings
Fig. 1 is emmission spectrum (a) and the exciting light spectrogram (b) of embodiment 1
Fig. 2 is emmission spectrum (a) and the exciting light spectrogram (b) of embodiment 21
Fig. 3 is emmission spectrum (a) and the exciting light spectrogram (b) of embodiment 31
Fig. 4 is emmission spectrum (a) and the exciting light spectrogram (b) of embodiment 41
Embodiment
Embodiment 1:Ca
0.985MoO
4: Pr
0.015The preparation embodiment of fluorescent material
Take by weighing MoO
33.6067g, CaO1.3841g, Pr
6O
110.0091g, H
3BO
30.05g above raw material is analytical pure, wherein, and H
3BO
3As reaction flux.With the above-mentioned raw materials mix grinding evenly after, the alumina crucible roasting in air of packing into, 800 ℃ of insulations 3 hours, products obtained therefrom promptly got burn red fluorescent material of the present invention through broken, washing removal of impurities, oven dry.Its emmission spectrum and excitation spectrum are seen Fig. 1, from scheming to find out that easily this fluorescent material can effectively be excited by the light of 280-320nm and 420-490nm wave band and launch the ruddiness that peak wavelength is positioned at 649nm.Its relative emissive porwer sees Table 1.
Embodiment 2-embodiment 20: take by weighing pairing raw material by each embodiment chemical formula composition and stoichiometry in the table 1, preparation process is identical with embodiment 1, wherein employed reaction flux is one or more in halogenide, ammonium chloride, boric acid, boron trioxide, sodium sulfate and the potassium primary phosphate of the halogenide that contains A, M, obtains chemical constitution and luminous intensity sees Table 1.
Chemical formula and the luminous intensity thereof of table 1 embodiment 1-20
| Embodiment | Chemical formula | Relative intensity (%) | |
| 300nm excites | 476nm excites | ||
| 1 | Ca 0.985MoO 4:Pr 0.015 | 92 | 100 |
| 2 | Sr 0.98WO 4:Pr 0.02 | 90 | 99 |
| 3 | Mg 0.92MoO 4:Pr 0.08 | 102 | 107 |
| 4 | Y 0.6WO 4:Pr 0.06 | 106 | 110 |
| 5 | La 0.61MoO 4:Pr 0.05 | 103 | 109 |
| 6 | Gd
0.54MoO
4: |
100 | 106 |
| 7 | Li 1.96MoO 4:Pr 0.02 | 112 | 126 |
| 8 | Na 1.92WoO 4:Pr 0.04 | 108 | 117 |
| 9 | K 1.98WO 4:Pr 0.01 | 111 | 121 |
| 10 | Rb 1.9MoO 4:Pr 0.05 | 107 | 115 |
| 11 | Cs 1.95WO 4:Pr 0.025 | 101 | 108 |
| 12 | Zn 0.88MoO 4:Pr 0.12 | 120 | 134 |
| 13 | Cd 0.9WO 4:Pr 0.1 | 116 | 129 |
| 14 | Ag 0.6MoO 4:Pr 0.06 | 109 | 114 |
| 15 | K 0.172Zn 0.9W 0.5Mo 0.5O 4:Pt 0.012 | 112 | 123 |
| 16 | Y 0.5Cd 0.4V 0.5W 0.5O 4:Pr 0.008 | 104 | 113 |
| 17 | K 1.2Ca 0.5Mo 0.6Cr 0.4O 4:Pr 0.01 | 101 | 108 |
| 18 | Sr 0.5Ca 0.8V 0.5Ti 0.5O 4:Pr 0.008 | 99 | 105 |
| 19 | La 0.72Gd 0.1Ta 0.52Hf 0.48O 4:Pr 0.005 | 98 | 105 |
| 20 | Y 0.05Ca 0.9Zr 0.5Nb 0.5O 4:Pr 0.008 | 97 | 103 |
Embodiment 21:Ca
0.99WO
4: Sm
0.01The preparation embodiment of fluorescent material
Take by weighing WO
34.0097g, CaO0.9602g, Sm
2O
30.0302g, NH
4Cl0.1g, above raw material is analytical pure, wherein, NH
4Cl is as reaction flux.With the above-mentioned raw materials mix grinding evenly after, the alumina crucible roasting twice in air of packing into is for the first time 1000 ℃ of insulations 2 hours, for the second time 1300 ℃ of insulations 5 hours, products obtained therefrom obtains of the present invention orange-red light fluorescent material through broken, alkali cleaning washing removal of impurities, oven dry.Its emmission spectrum and excitation spectrum are seen Fig. 2, find out easily from scheming, and this fluorescent material can effectively be excited by the light of 360-490nm wave band and launch peak wavelength and be positioned at ruddiness about 645nm.Its relative emissive porwer sees Table 2.
Embodiment 22:K
0.172Zn
0.9W
0.5Mo
0.5O
4: Sm
0.012The preparation embodiment of fluorescent material takes by weighing WO
32.0195g, MoO
31.2538g, Sm
2O
30.0365g, K
2CO
30.4141g, ZnO1.2761g, KH
2PO
40.15g, wherein, KH
2PO
4As reaction flux.Its preparation method is identical with embodiment 21.Obtain of the present invention orange-red light fluorescent material, its emmission spectrum and the same Fig. 2 of excitation spectrum shape.Embodiment 23-embodiment 40: take by weighing pairing raw material by each embodiment chemical formula composition and stoichiometry in the table 2, preparation process is identical with embodiment 21, wherein employed reaction flux is one or more in halogenide, ammonium chloride, boric acid, boron trioxide, sodium sulfate and the potassium primary phosphate of the halogenide that contains A, M, obtains chemical constitution and luminous intensity sees Table 2.
Chemical formula and the luminous intensity thereof of table 2 embodiment 21-40
| Embodiment | Chemical formula | Relative intensity (%) | |
| 406nm excites | 465nm excites | ||
| 21 | Ca 0.99WO 4:Sm 0.01 | 187 | 153 |
| 22 | K 0.172Zn 0.9W 0.5Mo 0.5O 4:Sm 0.012 | 172 | 150 |
| 23 | Ba 0.997MoO 4:Sm 0.0003 | 105 | 94 |
| 24 | Sr 0.975MoO 4:Sm 0.025 | 185 | 170 |
| 25 | La 0.6WO 4:Sm 0.1 | 164 | 145 |
| 26 | Gd 0.57WO 4:Sm 0.14 | 163 | 145 |
| 27 | Na 1.97MoO 4:Sm 0.06 | 177 | 156 |
| 28 | K 1.98WO 4:Sm 0.04 | 170 | 151 |
| 29 | Li 1.9CrO 4:Sm 0.25 | 123 | 105 |
| 30 | Cs 1.9MoO 4:Sm 0.05 | 104 | 90 |
| 31 | Rb 1.95WO 4:Sm 0.025 | 125 | 108 |
| 32 | Zn 0.85MoO 4:Sm 0.15 | 148 | 126 |
| 33 | Cd 0.91WO 4:Sm 0.09 | 169 | 147 |
| 34 | Ag 0.58MoO 4:Sm 0.4 | 155 | 137 |
| 35 | Ag 0.2Sr 0.8W 0.2Mo 0.8O 4:Sm 0.01 | 182 | 161 |
| 36 | Y 0.5Sr 0.4Ta 0.75W 0.25O 4:Sm 0.3 | 146 | 134 |
| 37 | Cs 1.2Ca 0.5Hf 0.56Cr 0.44O 4:Sm 0.01 | 133 | 119 |
| 38 | Sr 0.5Zn 0.8W 0.5Zr 0.5O 4:Sm 0.008 | 134 | 120 |
| 39 | Gd 0.72Ag 0.1Ta 0.52Mo 0.48O 4:Sm 0.005 | 136 | 119 |
| 40 | Y
0.05Ca
0.9Ti
0.5Nb
0.5O
4: |
100 | 90 |
Embodiment 41:Y
0.6WO
4: Tb
0.06The preparation embodiment of fluorescent material
Take by weighing WO
33.7298g, Y
2O
31.0898g, Tb
4O
70.1804g, H
3BO
30.005g, Na
2SO
40.1g, wherein, H
3BO
3And Na
2SO
4As reaction flux.Its preparation method is identical with embodiment 21.Obtain green-emitting phosphor of the present invention.Its emmission spectrum and excitation spectrum are seen Fig. 3, find out easily from scheming, and this fluorescent material can effectively be excited by the light about the 480nm wave band and launch peak wavelength and be positioned at green glow about 543nm.Its relative emissive porwer sees Table 3.
Embodiment 42-embodiment 60: take by weighing pairing raw material by each embodiment chemical formula composition and stoichiometry in the table 3, preparation process is identical with embodiment 21, wherein employed reaction flux is one or more in halogenide, ammonium chloride, boric acid, boron trioxide, sodium sulfate and the potassium primary phosphate of the halogenide that contains A, M, obtains chemical constitution and luminous intensity sees Table 3.
Chemical formula and the luminous intensity thereof of table 3 embodiment 41-60
| Embodiment | Chemical formula | Relative intensity (%) |
| 487nm excites | ||
| 41 | Y 0.6WO 4:Tb 0.06 | 165 |
| 42 | Sr 0.96WO 4:Tb 0.04 | 180 |
| 43 | Ca 0.9WO 4:Tb 0.1 | 188 |
| 44 | Ba 0.92MoO 4:Tb 0.08 | 165 |
| 45 | Gd 0.58MoO 4:Tb 0.12 | 148 |
| 46 | La 0.54WO 4:Tb 0.08 | 154 |
| 47 | Rb 1.96MoO 4:Tb 0.02 | 161 |
| 48 | Cs 1.92MoO 4:Tb 0.04 | 164 |
| 49 | Li 1.96WO 4:Tb 0.26 | 150 |
| 50 | K 1.92MoO 4:Tb 0.0008 | 152 |
| 51 | Na 1.94WO 4:Tb 0.03 | 155 |
| 52 | Zn 0.86WO 4:Tb 0.07 | 163 |
| 53 | Cd 0.94MoO 4:Tb 0.35 | 141 |
| 54 | Ag 0.5MoO 4:Tb 0.16 | 146 |
| 55 | K 0.2Ca 0.8W 0.7Mo 0.3O 4:Tb 0.012 | 178 |
| 56 | Gd 0.5Cd 0.4V 0.3Mo 0.7O 4:Tb 0.008 | 139 |
| 57 | KCa 0.6Mo 0.8Nb 0.2O 4:Tb 0.012 | 134 |
| 58 | Sr 0.5Ca 0.8V 0.5Ti 0.5O 4:Tb 0.4 | 121 |
| 59 | Li 0.72Y 0.72Ta 0.52Hf 0.48O 4:Tb 0.0005 | 111 |
| 60 | Y
0.02Ba
0.95Zr
0.55Ti
0.45O
4: |
100 |
Embodiment 61:Li
1.96MoO
4: Dy
0.02The preparation embodiment of fluorescent material
Take by weighing MoO
33.2745g, Li
2CO
31.6473g, Dy
2O
30.0783g, KF0.005g, wherein, KF is as reaction flux.Its preparation method is identical with embodiment 1.Obtain of the present inventionly sending out emitting phosphor orange-yellow.Its emmission spectrum and excitation spectrum are seen Fig. 4, find out easily from scheming, and this fluorescent material can effectively be excited by the light about the 300-490nm wave band and launch peak wavelength and be positioned at gold-tinted about 572nm.Its relative emissive porwer sees Table 4.
Embodiment 62-embodiment 80: take by weighing pairing raw material by each embodiment chemical formula composition and stoichiometry in the table 4, preparation process is identical with embodiment 1, wherein employed reaction flux is one or more in halogenide, ammonium chloride, boric acid, boron trioxide, sodium sulfate and the potassium primary phosphate of the halogenide that contains A, M, obtains chemical constitution and luminous intensity sees Table 4.
Chemical formula and the luminous intensity thereof of table 4 embodiment 61-80
| Embodiment | Chemical formula | Relative intensity (%) | |
| 388nm excites | 477nm excites | ||
| 61 | Li 1.96MoO 4:Dy 0.02 | 156 | 179 |
| 62 | Ba 0.9998WO 4:Dy 0.0002 | 108 | 115 |
| 63 | La 0.64MoO 4:Dy 0.02 | 137 | 144 |
| 64 | Mg 0.96MoO 4:Dy 0.04 | 140 | 152 |
| 65 | Gd 0.61WO 4:Dy 0.05 | 135 | 140 |
| 66 | Y 0.6MoO 4:Dy 0.25 | 138 | 142 |
| 67 | Ca 0.98WO 4:Dy 0.06 | 187 | 192 |
| 68 | Cs 1.9MoO 4:Dy 0.05 | 139 | 146 |
| 69 | Rb 1.98WO 4:Dy 0.01 | 130 | 141 |
| 70 | K 1.9MoO 4:Dy 0.35 | 128 | 137 |
| 71 | Na 1.95WO 4:Dy 0.025 | 136 | 140 |
| 72 | Cd 0.85MoO 4:Dy 0.15 | 117 | 124 |
| 73 | Zn 0.9994WO 4:Dy 0.0006 | 157 | 168 |
| 74 | Ag 0.63WO 4:Dy 0.03 | 144 | 156 |
| 75 | K 0.2Ca 0.9W 0.8Mo 0.2O 4:Dy 0.02 | 182 | 195 |
| 76 | Sr 0.5Zn 0.494Hf 0.1W 0.9O 4:Dy 0.006 | 130 | 139 |
| 77 | K 1.1Ca 0.6Mo 0.6Ta 0.4O 4:Dy 0.02 | 126 | 135 |
| 78 | Y 0.5Ca 0.8V 0.5Zr 0.5O 4:Dy 0.48 | 107 | 116 |
| 79 | La 0.72Ba 0.1Ta 0.52W 0.48O 4:Dy 0.005 | 118 | 127 |
| 80 | Gd 0.05Ca 0.76Zr 0.5Ti 0.5O 4:Dy 0.005 | 94 | 100 |
Embodiment 81-embodiment 100: take by weighing pairing raw material by each embodiment chemical formula composition and stoichiometry in the table 5, preparation process is identical with embodiment 1, wherein employed reaction flux is one or more in halogenide, ammonium chloride, boric acid, boron trioxide, sodium sulfate and the potassium primary phosphate of the halogenide that contains A, M, obtains chemical constitution and luminous intensity sees Table 5.
Chemical formula and the luminous intensity thereof of table 5 embodiment 81-100
| Embodiment | Chemical formula | Relative intensity (%) | |
| 406nm excites | 465nm excites | ||
| 81 | Sr
0.9994MoO
4:Pr
0.005， |
100 | 147 |
| 82 | La 0.6648WO 4:Pr 0.1，Tb 0.002 | -- | 142 |
| 83 | K 1.978CrO 4:Pr 0.02，Dy 0.008 | -- | 149 |
| 84 | Zn 0.95VO 4:Pr 0.04，Sm 0.008，Dy 0.002 | 110 | 148 |
| 85 | Ag 0.61Zr 0.2Hf 0.8O 4:Pr 0.01，Sm 0.002，Tb 0.003 | 113 | 131 |
| 86 | Ca 0.989WO 4:Sm 0.01，Pr 0.001 | 146 | 190 |
| 87 | Y 0.6545MoO 4:Sm 0.005，Tb 0.0005 | 139 | 184 |
| 88 | Na 1.972VO 4:Sm 0.02，Dy 0.008 | 137 | 176 |
| 89 | Cd 0.95ZrO 4:Sm 0.45，Tb 0.004，Dy 0.001 | 118 | 169 |
| 90 | Ca 0.988Cr 0.6Hf 0.4O 4:Sm 0.03，Pr 0.001，Tb 0.001 | 124 | 167 |
| 91 | Mg 0.9994TiO 4:Tb 0.005，Pr 0.001 | -- | 136 |
| 92 | Gd 0.6648ZrO 4:Tb 0.2，Sm 0.002 | 115 | 141 |
| 93 | Li 1.955HfO 4:Tb 0.04，Dy 0.005 | -- | 127 |
| 94 | Mg 0.97MoO 4:Tb 0.02，Pr 0.001，Dy 0.0009 | -- | 148 |
| 95 | Rb 1.95Ti 0.7Ta 0.3O 4:Tb 0.06，Sm 0.005，Dy 0.005 | 114 | 139 |
| 96 | Ba 0.96NbO 4:Dy 0.1，Pr 0.005 | -- | 144 |
| 97 | Y 0.33La 0.23TiO 4:Dy 0.009，Sm 0.0001 | 107 | 137 |
| 98 | Ca 0.4K 1.12ZrO 4:Dy 0.055，Tb 0.0025 | -- | 136 |
| 99 | Ag 0.14Zn 0.9HfO 4:Dy 0.25，Sm 0.003，Tb 0.002 | 103 | 125 |
| 100 | Gd 0.65Mo 0.6W 0.4O 4:Dy 0.01，Pr 0.002，Sm 0.008 | 108 | 132 |
In sum, fluorescent material of the present invention has characteristics such as chemical stability is good, luminous intensity is high, can effectively excite in 280～490nm scope, and manufacture method is simple, pollution-free, cost is low.
Claims (10)
1, a kind of phosphor powder of composite oxide that can effectively be excited by ultraviolet, purple light or blue-ray LED, it is characterized in that: the chemical formula of this material is: A
aMO
4: R
x
Wherein, A is Y, La, Gd, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, one or more among Cd and the Ag;
M is one or more among Cr, Mo, W, V, Nb, Ta, Ti, Zr and the Hf;
R is Pr, Sm, one or more among Tb and the Dy;
0.1≤a≤2，0.0001≤x＜0.5。
2, a kind of method for preparing the described a kind of phosphor powder of composite oxide that can effectively be excited by ultraviolet, purple light or blue-ray LED of claim 1 is characterized in that:
(1), metal or compound or salt to contain A, contain metal or compound or the salt of M, the compound or the salt that contain R are raw material, mole proportioning by above-mentioned chemical formula expression requirement converses the weight of pairing above-mentioned raw materials respectively, and adds an amount of fusing assistant, porphyrize mixes;
(2), the mixture that step (1) is obtained carries out high-temperature roasting in air;
(3), step (2) is obtained product of roasting again through last handling process, promptly make a kind of phosphor powder of composite oxide that can effectively be excited by ultraviolet, purple light or blue-ray LED.
3, the manufacture method of a kind of phosphor powder of composite oxide that can effectively be excited by ultraviolet, purple light or blue-ray LED according to claim 2, it is characterized in that: in described step (1), be reaction flux with at least a in the halogenide of the halogenide that contains A, M, ammonium chloride, boric acid, the boron trioxide, in sodium sulfate and the potassium primary phosphate.
4, the manufacture method of a kind of phosphor powder of composite oxide that can effectively be excited by ultraviolet, purple light or blue-ray LED according to claim 2, it is characterized in that: in described step (1), with respect to the gross weight of the fluorescent material that will make, the addition of fusing assistant is 0.001-10wt%.
5, the manufacture method of the fluorescent material of a kind of can effectively being excited according to claim 2 and burn red by ultraviolet, purple light or blue-ray LED, it is characterized in that: in the described step (2), high-temperature roasting is for once, or several times, each high-temperature roasting time is 0.5～15 hour.
6, the manufacture method of a kind of phosphor powder of composite oxide that can effectively be excited by ultraviolet, purple light or blue-ray LED according to claim 2 is characterized in that: in the described step (2), each high-temperature roasting temperature is 500～1500 ℃.
7, the manufacture method of a kind of phosphor powder of composite oxide that can effectively be excited by ultraviolet, purple light or blue-ray LED according to claim 2, it is characterized in that: in the described step (3), last handling process comprises fragmentation, comminution by gas stream, removal of impurities, oven dry, classification.
8, the manufacture method of a kind of phosphor powder of composite oxide that can effectively be excited by ultraviolet, purple light or blue-ray LED according to claim 7 is characterized in that: described removal of impurities process comprises alkali cleaning or/and washing.
9, according to the manufacture method of claim 7 or 8 described a kind of phosphor powder of composite oxide that can effectively be excited by ultraviolet, purple light or blue-ray LED, it is characterized in that: described classification process can adopt one or more in settling process, method of sieving, the gentle flow point level method of hydraulic classification.
10, a kind of electric light source is characterized in that: contain the described fluorescent material A of ultraviolet, purple light or blue-ray LED and claim 1
aMO
4: R
y
Wherein, A is Y, La, Gd, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, one or more among Cd and the Ag; M is one or more among Cr, Mo, W, V, Nb, Ta, Ti, Zr and the Hf; R is Pr, Sm, one or more among Tb and the Dy; 0.1≤a≤2,0.0001≤x＜0.5.
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| CN101126025B (en) * | 2007-09-26 | 2010-10-13 | 罗维鸿 | Red light fluorescent powder and multilayer light conversion film |
| CN101781555A (en) * | 2009-01-16 | 2010-07-21 | 中国科学院福建物质结构研究所 | Deep red phosphor powder suitable to be excited by blue LED, preparation method thereof, and electric light source made by same |
| CN101649199B (en) * | 2009-06-23 | 2014-01-22 | 北京航空航天大学 | Ultraviolet light stimulated phosphor |
| CN101629079B (en) * | 2009-08-17 | 2012-12-26 | 浙江理工大学 | Method for preparing green luminescent material of yttrium zirconate doped with terbium |
| CN101629078B (en) * | 2009-08-17 | 2012-11-14 | 浙江理工大学 | Method for preparing cubic shape green luminescent material of lanthanum zirconate doped with cerium and terbium |
| CN102002362B (en) * | 2010-09-14 | 2013-05-22 | 南昌大学 | Fluorescent powder for white light LED, preparation method and application thereof |
| CN101974334B (en) * | 2010-09-25 | 2014-08-20 | 西安理工大学 | Single-phase rare earth vanadium phosphate white fluorescent powder for mercury lamp and preparation method thereof |
| CN102002363B (en) * | 2010-09-25 | 2013-07-31 | 西安理工大学 | Single matrix white light fluorescent powder for deep ultraviolet LED (Light Emitting Diode) and preparation method thereof |
| CN101974329B (en) * | 2010-10-08 | 2013-12-11 | 东华大学 | La2Ti2O7:Sm3+ red phosphor and preparation method thereof |
| CN102268256B (en) * | 2011-06-09 | 2013-10-30 | 同济大学 | Fluorescent material able to emit red and green lights under excitation of blue lights and preparation method thereof |
| CN103436261B (en) * | 2013-08-16 | 2015-02-25 | 陕西科技大学 | Titanate red fluorescent powder suitable for applying to white-light LED and preparation method thereof |
| CN105133015B (en) * | 2015-08-06 | 2017-10-13 | 中国科学院理化技术研究所 | One kind doping vanadic acid terbium magneto-optical crystal, growing method and its application |
| CN110862822A (en) * | 2019-12-06 | 2020-03-06 | 成都理工大学 | Molybdate-based red fluorescent powder and preparation method and application thereof |
| CN114031400B (en) * | 2021-11-23 | 2023-01-20 | 松山湖材料实验室 | Single-phase warm white fluorescent ceramic and preparation method and application thereof |
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| CN1482208A (en) * | 2002-09-13 | 2004-03-17 | 北京有色金属研究总院 | Blue light-excitated white phosphor powder for LED and production method thereof |
| CN1506439A (en) * | 2002-12-07 | 2004-06-23 | 中国科学院长春光学精密机械与物理研 | Red RE oxide luminophor and its prepn |
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| CN1482208A (en) * | 2002-09-13 | 2004-03-17 | 北京有色金属研究总院 | Blue light-excitated white phosphor powder for LED and production method thereof |
| CN1506439A (en) * | 2002-12-07 | 2004-06-23 | 中国科学院长春光学精密机械与物理研 | Red RE oxide luminophor and its prepn |
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