US20100095705A1 - Method for forming a dry glass-based frit - Google Patents
Method for forming a dry glass-based frit Download PDFInfo
- Publication number
- US20100095705A1 US20100095705A1 US12/504,276 US50427609A US2010095705A1 US 20100095705 A1 US20100095705 A1 US 20100095705A1 US 50427609 A US50427609 A US 50427609A US 2010095705 A1 US2010095705 A1 US 2010095705A1
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- United States
- Prior art keywords
- glass
- frit
- melting
- batch material
- forming
- Prior art date
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- Abandoned
Links
- 239000011521 glass Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000002844 melting Methods 0.000 claims abstract description 31
- 230000008018 melting Effects 0.000 claims abstract description 24
- 150000004820 halides Chemical class 0.000 claims abstract description 9
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 9
- 150000005309 metal halides Chemical class 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 26
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 13
- 230000003750 conditioning effect Effects 0.000 claims description 10
- 239000000156 glass melt Substances 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 18
- 239000012298 atmosphere Substances 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 20
- 238000005259 measurement Methods 0.000 description 19
- 239000000758 substrate Substances 0.000 description 17
- 238000010943 off-gassing Methods 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 14
- 238000007789 sealing Methods 0.000 description 13
- 239000011368 organic material Substances 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 7
- 238000013459 approach Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002352 surface water Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000006063 cullet Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- -1 hydroxyl ions Chemical class 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004476 mid-IR spectroscopy Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 2
- 238000005382 thermal cycling Methods 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 238000013383 initial experiment Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012002 vanadium phosphate Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/871—Self-supporting sealing arrangements
- H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/842—Containers
- H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
Definitions
- the present invention relates to a method for forming a dry frit based on an inorganic glass. More particularly, the present invention relates to a method for forming a dry inorganic glass-based frit suitable for use as a sealing medium for glass packages.
- Electroluminescent (EL) devices such as organic light emitting diode devices, are typically manufactured by forming multiple devices in a single assembly using large master (mother) sheets of glass. That is, the devices are encapsulated between two large glass sheets or plates to form a composite assembly, after which individual devices are cut from the composite assembly.
- Each device of the composite assembly includes a seal surrounding the organic light emitting diodes of the individual device that seals the top and bottom plates together, and protects the organic light emitting diodes disposed within, since some devices, particularly organic light emitting diodes, degrade in the presence of oxygen and moisture that can be found in the ambient atmosphere.
- the EL devices may be sealed using an adhesive, e.g. epoxy, or more recently, using a glass frit that is heated to melt the frit and form the seal between the two plates.
- Frit sealed devices exhibit certain advantages over adhesive-sealed devices, not least of which is the superior hermeticity without the need for getters sealed within the device to scavenge contaminants. Thus, frit sealed devices are able to provide for a longer lived device than has been achievable with adhesive seals. Nevertheless, it has been found that frit sealed devices may succumb to deterioration due to moisture contained in and released by the frit into the cavity housing the organic light emitting material during the sealing process.
- Methods are disclosed for forming a dry glass-based frit suitable for sealing electronic devices, and in particular electronic devices comprising organic materials, such as organic light emitting diode displays, organic light emitting diode lighting panels, and certain classes of organic-based photovoltaic devices.
- organic materials such as organic light emitting diode displays, organic light emitting diode lighting panels, and certain classes of organic-based photovoltaic devices.
- a method of forming a dry glass frit comprising forming a batch material comprising vanadium and phosphorous, heating the batch material in a conditioning step to a temperature of between about 450° C. and 550° C. for at least about 1 hour, melting the batch material after the conditioning step to form a glass melt, cooling the glass melt to form a glass wherein an OH content of the glass is equal to or less than about 20 ppm as measured by direct insertion probe mass spectrometry.
- a glass powder for forming a glass-based frit wherein the glass powder comprises vanadium, phosphorous and a metal halide.
- a glass powder for forming a glass-based frit wherein the glass powder comprises V 2 O 5 , P 2 O 5 and a metal halide.
- a method of forming a glass frit comprising forming a batch material comprising V 2 O 5 , P 2 O 5 and a metal halide heating the batch material in a conditioning step to a temperature of between about 450° C. and 550° C. for at least about 1 hour, melting the batch material after the conditioning step to form a glass melt, cooling the glass melt to form a glass and wherein an OH content of the glass is equal to or less than about 20 ppm.
- FIG. 1 is a cross sectional view of an exemplary glass package comprising an organic material.
- FIG. 2 is plot of percent transmittance as a function of wavenumber illustrating a typical measurement for ⁇ -OH.
- FIG. 3 is a schematic diagram of a DIP-MS apparatus for measuring outgassed water vapor.
- FIG. 4 is a graphical representation of a Standard heating schedule according to embodiments of the present invention.
- FIG. 5 is a graphical representation of a compressed heating schedule according to embodiments of the present invention.
- FIG. 6 is a plot showing the results of a DIP-MS measurement conducted on a coarse hand-ground sample of frit composition C 1 , showing the extracted ion chromatogram for water.
- FIG. 7 is a plot showing the results of a control DIP-MS measurement as conducted in FIG. 6 , but without a sample, indicating that the events (spikes) shown in FIG. 6 are related to outgassing of structural water species during the 400-700° C. temperature ramp.
- FIG. 8 is a plot showing the results of a DIP-MS measurement conducted on coarse hand-ground samples of control (non-dry) frit composition C 1 , showing outgassing of structural water species during the 400-700° C. temperature ramp compared to results for sample C 2 showing no peaks.
- FIG. 9 is a photograph that shows fused quartz crucibles of the control batch composition following 485° calcination (left) and 600° C. calcination (right).
- Hermetically sealed glass packages may be used for a variety of uses, including such photonic devices as optical displays (e.g. flat panel television, cell phones displays, camera displays) and photovoltaic devices (e.g. solar cells). While epoxy seals have been used extensively for certain components, such as liquid crystal displays (LCDs), more recent work is being done on encapsulated organic materials that may be used for similar purposes. For example, organic light emitting diodes are finding application in both display devices and lighting. Certain organic materials are also finding use in the field of photovoltaics, wherein organic solar cells are showing promise.
- optical displays e.g. flat panel television, cell phones displays, camera displays
- photovoltaic devices e.g. solar cells
- epoxy seals have been used extensively for certain components, such as liquid crystal displays (LCDs)
- LCDs liquid crystal displays
- organic light emitting diodes are finding application in both display devices and lighting.
- Certain organic materials are also finding use in the field of photovoltaics, wherein organic solar cells are showing promise.
- the organic materials comprising the devices are susceptible to high temperature, oxygen and moisture exposure. That is, when exposed to temperatures in excess of about 100° C., or oxygen or water, the organic material can quickly degrade. For this reason, great care must be taken to ensure devices employing organic materials are hermetically sealed.
- One such method includes sealing the organic material between glass plates.
- Inorganic glasses are uniquely suited as containers for housing an organic material. They are substantially environmentally stable, and highly impervious to diffusion of moisture and oxygen. However, the resulting package is only as good as the material that forms the seal between the plates.
- Prior art devices have often employed epoxy adhesives as a sealing medium between glass plates.
- the manufacture of LCD displays is one such example.
- the degree of long term hermeticity required by certain organic materials suitable for use in electronic devices such as the previously mentioned displays, lighting panels and photovoltaic devices is better met by a glass seal between the plates.
- the use of an inorganic glass-based frit has become the sealing medium of choice for organic electronic devices.
- an exemplary frit sealing method for organic light emitting diode display 10 may comprise forming a photonic element 12 on a first (backplane) glass substrate 14 .
- Photonic element 12 typically includes an anode and cathode electrodes (not shown) and one or more layers of the photonic material (e.g. organic light emitting material) positioned between the two electrodes.
- a frit 16 is positioned between the backplane substrate and a second glass (cover) substrate 18 .
- the frit may, for example, be first dispensed onto the cover substrate. In some embodiments, the frit is first dispensed as a paste onto cover substrate 18 , then heated to sinter the frit and adhere it to the cover substrate.
- the sintering may be performed in an oven.
- Cover substrate 18 is then positioned in at least partial overlying registration with the backplane substrate, and the frit heated by an irradiation source 20 , such as laser 20 that emits laser beam 22 to soften the frit and form a hermetic seal between the cover substrate and the backplane substrate, thereby producing a hermetic glass package containing the OLED.
- an irradiation source 20 such as laser 20 that emits laser beam 22 to soften the frit and form a hermetic seal between the cover substrate and the backplane substrate, thereby producing a hermetic glass package containing the OLED.
- water present in glasses can be grouped into two broad categories: structural water where the water atoms (generally present as hydroxyl or OH ions) attach to the glass-forming polyhedra molecular structure during the melting process and become a basic part of the glass network; and surface water where, for example, water molecules present during ball-milling of a glass to produce a frit attach themselves during the milling to unsatisfied valence sites on the frit particle's surface created by broken bonds.
- surface water can be removed by a simple drying process, such as by heating the glass of the frit, whereas structural water is much more tenaciously bound, and can persist in the glass during any drying step.
- Water may take the form of a vapor phase (such as during outgassing, or as a hydroxyl ion, OH).
- a glass is formed by conventional glass forming methods e.g. sol-gel or by heating granular batch materials (sands).
- the resulting glass can then be melted, made into thin ribbon, and then ball-milled to a desired particle size.
- a mean particle size of 3 ⁇ m is suitable for use in the manufacture of OLED devices.
- the powdered frit glass may be blended with a filler to obtain a predetermined coefficient of thermal expansion of the frit blend.
- a suitable coefficient of thermal expansion filler is beta eucryptite.
- a paste is prepared by mixing the frit glass (or blended frit as the case may be) with an organic vehicle (e.g. texanol), an organic binder (e.g. ethylcellulose), and various dispersants and surfactants as needed.
- the frit paste is then dispensed into a specific pattern (for example a loop or frame-like pattern) on a glass substrate, heated in air to burn-out the organics, and thereafter exposed to a subsequent heating to 400° C. in N 2 to presenter the frit.
- the step of presintering consolidates the frit and adheres the frit to the (cover) substrate.
- Laser-sealing the pre-sintered substrate to a mating substrate (backplane substrate) of one or more OLED devices is typically accomplished using a laser that traverses the consolidated frit, heats and softens the frit and whereupon a seal is formed between the cover substrate and the backplane substrate when the frit cools and solidifies.
- the frit seal is heated above 400° C. for at least a few tenths of a second, causing structural water (i.e. OH) in the frit to be released, and possibly degrading the OLED.
- a dry glass (and resulting dry frit) is defined as possessing a ⁇ -OH value equal to or less than about 0.3 mm ⁇ 1 , or alternatively an OH content equal to or less than about 20 ppm when measured by direct insertion probe mass spectrometry.
- the glass comprises a ⁇ -OH value equal to or less than about 0.3 mm ⁇ 1 and an OH content equal to or less than about 20 ppm when measured by direct insertion probe mass spectrometry.
- the glass exhibits no water detectable out-gassing by DIP-MS when reheated to 700° C. either as a coarse hand-ground powder, or as a fine (3 ⁇ m) ball-milled powder.
- ⁇ -OH is a ratio of baseline transmittance to transmittance at the OH ⁇ absorption peak, and is directly proportional to hydroxyl ion concentration for glasses identical, or very similar, to each other in composition.
- ref % T is the transmittance level at a nearby non-OH absorbing region
- OH % T is the transmittance level at the base of the OH peak ( ⁇ 3380 cm ⁇ 1) and thk is the sample thickness (mm).
- ⁇ -OH is directly proportional to the hydroxyl ion concentration for glasses identical, or very similar, to each other in composition. ⁇ -OH measurements provide the relative hydroxyl (OH) absorption coefficient for all hydroxyl ions in the glass, not just on those hydroxyls which will de-absorb over a specific temperature region. Any conventional infrared spectroscopy technique can be utilized for the measurements, such as Fourier transform infrared spectroscopy.
- the DIP-MS arrangement shown diagrammatically in FIG. 3 , makes use of a heated probe 28 containing the sample to be tested 30 that is placed directly within the ionization region (electron impact ionizer 32 ) of the mass spectrometer 34 .
- the exemplary DIP-MS arrangement if FIG. 3 further includes quadrapole ion analyzer 36 and detector 38 .
- Wavy line 40 represents an ion path from sample 30 to detector 38 .
- a quartz transfer tube and associated problems of deposition of chemical species, or permeability of the tube at high temperatures.
- the DIP-MS measurement lends itself to more reliable quantitative analysis of chemical species.
- FIG. 6 Shown in FIG. 6 are the results of a DIP-MS measurement conducted on a coarse hand-ground sample of a frit glass composition suitable for laser sealing of an OLED device showing the extracted ion chromatogram for water (and plotted a nano-Amperes as a function of. time in minutes).
- the run was made on the Standard Schedule. A small amount of water outgassing from surface water was recorded in the first few minutes of the run as the sample was heated to 400° C. During the 4 hr hold at 400° C. (from 20 min to 260 min), no additional water out-gassing events were recorded, confirming that the initial water evolution was related to surface water. Once sample heating resumed, several discrete events related to water evolution are observed beginning at approximately 550° C.
- halide compounds As noted in Table I, the use of halide compounds was found to be particularly effective for reducing structural water levels, as indicated by both the significantly-lowered ⁇ -OH levels of the halide-containing compositions, as well as by the complete absence of detectable water outgassing during the 400-700° heating ramp as detected by the DIP-MS measurement.
- Table I provides a summary of the results for 4 compositions (C 2 -C 4 ) compared to a control composition (C 1 ) without a halide. Shown in FIG. 8 is a comparison of the high temperature portion of a DIP-MS scan for the non-halide containing C 1 sample, and the substantially identical C 2 sample with all Al 2 O 3 replaced by AlF 3 . Both materials were coarse, hand-ground glass powders.
- the scan for the fluorine-containing glass (C 2 ) represented by curve 42 shows a featureless pattern with no distinct events.
- the scan for the C 1 sample represented by curve 44 shows several discrete water evolution events occurring in the approximately 550-650° C. range.
- the ⁇ -OH value for the C5 sample was higher that expected, and out of line with the other halide results, and is believed to be a result of poor sample preparation (as the ⁇ -OH measurement is sensitive to surface cleanliness of the sample). DIP-MS measurements for sample C3 and C4 were not conducted.
- Table II Shown in Table II is a listing of the various process change experiments and the structural water level measured ( ⁇ -OH) and/or the quantity of structural water evolved (DIP-MS). As may be seen, these various experiments involved determining the effect of thermal cycling during melting (Experiment 1), air-calcining of the batch material with N 2 melting (Experiment 2), air-calcining of the batch material (either 485° or 600° C.) combined followed by air-melting (Experiments 3 and 4) of the batch material; melting all but the V 2 O 5 component of the basic glass, then re-melting with V 2 O 5 (Experiment 5); and re-melting standard cullet in an induction furnace and bubbling O 2 or N 2 /O 2 through the melt during re-melting (Experiments 6 and 7).
Abstract
A dry glass-based fit, and methods of making a dry glass fit are disclosed. In one embodiment a dry glass frit comprises vanadium, phosphorous and a metal halide. The halide may be, for example, fluorine or chlorine. In another embodiment, a method of producing a dry glass frit comprises calcining a batch material for the frit, then melting the batch material in an inert atmosphere, such as a nitrogen atmosphere. In still another embodiment, a method of producing a dry glass frit comprises calcining a batch material for the frit, then melting the batch material in an air atmosphere, such as a nitrogen atmosphere
Description
- This application claims the benefit of priority under 35 U.S.C. § 119(e) of U.S. Provisional Application Ser. No. 61/106,730 filed on Oct. 20, 2008 the content of which is relied upon and incorporated herein by reference in its entirety.
- The present invention relates to a method for forming a dry frit based on an inorganic glass. More particularly, the present invention relates to a method for forming a dry inorganic glass-based frit suitable for use as a sealing medium for glass packages.
- Electroluminescent (EL) devices, such as organic light emitting diode devices, are typically manufactured by forming multiple devices in a single assembly using large master (mother) sheets of glass. That is, the devices are encapsulated between two large glass sheets or plates to form a composite assembly, after which individual devices are cut from the composite assembly. Each device of the composite assembly includes a seal surrounding the organic light emitting diodes of the individual device that seals the top and bottom plates together, and protects the organic light emitting diodes disposed within, since some devices, particularly organic light emitting diodes, degrade in the presence of oxygen and moisture that can be found in the ambient atmosphere. The EL devices may be sealed using an adhesive, e.g. epoxy, or more recently, using a glass frit that is heated to melt the frit and form the seal between the two plates.
- Frit sealed devices exhibit certain advantages over adhesive-sealed devices, not least of which is the superior hermeticity without the need for getters sealed within the device to scavenge contaminants. Thus, frit sealed devices are able to provide for a longer lived device than has been achievable with adhesive seals. Nevertheless, it has been found that frit sealed devices may succumb to deterioration due to moisture contained in and released by the frit into the cavity housing the organic light emitting material during the sealing process.
- Methods are disclosed for forming a dry glass-based frit suitable for sealing electronic devices, and in particular electronic devices comprising organic materials, such as organic light emitting diode displays, organic light emitting diode lighting panels, and certain classes of organic-based photovoltaic devices.
- In one embodiment, a method of forming a dry glass frit is disclosed comprising forming a batch material comprising vanadium and phosphorous, heating the batch material in a conditioning step to a temperature of between about 450° C. and 550° C. for at least about 1 hour, melting the batch material after the conditioning step to form a glass melt, cooling the glass melt to form a glass wherein an OH content of the glass is equal to or less than about 20 ppm as measured by direct insertion probe mass spectrometry.
- In another embodiment a glass powder for forming a glass-based frit is disclosed wherein the glass powder comprises vanadium, phosphorous and a metal halide.
- In still another embodiment, a glass powder for forming a glass-based frit is disclosed wherein the glass powder comprises V2O5, P2O5 and a metal halide.
- In yet another embodiment, a method of forming a glass frit is disclosed comprising forming a batch material comprising V2O5, P2O5 and a metal halide heating the batch material in a conditioning step to a temperature of between about 450° C. and 550° C. for at least about 1 hour, melting the batch material after the conditioning step to form a glass melt, cooling the glass melt to form a glass and wherein an OH content of the glass is equal to or less than about 20 ppm.
- The invention will be understood more easily and other objects, characteristics, details and advantages thereof will become more clearly apparent in the course of the following explanatory description, which is given, without in any way implying a limitation, with reference to the attached Figures. It is intended that all such additional systems, methods features and advantages be included within this description, be within the scope of the present invention, and be protected by the accompanying claims.
-
FIG. 1 is a cross sectional view of an exemplary glass package comprising an organic material. -
FIG. 2 is plot of percent transmittance as a function of wavenumber illustrating a typical measurement for β-OH. -
FIG. 3 is a schematic diagram of a DIP-MS apparatus for measuring outgassed water vapor. -
FIG. 4 is a graphical representation of a Standard heating schedule according to embodiments of the present invention. -
FIG. 5 is a graphical representation of a compressed heating schedule according to embodiments of the present invention -
FIG. 6 is a plot showing the results of a DIP-MS measurement conducted on a coarse hand-ground sample of frit composition C1, showing the extracted ion chromatogram for water. -
FIG. 7 is a plot showing the results of a control DIP-MS measurement as conducted inFIG. 6 , but without a sample, indicating that the events (spikes) shown inFIG. 6 are related to outgassing of structural water species during the 400-700° C. temperature ramp. -
FIG. 8 is a plot showing the results of a DIP-MS measurement conducted on coarse hand-ground samples of control (non-dry) frit composition C1, showing outgassing of structural water species during the 400-700° C. temperature ramp compared to results for sample C2 showing no peaks. -
FIG. 9 is a photograph that shows fused quartz crucibles of the control batch composition following 485° calcination (left) and 600° C. calcination (right). - In the following detailed description, for purposes of explanation and not limitation, example embodiments disclosing specific details are set forth to provide a thorough understanding of the present invention. However, it will be apparent to one having ordinary skill in the art, having had the benefit of the present disclosure, that the present invention may be practiced in other embodiments that depart from the specific details disclosed herein. Moreover, descriptions of well-known devices, methods and materials may be omitted so as not to obscure the description of the present invention. Finally, wherever applicable, like reference numerals refer to like elements.
- Hermetically sealed glass packages may be used for a variety of uses, including such photonic devices as optical displays (e.g. flat panel television, cell phones displays, camera displays) and photovoltaic devices (e.g. solar cells). While epoxy seals have been used extensively for certain components, such as liquid crystal displays (LCDs), more recent work is being done on encapsulated organic materials that may be used for similar purposes. For example, organic light emitting diodes are finding application in both display devices and lighting. Certain organic materials are also finding use in the field of photovoltaics, wherein organic solar cells are showing promise.
- While organic materials provide some benefit, the organic materials comprising the devices are susceptible to high temperature, oxygen and moisture exposure. That is, when exposed to temperatures in excess of about 100° C., or oxygen or water, the organic material can quickly degrade. For this reason, great care must be taken to ensure devices employing organic materials are hermetically sealed. One such method includes sealing the organic material between glass plates. Inorganic glasses are uniquely suited as containers for housing an organic material. They are substantially environmentally stable, and highly impervious to diffusion of moisture and oxygen. However, the resulting package is only as good as the material that forms the seal between the plates.
- Prior art devices have often employed epoxy adhesives as a sealing medium between glass plates. The manufacture of LCD displays is one such example. However, the degree of long term hermeticity required by certain organic materials suitable for use in electronic devices such as the previously mentioned displays, lighting panels and photovoltaic devices is better met by a glass seal between the plates. Thus, the use of an inorganic glass-based frit has become the sealing medium of choice for organic electronic devices.
- By way of example and not limitation, an exemplary frit sealing method for organic light emitting diode display 10 (
FIG. 1 ) may comprise forming aphotonic element 12 on a first (backplane)glass substrate 14.Photonic element 12 typically includes an anode and cathode electrodes (not shown) and one or more layers of the photonic material (e.g. organic light emitting material) positioned between the two electrodes. A frit 16 is positioned between the backplane substrate and a second glass (cover)substrate 18. The frit may, for example, be first dispensed onto the cover substrate. In some embodiments, the frit is first dispensed as a paste ontocover substrate 18, then heated to sinter the frit and adhere it to the cover substrate. The sintering may be performed in an oven.Cover substrate 18 is then positioned in at least partial overlying registration with the backplane substrate, and the frit heated by anirradiation source 20, such aslaser 20 that emitslaser beam 22 to soften the frit and form a hermetic seal between the cover substrate and the backplane substrate, thereby producing a hermetic glass package containing the OLED. - In general, water present in glasses can be grouped into two broad categories: structural water where the water atoms (generally present as hydroxyl or OH ions) attach to the glass-forming polyhedra molecular structure during the melting process and become a basic part of the glass network; and surface water where, for example, water molecules present during ball-milling of a glass to produce a frit attach themselves during the milling to unsatisfied valence sites on the frit particle's surface created by broken bonds. Typically, surface water can be removed by a simple drying process, such as by heating the glass of the frit, whereas structural water is much more tenaciously bound, and can persist in the glass during any drying step.
- Although the presence of water in a glass does not necessarily degrade glass properties (save for increased mid-IR absorbance), its release (outgassing) during subsequent heating in a frit sealing process may have implications for commercial use of the glass. One particular application affected by water outgassing involves the use of glass frits for sealing OLED devices, which are extremely susceptible to even ppm levels of water. Water, as used herein, may take the form of a vapor phase (such as during outgassing, or as a hydroxyl ion, OH).
- In a typical frit manufacturing process, a glass is formed by conventional glass forming methods e.g. sol-gel or by heating granular batch materials (sands). The resulting glass can then be melted, made into thin ribbon, and then ball-milled to a desired particle size. For example, a mean particle size of 3 μm is suitable for use in the manufacture of OLED devices. Following ball-milling, the powdered frit glass may be blended with a filler to obtain a predetermined coefficient of thermal expansion of the frit blend. For example, a suitable coefficient of thermal expansion filler is beta eucryptite. Once the blend has been made and predried, such as heating the blend in an oven, a paste is prepared by mixing the frit glass (or blended frit as the case may be) with an organic vehicle (e.g. texanol), an organic binder (e.g. ethylcellulose), and various dispersants and surfactants as needed. The frit paste is then dispensed into a specific pattern (for example a loop or frame-like pattern) on a glass substrate, heated in air to burn-out the organics, and thereafter exposed to a subsequent heating to 400° C. in N2 to presenter the frit. As the term implies, the step of presintering consolidates the frit and adheres the frit to the (cover) substrate. Laser-sealing the pre-sintered substrate to a mating substrate (backplane substrate) of one or more OLED devices is typically accomplished using a laser that traverses the consolidated frit, heats and softens the frit and whereupon a seal is formed between the cover substrate and the backplane substrate when the frit cools and solidifies. During laser sealing the frit seal is heated above 400° C. for at least a few tenths of a second, causing structural water (i.e. OH) in the frit to be released, and possibly degrading the OLED.
- The effort to eliminate water outgassing in the glass during subsequent heating of the frit to 700° C. has focused on reducing the OH content of the glass. Two approaches were utilized: (1.) composition changes to the glass, and (2.) physical changes to the melting process. Measuring the amount of water was accomplished according to two methods: measuring β-OH (essentially measuring the mid-IR absorbance peak of the OH− ion), and DIP-MS (direct insertion probe mass spectrometry). In accordance with the present invention, a dry glass (and resulting dry frit) is defined as possessing a β-OH value equal to or less than about 0.3 mm−1, or alternatively an OH content equal to or less than about 20 ppm when measured by direct insertion probe mass spectrometry. Preferable, the glass comprises a β-OH value equal to or less than about 0.3 mm−1 and an OH content equal to or less than about 20 ppm when measured by direct insertion probe mass spectrometry. Preferably the glass exhibits no water detectable out-gassing by DIP-MS when reheated to 700° C. either as a coarse hand-ground powder, or as a fine (3 μm) ball-milled powder.
- The β-OH measurements were made on annealed pieces of glass that had been ground and then polished to a thickness of 0.1-0.4 mm. β-OH measurements provide data on the total concentration of hydroxyl ions in the glass, not just on those hydroxyls that will de-absorb over a specific temperature region. As shown in
FIG. 2 andequation 1 below, β-OH is a ratio of baseline transmittance to transmittance at the OH− absorption peak, and is directly proportional to hydroxyl ion concentration for glasses identical, or very similar, to each other in composition. -
β-OH=log(ref % T/OH % T)/(thk) 1 - where ref % T is the transmittance level at a nearby non-OH absorbing region, OH % T is the transmittance level at the base of the OH peak (˜3380 cm−1) and thk is the sample thickness (mm).
- β-OH is directly proportional to the hydroxyl ion concentration for glasses identical, or very similar, to each other in composition. β-OH measurements provide the relative hydroxyl (OH) absorption coefficient for all hydroxyl ions in the glass, not just on those hydroxyls which will de-absorb over a specific temperature region. Any conventional infrared spectroscopy technique can be utilized for the measurements, such as Fourier transform infrared spectroscopy.
- DIP-MS measurements were made on either coarse hand ground (−200M/+100M, or approximately 75-150 μm), or fine ball-milled (equal to or less than an average particle size of 3 μm) powder. Unlike the vacuum furnace mass spectroscopy technique used for many standard mass spec studies, the DIP-MS arrangement, shown diagrammatically in
FIG. 3 , makes use of aheated probe 28 containing the sample to be tested 30 that is placed directly within the ionization region (electron impact ionizer 32 ) of the mass spectrometer 34. In addition to the above components, the exemplary DIP-MS arrangement ifFIG. 3 further includesquadrapole ion analyzer 36 anddetector 38.Wavy line 40 represents an ion path fromsample 30 todetector 38. Unlike a vacuum furnace mass spectrometry measurement, there is no need for a quartz transfer tube and associated problems of deposition of chemical species, or permeability of the tube at high temperatures. Thus, the DIP-MS measurement lends itself to more reliable quantitative analysis of chemical species. - Two different heating schedules were used for the DIP-MS measurements: a) a Standard Cycle (
FIG. 4 ) where the sample was heated to 400° C., held for 5 hrs to remove any surface water, and then heated to 700° C. at a rate of 10° C./min., and b) a Compressed Schedule (FIG. 5 ) which utilizes the same temperature ramp-up to 400° C. as the Standard Schedule, but includes a shorter hold time at 400° C. (2 hrs), and utilizes a faster heat-up ramp to 700° C. (50° C./min.). All samples were heated in vacuum throughout the entire DIP-MS run. - Shown in
FIG. 6 are the results of a DIP-MS measurement conducted on a coarse hand-ground sample of a frit glass composition suitable for laser sealing of an OLED device showing the extracted ion chromatogram for water (and plotted a nano-Amperes as a function of. time in minutes). The run was made on the Standard Schedule. A small amount of water outgassing from surface water was recorded in the first few minutes of the run as the sample was heated to 400° C. During the 4 hr hold at 400° C. (from 20 min to 260 min), no additional water out-gassing events were recorded, confirming that the initial water evolution was related to surface water. Once sample heating resumed, several discrete events related to water evolution are observed beginning at approximately 550° C. - Note that these discrete events are not observed when a control measurement is run without a sample (
FIG. 7 ), further indicating that the events are related to outgassing of structural water species during the 400-700° C. temperature excursion. Only a broad undefined shallow peak is observed as a characteristic of the general background signal of the instrument during the control measurement. - As noted in Table I, the use of halide compounds was found to be particularly effective for reducing structural water levels, as indicated by both the significantly-lowered β-OH levels of the halide-containing compositions, as well as by the complete absence of detectable water outgassing during the 400-700° heating ramp as detected by the DIP-MS measurement. Table I provides a summary of the results for 4 compositions (C2-C4) compared to a control composition (C1) without a halide. Shown in
FIG. 8 is a comparison of the high temperature portion of a DIP-MS scan for the non-halide containing C1 sample, and the substantially identical C2 sample with all Al2O3 replaced by AlF3. Both materials were coarse, hand-ground glass powders. The scan for the fluorine-containing glass (C2) represented bycurve 42 shows a featureless pattern with no distinct events. By contrast, the scan for the C1 sample represented bycurve 44 shows several discrete water evolution events occurring in the approximately 550-650° C. range. The β-OH value for the C5 sample was higher that expected, and out of line with the other halide results, and is believed to be a result of poor sample preparation (as the β-OH measurement is sensitive to surface cleanliness of the sample). DIP-MS measurements for sample C3 and C4 were not conducted. -
TABLE I C2 C3 C4 C5 (all (50% of (25% of (67% of C1 Al2O3 Al2O3 Al2O3 Al2O3 (standard added added as added as added as (mole %) composition) as AlF3) AlF3) AlF3) AlCl3) Sb2O3 22.9 22.9 22.9 22.9 22.9 V2O5 46.3 46.3 46.3 46.3 46.3 P2O5 26.3 26.3 26.3 26.3 26.3 Fe2O3 2.4 2.4 2.4 2.4 2.4 Al2O3 1.0 1.0 1.0 1.0 1.0 TiO2 1.0 1.0 1.0 1.0 1.0 F− — 6.0 3.0 1.5 — (added) Cl− — — — — 2.0 (added) β-OH 0.42-0.43 0.15 0.18 0.23 0.548 (2 melts) H2O 175, 224, 251 None None evolved, (3 different detected detected DIP-MS, powder lots) ppm - In addition to the including halides in the frit, additional trials were conducted independently of halide incorporation where the melting process was modified to produce glasses with low β-OH values and which did not exhibit structural water outgassing during subsequent DIP-MS analysis.
- Shown in Table II is a listing of the various process change experiments and the structural water level measured (β-OH) and/or the quantity of structural water evolved (DIP-MS). As may be seen, these various experiments involved determining the effect of thermal cycling during melting (Experiment 1), air-calcining of the batch material with N2 melting (Experiment 2), air-calcining of the batch material (either 485° or 600° C.) combined followed by air-melting (Experiments 3 and 4) of the batch material; melting all but the V2O5 component of the basic glass, then re-melting with V2O5 (Experiment 5); and re-melting standard cullet in an induction furnace and bubbling O2 or N2/O2 through the melt during re-melting (Experiments 6 and 7). Most of these approaches resulted in a substantially lower β-OH value and/or no structural water outgassing detected by DIP-MS measurement relative to the standard process, with the exception of high-to-low-to-high thermal cycling during melting (Experiment 1); and 600° calcining plus standard 1000° C. melting (Experiment 5).
-
TABLE II Experi- DIP-MS ment # Details DSC Water, ppm β-OH control Melt at 1000° for 1 hr in 355° 175, 224, 251 0.471 air 1 Melt at 1000° for 1 hr, 354° 925 0.336 lower temp to 600°, hold 2 hrs, re-melt at 1000° for 1 hr (in air) 2 Calcine in air at 485°, 359° not detected 0.137 melt in N2 at 1000° 3 Calcine in air at 485°, 356° not detected 0.205 melt in air at 1000° 4 Melt Sb2O3—P2O5 glass not detected (using ammonium phosphate), grind, mix with V2O5 and re-melt at 1000° in air to yield a 25:25:50 Sb2O3—P2O5—V2O5 glass 895BHL 5 Calcine in air at 600°, 0.433 melt in air at 1000° 6 Induction melt 895ASF 220°, not detected cullet at 900° in N2, and 362° bubble O2 7 Induction melt 895ASF 359° not detected cullet at 900°in N2, and bubble 80% N2—20% O2 - An interesting feature of the results is the effect of calcining temperature. Calcining was selected as a potential means to reduce structural water since it would permit water present as a constituent of any raw materials of the frit blend to escape from the batch before being accommodated into the melt structure. Interestingly, 485° C. air-calcining/1000° C. air-melting (Experiment 3) had a substantial effect in lowering the amount of structural water (β-OH=0.205), but 600° C. air-calcining/1000° C. air-melting (Experiment 5) was relatively ineffective (β-OH=0.433). A possible explanation is provided by
FIG. 9 , which shows fusedquartz crucibles - Following the completion of the physical experiments in Table II, three approaches were selected for repeat testing to determine reproducibility of the water-free results. These were: halide replacement of Al2O3 (e.g. AlF3); 485° C. calcining in air for 2 hr. followed by melting at 1000° in air; and 485° C. calcining in air for 2hr followed by melting at 1000° in a N2 atmosphere. A comparison of these techniques are shown in Table III with respect to β-OH and water outgassing results. The three approaches which produced a dry glass in the initial experiments produced dry glass in the repeat work.
-
TABLE III 485° C.- 485° C.- 2 hr air + 2 hr air + 1000° C.- 1000° C.- C1 C2 1 hr (N2) 1 hr (air) DIP-MS H2O 175, 224, 251 Not Not Not (ppm) all samples (Av, 217 ppm) detected detected detected coarse-ground β-OH (abs/mm) 0.38-0.61 0.07-0.11 0.02-0.16 0.19-0.24 range all samples polished bulk - The absence of structural water out-gassing seen above for several of the approaches was also seen in a fine-ground (equal to an less than about 3 μm particle size) ball-milled powder, as well as for frit blend pastes made of the fine-ground powders after a 400° C. presintering treatment as indicated by the DIP-MS results provided in IV.
-
TABLE IV DIP-MS Results (high temperature regime, 400-700° C.) 2% AIF3 replacement 485° C.-2 hr for 1% Al2O3 air calcine + (standard 1000° C.- 1000° C.- 1 hr air melting) 1 hr N2 melting Coarse-ground powder Not detected Not detected (75-150 μm) Fine-balled milled Not detected Not detected powder (<3 μm) Presintered frit paste made Not detected Not detected from fine ball-milled powder and low CTE filler (70:30 blend) - The several techniques described above for producing dry glass and frits appear to have relevance to vanadium and phosphate containing glasses in general, rather than to just the Sb2O3 vanadium phosphate glasses currently used for OLED frit sealing. Shown below in Table V are β-OH values for an Sb-free, Fe2O3—V2O5—P2O5 glass according to an embodiment of the present invention.
-
TABLE V C6 Fe2O3 17.5 TiO2 17.5 ZnO 5.0 Composition P2O5 20.0 (mole %) V2O5 40.0 β-OH (abs/mm) 0.49 standard melting (1000° C.-1 hr, air) β-OH (abs/mm) 0.03 calcine + N2 melting (485° C.-2 hr, air + 1000° C.-1 hr, N2) - It should be emphasized that the above-described embodiments of the present invention, particularly any “preferred” embodiments, are merely possible examples of implementations, merely set forth for a clear understanding of the principles of the invention. Many variations and modifications may be made to the above-described embodiments of the invention without departing substantially from the spirit and principles of the invention. All such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (24)
1. A method of forming a glass frit comprising:
forming a batch material comprising vanadium and phosphorous;
heating the batch material in a conditioning step to a temperature of between about 450° C. and 550° C. for at least about 1 hour;
melting the batch material after the conditioning step to form a glass melt;
cooling the glass melt to form a glass; and
wherein an outgassed water content of the glass is equal to or less than about 20 ppm.
2. The method according to claim 1 , further comprising grinding the glass to form a glass particulate.
3. The method according to claim 1 , wherein the glass comprises a O-OH equal to or less than about 0.3 mm−1.
4. The method according to claim 2 , further comprising blending the glass particulate with a coefficient of thermal expansion lowering filler material.
5. The method according to claim 1 , wherein the batch material is heated in the conditioning step for a period of at least about 2 hours.
6. The method according to claim 1 , wherein the vanadium is V2O5.
7. The method according to claim 1 , wherein the phosphorous is P2O5.
8. The method according to claim 1 , wherein the glass is free of antimony
9. The method according to claim 1 , wherein the melting is performed in air.
10. The method according to claim 1 , wherein the melting is performed in a nitrogen atmosphere.
11. The method according to claim 1 , wherein the melting comprises heating the batch material to a temperature of at least about 1000° C. to melt the batch material.
12. A glass powder for forming a glass-based frit, wherein the glass powder comprises vanadium, phosphorous and a metal halide.
13. The glass powder according to claim 12 , wherein the glass powder is free of antimony.
14. A glass powder for forming a glass-based frit comprising V2O5, P2O5 and a metal halide.
15. The glass powder according to claim 14 , wherein the metal halide comprises AlF3.
16. The glass powder according to claim 14 , wherein the glass powder comprises AlCl3.
17. The glass powder according to claim 14 , wherein the metal halide is selected from a halide of a metal selected from the group consisting of iron, vanadium and aluminum.
18. The glass powder according to claim 14 , wherein the glass powder is free of antimony.
19. A method of forming a glass frit comprising:
forming a batch material comprising V2O5, P2O5 and a metal halide;
heating the batch material in a conditioning step to a temperature of between about 450° C. and 550° C. for at least about 1 hour;
melting the batch material after the conditioning step to form a glass melt;
cooling the glass melt to form a glass; and
wherein an OH content of the glass is equal to or less than about 20 ppm.
20. The method according to claim 19 , wherein the batch material comprises antimony.
21. The method according to claim 19 , wherein the glass comprises a β-OH equal to or less than about 0.3
22. The method according to claim 19 , wherein the batch material is heated in the conditioning step for a period of at least about 2 hours
23. The method according to claim 19 , wherein the melting is performed in air.
24. The method according to claim 19 , wherein the melting is performed in a nitrogen atmosphere.
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/504,276 US20100095705A1 (en) | 2008-10-20 | 2009-07-16 | Method for forming a dry glass-based frit |
JP2011533242A JP5718818B2 (en) | 2008-10-20 | 2009-10-16 | Method for producing a dry glass frit |
CN201610677859.5A CN106277796B (en) | 2008-10-20 | 2009-10-16 | The method for forming the frit based on dry glass |
KR1020117011423A KR101621997B1 (en) | 2008-10-20 | 2009-10-16 | Method for forming a dry glass-based frit |
PCT/US2009/060956 WO2010048042A1 (en) | 2008-10-20 | 2009-10-16 | Method for forming a dry glass-based frit |
TW098135206A TWI410384B (en) | 2008-10-20 | 2009-10-16 | Method for forming a dry glass-based frit |
KR1020167001804A KR101662977B1 (en) | 2008-10-20 | 2009-10-16 | Method for forming a dry glass-based frit |
CN200980142419.8A CN102186789B (en) | 2008-10-20 | 2009-10-16 | Method for forming a dry glass-based frit |
EP09740809A EP2349940A1 (en) | 2008-10-20 | 2009-10-16 | Method for forming a dry glass-based frit |
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US12/622,569 Active 2030-12-09 US8198203B2 (en) | 2008-10-20 | 2009-11-20 | Antimony-free glass, antimony-free frit and a glass package that is hermetically sealed with the frit |
US13/473,204 Expired - Fee Related US8434328B2 (en) | 2008-10-20 | 2012-05-16 | Antimony-free glass, antimony-free frit and a glass package that is hermetically sealed with the frit |
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US13/473,204 Expired - Fee Related US8434328B2 (en) | 2008-10-20 | 2012-05-16 | Antimony-free glass, antimony-free frit and a glass package that is hermetically sealed with the frit |
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