EP0190153A1 - Luminescent display device - Google Patents
Luminescent display deviceInfo
- Publication number
- EP0190153A1 EP0190153A1 EP85902773A EP85902773A EP0190153A1 EP 0190153 A1 EP0190153 A1 EP 0190153A1 EP 85902773 A EP85902773 A EP 85902773A EP 85902773 A EP85902773 A EP 85902773A EP 0190153 A1 EP0190153 A1 EP 0190153A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- equal
- less
- substrate
- luminescent material
- luminescent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
Definitions
- the invention is concerned with luminescent color display devices *
- Display devices such as, e.g., cathode ray tubes typically include a luminescent screen which locally emits optical radiation in response to locally incident electron or electromagnetic radiation.
- Luminescent screen materials may be chosen with respect to a number of criteria; in many applications such as, e.g., high resolution displays, projection systems, and direct viewing systems under strong ambient lighting conditions there is a particular concern with brightness of emitted radiation. Accordingly, luminescent screen materials are desired which are highly efficient in emitting radiation of a desired wavelength.
- Display devices may include luminescent materials or phosphors in powder form; however, such materials tend to have shortcomings such as, e.g., poor thermal properties, degradation of efficiency with stimulating radiation dose, and limited resolution.
- single-crystal slabs or layers of luminescent materials have been found to be capable of withstanding input power densities in excess of 10 10W/m2 without measurable degradation and to have improved resolution as compared to powder phosphor targets.
- Visual display devices embodying the invention comprise a source of stimulating electron or electromagnetic radiation, typically including deflection and modulation means, and a member comprising a substantially single-crystal phosphor material which is a garnet material consisting essentially of a composition substantially as represented by the formula
- R represents at least one rare earth element
- x_ is in the preferred range from 0.005 to 0.5, where preferably is less than or equal to 2.995, and where _z preferably is less than or equal to 5.
- rare earth elements Nd, Eu, Tm, and Tb are limited to amounts corresponding to y- values which are less than 0.01 and preferably less than or equal to 0.005.
- Preferred yttrium aluminum garnets have z_ less than or equal to 0.4 and preferably ⁇ _ less than or equal to 0 ⁇ 05,. and rare, earth elemeata other than Lu and Gd are preferably limited such that their combined contribution to the combined amount of rare earth elements is represented by a value of which is less than or equal to 0.2.
- suitable bismuth-containing garnet materials emit electromagnetic radiation whose spectrum has a peak at a wavelength which is greater than or equal to 425 nanometers.
- FIG. 1 is a schematic cross-sectional view of a cathode ray display device in accordance with the invention.
- FIG. 2 is a graphic representation of spectra of light output of two luminescent materials.
- FIG. 1 shows a cathode ray display device comprising electron radiation source 11 with electrical connection pins 12, enclosure 13, garnet substrate 14, and bismuth-activated luminescent film 15 in accordance with the invention.
- FIG. 2 shows light output intensity curve 21 representing luminescence intensity of a prior-art polycrystalline bismuth-activated garnet material, and curve 22 representing luminescence intensity of a bismuth- activated garnet material in accordance with the invention.
- Curve 22 shows an intensity peak corresponding to a wavelength near 450 nanometers.
- Display devices embodying the invention comprise a member such as, e.g., a screen comprising a substantially single-crystal material having a composition as described above.
- substantially single-crystal structure may include faults such as, e.g., dislocations.
- a member may comprise other phosphor materials which luminesce at different wavelengths as, e.g., in color display devices; however, monochromatic devices are not precluded.
- a luminescent material typically is .in the form of a layer as epitaxially deposited on a crystallographically compatible substrate.
- Yttrium- aluminum garnet substrates are customary, typically having a [111] crystalline orientation.
- compositions such as, e.g., those which comprise little or no yttrium and for which y_ is in a preferred range of from 2.5 to 2.995.
- such materials preferably comprise a significant amount of gallium as, e.g., in a composition such as
- a resulting layer may be conveniently matched to a gadolinium-gallium garnet substrate.
- ⁇ Deposition of the film on the substrate is conveniently effected by liquid phase epitaxy, i.e., by bringing a surface of a substrate in contact with a fluxed melt of garnet constituent oxides while melt temperature is regulated to result in supersaturation of garnet constituents in the vicinity of the liquid-solid interface.
- Example. A melt was prepared by heating a mixture of approximately 18.40 grams Y2O3, approximately 33.58 grams AI2O3, approximately 1100.0 grams Bi2 ⁇ 3, and approximately 41.07 grams B2O3.
- An yttrium-aluminum garnet substrate was brought in contact with the melt surface while the melt was at a temperature of 1025 degrees C, and a film having a thickness of approximately 5.86 micrometers was thus grown at a rate of approximately 1.43 micrometers per minute.
- the grown film had a composition as approximately represented by the formula * 2 .95 Bi 0.05 Al 5°12*
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
On s'attend à ce que des matériaux luminescents utilisés dans des dispositifs d'affichage présentent un rendement élevé, qu'ils soient très résistants aux brûlures, c'est-à-dire qu'ils permettent une longue utilisation même lorsqu'ils sont exposés à une radiation stimulante de haute intensité. Est décrit un dispositif de vibration comprenant un matériau activé par du bismuthe (par ex. 15) produisant une luminescence bleue et qui est particulièrement indiqué pour être utilisé dans des dispositifs d'affichage à haute intensité tels que, par ex., des tubes d'affichage cathodiques.It is expected that luminescent materials used in display devices have high efficiency, high burn-in resistance, i.e., long use even when exposed to high intensity stimulating radiation. Disclosed is a vibration device comprising a bismuth-activated material (e.g. 15) producing blue luminescence and which is particularly suitable for use in high intensity display devices such as, e.g. cathode display.
Description
LUMINESCENT DISPLAY DEVICE
Technical Field
The invention is concerned with luminescent color display devices*
Background of the Invention
Display devices such as, e.g., cathode ray tubes typically include a luminescent screen which locally emits optical radiation in response to locally incident electron or electromagnetic radiation. Luminescent screen materials may be chosen with respect to a number of criteria; in many applications such as, e.g., high resolution displays, projection systems, and direct viewing systems under strong ambient lighting conditions there is a particular concern with brightness of emitted radiation. Accordingly, luminescent screen materials are desired which are highly efficient in emitting radiation of a desired wavelength.
Up to a point brightness is directly related to the intensity of stimulating electron or UV radiation; however, eventual "burnout" of luminescent material limits the usable intensity of such stimulating radiation. Thus, in the interest of high brightness, it is desirable to find luminescent materials having a high burnout intensity threshold.
Display devices may include luminescent materials or phosphors in powder form; however, such materials tend to have shortcomings such as, e.g., poor thermal properties, degradation of efficiency with stimulating radiation dose, and limited resolution. On the -other hand, single-crystal slabs or layers of luminescent materials have been found to be capable of withstanding input power densities in excess of 10 10W/m2 without measurable degradation and to have improved resolution as compared to powder phosphor targets.
While luminescence properties of single-crystal phosphors tend to be similar to those of powder phosphors
of the same composition, features tend to differ in detail in a generally unpredictable manner. For example, since a powder phosphor is typically formed by a different process than the single-crystal phosphor, chemical differences such as, e.g., phase differences may be present. Also, while the crystal lattice in powder particles can be expected to be strained and to have numerous defects, the lattice of a single-crystal phosphor typically is relatively free of strain and of defects. Since luminescence is sensitive to details of the crystal field, such lattice differences can result in significant differences in luminescence. The following- printed items are cited as representative of the literature on luminescent materials, their preparation, and their use in display devices. U. S. Patent No. 3,431,066, "Method for Producing
Yttrium Aluminum Oxide Garnet Crystals", issued March 4, 1969 to R. Seitz;
U. S. Patent No. 3,564,322, "Cathode-Ray Tube for Flying-Spot Scanning", issued February 16, 1971 to G. Blasse et al.;
U. S* Patent o, 3,839,219, "Europium Activated Alkaline Earth Magnesium Aluminum Silicate Luminescent Material", issued October 1, 1974 to J. M. P. J. Verstegen et al. ; U. S. Patent No. 4,003,845, "Luminescent
Material", issued January 18, 1977 to P. F. J. van den Boom et al. ;
U. S. Patent No. 4,024,070, "Method of Manufacturing a Cerium Activated Luminescent Rare-Earth Aluminate", issued May 17, 1977 to R. E. Schull;
U. S. Patent No. 4,093,890, "Terbium-Activated Luminescent Garnet Material and Mercury Vapor Discharge Lamp Containing The Same", issued June 6, 1978 to J. G. Verriet et al. ; U. S. Patent No. 4,180,477, "Luminescent
Materials", issued December 25, 1979 to R. G. L. Barnes;
U. S. Patent No. 4,216,408, "Luminescent Material
and Discharge Lamp and Cathode Ray Tube Containing the Same", issued August 5, 1980 to J. M. P. J. Verstegen et al. ;
U. S. Patent No. 4,298,820, "Luminescent Screen", issued November 3, 1981 to P. F. Bongers et al.;
G. Blasse et al., "Study of Energy Transfer from S „,b3+, „Bi.3+, C„e3+ ,t_o S.m3+,
Eu , Tb , Dy " , The Journal of
Chemical Physics, Vol. 47, No. 6, September 1967, pp. 1920- 1926;
G. Blasse et al., "Investigation of Some Ce 3+-Activated Phosphors", Journal of Chemical
Physics, Vol. 47, No. 12, December 1967, pp. 5139-5145;
G. Blasse, "Energy Transfer in Oxidiσ Phosphors", Physics Letters, Vol. 28A, December 1968, pp. 444-445;
J. Kvapil et al. , "0~ Centre Formation in YAG
Crystals Doped with Rare Earth Ions", Kristall und Technik,
Vol. 10, No. 2, 1975, pp. 161-165; T. R. Johansen et al., "Lead Free Bismuth
Substituted Garnet Films by L.P.E-", AIP Conference
Proceedings, No. 29, Magnetism and Magnetic Materials-1975,
American Institute of Physics, 1976, pp. 580-582;
J. M. Robertson et al., "Thin Single Crystalline Phosphor Layers Grown by Liquid Phase Epitaxy",
Philips J Res. 35, 1980, pp. 354-371;
J. M. Robertson, "Epitaxially Grown
Monocrystalline Garnet Cathode-Ray Tube Phosphor Screens",
Appl. Phys. Lett. 37, No. 5, 1980, pp. 471-472; V. A. Andriiσhuk, "Photolu inescence of Garnets
Activated by Bismuth Ions", Fiz. Elektron (Lvov), Vol. 20,
1980, pp. 80-81; and
F. Kellendonk et al. , "On the Luminescence of
Bismuth, Cerium, and Chromium and Yttrium Aluminum Borate", J. Chem. Phys. 76, No. 3, 1982, pp. 1194-1201.
Summary of the Invention
Visual display devices embodying the invention
comprise a source of stimulating electron or electromagnetic radiation, typically including deflection and modulation means, and a member comprising a substantially single-crystal phosphor material which is a garnet material consisting essentially of a composition substantially as represented by the formula
Y 3_-x-yBixRyAl5.-zGaz0i1n2 where R represents at least one rare earth element, where x_ is in the preferred range from 0.005 to 0.5, where preferably is less than or equal to 2.995, and where _z preferably is less than or equal to 5. In the interest of limiting extraneous luminescence, rare earth elements" Nd, Eu, Tm, and Tb are limited to amounts corresponding to y- values which are less than 0.01 and preferably less than or equal to 0.005.
More narrow preferred limits are as follows: Preferred yttrium aluminum garnets have z_ less than or equal to 0.4 and preferably τ_ less than or equal to 0^05,. and rare, earth elemeata other than Lu and Gd are preferably limited such that their combined contribution to the combined amount of rare earth elements is represented by a value of which is less than or equal to 0.2. When stimulated by electron or ultraviolet radiation, suitable bismuth-containing garnet materials emit electromagnetic radiation whose spectrum has a peak at a wavelength which is greater than or equal to 425 nanometers. Brief Description of the Drawing
FIG. 1 is a schematic cross-sectional view of a cathode ray display device in accordance with the invention; and
FIG. 2 is a graphic representation of spectra of light output of two luminescent materials. Detailed Description FIG. 1 shows a cathode ray display device comprising electron radiation source 11 with electrical connection pins 12, enclosure 13, garnet substrate 14, and
bismuth-activated luminescent film 15 in accordance with the invention.
FIG. 2 shows light output intensity curve 21 representing luminescence intensity of a prior-art polycrystalline bismuth-activated garnet material, and curve 22 representing luminescence intensity of a bismuth- activated garnet material in accordance with the invention. Curve 22 shows an intensity peak corresponding to a wavelength near 450 nanometers. Display devices embodying the invention comprise a member such as, e.g., a screen comprising a substantially single-crystal material having a composition as described above. (While single-crystal structure is preferred, substantially single-crystal structure may include faults such as, e.g., dislocations.) A member may comprise other phosphor materials which luminesce at different wavelengths as, e.g., in color display devices; however, monochromatic devices are not precluded.
A luminescent material, typically is .in the form of a layer as epitaxially deposited on a crystallographically compatible substrate. Yttrium- aluminum garnet substrates are customary, typically having a [111] crystalline orientation.
Also suitable for purposes of the invention are more specific compositions such as, e.g., those which comprise little or no yttrium and for which y_ is in a preferred range of from 2.5 to 2.995. In the interest of lattice matching to yttrium-aluminum garnet, such materials preferably comprise a significant amount of gallium as, e.g., in a composition such as
Bi0.05 u2.95Ga2Al3°12; this and similar combinations of substrate and epitaxial layer result in an optical waveguide structure.
Alternately, and essentially in the absence of yttrium and aluminum, and if R is primarily gadolinium, a resulting layer may be conveniently matched to a gadolinium-gallium garnet substrate. ■
Deposition of the film on the substrate is conveniently effected by liquid phase epitaxy, i.e., by bringing a surface of a substrate in contact with a fluxed melt of garnet constituent oxides while melt temperature is regulated to result in supersaturation of garnet constituents in the vicinity of the liquid-solid interface.
Example. A melt was prepared by heating a mixture of approximately 18.40 grams Y2O3, approximately 33.58 grams AI2O3, approximately 1100.0 grams Bi2θ3, and approximately 41.07 grams B2O3. An yttrium-aluminum garnet substrate was brought in contact with the melt surface while the melt was at a temperature of 1025 degrees C, and a film having a thickness of approximately 5.86 micrometers was thus grown at a rate of approximately 1.43 micrometers per minute. The grown film had a composition as approximately represented by the formula *2.95Bi0.05Al5°12*
Internal efficiency was determined by low-power- density excitation and was found to be approximately
1.9 percent.. Power saturation was achieved at a power of 10 watts/ at which point internal efficiency was approximately 0.6 percent.
Claims
1. Visual display device comprising a member which comprises at least one luminescent material and a source of radiation for stimulating luminescence in said material,
CHARACTERIZED IN THAT said material is substantially single-crystal and consists essentially of a composition which is substantially as represented by the formula Y3-:<-yB i>.*yAl5-zGaz0 . 2 ' where R represents at least one rare earth element, where j∑ is in the range of from 0.005 to 0.5, where is less than or equal to 2.995, Nd, Eu, Tm, and Tb being present in said material in amounts corresponding to y-values which are less than 0.01, and where _z is less than or equal to 5, whereby stimulation of said material by said radiation results in luminescence having a peak of intensity at a wavelength which is greater than or equal to 425 nanometers.
2. Device according to claim 1, CHARACTERIZED IN THAT said luminescent material is a substantially single-crystal layer on an essentially single-crystal substrate.
3. Device according to claim 2, CHARACTERIZED IN THAT said substrate is an yttrium-aluminum garnet substrate.
4. Device according to claim 3,
CHARACTERIZED IN THAT said substrate has a crystalline orientation which is substantially [111].
5. Device according to claim 1, CHARACTERIZED IN THAT said source of radiation is selected from a source of electrons and a source of ultraviolet light.
6. Device according to claim 1, CHARACTERIZED IN THAT
_z in said formula for said material being less than or equal to 0*4, preferably less than or equal to 0.05.
7. Device according to claim 1, CHARACTERIZED IN THAT said luminescent material comprises Lu and Gd in a combined amount which corresponds to a value of γ_ in said formula which is less than or equal to 0.2.
8. Device according to claim 1, CHARACTERIZED IN THAT said luminescent material is such that j is in the range of from 2.5 to 2.995.
9. Device according to claim 8,
CHARACTERIZED IN THAT said luminescent material comprises a substantial amount of gallium, and is an essentially single-crystal layer on an yttrium-gallium garnet substrate.
10. Device according to claim 2, CHARACTERIZED IN THAT said luminescent material is such that R is essentially gadolinium, and is on a gadolinium-gallium garnet substrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62908484A | 1984-07-09 | 1984-07-09 | |
| US629084 | 1984-07-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0190153A1 true EP0190153A1 (en) | 1986-08-13 |
Family
ID=24521513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85902773A Withdrawn EP0190153A1 (en) | 1984-07-09 | 1985-05-09 | Luminescent display device |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0190153A1 (en) |
| JP (1) | JPS61502685A (en) |
| WO (1) | WO1986000633A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7354879B2 (en) | 2006-01-05 | 2008-04-08 | Saint-Gobain Ceramics & Plastics, Inc. | Thermally stable ceramic media for use in high temperature environments |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4713577A (en) * | 1985-12-20 | 1987-12-15 | Allied Corporation | Multi-layer faceted luminescent screens |
| CN106590646B (en) * | 2016-10-13 | 2019-03-15 | 长安大学 | A kind of white light LEDs blue light fluorescent powder of near ultraviolet excitation and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3282856A (en) * | 1965-12-21 | 1966-11-01 | Du Pont | Luminescent compositions containing europium and the oxyanion-yielding ingredient aluminum, gallium or germanium |
-
1985
- 1985-05-09 JP JP60502283A patent/JPS61502685A/en active Pending
- 1985-05-09 EP EP85902773A patent/EP0190153A1/en not_active Withdrawn
- 1985-05-09 WO PCT/US1985/000851 patent/WO1986000633A1/en not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO8600633A1 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7354879B2 (en) | 2006-01-05 | 2008-04-08 | Saint-Gobain Ceramics & Plastics, Inc. | Thermally stable ceramic media for use in high temperature environments |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61502685A (en) | 1986-11-20 |
| WO1986000633A1 (en) | 1986-01-30 |
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| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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| AK | Designated contracting states |
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| 17P | Request for examination filed |
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| 17Q | First examination report despatched |
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| STAA | Information on the status of an ep patent application or granted ep patent |
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| 18W | Application withdrawn |
Withdrawal date: 19870521 |
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| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: BERKSTRESSER, GEORGE, WAYNE Inventor name: HUO, TAI-CHAN, DONALD |