WO2013068975A1 - Organic- inorganic composition for the vapour release of alkali or alkali -earth metals - Google Patents
Organic- inorganic composition for the vapour release of alkali or alkali -earth metals Download PDFInfo
- Publication number
- WO2013068975A1 WO2013068975A1 PCT/IB2012/056290 IB2012056290W WO2013068975A1 WO 2013068975 A1 WO2013068975 A1 WO 2013068975A1 IB 2012056290 W IB2012056290 W IB 2012056290W WO 2013068975 A1 WO2013068975 A1 WO 2013068975A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkali
- earth metals
- composition
- composition according
- alloys
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J7/00—Details not provided for in the preceding groups and common to two or more basic types of discharge tubes or lamps
- H01J7/14—Means for obtaining or maintaining the desired pressure within the vessel
- H01J7/18—Means for absorbing or adsorbing gas, e.g. by gettering
- H01J7/183—Composition or manufacture of getters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J7/00—Details not provided for in the preceding groups and common to two or more basic types of discharge tubes or lamps
- H01J7/14—Means for obtaining or maintaining the desired pressure within the vessel
- H01J7/20—Means for producing, introducing, or replenishing gas or vapour during operation of the tube or lamp
Definitions
- the present invention relates in a first aspect thereof to an organic-inorganic composition containing compounds of alkali or alkali-earth metals that can be deposited through the common techniques for dispensing liquid compositions of varying viscosity and can, after its consolidation, release alkali or alkali-earth elements in their metallic form.
- the invention relates to dispensers for alkali metals obtained by using said composition and in a third aspect to electronic devices containing said dispensers.
- a further important aspect is related to the modulation of the release temperature of the alkali metal according to the specific particle size/surface of the reducing powders and/or of the alkali or alkali-earth compounds.
- alkali or alkali-earth metals In the field of electronic devices in general it is necessary for their operation to deposit within them alkali or alkali-earth metals, whether they are intended to have an active role within the peculiar functional structure of the device itself, to have a doping role with regard to the electronic properties of a layer constituting said functional structure, or simply to exercise a role of removing oxidizing species from the atmosphere enclosed within the structure that encapsulates the device.
- photocathodes there may be mentioned photocathodes, cathode-ray tubes, atomic clocks, atomic interferometers, atomic gyroscopes, refrigeration units based on the tunnel effect and all those generally included in the definition of microelectromechanical or optoelectronic devices (respectively designated by the acronyms MEMs and MOEMs, from Micro-Electro- Mechanical and Micro-Opto-Electro-Mechanical).
- the filiform configuration is generally well integrated with the manufacturing process of some devices such as, for example, photocathodes.
- dispensers are characterized by a variability in the control of their evaporable metal yield due to the limitations related to the mechanical production of a dispenser of very small dimensions and containing mixtures of different powders.
- the deposition techniques suitable for the types of deposits described herein are lithographic, chemical evaporation (known in the industry with the acronym CVD, Chemical Vapour Deposition) or physical vapour evaporation (the latter well known in the field as "sputtering") and they can be used to obtain on a substrate multi-layer structures of the precursor-getter type or to obtain a single layer resulting from their co-deposition. In both cases they require the optimization of various parameters of the deposition processes according to the materials to be used, limiting their potential use.
- the present invention allows to overcome the limitations of the prior art for obtaining deposits of compositions useful for the release of alkali and alkali-earth metals in the production of electronic devices, with particular reference to miniaturized ones.
- a dispensable composition of precursors for the release of alkali or alkali-earth metals containing at least a compound of alkali or alkali-earth metal and at least a reducing agent, characterized in that said compound and said reducing agent are dispersed in the form of powders within a hybrid organic- inorganic binder.
- the viscosity of the precursor composition object of the present invention is preferably between 50 and 5000 cP and allows to obtain deposits of materials which may be consolidated through thermal processes at temperatures between 100 and 400°C whereas the release takes place in correspondence of thermal processes at a temperature at least 50°C higher than said temperatures of consolidation and typically between 300 and 800°C.
- the compounds of alkali or alkali-earth metals suitable for use in the present invention may be compounds as zirconates, silicates, tantalates, niobates, tungstates, molybdates or titanates of alkali or alkali-earth metals or alloys in which one metal of said alloys is selected among alkali-earth metals such as those of binary systems Ca-Al or Cu-Mg, while the reducing agents may be selected among metallic elements such as titanium, zirconium, silicon, aluminum, tantalum and their alloys.
- compounds which may be considered preferred for use in the present invention result to be the molybdates or titanates of alkali or alkali-earth metals.
- the compounds of alkali or alkali- earth metals constitute a quantity comprised between 5 and 45% by weight with respect to the total weight of the composition.
- Zr-based getter alloys are considered preferable, such as for example Zr-Al alloys, being capable to perform not only the task of reducing the selected compound, but also the function of absorbing gaseous species that may be undesired or harmful during the manufacturing process or the life of the end device for which the composition is used.
- a component with a primarily reducing function can be provided, selected from those listed above, in association with a getter alloy that instead has a primarily absorbing function, as for example is the case of metal alloys such as for example those of the binary zirconium-aluminum system or of the ternary zirconium- vanadium-iron system.
- compositions in which the ratio of the concentrations by weight between the compound of alkali or alkali-earth metal and the reducing and getter agents is between 1 :6 and 2: 1, preferably between 1 :4 and 1 : 1.
- the hybrid organic-inorganic binder used in the present invention is characterized by the presence of at least one organic component, which acts as a thickener, and at least one inorganic component, which acts as a stabilizer, both dispersed in a solvent or in a mixture of solvents.
- the solvents used in the present invention can be water,organic solvents or their mixtures. Examples of organic solvents suitable for use in the present invention can be selected from propyl and isopropyl alcohol, acetone, ethers (e.g.
- propyl ether propylene glycol ethers, such as those commonly known as DPM (acronym for Di-Propylene-glycol-Monomethyl ether) and DPNB (acronym for Di-Propylene-glycol-N-Butyl ether).
- Said binder preferably constitutes a percentage by weight included between 30 and 60 wt% with respect to the total weight of the composition.
- the organic thickener commonly available in the market, particularly suitable result to be cellulose and alginates, in their various families, as well as thickeners of vegetable nature, agar-agar, xanthan gum.
- the inorganic stabilizer instead, can be selected among those based on colloidal silica or zeolites, commonly available in the market.
- the composition can provide for the use of additives useful to improve the adhesion to the substrate on which it must be deposited.
- additives useful to improve the adhesion to the substrate on which it must be deposited.
- the selection of such additives may be among those commonly known in the art (such as siloxane additives or vinyl resins) and their quantity in the composition preferably does not exceed 5% by weight with respect to the total weight, it being understood that the concentration of each of them can not exceed 3% by weight with respect to the total weight.
- the invention consists in a dispenser for the release of alkali or alkali-earth metals which is made up of a substrate and a deposit of a composition of precursors for the release of alkali or alkali-earth metals containing at least an alkali or alkali-earth metal compound and at least a reducing agent, characterized in that said compound and said reducing agent are dispersed in the form of powders within a hybrid organic-inorganic binder, as well as in the manufacturing method of said dispenser.
- the substrates suitable for depositing the composition can be selected from the usual materials used for the encapsulation of the devices at which it is aimed, as for example silicon, glass, silica, ceramics, kovar, quartz, sapphire, pyrex, germanium, silicon carbide, ITO (acronym for Indium Tin Oxide), metals.
- the deposits in the form of continuous or discrete deposits on the substrate, can be obtained through deposition techniques commonly known in the field, among which preferred are those known under the names of screen printing, spray-coating, micro- drop dispensation or inkjet.
- the devices of the present invention provide for thicknesses preferably between 1 and 250 microns.
- the dispenser for its use within the manufacturing processes or for the insertion in the end devices in which the release of the alkali or alkali-earth metal must take place, provides that the deposit is consolidated, preferably prior to said release, through a thermal process, usually at temperatures between 100 and 400°C for times between 1 and 240 minutes, a process which allows to eliminate at least 95% of the total amount of solvent present in the composition.
- a thermal process usually at temperatures between 100 and 400°C for times between 1 and 240 minutes, a process which allows to eliminate at least 95% of the total amount of solvent present in the composition.
- Such treatments can also occur in particular conditions such as those that include conditions of vacuum or exposure to inert gases.
- the consolidation temperatures are considerably lower than those corresponding to the release of the metal: the latter, in fact, depending on the metal to be released and on the selection of the reducing (and/or getter) material, as well as on the selection of the particle size of the reducing agent, are comprised between 300 and 800°C.
- the invention consists in a device containing a dispenser deposit for the release of alkali or alkali-earth metals, said deposit being positioned in correspondence of at least one surface in the internal volume of the device and consisting in a composition of precursors for the release of alkali or alkali-earth metals containing at least a compound of alkali or alkali-earth metal and at least a reducing agent, characterized in that said compound and said reducing agent are dispersed in the form of powders within a hybrid organic- inorganic binder.
- the device object of the invention provides for the dispenser deposit to be located at a part or on the whole of the free surface that is present inside the structure in which it is encapsulated.
- such devices may be photocathodes, cathode-ray tubes, atomic clocks, atomic interferometers, atomic gyroscopes, refrigeration units based on the tunnel effect and all those generally included in the definition of microelectromechanical or optoelectronic devices (respectively designated by the acronyms MEMs and MOEMs, from Micro-Electro-Mechanical and Micro- Opto -Electro -Mechanical) .
- the resulting paste deposited on the silicon substrate was then inserted in a crucible of an evaporation bench and through a thermocouple inside the crucible it was possible to record the temperature over time.
- a QCM instead made it possible to detect the moment at which the evaporation started.
- the release temperature observed experimentally was approximately 640°C.
- the resulting paste deposited on the silicon substrate was then inserted in a crucible of an evaporation bench and through a thermocouple inside the crucible it was possible to record the temperature over time.
- a QCM instead made it possible to detect the moment at which the evaporation started.
- the release temperature observed experimentally was approximately 690°C.
- the resulting paste deposited on the silicon substrate was then inserted in a crucible of an evaporation bench and through a thermocouple inside the crucible it was possible to record the temperature over time.
- a QCM instead made it possible to detect the moment at which the evaporation started.
- the release temperature observed experimentally was approximately 665 °C.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Physical Vapour Deposition (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Glass Compositions (AREA)
- Paints Or Removers (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Silicon Compounds (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014540619A JP5926395B2 (en) | 2011-11-11 | 2012-11-09 | Organic-inorganic composition for alkali metal or alkaline earth metal vapor release |
EP12799314.5A EP2768998B1 (en) | 2011-11-11 | 2012-11-09 | Organic-inorganic composition for the vapour release of alkali or alkali-earth metals |
SG11201401621QA SG11201401621QA (en) | 2011-11-11 | 2012-11-09 | Organic- inorganic composition for the vapour release of alkali or alkali -earth metals |
CN201280053867.2A CN103906854B (en) | 2011-11-11 | 2012-11-09 | For steam release alkali metal or the organicinorganic compositions of alkaline-earth metal |
KR1020147012241A KR101868667B1 (en) | 2011-11-11 | 2012-11-09 | Organic-inorganic composition for the vapour release of alkali or alkali-earth metals |
US14/352,446 US9175184B2 (en) | 2011-11-11 | 2012-11-09 | Organic-inorganic composition for the vapour release of alkali or alkali-earth metals |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT002051A ITMI20112051A1 (en) | 2011-11-11 | 2011-11-11 | ORGANIC-INORGANIC COMPOSITION FOR THE RELEASE IN STEAM PHASE OF ALKALINE AND ALKALINE-TERRAIN METALS |
ITMI2011A002051 | 2011-11-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013068975A1 true WO2013068975A1 (en) | 2013-05-16 |
Family
ID=45373752
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2012/056290 WO2013068975A1 (en) | 2011-11-11 | 2012-11-09 | Organic- inorganic composition for the vapour release of alkali or alkali -earth metals |
Country Status (8)
Country | Link |
---|---|
US (1) | US9175184B2 (en) |
EP (1) | EP2768998B1 (en) |
JP (1) | JP5926395B2 (en) |
KR (1) | KR101868667B1 (en) |
CN (1) | CN103906854B (en) |
IT (1) | ITMI20112051A1 (en) |
SG (1) | SG11201401621QA (en) |
WO (1) | WO2013068975A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7008584B2 (en) | 2018-06-11 | 2022-01-25 | 三菱重工業株式会社 | A blade and a rotating body equipped with this blade |
CN110752139A (en) * | 2019-09-27 | 2020-02-04 | 南京三乐集团有限公司 | Cylindrical threaded non-spot-welding internal alkali source for photomultiplier and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002093664A2 (en) | 2001-05-15 | 2002-11-21 | Saes Getters S.P.A | Cesium dispensers and process for the use thereof |
WO2008099256A1 (en) | 2007-02-16 | 2008-08-21 | Saes Getters S.P.A. | Air-stable alkali or alkaline-earth metal dispensers |
CN101621082A (en) * | 2009-07-28 | 2010-01-06 | 付天恩 | Aluminum conductive paste for silicon solar cell back surface field and preparation method thereof |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3579459A (en) * | 1966-12-13 | 1971-05-18 | Getters Spa | Metal vapor generating compositions |
JP4493260B2 (en) * | 2002-06-11 | 2010-06-30 | 株式会社クボタ | Titanate compound powder and cosmetics |
FR2860790B1 (en) * | 2003-10-09 | 2006-07-28 | Snecma Moteurs | TARGET FOR EVAPORATING UNDER ELECTRON BEAM, ITS MANUFACTURING METHOD, THERMAL BARRIER AND COATING OBTAINED FROM A TARGET, AND MECHANICAL PIECE COMPRISING SUCH A COATING |
ITMI20041736A1 (en) * | 2004-09-10 | 2004-12-10 | Getters Spa | MIXTURES FOR LITHIUM EVAPORATION AND LITHIUM DISPENSERS |
US7371335B2 (en) * | 2004-10-21 | 2008-05-13 | E.I. Dupont De Nemours And Company | Curable thick film compositions for use in moisture control |
ITMI20060444A1 (en) * | 2006-03-13 | 2007-09-14 | Getters Spa | USE OF MAGNESIUM-COPPER COMPOSITIONS FOR MAGNESIUM EVAPORATION AND MAGNESIUM DISPENSERS |
JP2012012272A (en) * | 2010-07-05 | 2012-01-19 | Sumitomo Chemical Co Ltd | Raw material mixture for alkali metal-based complex metal oxide |
-
2011
- 2011-11-11 IT IT002051A patent/ITMI20112051A1/en unknown
-
2012
- 2012-11-09 WO PCT/IB2012/056290 patent/WO2013068975A1/en active Application Filing
- 2012-11-09 KR KR1020147012241A patent/KR101868667B1/en active IP Right Grant
- 2012-11-09 US US14/352,446 patent/US9175184B2/en active Active
- 2012-11-09 SG SG11201401621QA patent/SG11201401621QA/en unknown
- 2012-11-09 CN CN201280053867.2A patent/CN103906854B/en active Active
- 2012-11-09 JP JP2014540619A patent/JP5926395B2/en active Active
- 2012-11-09 EP EP12799314.5A patent/EP2768998B1/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002093664A2 (en) | 2001-05-15 | 2002-11-21 | Saes Getters S.P.A | Cesium dispensers and process for the use thereof |
WO2008099256A1 (en) | 2007-02-16 | 2008-08-21 | Saes Getters S.P.A. | Air-stable alkali or alkaline-earth metal dispensers |
CN101621082A (en) * | 2009-07-28 | 2010-01-06 | 付天恩 | Aluminum conductive paste for silicon solar cell back surface field and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JP5926395B2 (en) | 2016-05-25 |
KR20140096278A (en) | 2014-08-05 |
KR101868667B1 (en) | 2018-07-17 |
JP2015505341A (en) | 2015-02-19 |
EP2768998A1 (en) | 2014-08-27 |
ITMI20112051A1 (en) | 2013-05-12 |
EP2768998B1 (en) | 2015-04-01 |
CN103906854B (en) | 2016-08-24 |
SG11201401621QA (en) | 2014-08-28 |
US20140283709A1 (en) | 2014-09-25 |
US9175184B2 (en) | 2015-11-03 |
CN103906854A (en) | 2014-07-02 |
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