US20040028957A1 - Multiple source deposition process - Google Patents
Multiple source deposition process Download PDFInfo
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- US20040028957A1 US20040028957A1 US10/606,992 US60699203A US2004028957A1 US 20040028957 A1 US20040028957 A1 US 20040028957A1 US 60699203 A US60699203 A US 60699203A US 2004028957 A1 US2004028957 A1 US 2004028957A1
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- 239000000203 mixture Substances 0.000 claims abstract description 98
- 230000008021 deposition Effects 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 79
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 239000010409 thin film Substances 0.000 claims abstract description 32
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- 230000008016 vaporization Effects 0.000 claims abstract description 14
- 238000010894 electron beam technology Methods 0.000 claims abstract description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000000737 periodic effect Effects 0.000 claims abstract description 9
- 239000002019 doping agent Substances 0.000 claims abstract description 5
- 150000003568 thioethers Chemical class 0.000 claims abstract 6
- 238000000151 deposition Methods 0.000 claims description 85
- 238000012544 monitoring process Methods 0.000 claims description 17
- 230000002123 temporal effect Effects 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 13
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- 229910014780 CaAl2 Inorganic materials 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 238000002207 thermal evaporation Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 description 51
- 239000010408 film Substances 0.000 description 40
- -1 cerium-activated strontium sulphide Chemical class 0.000 description 10
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- 239000000843 powder Substances 0.000 description 7
- 150000004763 sulfides Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 229910052693 Europium Inorganic materials 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000005424 photoluminescence Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000009977 dual effect Effects 0.000 description 5
- 229910016010 BaAl2 Inorganic materials 0.000 description 4
- 239000005132 Calcium sulfide based phosphorescent agent Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005566 electron beam evaporation Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- AGVJBLHVMNHENQ-UHFFFAOYSA-N Calcium sulfide Chemical compound [S-2].[Ca+2] AGVJBLHVMNHENQ-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 description 2
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 description 2
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
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- 230000007423 decrease Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- XXCMBPUMZXRBTN-UHFFFAOYSA-N strontium sulfide Chemical compound [Sr]=S XXCMBPUMZXRBTN-UHFFFAOYSA-N 0.000 description 2
- RVKZDIDATLDTNR-UHFFFAOYSA-N sulfanylideneeuropium Chemical compound [Eu]=S RVKZDIDATLDTNR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
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- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001849 group 12 element Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
-
- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
-
- 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
-
- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0623—Sulfides, selenides or tellurides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/548—Controlling the composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
Definitions
- the present invention relates to a method for the deposition of a ternary, quaternary or similar composition, especially a phosphor, in which components of the composition are located on different sources.
- the compositions are thioaluminates, thiogallates or thioindates of Group IIA and Group IIB elements, and the sulphides that form such compounds are located on the different sources.
- a preferred method of deposition is electron beam vaporization.
- the present invention relates to a method of improving the luminance and emission spectrum of phosphor materials, especially those used for full colour ac electroluminescent displays employing thick film dielectric layers with a high dielectric constant.
- TFEL Thin film electroluminescent
- electroluminescent displays with thin film phosphors employing thick film dielectric layers fabricated on ceramic substrates as exemplified by U.S. Pat. No. 5,432,015, provide greater luminance and superior reliability.
- Thick film dielectric structures provide superior resistance to dielectric breakdown, as well as a reduced operating voltage.
- the thick film dielectric structure When deposited on a ceramic substrate, the thick film dielectric structure will withstand higher processing temperatures than TFEL devices on glass substrates. The increased tolerance to higher temperatures facilitates annealing of the phosphor films at higher temperatures, to improve luminosity.
- electroluminescent displays employing a thick film dielectric layer have not achieved the phosphor luminance and colour coordinates needed to be fully competitive with cathode ray tube (CRT) displays.
- CRT cathode ray tube
- recent trends in CRT specifications are to higher luminance and higher colour temperature.
- a high luminosity full colour electroluminescent display requires the use of red, green and blue sub-pixels.
- Optical filters are needed to achieve the required colour coordinates for each sub-pixel. Consequently, the thin film phosphor materials used for each sub-pixel must be patterned so that there is minimal attenuation of the emission spectrum for each colour of pixel by the optical filters.
- the required patterning can be achieved by depositing the phosphor materials through a shadow mask.
- the shadow mask technique does not provide adequate accuracy, and photolithographic methods must be employed. Photolithographic techniques require the deposition of photoresist films and the etching or lift-off of portions of the phosphor film to provide the required pattern.
- cerium-activated strontium sulphide for blue and manganese-activated zinc sulphide for red and green have been the phosphor materials of choice for full colour electroluminescent displays.
- the optical emission from these phosphor materials must be passed through an appropriate chromatic filter to achieve the necessary colour coordinates for red, green and blue sub-pixels, resulting in a loss of luminance and energy efficiency.
- the manganese-activated zinc sulphide phosphor has a relatively high electrical to optical energy conversion efficiency of up to about 10 lumens per watt of input power and the cerium activated strontium sulphide phosphor has an energy conversion efficiency of 1 lumen per watt, relatively high for blue emission.
- the spectral emission for these phosphors is quite wide, with that for the zinc sulphide-based phosphor spanning the colour spectrum from green to red and that for the strontium sulphide-based material spanning the range from blue to green. This necessitates the use of the optical filters to obtain acceptable colour coordinates.
- the spectral emission of the cerium activated strontium sulphide phosphor can be shifted to some degree towards the blue by controlling the deposition conditions and activator concentration, but not to the extent required to eliminate the need for an optical filter.
- Alternate blue phosphor materials that have narrower emission spectra tuned to provide the colour coordinates required for blue sub-pixel have been evaluated. These include cerium activated alkaline earth thiogallate compounds, which give good blue colour coordinates, but have relatively poor luminosity and stability. Since the host materials are ternary compounds, it is relatively difficult to control the stoichiometry of the phosphor films. Europium-activated barium thioaluminate provides excellent blue colour coordinates and higher luminance, but it too is a ternary compound whose stoichiometry is difficult to control.
- Vacuum deposition of phosphor films comprising europium-activated barium thioaluminate from a single source pellet using sputtering or electron beam evaporation has not yielded films with high luminosity.
- Improved luminance of barium thioaluminate phosphors has been achieved by using a hopping electron beam deposition technique to deposit films from two source pellets.
- the stoichiometry of the deposited film is controlled by controlling the relative dwell time of the electron beam impinging on each of the two source materials.
- this technique is not readily scalable to facilitate commercial production of large area displays and the process cannot be controlled to compensate for changes in the evaporation rates from the two sources as the deposition proceeds and the source pellets are depleted.
- compositions e.g. phosphors, especially ternary and other chemically complex phosphors, has now been found.
- one aspect of the present invention provides a method for the deposition of a thin film of a pre-determined composition onto a substrate, said composition comprising a ternary, quaternary or higher compound, comprising the steps of:
- said first and second coating rate monitors are at a distance from the respective sources that is substantially the same as the distance of the substrate from said sources.
- the temperature of said first and second sources is controlled.
- the temperature of each of the first and second coating rate monitors is monitored and controlled.
- the composition is a thin film phosphor or a dielectric thin film.
- said composition is selected from the group consisting of ternary, quaternary and higher compositions of at least one cation from Groups IIA and IIB of the Periodic Table, especially thioaluminates, thiogallates and thioindates of at least one cation from Groups IIA and IIB of the Periodic Table.
- sulphide is located at a third source, said third source having a coating rate monitor that is screened from the first and second sources, said rate of coating from the third source being monitored and controlled.
- the third coating monitor is at a distance from the third source that is substantially the same as the distance of the substrate from said source.
- said substrate is opaque in the visible and infrared regions of the electromagnetic spectrum.
- the present invention provides a method for the deposition of a thin film of a pre-determined composition onto a substrate, said composition comprising a ternary, quaternary or higher composition, comprising the steps of:
- said temporal variation is obtained by monitoring the rate of vaporizing from the first source with a first coating rate monitor and monitoring the rate of vaporizing from the second source with a second coating rate monitor, said first coating rate monitor being shielded from deposition from the second source and said second coating rate monitor being shielded from deposition from the first source.
- said monitoring is used as the determining of temporal deposition of step (ii).
- said monitoring of step (ii) may be used in step (iii).
- FIG. 1 is a schematic representation of a side view of a dual electron beam evaporator
- FIG. 2 is a schematic representation of a plan view of the dual electron beam evaporator of FIG. 1;
- FIG. 3 is a schematic representation of a section of an electroluminescent element comprising a thick film dielectric layer and a phosphor composition
- FIG. 4 is a schematic representation of a plan view of a full colour electroluminescent pixel and its constituent sub-pixels.
- FIG. 5 is a graphical representation of photoluminescence and CIE colour versus “a” for phosphor materials having the formula Ba a Ca 1-a Al 2 S 4 :Eu incorporated into a thick film electroluminescent device.
- the present invention relates to a method of deposition of ternary, quaternary and higher compounds, including other chemically complex compositions, especially phosphors, to achieve the desired stoichiometry, and high energy efficiency and high luminosity phosphor films.
- Phosphors in the form of ternary, quaternary or higher compounds may be deposited to provide high electroluminescence.
- the ratio of the three or four, or more, constituent elements must be controlled to close tolerances. Control of stoichiometry is important in achieving optimum performance of the phosphor.
- the phosphor material may form into more than one crystal phase, thus reducing the luminosity and energy efficiency of the phosphor and shifting the colour coordinates of the emission spectrum from desired values.
- the phosphor may comprise a composite film with more than one crystal phase.
- the light generation mechanism could involve a cascading excitation whereby the injected electrons activate a short wavelength of visible or ultraviolet light in one of the phases that subsequently excites a useful visible wavelength of light in a second or third phase.
- control of the ratio of the relative abundance of the constituent phases is important to optimize the luminosity and colour coordinates of the composite phosphor materials.
- control of stoichiometry during deposition is effected using two or more deposition sources with different chemical compositions, together with a deposition rate measuring system for at least two of the sources that measures the deposition rate for these sources independently from the deposition rate of the remaining source materials and a feedback system that controls the relative deposition rates commensurate with the measured rates.
- the invention is believed to be applicable to a variety of physical vapour deposition techniques including but not limited to electron beam evaporation, thermal evaporation, sputtering and reactive sputtering methods.
- phosphor materials comprising europium activated calcium thioaluminate (CaAl 2 S 4 :Eu), barium thioaluminate (BaAl 2 S 4 :Eu) and barium-calcium thioaluminate (Ba a Ca 1-a Al 2 S 4 :Eu ) may be deposited using the method described herein and have shown high luminance and energy efficiency.
- the method is also applicable to other ternary, quaternary or higher thioaluminate, thiogallate and thioindate phosphors and composites thereof synthesized with the cation or cations for these compounds selected from Groups IIA and IIB of the Periodic Table of Elements.
- cations include barium, calcium, strontium, magnesium, zinc and cadmium.
- the method is also believed to be applicable to other ternary, quaternary or higher compositions, especially compositions formed with cations of Groups IIA and IIB of the Periodic Table.
- the utility of the invention also extends to the deposition of single phase ternary, quaternary or higher dielectric films that may be deposited in juxtaposition with the phosphor films to enhance phosphor performance.
- the phosphor compositions may be activated with a variety of dopants, especially europium and cerium.
- the method of the invention is believed to be applicable to any ternary, quaternary or higher composition deposited on a substrate. It will be understood that the various source materials would be selected so that a vapour may be created for condensation on the substrate.
- the preferred substrate is a substrate that is opaque in the visible and infrared regions of the electromagnetic spectrum.
- the substrate is a thick film dielectric layer on a ceramic substrate. Examples of such substrates include alumina, and metal ceramic composites.
- components of the phosphor are placed on each of the sources. For instance, if the phosphor is CaAlS 4 :Eu, then Al 2 S 3 is placed on one source and europium-doped CaS on the other source. If the phosphor is Ba a Ca 1-a Al 2 S 4 :Eu, then Al 2 S 3 is preferably placed on one source and a europium-doped mixture of BaS and CaS, in the ratio's defined by “a” and “1-a”, is placed on the other source.
- the phosphors are europium-activated barium-calcium thioaluminates, which are believed to be less susceptible to hydrolysis than cerium-activated strontium sulphide, thus rendering them easier to pattern using photolithographic techniques.
- the present invention relates to a novel process for depositing multi-element thin films for electroluminescent phosphors and adjacent dielectric layers from which electrons are injected into the phosphors that provide a high luminosity and an emission color.
- FIG. 1 shows a side view of the dual electron beam evaporator, which is an apparatus generally indicated by 10 .
- Apparatus 10 has source materials 12 and 14 .
- Crystal rate monitor 16 is located near substrate 18 , and is behind shield 20 .
- Shield 20 is located so that it receives depositions of evaporant from source material 12 but not from source material 14 .
- crystal rate monitor 22 is located near substrate 18 , in a position opposed to crystal rate monitor 16 , and is behind shield 24 .
- Shield 24 is located so that it receives depositions of evaporant from source material 14 and not from source material 12 .
- Crystal rate monitors 16 and 22 are located juxtaposed to substrate 18 , in a position that is preferably as near as is practical. Differences in distances can be allowed for in control of the method. Location of crystal rate monitors 16 and 22 spaced from source materials 12 and 14 but close to substrate 18 more accurately monitors the deposition of source materials on substrate 18 .
- Substrate 18 is rotatable, as indicated.
- the respective samples of source material are placed as source materials 12 and 14 .
- Separate electron beam guns are directed at each of source materials 12 and 14 and operated simultaneously.
- the flux density of evaporant from source material 12 is monitored by crystal rate monitor 16 and from source material 14 by crystal rate monitor 22 .
- a computer-based feedback system is used to control the evaporation of each of source materials 12 and 14 , using crystal rate monitors 16 and 22 respectively.
- the evaporation rate of each source material is independently controlled.
- the independent control facilitates control of deposition of the phosphor on substrate 18 , to achieve optimum performance for phosphors with ternary, quaternary or higher elemental composition.
- Substrate 18 is rotated during deposition.
- the deposition of the composition may be carried out in an atmosphere of H 2 S, sulphur or other volatile sulphur bearing compounds that will not contaminate the phosphor film as it is deposited if there is a tendency for the deposited compound to be deficient in sulphur. However, in some instances, it may be possible to operate the method without an atmosphere of H 2 S.
- the sticking coefficient, also known as condensation rate, of an individual evaporant on the respective rate monitors may differ, and generally will differ, from the sticking coefficient of the evaporant when it is co-deposited onto the substrate. Thus, such differences in sticking coefficients must be understood in order to obtain optimization of the co-deposition on the substrate.
- FIG. 2 shows a plan view of apparatus 10 .
- platforms 26 A, 26 B, 26 C and 26 D all of which rotate.
- Substrate 18 is shown on platform 26 C.
- source materials 12 and 14 are widely spaced apart, with each source material more closely aligned with the respective crystal monitors 16 and 22 , and shields 20 and 24 .
- the deposition apparatus comprises a TemescalTM electron beam evaporation system with four 40 cc source material pockets.
- the apparatus has two Temescal STIH-270-3CK electron beam guns and two independent deposition rate feedback control systems, each of which includes MDC e-Vap programmable sweep controllers, MDC e-Vap source controls, Sycon STC-200 deposition rate controllers and MDC e-Vap CVS-15KW electron beam power supplies. Other apparatus may be used.
- FIG. 3 shows a cross-section of an electroluminescent device utilizing a phosphor.
- FIG. 4 shows a plan view of the electroluminescent device.
- the electroluminescent device generally indicated by 40 , has a substrate 42 on which is located row electrode 44 .
- Thick film dielectric 46 has thin film dielectric 48 thereon.
- Thin film dielectric 48 is shown with three pixel columns, referred to as 50 , 52 and 54 , located thereon.
- the pixel columns contain phosphors to provide the three basic colours viz. red, green and blue.
- Pixel column 50 has red phosphor 56 located in contact with thin film dielectric 48 .
- Another thin film dielectric 58 is located on red phosphor 56
- column electrode 60 is located on thin film dielectric 58
- pixel column 52 has green phosphor 62 on thin film dielectric 48 , with thin film dielectric 64 and column electrode 66 thereon.
- Pixel column 54 has blue phosphor 68 on thin film dielectric 48 , with thin film dielectric 70 and column electrode 72 thereon.
- the present invention provides a method for the deposition of a thin film of a pre-determined composition onto a substrate, said composition comprising a ternary, quaternary or higher composition.
- a first deposit is placed at a first source of a vapour deposition apparatus and a second deposit is placed at a second source of the vapour deposition apparatus.
- the first and second deposits are different, and may or may not be sulphides.
- the deposits could be sulphides.
- the components of the first and second deposits in combination form the pre-determined composition. Simultaneous vapour deposition is effected from the first and second sources to form said pre-determined composition on said substrate.
- the simultaneous vapour deposition may be sputtering, electron beam, or thermal evaporation, or other kind of simultaneous vapour deposition.
- the temporal variation of deposition of the components onto said substrate from the first and second sources is determined.
- the temporal variation is used for controlling the first and second sources e.g. by controlling the temperatures of the sources, so as to obtain homogeneous temporal deposition of the composition on the substrate by simultaneous vapour deposition from the sources.
- the temporal variation is obtained by monitoring the rate of vaporizing from the first source with a first coating rate monitor and monitoring the rate of vaporizing from the second source with a second coating rate monitor.
- the first coating rate monitor is shielded from deposition from the second source and the second coating rate monitor is shielded from deposition from the first source.
- the monitoring is preferably used as the determining of temporal deposition of step (ii). In particular, the monitoring of step (ii) may be used in step (iii).
- the present invention provides a method for depositing controlled composition multi-element thin films for use as electroluminescent phosphors that can be tuned by adjusting the film composition.
- Phosphors with a high luminosity and emission colour are obtained.
- the process entails the use of at least two source materials that can be deposited using for example, low pressure physical vapour deposition methods and deposition rate monitors placed in the deposition chamber that can independently measure the deposition rate of each source material.
- the rate monitors combined with appropriate feedback control, can be used to control the compositions of deposited films that comprise the combined elemental composition of the source materials.
- Such films may comprise a ternary or quaternary elemental composition, but films including a larger number of elements are also possible by use of multiple sources.
- the luminosity and emission spectra of electroluminescent phosphor films can be optimized by controlling and adjusting the elemental composition of the films.
- the present invention provides a method of deposition of ternary, quaternary or higher phosphor compositions, especially onto an opaque substrate.
- the method permits control of the relative rates of deposition from more than one source, to provide improved electroluminescent phosphors, especially phosphors of more consistent composition.
- the phosphors obtained are believed to exhibit higher luminosity and improved emission colour.
- a series of europium-doped barium calcium thioaluminate powders were prepared by blending powders of barium sulphide, calcium sulphide, aluminum sulphide and europium sulphide in various ratios. The blended powders were pressed to form pellets with a diameter of 1.3 cm and a height of 0.75 cm.
- the fraction “a” in the formula Ba a Ca 1-a Al 2 S 4 :Eu was varied as follows: 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0. All of the phosphor materials had a nominal concentration of europium corresponding to 3 atomic percent of the sum of the barium and calcium concentrations.
- the pellets were annealed at 900° C. for 20 minutes in nitrogen.
- One of the two source materials used to deposit the phosphor was aluminum sulphide (Al 2 S 3 ) formed into a pellet. This pellet was not annealed.
- the other source material was a europium-doped calcium sulphide pellet (CaS:Eu). This pellet was annealed at 800° C. for 20 minutes in nitrogen. The diameter and height of each of the Al 2 S 3 and CaS:Eu pellets were 2.5 and 1.8 centimeters, respectively.
- the pellets were slowly degassed and preconditioned with a low electron beam current from their respective electron guns.
- the substrate was alumina upon which a gold electrode pattern was deposited and overlaid with a high dielectric constant thick film dielectric layer comprising PMN-PT coated with lead zirconate-titanate, and further overlaid with a thin film layer of alumina as described in U.S. patent application Ser. No. 09/540,288 of Wu et al.
- PMN-PT is a material that includes lead and magnesium niobates and titanates.
- both Al 2 S 3 and CaS:Eu materials were vaporized simultaneously in an atmosphere having a hydrogen sulphide partial pressure of 2 ⁇ 10 ⁇ 4 Torr.
- the deposition substrate temperature was about 500° C.
- the deposition rates of Al 2 S 3 and CaS:Eu were 2.8 and 1.8 Angstroms per second, respectively, as measured independently using the two deposition rate monitoring systems. It is understood that the relative deposition rates need to be adjusted to account for differences between the sticking coefficient of the two source materials on the rate monitors, and the sticking coefficients for the combined materials on the workpiece substrate.
- the thickness of the CaAl 2 S 4 :Eu phosphor film was 2300 Angstroms, as measured using scanning electron microscopy. Examples of structures incorporating the phosphor films are shown in cross section and in plan view in FIGS. 3 and 4.
- the deposited phosphors were annealed following deposition at a temperature of about 700° C. for 2 minutes under nitrogen.
- a second thin film of alumina was deposited on top of the phosphor layer, and a second electrode structure comprising indium tin oxide was deposited on top of the alumina layer.
- the peak emission wavelength of both photoluminescence and electroluminescence spectra was 515 mn.
- the luminance was about 40 cd/m 2 at 70 volts above the threshold voltage of 190 volts.
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Abstract
Description
- This application is a divisional of U.S. patent application Ser. No. 09/747,315 filed Dec. 22, 2000.
- The present invention relates to a method for the deposition of a ternary, quaternary or similar composition, especially a phosphor, in which components of the composition are located on different sources. In particular, the compositions are thioaluminates, thiogallates or thioindates of Group IIA and Group IIB elements, and the sulphides that form such compounds are located on the different sources. A preferred method of deposition is electron beam vaporization. In particular aspects, the present invention relates to a method of improving the luminance and emission spectrum of phosphor materials, especially those used for full colour ac electroluminescent displays employing thick film dielectric layers with a high dielectric constant.
- Thin film electroluminescent (TFEL) displays are known and are typically fabricated on glass substrates. However, electroluminescent displays with thin film phosphors employing thick film dielectric layers fabricated on ceramic substrates, as exemplified by U.S. Pat. No. 5,432,015, provide greater luminance and superior reliability.
- Thick film dielectric structures provide superior resistance to dielectric breakdown, as well as a reduced operating voltage. When deposited on a ceramic substrate, the thick film dielectric structure will withstand higher processing temperatures than TFEL devices on glass substrates. The increased tolerance to higher temperatures facilitates annealing of the phosphor films at higher temperatures, to improve luminosity. However, even with the enhanced luminosity that is obtained, electroluminescent displays employing a thick film dielectric layer have not achieved the phosphor luminance and colour coordinates needed to be fully competitive with cathode ray tube (CRT) displays. Moreover, recent trends in CRT specifications are to higher luminance and higher colour temperature. Some improvement has been realized by increasing the operating voltage of electroluminescent displays, but this increases the power consumption of the displays, decreases the reliability and increases the cost of operating electronics for the displays.
- A high luminosity full colour electroluminescent display requires the use of red, green and blue sub-pixels. Optical filters are needed to achieve the required colour coordinates for each sub-pixel. Consequently, the thin film phosphor materials used for each sub-pixel must be patterned so that there is minimal attenuation of the emission spectrum for each colour of pixel by the optical filters. For relatively low-resolution displays, the required patterning can be achieved by depositing the phosphor materials through a shadow mask. For displays with high resolution, however, the shadow mask technique does not provide adequate accuracy, and photolithographic methods must be employed. Photolithographic techniques require the deposition of photoresist films and the etching or lift-off of portions of the phosphor film to provide the required pattern.
- Deposition and removal of photoresist films and etching or lift-off of phosphor films typically require the use of solvent solutions that contain water or other protic solvents. Some phosphor materials, for example strontium sulphide are susceptible to hydrolysis, and water and protic solvents may degrade the properties of the phosphor materials.
- The deficiencies in phosphor materials are most severe with the phosphors used for blue sub-pixels, and may be compensated for to some extent by increasing the area of the blue sub-pixels relative to the area of the red and green sub-pixels. However, such a design modification demands increased performance from the phosphor materials used for the red and green phosphor materials, and requires the use of higher display operating voltages. The higher operating voltages increase the power consumption of the display, decrease the reliability and increase the cost of operating the electronics of the display.
- Traditionally, cerium-activated strontium sulphide for blue and manganese-activated zinc sulphide for red and green have been the phosphor materials of choice for full colour electroluminescent displays. The optical emission from these phosphor materials must be passed through an appropriate chromatic filter to achieve the necessary colour coordinates for red, green and blue sub-pixels, resulting in a loss of luminance and energy efficiency. The manganese-activated zinc sulphide phosphor has a relatively high electrical to optical energy conversion efficiency of up to about 10 lumens per watt of input power and the cerium activated strontium sulphide phosphor has an energy conversion efficiency of 1 lumen per watt, relatively high for blue emission. However, the spectral emission for these phosphors is quite wide, with that for the zinc sulphide-based phosphor spanning the colour spectrum from green to red and that for the strontium sulphide-based material spanning the range from blue to green. This necessitates the use of the optical filters to obtain acceptable colour coordinates. The spectral emission of the cerium activated strontium sulphide phosphor can be shifted to some degree towards the blue by controlling the deposition conditions and activator concentration, but not to the extent required to eliminate the need for an optical filter.
- Alternate blue phosphor materials that have narrower emission spectra tuned to provide the colour coordinates required for blue sub-pixel have been evaluated. These include cerium activated alkaline earth thiogallate compounds, which give good blue colour coordinates, but have relatively poor luminosity and stability. Since the host materials are ternary compounds, it is relatively difficult to control the stoichiometry of the phosphor films. Europium-activated barium thioaluminate provides excellent blue colour coordinates and higher luminance, but it too is a ternary compound whose stoichiometry is difficult to control.
- Vacuum deposition of phosphor films comprising europium-activated barium thioaluminate from a single source pellet using sputtering or electron beam evaporation has not yielded films with high luminosity. Improved luminance of barium thioaluminate phosphors has been achieved by using a hopping electron beam deposition technique to deposit films from two source pellets. The stoichiometry of the deposited film is controlled by controlling the relative dwell time of the electron beam impinging on each of the two source materials. However, this technique is not readily scalable to facilitate commercial production of large area displays and the process cannot be controlled to compensate for changes in the evaporation rates from the two sources as the deposition proceeds and the source pellets are depleted.
- A method for the deposition of zinc sulphide thin films on transparent substrates was disclosed in JP 63-259067 of Shiro Kobayashi et al.
- Improvements in methods of deposition of compositions, especially phosphors, to improve the luminance and emission spectrum of phosphor materials for electroluminescent displays employing thick film dielectric layers would be useful.
- A method for the deposition of compositions e.g. phosphors, especially ternary and other chemically complex phosphors, has now been found.
- Accordingly, one aspect of the present invention provides a method for the deposition of a thin film of a pre-determined composition onto a substrate, said composition comprising a ternary, quaternary or higher compound, comprising the steps of:
- (i) placing a pellet of at least one sulphide on a first source and placing a pellet of at least one sulphide on a second source, the sulphides on the first and second sources being different, said sulphides being the components of said composition, at least one of the pellets on the first and second sources additionally containing dopant for the composition;
- (ii) effecting vapour deposition of said composition on said substrate by simultaneously vaporizing the pellets on the first and second sources with separate electron beams; and
- (iii) monitoring the rate of vaporizing of sulphide from the first source with a first coating rate monitor and monitoring the rate of vaporizing of sulphide from the second source with a second coating rate monitor, said first coating rate monitor being shielded from deposition of sulphide from the second source and said second coating rate monitor being shielded from deposition of sulphide from the first source.
- In a preferred embodiment of the present invention, said first and second coating rate monitors are at a distance from the respective sources that is substantially the same as the distance of the substrate from said sources.
- In another embodiment, the temperature of said first and second sources is controlled. Preferably, the temperature of each of the first and second coating rate monitors is monitored and controlled.
- In further embodiments, the composition is a thin film phosphor or a dielectric thin film.
- In further preferred embodiments, said composition is selected from the group consisting of ternary, quaternary and higher compositions of at least one cation from Groups IIA and IIB of the Periodic Table, especially thioaluminates, thiogallates and thioindates of at least one cation from Groups IIA and IIB of the Periodic Table.
- In other embodiments, sulphide is located at a third source, said third source having a coating rate monitor that is screened from the first and second sources, said rate of coating from the third source being monitored and controlled. In particular, the third coating monitor is at a distance from the third source that is substantially the same as the distance of the substrate from said source.
- In further preferred embodiments, said substrate is opaque in the visible and infrared regions of the electromagnetic spectrum.
- In another aspect, the present invention provides a method for the deposition of a thin film of a pre-determined composition onto a substrate, said composition comprising a ternary, quaternary or higher composition, comprising the steps of:
- (i) placing a first deposit at a first source of a vapour deposition apparatus and placing a second deposit at a second source of the vapour deposition apparatus, said first and second deposits being different, components of said first and second deposits in combination forming said pre-determined composition;
- (ii) determining temporal variation of deposition of said components onto said substrate from said first and second sources; and
- (iii) using said temporal variation for controlling said first and second sources so as to obtain homogeneous temporal deposition of said composition on the substrate by simultaneous vapour deposition from said sources.
- In preferred embodiments of the method, said temporal variation is obtained by monitoring the rate of vaporizing from the first source with a first coating rate monitor and monitoring the rate of vaporizing from the second source with a second coating rate monitor, said first coating rate monitor being shielded from deposition from the second source and said second coating rate monitor being shielded from deposition from the first source.
- In another embodiment, said monitoring is used as the determining of temporal deposition of step (ii). In particular, said monitoring of step (ii) may be used in step (iii).
- The present invention is illustrated by the embodiments shown in the drawings, in which:
- FIG. 1 is a schematic representation of a side view of a dual electron beam evaporator;
- FIG. 2 is a schematic representation of a plan view of the dual electron beam evaporator of FIG. 1;
- FIG. 3 is a schematic representation of a section of an electroluminescent element comprising a thick film dielectric layer and a phosphor composition;
- FIG. 4 is a schematic representation of a plan view of a full colour electroluminescent pixel and its constituent sub-pixels; and
- FIG. 5 is a graphical representation of photoluminescence and CIE colour versus “a” for phosphor materials having the formula BaaCa1-aAl2S4:Eu incorporated into a thick film electroluminescent device.
- The present invention relates to a method of deposition of ternary, quaternary and higher compounds, including other chemically complex compositions, especially phosphors, to achieve the desired stoichiometry, and high energy efficiency and high luminosity phosphor films. Phosphors in the form of ternary, quaternary or higher compounds may be deposited to provide high electroluminescence. However, the ratio of the three or four, or more, constituent elements must be controlled to close tolerances. Control of stoichiometry is important in achieving optimum performance of the phosphor. In some embodiments of the invention, if the stoichiometry of the phosphor is not adequately controlled, the phosphor material may form into more than one crystal phase, thus reducing the luminosity and energy efficiency of the phosphor and shifting the colour coordinates of the emission spectrum from desired values. In the other embodiments, the phosphor may comprise a composite film with more than one crystal phase. In such embodiments, the light generation mechanism could involve a cascading excitation whereby the injected electrons activate a short wavelength of visible or ultraviolet light in one of the phases that subsequently excites a useful visible wavelength of light in a second or third phase. In these embodiments, control of the ratio of the relative abundance of the constituent phases is important to optimize the luminosity and colour coordinates of the composite phosphor materials.
- In the present invention, control of stoichiometry during deposition is effected using two or more deposition sources with different chemical compositions, together with a deposition rate measuring system for at least two of the sources that measures the deposition rate for these sources independently from the deposition rate of the remaining source materials and a feedback system that controls the relative deposition rates commensurate with the measured rates. The invention is believed to be applicable to a variety of physical vapour deposition techniques including but not limited to electron beam evaporation, thermal evaporation, sputtering and reactive sputtering methods.
- As exemplified hereinafter, phosphor materials comprising europium activated calcium thioaluminate (CaAl2S4:Eu), barium thioaluminate (BaAl2S4:Eu) and barium-calcium thioaluminate (BaaCa1-aAl2S4:Eu ) may be deposited using the method described herein and have shown high luminance and energy efficiency. It is believed that the method is also applicable to other ternary, quaternary or higher thioaluminate, thiogallate and thioindate phosphors and composites thereof synthesized with the cation or cations for these compounds selected from Groups IIA and IIB of the Periodic Table of Elements. Examples of such cations include barium, calcium, strontium, magnesium, zinc and cadmium. The method is also believed to be applicable to other ternary, quaternary or higher compositions, especially compositions formed with cations of Groups IIA and IIB of the Periodic Table. The utility of the invention also extends to the deposition of single phase ternary, quaternary or higher dielectric films that may be deposited in juxtaposition with the phosphor films to enhance phosphor performance.
- The phosphor compositions may be activated with a variety of dopants, especially europium and cerium.
- The method of the invention is believed to be applicable to any ternary, quaternary or higher composition deposited on a substrate. It will be understood that the various source materials would be selected so that a vapour may be created for condensation on the substrate. The preferred substrate is a substrate that is opaque in the visible and infrared regions of the electromagnetic spectrum. In particular, the substrate is a thick film dielectric layer on a ceramic substrate. Examples of such substrates include alumina, and metal ceramic composites.
- As discussed herein, components of the phosphor are placed on each of the sources. For instance, if the phosphor is CaAlS4:Eu, then Al2S3 is placed on one source and europium-doped CaS on the other source. If the phosphor is BaaCa1-aAl2S4:Eu, then Al2S3 is preferably placed on one source and a europium-doped mixture of BaS and CaS, in the ratio's defined by “a” and “1-a”, is placed on the other source.
- In preferred embodiments, the phosphors are europium-activated barium-calcium thioaluminates, which are believed to be less susceptible to hydrolysis than cerium-activated strontium sulphide, thus rendering them easier to pattern using photolithographic techniques.
- The present invention relates to a novel process for depositing multi-element thin films for electroluminescent phosphors and adjacent dielectric layers from which electrons are injected into the phosphors that provide a high luminosity and an emission color.
- FIG. 1 shows a side view of the dual electron beam evaporator, which is an apparatus generally indicated by10.
Apparatus 10 hassource materials Crystal rate monitor 16 is located nearsubstrate 18, and is behindshield 20.Shield 20 is located so that it receives depositions of evaporant fromsource material 12 but not fromsource material 14. Similarly,crystal rate monitor 22 is located nearsubstrate 18, in a position opposed tocrystal rate monitor 16, and is behindshield 24.Shield 24 is located so that it receives depositions of evaporant fromsource material 14 and not fromsource material 12. - Crystal rate monitors16 and 22 are located juxtaposed to
substrate 18, in a position that is preferably as near as is practical. Differences in distances can be allowed for in control of the method. Location of crystal rate monitors 16 and 22 spaced fromsource materials substrate 18 more accurately monitors the deposition of source materials onsubstrate 18. -
Substrate 18 is rotatable, as indicated. - In operation, the respective samples of source material, as discussed herein, are placed as
source materials source materials source material 12 is monitored bycrystal rate monitor 16 and fromsource material 14 bycrystal rate monitor 22. A computer-based feedback system is used to control the evaporation of each ofsource materials substrate 18, to achieve optimum performance for phosphors with ternary, quaternary or higher elemental composition.Substrate 18 is rotated during deposition. - It is understood that more than two source materials could be used, if appropriate to the phosphor composition.
- The deposition of the composition may be carried out in an atmosphere of H2S, sulphur or other volatile sulphur bearing compounds that will not contaminate the phosphor film as it is deposited if there is a tendency for the deposited compound to be deficient in sulphur. However, in some instances, it may be possible to operate the method without an atmosphere of H2S.
- It is to be understood that the sticking coefficient, also known as condensation rate, of an individual evaporant on the respective rate monitors may differ, and generally will differ, from the sticking coefficient of the evaporant when it is co-deposited onto the substrate. Thus, such differences in sticking coefficients must be understood in order to obtain optimization of the co-deposition on the substrate.
- FIG. 2 shows a plan view of
apparatus 10. In FIG. 2, there are fourplatforms 26A, 26B, 26C and 26D, all of which rotate.Substrate 18 is shown on platform 26C. It will be noted thatsource materials - In an embodiment, the deposition apparatus comprises a Temescal™ electron beam evaporation system with four 40 cc source material pockets. The apparatus has two Temescal STIH-270-3CK electron beam guns and two independent deposition rate feedback control systems, each of which includes MDC e-Vap programmable sweep controllers, MDC e-Vap source controls, Sycon STC-200 deposition rate controllers and MDC e-Vap CVS-15KW electron beam power supplies. Other apparatus may be used.
- The present invention is further illustrated by the embodiment shown in FIGS. 3 and 4. FIG. 3 shows a cross-section of an electroluminescent device utilizing a phosphor. FIG. 4 shows a plan view of the electroluminescent device. The electroluminescent device, generally indicated by40, has a
substrate 42 on which is locatedrow electrode 44.Thick film dielectric 46 hasthin film dielectric 48 thereon.Thin film dielectric 48 is shown with three pixel columns, referred to as 50, 52 and 54, located thereon. The pixel columns contain phosphors to provide the three basic colours viz. red, green and blue.Pixel column 50 hasred phosphor 56 located in contact withthin film dielectric 48. Anotherthin film dielectric 58 is located onred phosphor 56, andcolumn electrode 60 is located onthin film dielectric 58. Similarly,pixel column 52 hasgreen phosphor 62 onthin film dielectric 48, withthin film dielectric 64 andcolumn electrode 66 thereon.Pixel column 54 hasblue phosphor 68 onthin film dielectric 48, withthin film dielectric 70 andcolumn electrode 72 thereon. - In another aspect, the present invention provides a method for the deposition of a thin film of a pre-determined composition onto a substrate, said composition comprising a ternary, quaternary or higher composition. In this embodiment, a first deposit is placed at a first source of a vapour deposition apparatus and a second deposit is placed at a second source of the vapour deposition apparatus. The first and second deposits are different, and may or may not be sulphides. For example, the deposits could be sulphides. The components of the first and second deposits in combination form the pre-determined composition. Simultaneous vapour deposition is effected from the first and second sources to form said pre-determined composition on said substrate. The simultaneous vapour deposition may be sputtering, electron beam, or thermal evaporation, or other kind of simultaneous vapour deposition. In this embodiment, the temporal variation of deposition of the components onto said substrate from the first and second sources is determined. The temporal variation is used for controlling the first and second sources e.g. by controlling the temperatures of the sources, so as to obtain homogeneous temporal deposition of the composition on the substrate by simultaneous vapour deposition from the sources.
- In preferred embodiments of the method, the temporal variation is obtained by monitoring the rate of vaporizing from the first source with a first coating rate monitor and monitoring the rate of vaporizing from the second source with a second coating rate monitor. The first coating rate monitor is shielded from deposition from the second source and the second coating rate monitor is shielded from deposition from the first source. The monitoring is preferably used as the determining of temporal deposition of step (ii). In particular, the monitoring of step (ii) may be used in step (iii).
- The present invention provides a method for depositing controlled composition multi-element thin films for use as electroluminescent phosphors that can be tuned by adjusting the film composition. Phosphors with a high luminosity and emission colour are obtained. The process entails the use of at least two source materials that can be deposited using for example, low pressure physical vapour deposition methods and deposition rate monitors placed in the deposition chamber that can independently measure the deposition rate of each source material. The rate monitors, combined with appropriate feedback control, can be used to control the compositions of deposited films that comprise the combined elemental composition of the source materials. Such films may comprise a ternary or quaternary elemental composition, but films including a larger number of elements are also possible by use of multiple sources. The luminosity and emission spectra of electroluminescent phosphor films can be optimized by controlling and adjusting the elemental composition of the films.
- Thus, the present invention provides a method of deposition of ternary, quaternary or higher phosphor compositions, especially onto an opaque substrate. The method permits control of the relative rates of deposition from more than one source, to provide improved electroluminescent phosphors, especially phosphors of more consistent composition. The phosphors obtained are believed to exhibit higher luminosity and improved emission colour.
- A series of europium-doped barium calcium thioaluminate powders were prepared by blending powders of barium sulphide, calcium sulphide, aluminum sulphide and europium sulphide in various ratios. The blended powders were pressed to form pellets with a diameter of 1.3 cm and a height of 0.75 cm. In the series of samples, the fraction “a” in the formula BaaCa1-aAl2S4:Eu was varied as follows: 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0. All of the phosphor materials had a nominal concentration of europium corresponding to 3 atomic percent of the sum of the barium and calcium concentrations. The pellets were annealed at 900° C. for 20 minutes in nitrogen.
- The photoluminescence of the powders was evaluated by illumination of the powder under an ultraviolet light source. As the concentration of “a” was increased from 0 to 1, i.e. from CaAl2S4:Eu towards BaAl2S4:Eu, and the phosphor pellets were photo-stimulated using 365 nanometer ultraviolet light, it was found that the CIE colour coordinate “x” decreased from 0.17 to 0.15 and the CIE colour coordinate “y” decreased from 0.67 to 0.15. The photoluminescence decreased, from 98 to 45 cd/m2. The colour of the pellets gradually changed from green to blue. The change in physical appearance of the pellets was also visible. For a=0.7 and below, the colour of the pellets was greenish to the unaided eye.
- The photoluminescent emission and colour coordinates for pellets with different values of “a” are shown in FIG. 5.
- A europium-doped calcium thioaluminate phosphor film of the type described in Example 1 with a=0 was formed on a thick film opaque substrate using the dual source method and apparatus described above.
- One of the two source materials used to deposit the phosphor was aluminum sulphide (Al2S3) formed into a pellet. This pellet was not annealed. The other source material was a europium-doped calcium sulphide pellet (CaS:Eu). This pellet was annealed at 800° C. for 20 minutes in nitrogen. The diameter and height of each of the Al2S3 and CaS:Eu pellets were 2.5 and 1.8 centimeters, respectively. The pellets were slowly degassed and preconditioned with a low electron beam current from their respective electron guns.
- The substrate was alumina upon which a gold electrode pattern was deposited and overlaid with a high dielectric constant thick film dielectric layer comprising PMN-PT coated with lead zirconate-titanate, and further overlaid with a thin film layer of alumina as described in U.S. patent application Ser. No. 09/540,288 of Wu et al. PMN-PT is a material that includes lead and magnesium niobates and titanates.
- During phosphor deposition, both Al2S3 and CaS:Eu materials were vaporized simultaneously in an atmosphere having a hydrogen sulphide partial pressure of 2×10−4 Torr. The deposition substrate temperature was about 500° C. The deposition rates of Al2S3 and CaS:Eu were 2.8 and 1.8 Angstroms per second, respectively, as measured independently using the two deposition rate monitoring systems. It is understood that the relative deposition rates need to be adjusted to account for differences between the sticking coefficient of the two source materials on the rate monitors, and the sticking coefficients for the combined materials on the workpiece substrate.
- The thickness of the CaAl2S4:Eu phosphor film was 2300 Angstroms, as measured using scanning electron microscopy. Examples of structures incorporating the phosphor films are shown in cross section and in plan view in FIGS. 3 and 4. The deposited phosphors were annealed following deposition at a temperature of about 700° C. for 2 minutes under nitrogen. To complete the test device, a second thin film of alumina was deposited on top of the phosphor layer, and a second electrode structure comprising indium tin oxide was deposited on top of the alumina layer.
- The phosphor obtained provided a relatively high energy conversion efficiency and a luminosity of 90 candelas per square meter with unfiltered CIE colour coordinates of x=0.19 and y=0.62 when operated at an excitation frequency of 120 Hz at a voltage of 70 volts above the threshold voltage of 190 volts and a pulse width of 30μ seconds. The peak emission wavelength of both photoluminescence and electroluminescence spectra was 515 mn.
- As a comparison, it was reported in JP 8-134440 of the Mitsui Mining & Smelting Ltd and Sharp Corporation, published May 28, 1996, that electroluminescent luminosity for sputtered thin films of CaAl2S:Eu phosphor was 1 cd/m2 at a 1 kHz excitation frequency with CIE coordinates of x=0.13, y=0.377. With the method of the present invention, the same phosphor material provided much higher luminosity and improved colour saturation, the luminosity being approximately two orders of magnitude higher.
- A phosphor film was prepared using the material described in Example 1 with a=1. The procedure used was the same as that described in Example I. For this phosphor, one pellet was formed from Al2S3 and the other pellet was formed from the required mixture of barium sulphide and europium sulphide. The thickness of the BaAl2S4:Eu phosphor film was 2700 Angstroms, measured using scanning electron microscopy.
- As reported in Example I, for the composition corresponding to a=0, i.e. CaAl2S4:Eu, and using an excitation frequency of 120 Hz and a pulse width of 30μ seconds, the electroluminescent pixel had a brightness of 90 cd/m2 at 70 volts above the threshold voltage of 180 volts while its CIE colour coordinates were x=0.19 and y=0.62. This is reasonably similar to the photoluminescence values observed for the pellets having the same nominal composition.
- For the composition corresponding to a=1, i.e. BaAl2S4:Eu, the luminance was about 40 cd/m2 at 70 volts above the threshold voltage of 190 volts. The CIE colour coordinates were x=0.15 and y=0.14, which are again similar to the photoluminescence values observed for the pellets having the same nominal composition.
- The similar results for the electroluminescent colour coordinates of the deposited films to those of the photoluminescence of pressed powders provide good evidence that the composition of the thin films was close to that for the corresponding powders and therefore that the dual source deposition method facilitates good control over the stoichiometry of the deposited films.
Claims (44)
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US09/747,315 US6610352B2 (en) | 2000-12-22 | 2000-12-22 | Multiple source deposition process |
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US20060027788A1 (en) * | 2004-08-06 | 2006-02-09 | Stiles James A R | Barium thioaluminate phosphor materials with novel crystal structures |
US7427367B2 (en) | 2004-08-06 | 2008-09-23 | Ifire Technology Corp. | Barium thioaluminate phosphor materials with novel crystal structures |
US20080296533A1 (en) * | 2004-08-06 | 2008-12-04 | Ifire Technology Corp. | Barium thioaluminate phosphor materials with novel crystal structures |
US7582228B2 (en) | 2004-08-06 | 2009-09-01 | Ifire Ip Corporation | Barium thioaluminate phosphor materials with novel crystal structures |
US20060046594A1 (en) * | 2004-08-30 | 2006-03-02 | David Starrett | Flame retardant sound dampening appliance insulation |
US20070268205A1 (en) * | 2006-05-19 | 2007-11-22 | Canon Kabushiki Kaisha | Multiprimary color display |
US10276740B1 (en) | 2018-03-19 | 2019-04-30 | The United States Of America As Represented By The Secretary Of The Air Force | Co-deposition of black silicon |
Also Published As
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ATE296335T1 (en) | 2005-06-15 |
WO2002051960A1 (en) | 2002-07-04 |
KR20030091948A (en) | 2003-12-03 |
JP2009062619A (en) | 2009-03-26 |
DE60111077D1 (en) | 2005-06-30 |
US20020081371A1 (en) | 2002-06-27 |
DE60111077T2 (en) | 2006-01-26 |
US6610352B2 (en) | 2003-08-26 |
JP2004522826A (en) | 2004-07-29 |
CA2431084C (en) | 2010-03-23 |
KR100874523B1 (en) | 2008-12-16 |
EP1346007A1 (en) | 2003-09-24 |
CA2431084A1 (en) | 2002-07-04 |
EP1346007B1 (en) | 2005-05-25 |
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