CN1067423C - High-lightness high-distinguishability single-crystal colour projection display bube - Google Patents
High-lightness high-distinguishability single-crystal colour projection display bube Download PDFInfo
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- CN1067423C CN1067423C CN96117603A CN96117603A CN1067423C CN 1067423 C CN1067423 C CN 1067423C CN 96117603 A CN96117603 A CN 96117603A CN 96117603 A CN96117603 A CN 96117603A CN 1067423 C CN1067423 C CN 1067423C
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- 239000013078 crystal Substances 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000002223 garnet Substances 0.000 claims abstract description 19
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- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 59
- 239000000758 substrate Substances 0.000 claims description 27
- 239000012071 phase Substances 0.000 claims description 16
- 230000005284 excitation Effects 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910010293 ceramic material Inorganic materials 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 5
- 239000000155 melt Substances 0.000 claims 5
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims 3
- 238000004943 liquid phase epitaxy Methods 0.000 claims 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims 1
- 229910003443 lutetium oxide Inorganic materials 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 229910052706 scandium Inorganic materials 0.000 abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 23
- 238000001228 spectrum Methods 0.000 description 17
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 14
- 230000003595 spectral effect Effects 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
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- 230000004044 response Effects 0.000 description 6
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- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000407 epitaxy Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000005090 crystal field Methods 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 206010027476 Metastases Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 210000000080 chela (arthropods) Anatomy 0.000 description 1
- 238000012505 colouration Methods 0.000 description 1
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- 230000006735 deficit Effects 0.000 description 1
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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- 210000000088 lip Anatomy 0.000 description 1
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- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明介绍了一种高亮度、高分辨率单晶彩色投影显示管及制作工艺。其显示屏是用外延技术制备的单晶荧光体。外延单晶石榴石相荧光膜成分Y3-x-y-zCexREyMzAl5-wQwO12，其中0≤x≤0.1、0≤y≤3、0≤z≤1、0＜w≤3，且x+y+z≤3。RE指除Ce外的一种或几种稀土元素。M指Bi、Cr等元素，Q指V、Ga、Cr、Sc等元素，其中V为敏化剂，通过采用选择不同的熔料配方控制外延膜成分结构、晶格参数的办法，可在衬底上外延出晶格完整无缺陷的红、绿、蓝单晶荧光膜。采用该三色单晶屏的CRT管，实现了高亮度、高分辩率投影显示系统。The invention introduces a high-brightness, high-resolution single-crystal color projection display tube and its manufacturing process. Its display screen is a single crystal phosphor prepared by epitaxial technology. Composition of epitaxial single crystal garnet phase fluorescent film Y 3-xyz Ce x RE y M z Al 5-w Q w O 12 , where 0≤x≤0.1, 0≤y≤3, 0≤z≤1, 0<w ≤3, and x+y+z≤3. RE refers to one or several rare earth elements other than Ce. M refers to elements such as Bi and Cr, and Q refers to elements such as V, Ga, Cr, and Sc, among which V is a sensitizer. Red, green and blue single crystal fluorescent films with complete crystal lattice and no defects are epitaxially grown on the bottom. The CRT tube of the three-color single-crystal screen is used to realize a projection display system with high brightness and high resolution.
Description
The invention belongs to and make colour projection's typotron, particularly the manufacturing technology of luminescent screen wherein.
Window of tube in the colour display tube is key part in the technique of display.The display equipment CRT pipe (cathode tube) that utilization now is very general, its luminescent material is the Powdered fluorescent substance of three looks (red, green, blue) that is deposited on the transparent screen, the display brightness of CRT pipe is decided by the luminous efficiency of fluorescent substance and the height of incident excited electrons beam energy fully, the fluorescent material of present common employing only under lower electron impact power density＜10
4W/m
2, could guarantee certain luminous efficiency, if the incident excitation energy be higher than＞10
4W/m
2The time, light-emitting phosphor efficient can descend rapidly, and this is that the electronics of high projectile energy causes burning of fluorescent material, has restricted the brightness and the life-span of CRT pipe because the thermal characteristics of fluorescent material is relatively poor; For the powder window of tube, the size of luminous spot not only depends on the size of screen bundle spot on the electron beam, and depends on the intergranular scattering of light of fluorescent substance.Screen bundle spot became enough hour on the electron beam when well-designed electron beam gun makes, and the intergranular scattering of light of fluorescent substance is the deciding factor of restriction window of tube limiting resolution.Along with the development of information technology, urgent day by day to the requirement of high brightness, high resolving power demonstration in recent years, the CRT pipe of traditional employing powder screen structure can't satisfy this requirement, is necessary to seek a kind of novel luminescent material.Find single crystal fluorescent material in the research, particularly garnet phase monocrystal fluor has higher luminescence quenching temperature, up to 10
9W/m
2Projectile energy when exciting, its luminous intensity does not have obvious saturated phenomenon, material itself has good thermal characteristics, and to unrestricted or the like the excellent properties of display resolution, it is the ideal material of realizing that high brightness, high resolving power show, therefore become a focus in the luminescent material research field in recent years, below several pieces of documents can embody the progress of this research direction over 30 years:
1.G.Blasse A.Bril is published in " Applied Physics wall bulletin " (Appl.phys.letts) 1967.11 one piece of article rolling up on 53 phases: " the novel fluorescence body Ce of the flying-spot scanner CRT of jaundice light
3+: Y
3Al
5O
12" (A new phosphor for flying spot cathode-ray tubes for yellowemitting Y
3Al
5O
12: Ce
3+) and they 1971 the application US.patent No.3,564,322 " flying-spot scanner CRT pipes " (Cathode-ray tube for flying-spot scanning).Ce in the report
3+: Y
3Al
5O
12Material (Ce-cerium, YAG-yttrium aluminum garnet) is to be the Ce of host lattice with YAG
3+Ion is the wavelength X of luminescence center
MaxThe single crystal fluorescent material of=555nm, glow color is yellow-green colour, is not suitable for visual custom, also the green standard of discontented football lottery look display requirement, but it demonstrates the superiority of monocrystalline garnet phase material as fluorescent material fully, and this is found to be follow-up further research and has indicated direction.Then pass through the research experiment in many years of numerous researchers, sum up that available other rare earth element replaced C e makes light emitting ionic on this material foundation, or substitute yttrium (Y in the YAG host lattice with rare earth element and other trivalent element such as gallium (Ga), indium (In), scandium (Sc) or the like
3+), aluminium (Al
3+) crystallographic site, with of the effect of change crystal field, thereby adjust Ce to light emitting ionic
3+The spectral response curve of ionoluminescence, and think that this class garnet phase fluor should have so chemical ingredients:
Y
3-x-yCe
xRE
yAL
5-wZ
wO
12
Wherein Y-yttrium, Ce-cerium, RE-refer to one or more rare earth elements except that Ce
Al-aluminium, Z-refer to Ga, In, Sc trivalent element, O-oxygen
0≤x≤0.1,0≤y≤3,0≤w≤3
X+y≤3 wherein
2.J.M.ROBERTSON Deng the article " Ce in the epitaxy single-crystal garnet layer that on " Philips's research " (philipsjoumal ofresearch) first phases 36 in 1981 volume, delivers
3+The color of ionoluminescence shifts " (Colourshift of the Ce
3+Emission in monocrys-talline epitaxially grown garnetlayers) reported transfer Ce in the article
3+The research of luminosity spectral characteristic, they on the YAG substrate extension Y
1.903Ce
0.008Lu
1.080Al
4.339Ga
0.668O
12Fluorescent layer, its λ
Max=538nm is with the λ of Ce:YAG
MaxThe spectral response curve of=555nm is compared, and this material has the ideal green spectral response curve, but Ce in this material
3+Ionoluminescence efficiency ratio Ce: the YAG material has descended 40%; At Ce
3+Ionoluminescence is to long wave direction study of metastasis aspect, the Ce of people such as Robertson extension on the YAG substrate
0.010Y
1.507Gd
1.395Al
5.006O
12Fluorescent layer, λ
Max=574nm, but Ce
3+Ionoluminescence efficiency ratio Ce: the YAG material has descended 15%, and spectral response curve is also not ideal, and the epitaxial film defective is serious; They are at Y
3Al
3.5Ga
1.5O
12The Ce of extension: Gd on the substrate
3Al
5O
12Film, luminous efficiency approaches Ce: YAG material, λ
Max=587nm thinks by suitable filtering, can be used as red fluorescence material, but because Gd
3Al
5O
12Lattice parameter bigger, can't mate with present obtainable substrate material, therefore, above-mentioned epitaxial film has a large amount of facet defectives to produce, quality of forming film is poor; For realizing Ce
3+Ionoluminescence is shifted to the shortwave direction, they on the YAG substrate extension composition be Ce
0.006Lu
2.967Al
3.972Ga
1.025In
0.029O
12Fluorescent screen, but serious be full of cracks defective has appearred in the film, by the visible λ of this material luminous spectrum
Max=513nm+405nm is two peak structure, luminous efficiency and Ce: the YAG material is compared the order of magnitude that descended, and can't satisfy the blue requirement that shows.
3.1985 No. 014293 " utilizing the indicating system of high luminous intensity monocrystalline garnet material " (Visual display systemutilizing high luminosity single crystal garnet material) of European patent EP that philtrums such as year Berkstresser George Wayne are asked points out that composition is Y
3-x-y-zCe
xTb
yRE
zAl
5-wX
wO
12The monocrystalline garnet phase structure epitaxial film of (wherein Tb-terbium, Al-aluminium, RE-refer to one or more rare earth elements that Tb, Ce are outer, and X-refers to Ga, In, Sc element) is a kind of comparatively ideal green fluorescent material, and has enumerated extension Y on the YAG substrate
1.958Lu
0.93Tb
0.10Ce
0.012Al
4.24Ga
0.76O
12The melt prescription and the processing parameter of film have provided the spectrum synoptic diagram, and as seen its luminescent spectrum is typical Tb
3+, Ce
3+Luminous stack spectral is fit to the green needs that show, but Lu/Ga ≌ 1.22 in the epitaxial film, and ratio is improper to cause between epitaxial film and YAG substrate lattice mismatch serious, and defective is obvious, and quality of forming film is poor.
4.Berkstresser Deng in another part PCT patent WO86/00633 " light-emitting display apparatus " (Luminescent displaydevice) in 1985, pointing out to utilize Bi
3+The Y of (bismuth) ionoluminescence
3-x-yBi
xRE
yAl
5-zGa
zO
12Monocrystalline garnet phase epitaxy layer can be used as a kind of blue emitting phophor.Patent has also specifically provided Y
2.95Bi
0.05Al
5O
12The melt prescription of epitaxial film, the manufacture craft parameter is by visible this material λ of the curve of spectrum of data
Max〉=425nm, wavelength are short partially, and luminous efficiency is lower.
Comprehensive above-mentioned document can find to have seen that work reported only is confined to the luminous single crystal phosphor material of certain solid color, these materials still have some deficits on effciency of energy transfer, epitaxial film crystalline network (being epitaxial film and the material coupling at the end), are difficult to realize that high brightness, high-resolution color show.
Purpose of the present invention is in order to overcome the weak point in the monocrystalline demonstration aspect prior art, to realize high brightness, high-resolution color Projection Display.
To achieve these goals, technical scheme of the present invention is: by adopting new melt prescription, epitaxy technique prepares novel monocrystalline garnet phase fluorescent material, reaches from constituent structure and optimizes, and improves the purpose of material property on the crystalline network.
High brightness of the present invention, high resolving power monocrystalline colour projection typotron, consist predominantly of the shell of the modulation, convergence, deflection system, glass or the ceramic material that encourage electron gun (electron beam, ultraviolet light beam etc.), excitation beam and special window of tube, it is characterized in that this window of tube is a single crystal fluorescent material, the single crystal fluorescent material that constitutes this screen has following composition:
Y
3-x-y-zCe
xRe
yM
zAl
5-wQ
wO
12
0≤x≤0.1?0≤y≤3?0≤z≤1?0＜w≤3
Wherein: x+y+z≤3, Y (yttrium), Ce (cerium), RE (one or more rare earth elements except that Ce), M (elements such as Cr-chromium, Bi-bismuth); Al (aluminium), Q (elements such as Sc-scandium, Cr-chromium, V-vanadium, Ga-gallium, In-indium); X, y, z, w are mole number.
Also different according to the single crystal fluorescent material composition that the difference formation of the colouration of screen is shielded, can be divided three classes.
One, green single crystal phosphor
The epitaxial film that constitutes green single crystal phosphor has following composition:
Y
3-x-y-zCe
xTb
yRE
zAl
5-w-uQ
wV
uO
12
0≤x≤0.1 0≤y≤1 0≤z≤2 0≤w＜30＜u≤3 are x+y+z≤3 wherein, x+y＞0, u+w≤3
RE refers to the lanthanide series rare-earth elements except that Ce (cerium), Tb (terbium), and Q refers to Ga (gallium), Sc (scandium) element, and V (vanadium) is a sensitizing agent.
Adopt Ce
3++ Tb
3+The two luminescence center structures of ionic can make material in spectral response curve, improve significantly than the Ce:YAG material on the performances such as effciency of energy transfer, in order further to improve the material luminescent properties, adopt V
3+Ion is as sensitizing agent, the V of excited state
3+Ion energy is to Ce
3+, Tb
3+Ion shifting can make Ce
3+, Tb
3+Ionoluminescence intensity is strengthened greatly.
In the YAG host lattice, use the less Lu of ionic radius
3+, Yb
3+Plasma partly replaces Y
3+Ion is with the bigger Ga of ionic radius
3+, Sc
3+Plasma substitutes part A l
3+Ion changes crystal field to Ce
3+The ionic effect can make Ce
3+The ionoluminescence spectral response curve is more suitable for the green requirement that shows, but the lattice parameter of epitaxial film can change along with different ion incorporations simultaneously, need select the ratio between the various ion components in the controlling diaphragm in order to ensure the lattice match of epitaxial film and substrate, extension Lu on the YAG substrate
3++ Ga
3+(replace RE with Lu in the mentioned component formula, substitute Q with Ga) during the codope film, at this moment the Lu/Ga ratio should remain on about 1.5, can realize excellent lattice matching between epitaxial film and YAG substrate.
Two, red single crystal phosphor
The epitaxial film that constitutes red single crystal has following composition:
Gd
3-x-y-zCe
xRE
yY
zAl
5-w-uQ
wV
uO
12
0≤x≤0.1 0≤y≤2 0≤z≤2 0≤w＜30＜u≤3 are x+y+z≤3 wherein, x+y＞0, u+w≤3
RE refers to other lanthanide series rare-earth elements except that Gd (gadolinium), Ce (cerium), and Q refers to Cr (chromium) or Ga (gallium) or Sc (scandium) trivalent element, and V (vanadium) is a sensitizing agent.
At Gd
3Al
5O
12In the host lattice of (yttrium aluminum garnet), Ce
3+The residing crystal field of ion is different from YAG host lattice field, Ce
3+Ionoluminescence is shifted to the long wave direction, λ
MaxCan reach more than the 590nm, in order to strengthen Ce
3+Ionoluminescence intensity adopts V
3+Ion is made sensitizing agent, simultaneously V
3+Ionic radius is less than Al
3+Ion, but the bigger Gd of counterion radius
3+Ion, suitable Gd/V ratio can guarantee epitaxial film and the good coupling of YAG substrate.
Adopt two luminescence center Cr
3++ Ce
3+Structure can further be improved the material spectrum characteristic, improves effciency of energy transfer.
Three, blue single crystal phosphor
The epitaxial film that constitutes blue single crystal has following composition:
Lu
3-x-y-zCe
xRE
yY
zAl
5-w-uQ
wV
uO
12
0≤x≤0.1 0≤y≤0.5 0≤z≤2 0≤w＜30＜u≤3 are x+y＞0 wherein, u+w≤3,
RE refers to the lanthanide series rare-earth elements except that Lu (lutetium), Ce (cerium), and Q refers to Ga, Sc, In element, and V is a sensitizing agent.
Luetcium aluminum garnet (Lu
3Al
5O
12) crystal field of host lattice is to Ce
3+The ionic effect can be effectively with Ce
3+Ionoluminescence is shifted to the shortwave direction, λ
MaxCan reach about 500nm.
Tb
3+Ionic concn is lower than 1.5 * 10
-2The time, the stimulated radiation transition mainly is
5D
3-
7F attitude, energy are higher than is excited Tb
3+Ion is common
5D
4-
7F attitude (λ ≈ 540nm) transition, luminescent spectrum is in blue wave band, adopts Ce
3++ Tb
3+Two luminescence center structures, can improve the blue color spectrum characteristic of material, improve effciency of energy transfer.Utilize Lu
3+, Ga
3+The ionic radius compensation effect is suitably adjusted the lattice match that the Lu/Ga ratio can realize epitaxial film and substrate effectively.Adopt V
3+Ion can make Ce as sensitizing agent
3+, Tb
3+Ionoluminescence is greatly strengthened.
The preparation of monocrystal epitaxial film is that employing liquid phase epitaxial method on garnet phase substrate is grown.
During making, at first will contain the oxide compound of epitaxial film composition, by the certain melt formula rate and the molten auxiliary agent uniform mixing of a great deal of, more than all batching purity requirement 4N (99.99%), fusing assistant adopts plumbous oxide (PbO), boron oxide (B
2O
3), bismuth oxide (Bi
2O
3), plumbous fluoride (PbF
2) in one or more combination all can.The batching that mixes is contained in the platinum pincers pot, under atmospheric atmosphere, carry out the thermostatically heating refining, temperature is 1250 ℃～1300 ℃, allow the oxide compound that contains garnet phase material composition under the fusing assistant effect, fully melt, form uniform aqueous melt, (supersolubility temperature is generally 10 ℃～50 ℃ then melt to be cooled to hypersaturated state, optimum value is about 30 ℃), stretch in melt Rotating with Uniform with the monocrystalline garnet phase substrate (as YAG) that cleans up behind the rubbing down this moment, can be on substrate the required monocrystalline fluorescent screen of epitaxy one deck.
The present invention is by selecting, in the control melt between various oxide components ratio be implemented in the mix lattice match of (promptly selecting volumetric molar concentration x, the y of each composition in the control epitaxial film, the size of z, w) and epitaxial film and substrate of the selection to epitaxial film in the epitaxial process, thereby epitaxy goes out the good red, green, blue monocrystalline garnet phase fluorescent screen of lattice perfection zero defect luminescent properties on the garnet phase substrate of selection.Adopt the CRT pipe of above-mentioned three look monocrystalline screen, can realize high brightness, high-resolution color projection display system.
Description of drawings:
Fig. 1 Ce
3+: Tb
3+: YLuAlGaO material luminescent spectrum figure
Fig. 2 Ce
3+: Tb
3+: V
3+: YLuAlGaO material luminescent spectrum figure
Fig. 3 Ce
3+: V
3+: GdYAlO material luminescent spectrum figure
Fig. 4 Ce
3+: Cr
3+: V
3+: GdYAlO material luminescent spectrum figure
Fig. 5 Ce
3+: Tb
3+: LuAlGaO material luminescent spectrum figure
Further specify the present invention by embodiment in conjunction with the accompanying drawings:
Embodiment one makes green-emitting phosphor
Melt prescription 1:Y
2O
3Be 10.259 grams; CeO
2Be 3.670 grams; Tb
4O
7It is 0.410 gram; Lu
2O
3Be 8.418 grams; Al
2O
3Be 17.386 grams; Ga
2O
3Be 17.186 grams; B
2O
3Be 31.08 grams; PbO is 1200 grams.
Above-mentioned batching evenly after the fusing, is cooled to 1060 ℃ and can carries out extension,＜111 the orientation diameter is the fluorescent screen that extension has gone out lattice perfection on the YAG substrate of 54mm, composition is Y
2.177Ce
0.014Tb
0.042Lu
0.860Al
4.321Ga
0.582O
12, luminescent spectrum is seen Fig. 1.λ
Max=540nm is a kind of ideal green fluorescent material, and test finds that luminous light intensity is 2 times of Ce:YAG material of early stage prepared, and its Lu/Ga=1.48 meets the coupling requirement.
Melt prescription 2:Y
2O
3Be 10.259 grams; CeO
2Be 3.155 grams; Tb
4O
7It is 0.683 gram; Lu
2O
3Be 5.413 grams; Al
2O
3Be 17.387 grams; Ga
2O
3Be 13.067 grams; V
2O
5Be 9.6 grams; B
2O
3Be 31.08 grams; PbO is 1200 grams.
Epitaxial temperature is that 1030 ℃, substrate are＜111〉the orientation diameter reaches the YAG wafer of 54mm, and the epitaxial film composition is Y
2.123Ce
0.017Tb
0.042Lu
0.807Al
4.462Ga
0.546V
0.002O
12, spectrum is seen Fig. 2, brightness measured is not add V
3+1.6 times of the aforementioned fluorescent layer brightness of sensitization, adopt 2 inches projection tubes that this fluor prepares as the CRT tube fluorescent screen under the exciting power of energy up to 50W, effciency of energy transfer is greater than 3.8Lu/w, resolving power can satisfy high brightness, high resolving power display requirement fully greater than 2000 line/inches.
Embodiment two makes red single crystal phosphor
Melt prescription 1:CeO
2Be 4.0 grams; Y
2O
3Be 4.159 grams; Gd
2O
3Be 17.313 grams; Al
2O
3Be 23.58 grams; V
2O
5Be 9.0 grams; B
2O
3Be 29.126 grams; PbO is 1125 grams.
Epitaxial temperature is 1060 ℃, and substrate is for＜111〉the orientation diameter is the YAG wafer of 54mm, epitaxial film composition: Gd
1.740Y
0.969Ce
0.015Al
5.272V
0.002O
12, spectrum is seen Fig. 3, λ
Max=590nm, adopt the CRT structure projection tube of this phosphor preparation, under the incident power of 50W, effciency of energy transfer can reach 1.5Lu/W, resolving power is greater than 2000 line/inches, after adopting suitable colour filter (620nm colour filter), can reach coupling, satisfy desirable colored display requirement with aforementioned green pipe.
Melt prescription 2:CeO
2Be 3.2 grams; Y
2O
3Be 3.763 grams; Gd
2O
3Be 15.66 grams; Al
2O
3Be 21.33 grams; V
2O
5Be 9.05 grams; Cr
2O
3Be 26.67 grams; B
2O
3Be 31.07 grams; PbO is 1120 grams.
When epitaxial temperature was 1060 ℃, the fluorescent screen composition of extension was Gd on the YAG substrate
1.782Y
0.894Ce
0.019Al
5.255Cr
0.046V
0.002O
12, spectrogram is seen Fig. 4.
Embodiment three makes blue single crystal phosphor
Melt prescription 1:CeO
2Be 1.25 grams; Tb
4O
7It is 0.042 gram; Lu
2O
3Be 7.725 grams; Y
2O
3It is 0.997 gram; Al
2O
3Be 11.210 grams; Ga
2O
3Be 39.642 grams; B
2O
3Be 29.125 grams; PbO is 1125 grams.
Epitaxial temperature is 1030 ℃, and substrate is for＜111〉the orientation diameter is the monocrystalline YAG of 54mm, the epitaxial film composition is Lu
2.213Y
0.780Ce
0.011Tb
0.011Al
3.613Ga
1.372O
12, spectrum is seen Fig. 5, λ
Max≤ 490nm, luminance test show that its luminous intensity reaches the Ce:YAG material of early stage technology, and 2 inches projection tubes that utilize this fluorescent material preparation are when incident power 50W, effciency of energy transfer is greater than 0.5Lu/W, resolving power is higher than 2000 line/inches, for satisfying blue display requirement, can adopt λ
MaxThe colour filter of=450nm, filtering its brightness of back can reach the requirement of ideal colour mixture with aforesaid redness, drop shadow green's pipe.
Melt prescription 2:CeO
2Be 2.955 grams; Tb
4O
7It is 0.034 gram; Lu
2O
3Be 8.236 grams; Y
2O
3Be 1.05 grams; Al
2O
3Be 11.771 grams; Ga
2O
3Be 31.833 grams; V
2O
5Be 11.56 grams; B
2O
3Be 29.125 grams; PbO is 1125 grams.
At epitaxial temperature is 1040 ℃, and substrate is for＜111〉the orientation diameter is on the YAG wafer of 54mm, and extension has gone out the flawless fluorescent screen of lattice perfection, and the epitaxial film composition is Lu
2.205Y
0.773Ce
0.018Tb
0.009Al
3.767Ga
1.225V
0.003O
12, its spectrum is similar to Fig. 5, is Ce
3++ Tb
3+Luminous stack spectral structure, luminance test show because V
3+Sensibilized and fluorescent screen in light emitting ionic Ce
3+The increase of concentration, its brightness have reached 2.5 times of the fluorescent screen that adopts 1 preparation of melt prescription.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117603A CN1067423C (en) | 1996-06-28 | 1996-06-28 | High-lightness high-distinguishability single-crystal colour projection display bube |
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|---|---|---|---|
| CN96117603A CN1067423C (en) | 1996-06-28 | 1996-06-28 | High-lightness high-distinguishability single-crystal colour projection display bube |
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|---|---|
| CN1169587A CN1169587A (en) | 1998-01-07 |
| CN1067423C true CN1067423C (en) | 2001-06-20 |
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|---|---|---|---|---|
| CN100366097C (en) * | 2005-07-13 | 2008-01-30 | 四川大学 | CRT projection true three-dimensional display system |
| CN100334185C (en) * | 2005-12-09 | 2007-08-29 | 天津理工大学 | Rare-earth yttrium-aluminium garnet luminous material and its gas-phase preparing method |
| DE102010021341A1 (en) * | 2010-05-22 | 2011-11-24 | Merck Patent Gmbh | phosphors |
| TWI491706B (en) * | 2010-10-05 | 2015-07-11 | Nemoto Lumi Materials Company Ltd | Green luminescent phosphor and light emitting device |
| CN102241982B (en) * | 2011-05-20 | 2014-02-19 | 电子科技大学 | A kind of LED fluorescent powder and preparation method thereof |
| CN102311734B (en) * | 2011-09-23 | 2013-09-04 | 辽宁大学 | Upconversion UV (ultraviolet) luminescent material of broadband spectral adsorption and application thereof |
| WO2013161683A1 (en) * | 2012-04-24 | 2013-10-31 | 株式会社光波 | Phosphor, method for manufacturing same, and light-emitting device |
| WO2015099145A1 (en) * | 2013-12-27 | 2015-07-02 | 国立大学法人京都大学 | Phosphor and method for producing phosphor |
| CH717559B1 (en) * | 2020-06-22 | 2024-11-15 | Brevalor Sarl | Translucent object consisting of a phosphorescent material and its use |
| CN113582679B (en) * | 2021-07-26 | 2023-02-07 | 江苏师范大学 | Fluorescent ceramic with high color rendering index and high thermal stability for white light illumination and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4550256A (en) * | 1983-10-17 | 1985-10-29 | At&T Bell Laboratories | Visual display system utilizing high luminosity single crystal garnet material |
-
1996
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4550256A (en) * | 1983-10-17 | 1985-10-29 | At&T Bell Laboratories | Visual display system utilizing high luminosity single crystal garnet material |
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