CN109879240B - Preparation method of thick film getter material - Google Patents
Preparation method of thick film getter material Download PDFInfo
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- CN109879240B CN109879240B CN201711277777.2A CN201711277777A CN109879240B CN 109879240 B CN109879240 B CN 109879240B CN 201711277777 A CN201711277777 A CN 201711277777A CN 109879240 B CN109879240 B CN 109879240B
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Abstract
The invention discloses a preparation method of a thick film getter material, belonging to the technical field of preparation of electric vacuum getter elements. Uniformly mixing non-evaporable getter material powder with an organic binder to obtain thick film paste; simultaneously, mixing the low-melting-point glass powder and the nitrocotton solution or the solder and the nitrocotton solution uniformly, and coating a layer of low-melting-point glass powder slurry or solder slurry on the device substrate uniformly; depositing the thick film slurry on the surface of the low-melting-point glass powder or solder coating by adopting the casting, printing, spraying, brushing or scraper coating process; and finally, carrying out vacuum sintering to obtain the non-evaporable thick film getter material. The thick film getter material of the invention overcomes the disadvantages of bulk getter materials and thin film getter materials, effectively solves the problem of incompatibility of assembly space and getter capacity, and adopts a composite double-layer structure consisting of a bottom welding layer and a getter material layer, thereby improving the adhesion strength of the non-evaporable thick film getter material on a device substrate and improving the reliability of the device.
Description
Technical Field
The invention relates to a preparation method of a thick film getter material, belonging to the technical field of preparation of electric vacuum getter elements.
Background
The air suction material is a special functional material for ensuring the vacuum quality of an electric vacuum or sealing device and an ideal working environment, and can avoid the reduction of the vacuum quality along with time by absorbing residual active gas or active gas released in the long-term use process of the device, reduce pollution or function loss caused by the reaction of gas and precision elements, reduce the vibration damping of a movable part, reduce the heat dissipation of an inner cavity and the like. It has been found that to obtain high-performance, long-life electrovacuum devices, high-quality getter elements are necessary as warranted.
Getter materials are mainly classified into evaporable and non-evaporable types. The evaporable getter material absorbs active gases by adopting a film which is evaporated or evaporated at high temperature and deposited on the wall of a vacuum vessel, also called as diffusion type or flash type, and usually mainly comprises barium, strontium, calcium, magnesium and alloys thereof, and has limited application fields because the evaporable property of barium, strontium, calcium, magnesium and alloys thereof can cause the problems of electric leakage between electrodes, unrepairable equipment, large manufacturing and designing difficulty of vacuum devices and the like; the non-evaporable getter material does not need to be evaporable, but obtains an active surface to absorb gas by activation modes such as heating, electrifying or reducing gas partial pressure, and the like, and is usually an alloy consisting of metals such as titanium, zirconium, hafnium, yttrium and the like and transition group metal elements such as aluminum, rare earth elements or iron, cobalt, manganese and the like, and can be made into blocks, strips, bodies and films.
With the trend of miniaturization and miniaturization of modern high-precision electronic devices, non-evaporable getter materials are being developed from bulk materials to thin film materials. The block getter material has relatively large volume, wide activation temperature range, large getter capacity and flexible and diverse structure, but generally needs a separate space for assembly; the film getter material is a film which is formed by depositing getter components or alloys on the wall of a vacuum container or solid substrates in various shapes by a vapor deposition method to form hundreds of nanometers to a few micrometers, can be prepared into various patterns or sizes, has high deposition precision and small getter capacity, and is mainly applied to the field of micro-electro-mechanical systems (MEMS) devices. For miniaturized devices with relatively small vacuum space, the bulk getter material does not have enough space for assembly, and the thin film getter material does not meet the absorption requirements of the impurities in terms of getter rate and getter capacity.
Disclosure of Invention
The invention aims to provide a preparation method of a non-evaporable thick film getter material. The thick film getter material prepared by the method has excellent getter performance and can meet the assembly requirement of small device space.
The invention uses different methods to prepare the non-evaporable thick film getter material with high efficiency, can flexibly and conveniently regulate and control various process parameters, overcomes the disadvantages of the block getter material and the thin film getter material, effectively solves the problem that the assembly space and the getter capacity can not be compatible at the same time, and prepares the thick film getter material which has excellent performance, good bonding strength with the device and meets the use requirement of the device.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of a non-evaporable thick film getter material comprises the following steps:
(1) uniformly mixing non-evaporable getter material powder with an organic binder to obtain thick film paste; simultaneously, mixing the low-melting-point glass powder or solder with the nitrocotton solution uniformly to obtain low-melting-point glass powder slurry or solder slurry;
(2) uniformly coating a layer of low-melting-point glass powder slurry or solder slurry on a device substrate;
(3) depositing the thick film slurry on the surface of the low-melting-point glass powder or solder coating by adopting coating processes such as casting, printing, spraying, brushing or scraping to obtain a getter material film;
(4) and (3) carrying out vacuum sintering on the substrate coated with the getter material film to prepare the non-evaporable thick film getter material.
In step (1), the non-evaporable getter material used may be any of zirconium ferrovanadium, zirconium aluminum, zirconium + zirconium ferrovanadium, titanium vanadium or titanium molybdenum. Wherein, the preferred selection of the zirconium and the zirconium vanadium iron is 70-90 wt% of zirconium and 30-10 wt% of zirconium vanadium iron.
The organic binder is a mixed solution of terpineol, ethyl cellulose and dibutyl phthalate, and the mass percentage of the organic binder is 83 wt% of terpineol, 7 wt% of ethyl cellulose and 10 wt% of dibutyl phthalate.
In the thick film paste, the non-evaporable getter material powder accounts for 50-75 wt% and the organic binder accounts for 25-50 wt% by mass.
The low-melting-point glass powder can be glass powder with a melting point of 400-700 ℃, and the solder is Ag-Cu or Cu-Ti; preferably, the weight ratio of Ag to Cu in the Ag-Cu solder is 60:40, and the weight ratio of Cu to Ti in the Cu-Ti solder is 76: 24.
In the low-melting-point glass powder slurry or solder slurry, the low-melting-point glass powder or solder accounts for 75-85% by mass, and the nitrocotton solution accounts for 15-25%; wherein the concentration of the nitro-cotton solution is preferably 5-10 wt%.
In step (2), the device substrate is stainless steel, kovar, ceramic, or germanium sheet, etc.
In the step (2), the thickness of the low-melting-point glass powder or the solder coating is 40 micrometers to 1 millimeter.
In step (3), the thickness of the getter material film is comprised between 100 μm and 2 mm. Preferably, the thickness of the getter material film is greater than or equal to the thickness of the low melting point glass frit or solder coating.
In step (4), the sintering temperature selected depends on the melting point temperature of the low melting point glass powder or solder used; preferably, the sintering is carried out under the condition of 400-950 ℃ in vacuum, and the sintering time is 30 minutes-1 hour.
The preparation method of the non-evaporable thick film getter material comprises the steps of uniformly mixing non-evaporable getter material powder with an organic binder, and simultaneously fully and uniformly mixing low-melting-point glass powder or solder with nitro-cotton; uniformly coating a layer of low-melting-point glass powder or solder slurry with the thickness of 40 micrometers-1 mm on a device substrate according to a certain shape, and depositing a getter material film with the thickness of 100 micrometers-2 mm in a required shape on the surface of the device substrate; and (3) sintering the substrate coated with the getter material in vacuum at the temperature of 400-950 ℃ for 30 minutes-1 hour to prepare the non-evaporable thick film getter material.
The invention has the advantages that:
the thick film getter material of the invention overcomes the disadvantages of the bulk getter material and the thin film getter material and effectively solves the problem that the assembly space and the getter capacity are incompatible.
The invention adopts a composite non-evaporable getter material thick film structure consisting of a bottom welding layer and an active getter material layer, and can flexibly select getter materials, thereby meeting different requirements of devices on activation temperature and getter performance, and selecting different film thicknesses of 100 micrometers-2 millimeters according to the space characteristics and the getter capacity of the devices; and the double-layer structure is adopted, so that the adhesion strength of the non-evaporable thick film getter material on a device substrate is improved, the reliability of the device is improved, the manufacturing method is flexible and various, and the process operation is simple and convenient.
Detailed Description
The invention relates to a preparation method of a non-evaporable thick film getter material, which comprises the following steps:
(1) 50-75 wt% of non-evaporable getter material powder and organic binder: uniformly mixing 25-50 wt% of the mixture to obtain thick film paste with certain fluidity and viscosity, and simultaneously fully and uniformly mixing low-melting-point glass powder or solder and nitrocotton, wherein the concentration of a nitrocotton solution is 9 wt%; the non-evaporable getter material powder used can be any one of zirconium ferrovanadium, zirconium aluminum, zirconium + zirconium ferrovanadium, titanium vanadium, titanium molybdenum. The organic binder is a mixed solution of terpineol, ethyl cellulose and dibutyl phthalate, and the proportion of the terpineol, the ethyl cellulose and the dibutyl phthalate is 83 wt%: 7 wt%: 10 wt%. The low-melting-point glass powder can be glass powder with a melting point of 400-700 ℃, and the solder is Ag-Cu or Cu-Ti.
(2) Uniformly coating a layer of low-melting-point glass powder or solder paste on a device substrate according to a certain shape; the device substrate may be stainless steel, kovar, ceramic, or germanium sheet.
(3) Depositing thick film getter material with required shape and thickness on the surface of low-melting-point glass powder or solder by adopting any coating process such as casting, printing, spraying, brushing, scraping and the like; the thickness of the film is 100 micrometers to 2 millimeters.
(4) And (3) sintering the substrate coated with the getter material in vacuum at 400-950 ℃, wherein the selected sintering temperature depends on the temperatures of the selected low-melting-point glass powder and the solder, and the sintering time is 30 minutes-1 hour, so as to prepare the non-evaporable thick-film getter material.
Example 1
Mixing zirconium vanadium iron getter material powder with a ratio of 83 wt%: 7 wt%: uniformly mixing and stirring 10 wt% of organic binder consisting of terpineol, ethyl cellulose and dibutyl phthalate for 4 hours according to the weight ratio of 6:4, and simultaneously preparing glass powder with the melting point of 400 ℃ into slurry according to the weight ratio of 15:85 by adopting a nitro-cotton solution (the concentration is 9 wt%, the same applies below); placing a rectangular mask plate with the thickness of 1 mm at a position needing to be coated with an air suction material on a stainless steel substrate, uniformly coating a layer of glass powder with the thickness of 1 mm and low melting point, and then filling air suction material slurry into the mask plate in a blade coating mode, wherein the thickness of an air suction material film is 1 mm; the substrate coated with the getter material is sintered at 400 ℃ for 1 hour under vacuum condition to prepare the non-evaporable thick film getter material.
The prepared non-evaporable thick film getter material is subjected to heat preservation at the temperature of 350 ℃ for 30 minutes to activate a getter, and the getter performance test results are shown in table 1.
Example 2
The operation method and the process conditions are basically the same as those of the embodiment 1, the only difference is that zirconium (85 wt%) + zirconium ferrovanadium (15 wt%) getter material powder and an organic binder are uniformly mixed according to the weight ratio of 1:1, a copper-titanium (Cu-Ti) solder (76: 24) is mixed into slurry according to the weight ratio of 25:75 by using a nitro-cotton solution, a circular mask plate with the thickness of 50 microns is placed at the position on a ceramic substrate where the getter material needs to be coated, a layer of solder with the thickness of 50 microns is uniformly coated, and a thick film getter material with the circular thickness of 100 microns is printed on the ceramic substrate solder by adopting a screen printing mode; the substrate coated with the getter material is sintered at 920 ℃ for 30 minutes under vacuum condition to prepare the non-evaporable thick film getter material.
The prepared non-evaporable thick film getter material is subjected to heat preservation at the temperature of 350 ℃ for 30 minutes to activate a getter, and the getter performance test results are shown in table 1.
Example 3
The operation method and the process conditions are basically the same as those of the embodiment 1, and the only difference is that titanium molybdenum getter material powder and an organic binder are selected to be uniformly mixed according to the weight ratio of 3:1, an Ag-Cu solder is mixed into slurry according to the weight ratio of 20:80 by adopting a nitrocotton solution, a rectangular mask plate with the thickness of 1 mm is placed at the position of the kovar alloy substrate needing to be coated with the getter material, a layer of solder with the thickness of 1 mm is uniformly coated, and a thick film getter material with the thickness of 2 mm is brushed on the kovar alloy substrate solder by adopting a brushing way; the substrate coated with the getter material is sintered at 850 ℃ for 30 minutes under vacuum conditions to prepare the non-evaporable thick film getter material.
The prepared non-evaporable thick film getter material is subjected to heat preservation at the temperature of 500 ℃ for 30 minutes to activate a getter, and the getter performance test results are shown in table 1.
TABLE 1 comparison of Thick film and thin film getter Properties
It can be seen from the above embodiments that the present invention adopts a composite double-layer structure composed of a bottom welding layer and a getter material layer, which improves the getter performance, and simultaneously improves the adhesion strength of the non-evaporable thick film getter material on the device substrate, and improves the reliability of the device.
In the above examples, only some of the examples of the process for the preparation of the non-evaporable thick film getter material according to the invention are given, in the solution of the invention: the selection of the non-evaporable getter material and the organic binder, the mass ratio of the non-evaporable getter material powder to the organic binder, the mass ratio of the low melting point glass powder or solder to the nitrocellulose solution, the thickness of the applied low melting point glass powder paste or solder paste layer, the thickness of the getter material film, etc. can be freely selected within the limited range, and are not listed here, so the technical solutions contained in the above description should be regarded as exemplary and not as limiting the protection scope of the present invention.
Claims (3)
1. A method of preparing a thick film getter material comprising the steps of:
(1) uniformly mixing non-evaporable getter material powder with an organic binder to obtain thick film paste; simultaneously, uniformly mixing the solder and the nitro-cotton solution to obtain solder paste;
(2) uniformly coating a layer of solder paste on a device substrate, wherein the thickness of the solder coating is 40 micrometers-1 mm;
(3) depositing the thick film slurry on the surface of the solder coating by adopting the casting, printing, spraying, brushing or scraper coating process to obtain a gas absorbing material film, wherein the thickness of the gas absorbing material film is 100 micrometers-2 millimeters;
(4) vacuum sintering the substrate coated with the getter material film to prepare a non-evaporable thick film getter material; the non-evaporable getter material is zirconium aluminum, zirconium + zirconium ferrovanadium or titanium vanadium; the organic binder is a mixed solution of terpineol, ethyl cellulose and dibutyl phthalate, wherein the terpineol accounts for 83 wt%, the ethyl cellulose accounts for 7 wt%, and the dibutyl phthalate accounts for 10 wt%; in the thick film paste, 50-75 wt% of non-evaporable getter material powder and 25-50 wt% of organic binder are used; the solder is Ag-Cu solder or Cu-Ti solder; in the solder paste, the solder accounts for 75-85% by mass, and the nitro-cotton solution accounts for 15-25% by mass.
2. A method of preparing a thick film getter material according to claim 1, wherein: the device substrate is a kovar alloy, ceramic or germanium sheet.
3. A method of preparing a thick film getter material according to claim 1, wherein: the temperature of the vacuum sintering is 400-950 ℃, and the sintering time is 30 minutes-1 hour.
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| CN109879240B true CN109879240B (en) | 2021-11-09 |
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| CN101663723A (en) * | 2007-04-24 | 2010-03-03 | 西门子公司 | Method for securing a getter for a vacuum switching tube and vacuum switching tube |
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| CN104743502A (en) * | 2013-12-31 | 2015-07-01 | 北京有色金属研究总院 | MEMS component with composite getter layer and preparation method thereof |
| CN105358473A (en) * | 2013-07-11 | 2016-02-24 | 雷神公司 | Wafer level package solder barrier used as vacuum getter |
| CN106571282A (en) * | 2016-11-04 | 2017-04-19 | 北京有色金属研究总院 | Low temperature forming preparation method for getter |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8736045B1 (en) * | 2012-11-02 | 2014-05-27 | Raytheon Company | Integrated bondline spacers for wafer level packaged circuit devices |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1816731A (en) * | 2003-05-07 | 2006-08-09 | 霍尼韦尔国际公司 | Methods and apparatus for particle reduction in mems devices |
| CN101291873A (en) * | 2005-12-06 | 2008-10-22 | 工程吸气公司 | Process for manufacturing micromechanical devices containing a getter material and devices so manufactured |
| CN101663723A (en) * | 2007-04-24 | 2010-03-03 | 西门子公司 | Method for securing a getter for a vacuum switching tube and vacuum switching tube |
| JP2009156353A (en) * | 2007-12-27 | 2009-07-16 | Hitachi Appliances Inc | Vacuum insulation material and instrument using the same |
| CN103182297A (en) * | 2011-12-28 | 2013-07-03 | 北京有色金属研究总院 | Thin-film getter with high gas absorption performance and preparation method thereof |
| CN105358473A (en) * | 2013-07-11 | 2016-02-24 | 雷神公司 | Wafer level package solder barrier used as vacuum getter |
| CN104743502A (en) * | 2013-12-31 | 2015-07-01 | 北京有色金属研究总院 | MEMS component with composite getter layer and preparation method thereof |
| CN106571282A (en) * | 2016-11-04 | 2017-04-19 | 北京有色金属研究总院 | Low temperature forming preparation method for getter |
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