CN103435357A - Preparation method for support-free micronscale ultrathin ceramic chip - Google Patents
Preparation method for support-free micronscale ultrathin ceramic chip Download PDFInfo
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Abstract
The invention discloses a preparation method for a support-free micronscale ultrathin ceramic chip. According to the method, metallic oxides or metallic salts comprising manganese, cobalt, nickel, copper and ferrum are adopted as raw materials; nanoscale ceramic oxide powder is prepared firstly; uniformly-pelleted ceramic oxide powder is then prepared; the ceramic oxide powder and dispersing agent are uniformly mixed with each other, dried, filtered through a sieve, and mixed uniformly with an organic solvent through ball milling, so that a ceramic sizing material used for serigraphy is prepared; the sizing material is uniformly printed onto a substrate through the serigraphy technology to form a chip; the chip is separated from the substrate through drying, vacuum encapsulation, cold isostatic pressing, and other technologies, so that the support-free chip is generated; the chip is sintered at high temperature to form ceramic, and the support-free ceramic chip with excellent crystallinity and excellent compactness is obtained. The method is cheap, has the advantages of good reliability, high finished product ratio, high flatness, accuracy in thickness control, interior uniformity, and the like, is suitable for manufacturing the support-free micronscale ultrathin ceramic chip in various thicknesses for various ceramic materials, and has a great application prospect.
Description
Technical field:
The present invention relates to a kind of preparation method without supporting micron order ultra-thin ceramic sheet.Be specifically related to non-refrigeration type thermosensitive resistance infrared detector technical field.
Background technology:
The non-refrigeration type thermosensitive resistance infrared detector is a kind of temperature sensor, when heat radiation projects on thermistor material, can cause that material temperature raises, and resistance changes thereupon.Thermosensitive resistance infrared detector is a kind of novel contactless bolometric measurement sensor worked under envrionment temperature, is widely used in aerospace and civilian technology.Such as the temperature survey of the attitude measurement of horizon instrument core parts, satellite for star, moving parts, the measurement of train wheel bearing temperature etc.Owing to being the core of non-refrigeration type thermosensitive resistance infrared detector without supporting micron order ultra-thin ceramic sheet, therefore prepare good reliability, yield rate is high, planeness is high, thickness is accurately controlled, inner has very important significance without supporting micron order ultra-thin ceramic sheet uniformly.
Along with the development of modern micro-processing technology and ceramics processing, substantially realized the micro machining of various ceramic components.Micron order made up block body ceramic material due to problems such as subsurface defect are many, the large electric property caused of thermal capacity is unstable on the one hand without the appearance of supporting ceramic sheet, got rid of on the other hand the film type stupalith in application process substrate to the limitation aspect the performance measurements such as element optics, calorifics, electricity.Therefore have great application prospect.It is the technology barriers that people run into without supporting ceramic sheet that yet industrialization prepares high-quality micron order always.
At present, for the micron order ceramic sheet element for preparing thickness and be greater than 5um, there have been a lot of scientists to propose more feasible experimental technique and the means of production.Roughly can be divided into physical mechanical technique, chemical etching technique, powder complete processing and physical chemistry growth technique totally four kinds of methods, as shown in the table:
Although different traditional technologys has all solved some problems in the certain period, they also have some other current insoluble challenge and a difficult problem.Such as, for physical mechanical technique, wanting to realize that thickness is the following preparation of sections of 20um, mechanical micro-difficulty of processing is very large, and size is less, and the yield rate of processing is lower.Although compressing tablet likely reaches the thin slice preparation that 10um is thick, can not guarantee the homogeneity of sheet thickness and density; For chemical etching technique, dry etching speed is lower, can't carry out deep etching and sidewall shape undesirable, resultant of reaction has residue problem; And, for wet etching, due to the impact that is subject to the factors such as pore and crackle, therefore can't guarantee the isotropic etching of sample; During powder machine-shaping, the injection molding metal die is made numerous and diverse, and price is high, and lose mold forming, utilizes mould of plastics, and both easily cause required thin metal plate in high-temperature sintering process.The physical chemistry growth method, along with more than film thickness is increased to 5-6um, be easy to form tiny crack on surface, and pattern is unsatisfactory.
The silk screen print method proposed in the present invention prepares the advantages such as 5um is above has not only solved the problem of current existence without supporting ceramic sheet, and the while is easy and simple to handle owing to having, with low cost, has realized that micron order changes into product without the industry that supports ceramic sheet.
Summary of the invention:
The object of the invention is, a kind of preparation method without supporting micron order ultra-thin ceramic sheet is provided, and the method, with manganese, cobalt, nickel, copper and ferroelectric metal oxide or metal-salt raw material, at first prepares the nanometer scale ceramics oxide powder; Then prepare the uniform ceramic oxide powder of granulation, ceramic oxide powder and the dispersant post-drying that is uniformly dispersed is sieved, mix with the organic solvent ball milling, be mixed with the silk screen printing ceramic size; Then adopt silk-screen printing technique that slurry evenly is printed on substrate and forms thin slice, through art breading such as drying and processing, Vacuum Package, isostatic cool pressings, thin slice and substrate are broken away from, formation is without support slice, at high temperature thin slice is sintered into to porcelain again, obtain the good nothing of degree of crystallinity and compactness and support ceramic sheet.The present invention has realized without the preparation of supporting micron order ceramic ultra-thin sheet.Because this technology easily realizes, with low cost, the micron order of various thickness that is applicable to prepare various stupaliths is ultra-thin without supporting ceramic plate, and there is good reliability, yield rate is high, planeness is high, accurate controlled, the inner advantage such as even of thickness, therefore be applicable to very much mass production, have great application prospect.
A kind of preparation method without supporting micron order ultra-thin ceramic sheet of the present invention, the device related in the method is comprised of ceramic sheet (1), ceramic sheet (4), subtegulum (2), upper substrate (3), lower alumina ceramic plate (5), upper alumina ceramic plate (7) and pad (6), and concrete operations follow these steps to carry out:
A, by raw material, be three kinds in manganese, cobalt, nickel, copper and ferroelectric metal oxide or metal-salt, adopt the indoor temperature solid phase method mixed grinding to reacting completely, constant temperature pre-burning 1h under temperature 500-700 ℃ condition, obtain the nanometer scale ceramics oxide powder of stable and uniform;
B, by adding the dispersion agent that mass concentration is 4-6wt% in the nanometer scale ceramics oxide powder of step a gained, be polyvinyl alcohol water solution or polyvinyl butyral acetal alcoholic solution, add again the excessive dehydrated alcohol of 5-10 times of quality to form mixed solution, the vessel that mixed solution is housed are put into to supersonic cleaning machine, ultrasonic dispersion 40-60min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, grind again, cross the 400-500 order and all just sieve, obtain the uniform ceramic oxide powder of granulation;
C, by the uniform ceramic oxide powder of step b granulation, adding organic solvent, be Terpineol 350, ethanol, ethylene glycol or glycerol, adopting planetary high-energy ball mill to carry out ball milling sizes mixing, in mechanical milling process, the ball mill frequency is 30-45HZ, Ball-milling Time is 10-60min, obtain the ceramic oxide slurry, wherein the mass ratio of oxide powder and organic solvent is 6-8:2-4;
D, adopt conventional method for printing screen, regulate the silk-screen plate specification, the subtegulum (2) that ceramic oxide slurry in step c evenly is coated in to silk-screen plate is upper, the ceramic sheet (1) that to form thickness be 5-35um;
E, silk screen printing gained ceramic sheet (1) is placed in to the dry 10-30 hour of constant temperature oven of 100 ℃ of temperature, the ceramic sheet (1) on subtegulum (2) surface is fully solidified, the ceramic sheet of completion of cure (1) is taken out together with subtegulum (2), on the ceramic surface lid is pressed one, substrate (3) forms interlayer, adopt Vacuum Package that the ceramic sheet (1) clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 100-400MPa, pressurize 1-5min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper strata substrate (3) slowly level push open, ceramic sheet (1) is peeled off and is taken off, make itself and subtegulum (2) complete separation, the unsupported ceramic sheet (4) that to obtain thickness be 5-35um;
G, will be placed on lower alumina ceramic plate (5) without supporting micron order ceramic sheet (4), at the placed around pad (6) without supporting micron order ceramic sheet (4), again upper alumina ceramic plate (7) is placed on pad (6), make between two alumina plates to form a gap, again unsupported ceramic sheet (4) is carried out to sintering, sintering temperature is 900-1200 ℃, after sintering, can obtain without supporting micron order ultra-thin ceramic sheet.
In step a, the metal oxide of manganese, cobalt, nickel, copper and iron is manganese oxide, cobalt oxide, nickel oxide, cupric oxide, ferric oxide; Metal-salt is manganous sulfate, rose vitriol, single nickel salt, copper sulfate, ferric sulfate, manganous acetate, ironic acetate, nickelous acetate, cobaltous acetate and venus crystals.
The particle diameter of the described nanometer oxide powder of step a is less than 150nm.
Silk-screen plate specification described in steps d is that half tone order number is the 100-400 order, and screen cloth tension force is 18-25N, and the half tone material is steel wire half tone, nylon half tone or spun silk half tone.
Subtegulum described in steps d (2), upper substrate (3) surface are the smooth silicon chip of atomic level, sapphire sheet or quartz plate.
In step e, vacuum tightness is 10
-5-10
-2pa.
Step g Intermediate gasket (6) is resistant to elevated temperatures silicon chip, sapphire sheet or quartz plate.
A kind of preparation method without supporting micron order ultra-thin ceramic sheet of the present invention, the method mainly adopts silk-screen printing technique to realize, and concrete operation step is:
Raw material is three kinds in manganese, cobalt, nickel, copper and ferroelectric metal oxide or metal-salt, prepares the little and uniform nanometer scale ceramics oxide powder of size distribution of particle;
Powder to preparation carries out granulation, add polyvinyl alcohol water solution or the polyvinyl butyral acetal alcoholic solution dispersion agent of 4-6wt% in powder, the quality of before wherein using, polyvinyl alcohol being pressed to 5wt% is the aqueous solution to formation polyvinyl alcohol in deionized water than stirring and dissolving; Or the quality that polyvinyl alcohol carboxylic butyraldehyde is pressed to 5wt% than stirring and dissolving to forming the alcoholic solution of polyvinyl butyral acetal in dehydrated alcohol, add again the excessive dehydrated alcohol of 5-10 times of quality to form mixed solution, the vessel that mixed solution is housed are put into to supersonic cleaning machine, ultrasonic dispersion 40-60min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, mechanical mill or manually agate mortar grinding again, cross the 400-500 order and all just sieve, obtain the uniform ceramic oxide powder of granulation;
Preparation is applicable to the ceramic oxide slurry that silk-screen printing technique is used: by the uniform ceramic oxide powder of granulation, adding organic solvent, be Terpineol 350, ethanol, ethylene glycol or propyl carbinol, adopting planetary high-energy ball mill to carry out ball milling sizes mixing, in mechanical milling process, the ball mill frequency is 30-45HZ, Ball-milling Time is 10-60min, obtains the ceramic size of uniform and stable, modest viscosity, favorable dispersity;
Adopt the standby thin slice of traditional silk-screened legal system: adopt the cantilevered Semi-automatic screen process press that the ceramic size prepared is evenly printed and is coated on the substrate of silk-screen plate, in screen printing process, to the thin micron order ceramic sheet that obtains successively different thickness, the silk-screen plate tension control is between 18-25N by thick for employing 100-400 purpose steel wire half tone, spun silk half tone or nylon half tone;
The aftertreatment of ceramic sheet: by the substrate of silk screen printing gained micron order ceramic sheet and another piece formed objects shape formation sandwich-like that mutually superposes, process with doing isostatic cool pressing after plastic packaging bag Vacuum Package;
The sintering of unsupported ceramic sheet: select the mode that only lid is not pressed to carry out sintering to the ultra-thin ceramic sheet of nothing support micron order, sintering temperature is 900-1200 ℃;
The method major technique technique is silk screen print method, adopt the mode of silk screen printing to be coated on the smooth substrate of the surface atom ranks such as silicon chip, sapphire sheet deployed ceramic size, introducing by aftertreatment technologys such as curing, Vacuum Package, isostatic cool pressings, realize the Automatic-falling of ceramic sheet and substrate, obtain unsupported ceramic sheet, and carry out sintering under the temperature condition of 900-1200 ℃, the final nothing that obtains supports micron order ultra-thin ceramic sheet.
A kind of preparation method without supporting micron order ultra-thin ceramic sheet of the present invention, its characteristics are:
Conventional powder technology of preparing and ceramic post sintering method and advanced silk-screen printing technique are combined cleverly, realized that 5um above good reliability, yield rate are high, planeness is high, thickness accurately controlled, inner micron order uniformly without supporting the preparation of sections of micron order ultra-thin ceramic;
Be applicable to various material systems, different oxide ceramics thin slices is all had to suitability.
The method easily realizes, with low cost, for preparation high precision, high interchangeability microdevice, lays a good foundation, and can realize mass, industrialization production.
The accompanying drawing explanation
The sandwich-like thing figure to be packaged that when Fig. 1 is Vacuum Package of the present invention, pottery and substrate form;
Fig. 2 is the sintering processing figure of the present invention without support slice;
Fig. 3 is that the present invention is without support slice figure.
Embodiment
A, according to molar ratio weighing raw material manganese oxide, cobalt oxide, the nickel oxide of 1:1:1, adopt indoor temperature solid phase method ball milling 8h raw material is mixed and extremely fully react completely, generate the MnCoNi base oxide, by the MnCoNi base oxide constant temperature pre-burning 1h under 500 ℃ of conditions of temperature generated, obtain stable nano level MnCoNi base ceramic oxide powder, size distribution is less than 150um;
B, by adding dispersion agent that mass concentration is 4wt% in nano level MnCoNi base ceramic oxide powder, be polyvinyl butyral acetal alcoholic solution (quality that polyvinyl alcohol carboxylic butyraldehyde press to 5wt% is the alcoholic solution to formation polyvinyl butyral acetal in dehydrated alcohol than stirring and dissolving), add again the excessive dehydrated alcohol of 5 times of quality to form mixed solution, the vessel that mixed solution is housed are put into to supersonic cleaning machine, ultrasonic dispersion 40min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, grind again, crossing 400 orders all just sieves, obtain the uniform ceramic oxide powder of granulation,
C, 6:4 adds the organic solvent propyl carbinol by the uniform nano level MnCoNi of granulation base ceramic oxide powder in mass ratio, adopts the planetary high-energy ball mill ball milling to be sized mixing, and the ball mill frequency is 30Hz, and Ball-milling Time is 10min, obtains the ceramic oxide slurry;
D, adopt conventional method for printing screen, regulate steel wire version specification 400 orders, screen cloth tension force is 18N, and subtegulum 2 surfaces that step c ceramic oxide slurry evenly are coated in to the steel wire half tone are on the smooth silicon chip of atomic level, the ceramic sheet 1 that to form thickness be 5um;
E, silk-screen gained ceramic sheet 1 is placed in to dry 30 hours of the constant temperature oven of 100 ℃ of temperature, make subtegulum 2 surfaces fully curing for the ceramic sheet 1 of the smooth silicon chip surface of atomic level, the ceramic sheet of completion of cure 1 and subtegulum 2 surfaces are taken out together with the smooth silicon chip of atomic level, press substrate 3 surfaces at the ceramic surface lid and form interlayer for the smooth silicon chip of atomic level, adopt Vacuum Package that the ceramic sheet 1 clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film, vacuum tightness is 10
-5pa;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 100MPa, pressurize 1min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper strata substrate 3 surface for the smooth resistant to elevated temperatures silicon chip of atomic level slowly level push open, ceramic sheet 1 is peeled off and is taken off, making it is smooth complete separation of silicon chip of atomic level with subtegulum 2 surfaces, the unsupported ceramic sheet 4 that acquisition thickness is 5um;
G, will be placed on lower alumina ceramic plate 5 without supporting micron order ceramic sheet 4, at the placed around pad 6 without supporting micron order ceramic sheet 4, it is resistant to elevated temperatures silicon chip, again upper alumina ceramic plate 7 is placed on to pad 6 on resistant to elevated temperatures silicon chip, make between two alumina plates to form a gap, again unsupported ceramic sheet 4 is carried out to sintering, sintering temperature is 900 ℃, can obtain without supporting micron order ultra-thin ceramic sheet.
A, according to molar ratio weighing raw material manganese oxide, ferric oxide, the nickel oxide of 52:32:16, adopt indoor temperature solid phase method ball milling 20h that raw material is mixed and react to abundant, generate the MnFeNi base oxide, again by the MnFeNi base oxide constant temperature pre-burning 1h under 700 ℃ of conditions of temperature generated, obtain stable nano level MnFeNi base ceramic oxide powder, size distribution is less than 150um;
B, the dispersion agent that to add mass concentration in nano level MnFeNi base ceramic oxide powder be 6wt% is polyvinyl alcohol water solution (quality of polyvinyl alcohol press to 5wt% is the aqueous solution to formation polyvinyl alcohol in deionized water than stirring and dissolving), add again the excessive dehydrated alcohol of 10 times of quality to form mixed solution, the beaker that mixed solution is housed is put into to supersonic cleaning machine, ultrasonic dispersion 60min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, crossing 500 orders after powder is ground all just sieves, obtain the uniform nano level MnFeNi of granulation base ceramic oxide powder,
C, by the uniform ceramic oxide powder of granulation, adding organic solvent, be Terpineol 350, adopting planetary high-energy ball mill to carry out ball milling sizes mixing, in mechanical milling process, the ball mill frequency is 45HZ, Ball-milling Time is 60min, obtain the ceramic oxide slurry, wherein the mass ratio of oxide powder and organic solvent is 8:2;
D, adopt conventional method for printing screen, regulate spun silk half tone specification 400 orders, screen cloth tension force is 25N, and subtegulum 2 surfaces that step c ceramic oxide slurry evenly are coated in to the spun silk half tone are on the smooth quartz plate of atomic level, the ceramic sheet 1 that formation thickness is 25um;
E, silk-screen gained ceramic sheet 1 is placed in to dry 20 hours of the constant temperature oven of 100 ℃ of temperature, make subtegulum 2 surfaces fully curing for the ceramic sheet 1 on the smooth quartz plate surface of atomic level, the ceramic sheet of completion of cure 1 and subtegulum 2 surfaces are taken out together with the smooth resistant to elevated temperatures quartz plate of atomic level, press substrate 3 surfaces at the ceramic surface lid and form interlayer for the smooth quartz plate of atomic level, adopt Vacuum Package that the ceramic sheet 1 clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film, vacuum tightness is 10E
-4pa;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 400MPa, pressurize 5min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper substrate 3 surfaces for the smooth quartz plate of atomic level slowly level push open, ceramic sheet 1 is peeled off and is taken off, making it is smooth complete separation of quartz plate of atomic level with subtegulum 2 surfaces, the unsupported ceramic sheet 4 that acquisition thickness is 25um;
G, will be placed on lower alumina ceramic plate 5 without supporting micron order ceramic sheet 4, at the placed around pad 6 without supporting micron order ceramic sheet 4, it is resistant to elevated temperatures quartz plate, again upper alumina ceramic plate 7 is placed on to pad 6 on resistant to elevated temperatures quartz plate, form a gap between two alumina plates, again unsupported ceramic sheet 4 is carried out to sintering, sintering temperature is 1200 ℃, can obtain without supporting micron order ultra-thin ceramic sheet.
A, according to molar ratio weighing raw material manganese oxide, cobalt oxide, the cupric oxide of 3:2:1, adopt indoor temperature solid phase method ball milling 13h that raw material is mixed and react to abundant, generate the MnCoCu base oxide, again by the MnCoCu base oxide constant temperature pre-burning 1h under 550 ℃ of conditions of temperature generated, obtain stable nano level MnCoCu base ceramic oxide powder, size distribution is less than 150um;
B, the dispersion agent that to add mass concentration in nano level MnCoCu base ceramic oxide powder be 5wt% is polyvinyl alcohol water solution (quality of polyvinyl alcohol press to 5wt% is the aqueous solution to formation polyvinyl alcohol in deionized water than stirring and dissolving), add again the excessive dehydrated alcohol of 8 times of quality to form mixed solution, the beaker that mixed solution is housed is put into to supersonic cleaning machine, ultrasonic dispersion 60min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, crossing 500 orders after powder is ground all just sieves, obtain the uniform nano level MnCoCu of granulation base ceramic oxide powder,
C, by the uniform ceramic oxide powder of granulation, adding organic solvent, be ethylene glycol, adopting planetary high-energy ball mill to carry out ball milling sizes mixing, in mechanical milling process, the ball mill frequency is 35HZ, Ball-milling Time is 35min, obtain the ceramic oxide slurry, wherein the mass ratio of oxide powder and organic solvent is 6.5:3.5;
D, adopt conventional method for printing screen, regulate steel wire half tone specification 150 orders, screen cloth tension force is 20N, and subtegulum 2 surfaces that step c ceramic oxide slurry evenly are coated in to the steel wire half tone are on the smooth sapphire sheet of atomic level, the ceramic sheet 1 that formation thickness is 10um;
E, silk-screen gained ceramic sheet 1 is placed in to dry 20 hours of the constant temperature oven of 100 ℃ of temperature, make subtegulum 2 surfaces fully curing for the ceramic sheet 1 on the smooth sapphire sheet surface of atomic level, the ceramic sheet of completion of cure 1 and subtegulum 2 surfaces are taken out together with the smooth sapphire sheet of atomic level, press substrate 3 at the ceramic surface lid and form interlayer for the smooth sapphire sheet of atomic level, adopt Vacuum Package that the ceramic sheet 1 clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film, vacuum tightness is 10E
-2pa;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 300MPa, pressurize 3min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper substrate 3 surfaces for the smooth sapphire sheet of atomic level slowly level push open, ceramic sheet 1 is peeled off and is taken off, making it is smooth complete separation of sapphire sheet of atomic level with subtegulum 2 surfaces, the unsupported ceramic sheet 4 that acquisition thickness is 10um;
G, will be placed on lower alumina ceramic plate 5 without supporting micron order ceramic sheet 4, at the placed around pad 6 without supporting micron order ceramic sheet 4, it is resistant to elevated temperatures sapphire sheet, again upper alumina ceramic plate 7 is placed on to pad 6 on resistant to elevated temperatures sapphire sheet, form a gap between two alumina plates, again unsupported ceramic sheet 4 is carried out to sintering, sintering temperature is 1100 ℃, can obtain without supporting micron order ultra-thin ceramic sheet.
A, according to molar ratio weighing raw material manganese oxide, ferric oxide, the cupric oxide of 25:17:8, adopt indoor temperature solid phase method ball milling 10h that raw material is mixed and react to abundant, generate the MnFeCu base oxide, again by the MnFeCu base oxide constant temperature pre-burning 1h under 700 ℃ of conditions of temperature generated, obtain stable nano level MnFeCu base ceramic oxide powder, size distribution is less than 150um;
B, the dispersion agent that to add mass concentration in nano level MnFeCu base ceramic oxide powder be 6wt% is polyvinyl alcohol water solution (quality of polyvinyl alcohol press to 5wt% is the aqueous solution to formation polyvinyl alcohol in deionized water than stirring and dissolving), add again the excessive dehydrated alcohol of 8.5 times of quality to form mixed solution, the beaker that mixed solution is housed is put into to supersonic cleaning machine, ultrasonic dispersion 50min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, crossing 400 orders after powder is ground all just sieves, obtain the uniform nano level MnFeCu of granulation base ceramic oxide powder,
C, by the uniform ceramic oxide powder of granulation, adding organic solvent, be ethanol, adopting planetary high-energy ball mill to carry out ball milling sizes mixing, in mechanical milling process, the ball mill frequency is 40HZ, Ball-milling Time is 60min, obtain the ceramic oxide slurry, wherein the mass ratio of oxide powder and organic solvent is 8:2;
D, adopt conventional method for printing screen, regulate nylon half tone specification 100 orders, screen cloth tension force is 25N, and subtegulum 2 surfaces that step c ceramic oxide slurry evenly are coated in to thin,tough silk nylon version are on the smooth quartz plate of atomic level, the ceramic sheet 1 that formation thickness is 35um;
E, silk-screen gained ceramic sheet 1 is placed in to dry 20 hours of the constant temperature oven of 100 ℃ of temperature, make subtegulum 2 surfaces fully curing for the ceramic sheet 1 on the smooth quartz plate surface of atomic level, the ceramic sheet of completion of cure 1 and subtegulum 2 surfaces are taken out together with the smooth quartz plate of atomic level, press substrate 3 surfaces at the ceramic surface lid and form interlayer for the smooth quartz plate of atomic level, adopt Vacuum Package that the ceramic sheet 1 clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film, vacuum tightness is 10E
-4pa;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 100MPa, pressurize 5min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper substrate 3 surfaces for the smooth quartz plate of atomic level slowly level push open, ceramic sheet 1 is peeled off and is taken off, making it is smooth complete separation of quartz plate of atomic level with subtegulum 2 surfaces, the unsupported ceramic sheet 4 that acquisition thickness is 35um;
G, will be placed on lower alumina ceramic plate 5 without supporting micron order ceramic sheet 4, at the placed around pad 6 without supporting micron order ceramic sheet 4, it is resistant to elevated temperatures quartz plate, again upper alumina ceramic plate 7 is placed on to pad 6 on resistant to elevated temperatures quartz plate, form a gap between two alumina plates, again unsupported ceramic sheet 4 is carried out to sintering, sintering temperature is 1200 ℃, can obtain without supporting micron order ultra-thin ceramic sheet.
A, according to molar ratio weighing raw material sulphuric acid manganese, ferric sulfate, the single nickel salt of 47:32:21, adopt indoor temperature solid phase method ball milling 11h, raw material is mixed and react to abundant, generate the MnFeNi based hybroxide, again by the MnFeNi based hybroxide constant temperature pre-burning 1h under 500 ℃ of temperature condition of temperature generated, obtain stable nano level MnFeNi base ceramic oxide powder, size distribution is less than 150um;
B, the dispersion agent that to add mass concentration in nano level MnFeNi base ceramic oxide powder be 6wt% is polyvinyl butyral acetal alcoholic solution (quality that polyvinyl alcohol carboxylic butyraldehyde press to 5wt% is the alcoholic solution to formation polyvinyl butyral acetal in dehydrated alcohol than stirring and dissolving), add again the excessive dehydrated alcohol of 5 times of quality to form mixed solution, the vessel that mixed solution is housed are put into to supersonic cleaning machine, ultrasonic dispersion 60min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, grind again, crossing 500 orders all just sieves, obtain the uniform nano level MnFeNi of granulation base ceramic oxide powder,
C, 6:4 is ethanol by the uniform ceramic oxide powder of granulation, adding organic solvent in mass ratio, adopts planetary high-energy ball mill to carry out ball milling and sizes mixing, and in mechanical milling process, the ball mill frequency is 45HZ, and Ball-milling Time is 60min, obtains the ceramic oxide slurry;
D, adopt conventional method for printing screen, regulate silk-screen plate specification 200 orders, screen cloth tension force is 25N, step c ceramic oxide slurry evenly is coated in to the subtegulum 2 of nylon half tone on sapphire sheet, the ceramic sheet 1 that to form thickness be 10um;
E, silk-screen gained ceramic sheet 1 is placed in to dry 30 hours of the constant temperature oven of 100 ℃ of temperature, make subtegulum 2 surfaces fully curing for the ceramic sheet 1 on the smooth sapphire sheet surface of atomic level, the ceramic sheet of completion of cure 1 and subtegulum 2 surfaces are taken out together with the smooth sapphire sheet of atomic level, press substrate 3 surfaces at the ceramic surface lid and form interlayer for the smooth sapphire sheet of atomic level, adopt Vacuum Package that the ceramic sheet 1 clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film, vacuum tightness is 10
-3pa;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 200MPa, pressurize 5min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper substrate 3 surfaces for the smooth resistant to elevated temperatures sapphire sheet of atomic level slowly level push open, ceramic sheet 1 is peeled off and is taken off, making itself and subtegulum surface is smooth complete separation of sapphire sheet of atomic level, the unsupported ceramic sheet 4 that acquisition thickness is 10um;
G, will be placed on lower alumina ceramic plate 5 without supporting micron order ceramic sheet 4, at the placed around pad 6 without supporting micron order ceramic sheet 4, it is resistant to elevated temperatures silicon chip, again upper alumina ceramic plate 7 is placed on to pad 6 on resistant to elevated temperatures silicon chip, make between two alumina plates to form a gap, again unsupported ceramic sheet 4 is carried out to sintering, sintering temperature is 1120 ℃, can obtain without supporting micron order ultra-thin ceramic sheet.
Embodiment 6
A, according to molar ratio weighing raw material sulphuric acid manganese, rose vitriol, the single nickel salt of 3:1:1, adopt indoor temperature solid phase method ball milling 15h, raw material is mixed and react to abundant, generate the MnCoNi based hybroxide, again by the MnCoNi based hybroxide constant temperature pre-burning 1h under 580 ℃ of temperature condition of temperature generated, obtain stable nano level MnCoNi base ceramic oxide powder, size distribution is less than 150um;
B, the dispersion agent that to add mass concentration in nano level MnCoNi base ceramic oxide powder be 5.5wt% is polyvinyl butyral acetal alcoholic solution (quality that polyvinyl alcohol carboxylic butyraldehyde press to 5wt% is the alcoholic solution to formation polyvinyl butyral acetal in dehydrated alcohol than stirring and dissolving), add again the excessive dehydrated alcohol of 7 times of quality to form mixed solution, the vessel that mixed solution is housed are put into to supersonic cleaning machine, ultrasonic dispersion 45min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, grind again, crossing 450 orders all just sieves, obtain the uniform nano level MnCoNi of granulation base ceramic oxide powder,
C, 7:3 is Terpineol 350 by the uniform ceramic oxide powder of granulation, adding organic solvent in mass ratio, adopts planetary high-energy ball mill to carry out ball milling and sizes mixing, and in mechanical milling process, the ball mill frequency is 45HZ, and Ball-milling Time is 50min, obtains the ceramic oxide slurry;
D, adopt conventional method for printing screen, regulate silk-screen plate specification 200 orders, screen cloth tension force is 19N, step c ceramic oxide slurry evenly is coated in to the subtegulum 2 of nylon half tone on sapphire sheet, the ceramic sheet 1 that to form thickness be 15um;
E, silk-screen gained ceramic sheet 1 is placed in to dry 30 hours of the constant temperature oven of 100 ℃ of temperature, make subtegulum 2 surfaces fully curing for the ceramic sheet 1 on the smooth sapphire sheet surface of atomic level, the ceramic sheet of completion of cure 1 and subtegulum 2 surfaces are taken out together with the smooth sapphire sheet of atomic level, press substrate 3 surfaces at the ceramic surface lid and form interlayer for the smooth sapphire sheet of atomic level, adopt Vacuum Package that the ceramic sheet 1 clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film, vacuum tightness is 10
-3pa;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 200MPa, pressurize 4min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper substrate 3 surfaces for the smooth sapphire sheet of atomic level slowly level push open, ceramic sheet 1 is peeled off and is taken off, making it is smooth complete separation of sapphire sheet of atomic level with subtegulum 2 surfaces, the unsupported ceramic sheet 4 that acquisition thickness is 15um;
G, will be placed on lower alumina ceramic plate 5 without supporting micron order ceramic sheet 4, at the placed around pad 6 without supporting micron order ceramic sheet 4, it is resistant to elevated temperatures quartz plate, again upper alumina ceramic plate 7 is placed on to pad 6 on resistant to elevated temperatures quartz plate, make between two alumina plates to form a gap, again unsupported ceramic sheet 4 is carried out to sintering, sintering temperature is 1120 ℃, can obtain without supporting micron order ultra-thin ceramic sheet.
A, according to molar ratio weighing raw material sulphuric acid manganese, rose vitriol, the copper sulfate of 4:2:1, adopt indoor temperature solid phase method ball milling 16h, raw material is mixed and react to abundant, generate the MnCoCu based hybroxide, again by the MnCoCu based hybroxide constant temperature pre-burning 1h under 500 ℃ of temperature condition of temperature generated, obtain stable nano level MnCoCu base ceramic oxide powder, size distribution is less than 150um;
B, the dispersion agent that to add mass concentration in nano level MnCoCu base ceramic oxide powder be 5wt% is polyvinyl alcohol water solution (polyvinyl alcohol is formed to polyvinyl alcohol water solution than stirring and dissolving by the quality of 5wt% in deionized water), add again the excessive dehydrated alcohol of 7 times of quality to form mixed solution, the vessel that mixed solution is housed are put into to supersonic cleaning machine, ultrasonic dispersion 50min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, grind again, crossing 400 orders all just sieves, obtain the uniform nano level MnCoCu of granulation base ceramic oxide powder,
C, 7.5:2.5 is propyl carbinol by the uniform ceramic oxide powder of granulation, adding organic solvent in mass ratio, adopting planetary high-energy ball mill to carry out ball milling sizes mixing, in mechanical milling process, the ball mill frequency is 35HZ, and Ball-milling Time is 20min, obtains the ceramic oxide slurry;
D, adopt conventional method for printing screen, regulate silk-screen plate specification 300 orders, screen cloth tension force is 20N, step c ceramic oxide slurry evenly is coated in to the subtegulum 2 of spun silk half tone on silicon chip, the ceramic sheet 1 that to form thickness be 18um;
E, silk-screen gained ceramic sheet 1 is placed in to dry 30 hours of the constant temperature oven of 100 ℃ of temperature, make subtegulum 2 surfaces fully curing for the ceramic sheet 1 of the smooth silicon chip surface of atomic level, the ceramic sheet of completion of cure 1 and subtegulum 2 surfaces are taken out together with the smooth silicon chip of atomic level, press substrate 3 surfaces at the ceramic surface lid and form interlayer for the smooth silicon chip of atomic level, adopt Vacuum Package that the ceramic sheet 1 clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film, vacuum tightness is 10
-3pa;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 400MPa, pressurize 2.5min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper substrate 3 surfaces for the smooth silicon chip of atomic level slowly level push open, ceramic sheet 1 is peeled off and is taken off, making it is smooth complete separation of silicon chip of atomic level with subtegulum 2 surfaces, the unsupported ceramic sheet 4 that acquisition thickness is 18um;
G, will be placed on lower alumina ceramic plate 5 without supporting micron order ceramic sheet 4, at the placed around pad 6 without supporting micron order ceramic sheet 4, it is resistant to elevated temperatures sapphire sheet, again upper alumina ceramic plate 7 is placed on to pad 6 on resistant to elevated temperatures sapphire sheet, make between two alumina plates to form a gap, again unsupported ceramic sheet 4 is carried out to sintering, sintering temperature is 1000 ℃, can obtain without supporting micron order ultra-thin ceramic sheet.
Embodiment 8
A, according to molar ratio weighing raw material sulphuric acid manganese, ferric sulfate, the copper sulfate of 4:2:1, adopt indoor temperature solid phase method ball milling 17h, raw material is mixed and react to abundant, generate the MnFeCu based hybroxide, again by the MnFeCu based hybroxide constant temperature pre-burning 1h under 550 ℃ of temperature condition of temperature generated, obtain stable nano level MnFeCu base ceramic oxide powder, size distribution is less than 150um;
B, the dispersion agent that to add mass concentration in nano level MnFeCu base ceramic oxide powder be 5wt% is polyvinyl alcohol water solution (polyvinyl alcohol is formed to polyvinyl alcohol water solution than stirring and dissolving by the quality of 5wt% in deionized water), add again the excessive dehydrated alcohol of 7 times of quality to form mixed solution, the vessel that mixed solution is housed are put into to supersonic cleaning machine, ultrasonic dispersion 60min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, grind again, crossing 400 orders all just sieves, obtain the uniform nano level MnFeCu of granulation base ceramic oxide powder,
C, 7.5:2.5 is Terpineol 350 by the uniform ceramic oxide powder of granulation, adding organic solvent in mass ratio, adopting planetary high-energy ball mill to carry out ball milling sizes mixing, in mechanical milling process, the ball mill frequency is 35HZ, and Ball-milling Time is 30min, obtains the ceramic oxide slurry;
D, adopt conventional method for printing screen, regulate silk-screen plate specification 300 orders, screen cloth tension force is 20N, step c ceramic oxide slurry evenly is coated in to the subtegulum 2 of spun silk half tone on silicon chip, the ceramic sheet 1 that to form thickness be 18um;
E, silk-screen gained ceramic sheet 1 is placed in to dry 30 hours of the constant temperature oven of 100 ℃ of temperature, make subtegulum 2 surfaces fully curing for the ceramic sheet 1 of the smooth silicon chip surface of atomic level, the ceramic sheet of completion of cure 1 and subtegulum 2 surfaces are taken out together with the smooth silicon chip of atomic level, press substrate 3 surfaces at the ceramic surface lid and form interlayer for the smooth silicon chip of atomic level, adopt Vacuum Package that the ceramic sheet 1 clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film, vacuum tightness is 10
-5pa;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 400MPa, pressurize 3min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper substrate 3 surfaces for the smooth silicon chip of atomic level slowly level push open, ceramic sheet 1 is peeled off and is taken off, making it is smooth complete separation of silicon chip of atomic level with subtegulum 2 surfaces, the unsupported ceramic sheet 4 that acquisition thickness is 18um;
G, will be placed on lower alumina ceramic plate 5 without supporting micron order ceramic sheet 4, at the placed around pad 6 without supporting micron order ceramic sheet 4, it is resistant to elevated temperatures sapphire sheet, again upper alumina ceramic plate 7 is placed on to pad 6 on resistant to elevated temperatures sapphire sheet, make between two alumina plates to form a gap, again unsupported ceramic sheet 4 is carried out to sintering, sintering temperature is 1000 ℃, can obtain without supporting micron order ultra-thin ceramic sheet.
Embodiment 9
A, according to molar ratio weighing raw acetic acid manganese, cobaltous acetate, the venus crystals of 5:4:2, adopt indoor temperature solid phase method ball milling 24h that raw material is mixed and react to abundant, generate the MnCoCu base oxide, again by the MnCoCu base oxide constant temperature pre-burning 1h under 600 ℃ of conditions of temperature generated, obtain stable nano level MnCoCu base ceramic oxide powder, size distribution is less than 150um;
B, the dispersion agent that to add mass concentration in nano level MnCoCu base ceramic oxide powder be 5wt% is polyvinyl alcohol water solution (quality of polyvinyl alcohol press to 5wt% is the aqueous solution to formation polyvinyl alcohol in deionized water than stirring and dissolving), add again the excessive dehydrated alcohol of 8 times of quality to form mixed solution, the beaker that mixed solution is housed is put into to supersonic cleaning machine, ultrasonic dispersion 55min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, crossing 500 orders after powder is ground all just sieves, obtain the uniform nano level MnCoCu of granulation base ceramic oxide powder,
C, by the uniform ceramic oxide powder of granulation, adding organic solvent, be ethylene glycol, adopting planetary high-energy ball mill to carry out ball milling sizes mixing, in mechanical milling process, the ball mill frequency is 30HZ, Ball-milling Time is 30min, obtain the ceramic oxide slurry, wherein the mass ratio of oxide powder and organic solvent is 7:3;
D, adopt conventional method for printing screen, regulate steel wire half tone specification 150 orders, screen cloth tension force is 20N, and subtegulum 2 surfaces that step c ceramic oxide slurry evenly are coated in to the steel wire half tone are on the smooth quartz plate of atomic level, the ceramic sheet 1 that formation thickness is 20um;
E, silk-screen gained ceramic sheet 1 is placed in to dry 20 hours of the constant temperature oven of 100 ℃ of temperature, make subtegulum 2 surfaces fully curing for the ceramic sheet 1 on the smooth quartz plate surface of atomic level, the ceramic sheet of completion of cure 1 and subtegulum 2 surfaces are taken out together with the smooth quartz plate of atomic level, press substrate 3 surfaces at the ceramic surface lid and form interlayer for the smooth resistant to elevated temperatures quartz plate of atomic level, adopt Vacuum Package that the ceramic sheet 1 clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film, vacuum tightness is 10E
-4pa;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 400MPa, pressurize 3min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper substrate 3 surfaces for the smooth quartz plate of atomic level slowly level push open, ceramic sheet 1 is peeled off and is taken off, making it is smooth complete separation of resistant to elevated temperatures quartz plate of atomic level with subtegulum 2 surfaces, the unsupported ceramic sheet 4 that acquisition thickness is 20um;
G, will be placed on lower alumina ceramic plate 5 without supporting micron order ceramic sheet 4, at the placed around pad 6 without supporting micron order ceramic sheet 4, it is resistant to elevated temperatures sapphire sheet, again upper alumina ceramic plate 7 is placed on to pad 6 on resistant to elevated temperatures sapphire sheet, form a gap between two alumina plates, again unsupported ceramic sheet 4 is carried out to sintering, sintering temperature is 1050 ℃, can obtain without supporting micron order ultra-thin ceramic sheet.
Embodiment 10
A, according to molar ratio weighing raw acetic acid manganese, cobaltous acetate, the nickelous acetate of 50:34:16, adopt indoor temperature solid phase method ball milling 14h that raw material is mixed and react to abundant, generate the MnCoNi base oxide, again by the MnCoNi base oxide constant temperature pre-burning 1h under 500 ℃ of conditions of temperature generated, obtain stable nano level MnCoNi base ceramic oxide powder, size distribution is less than 150um;
B, the dispersion agent that to add mass concentration in nano level MnCoNi base ceramic oxide powder be 5wt% is polyvinyl alcohol water solution (quality of polyvinyl alcohol press to 5wt% is the aqueous solution to formation polyvinyl alcohol in deionized water than stirring and dissolving), add again the excessive dehydrated alcohol of 5 times of quality to form mixed solution, the beaker that mixed solution is housed is put into to supersonic cleaning machine, ultrasonic dispersion 50min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, crossing 400 orders after powder is ground all just sieves, obtain the uniform nano level MnCoNi of granulation base ceramic oxide powder,
C, by the uniform ceramic oxide powder of granulation, adding organic solvent, be propyl carbinol, adopting planetary high-energy ball mill to carry out ball milling sizes mixing, in mechanical milling process, the ball mill frequency is 30HZ, Ball-milling Time is 35min, obtain the ceramic oxide slurry, wherein the mass ratio of oxide powder and organic solvent is 7:3;
D, adopt conventional method for printing screen, regulate steel wire half tone specification 150 orders, screen cloth tension force is 20N, and subtegulum 2 surfaces that step c ceramic oxide slurry evenly are coated in to the steel wire half tone are on the smooth silicon chip of atomic level, the ceramic sheet 1 that formation thickness is 20um;
E, silk-screen gained ceramic sheet 1 is placed in to dry 18 hours of the constant temperature oven of 100 ℃ of temperature, make subtegulum 2 surfaces fully curing for the ceramic sheet 1 of the smooth silicon chip surface of atomic level, the ceramic sheet of completion of cure 1 and subtegulum 2 surfaces are taken out together with the smooth silicon chip of atomic level, press substrate 3 surfaces at the ceramic surface lid and form interlayer for the smooth resistant to elevated temperatures silicon chip of atomic level, adopt Vacuum Package that the ceramic sheet 1 clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film, vacuum tightness is 10E
-3pa;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 400MPa, pressurize 2min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper substrate 3 surfaces for the smooth silicon chip of atomic level slowly level push open, ceramic sheet 1 is peeled off and is taken off, making it is smooth complete separation of resistant to elevated temperatures silicon chip of atomic level with subtegulum 2 surfaces, the unsupported ceramic sheet 4 that acquisition thickness is 20um;
G, will be placed on lower alumina ceramic plate 5 without supporting micron order ceramic sheet 4, at the placed around pad 6 without supporting micron order ceramic sheet 4, it is resistant to elevated temperatures quartzy flag, again upper alumina ceramic plate 7 is placed on to pad 6 on resistant to elevated temperatures quartz plate, form a gap between two alumina plates, again unsupported ceramic sheet 4 is carried out to sintering, sintering temperature is 1150 ℃, can obtain without supporting micron order ultra-thin ceramic sheet.
Embodiment 11
A, according to molar ratio weighing raw acetic acid manganese, ironic acetate, the nickelous acetate of 5:3:1, adopt indoor temperature solid phase method ball milling 20h that raw material is mixed and react to abundant, generate the MnFeNi base oxide, again by the MnFeNi base oxide constant temperature pre-burning 1h under 600 ℃ of conditions of temperature generated, obtain stable nano level MnFeNi base ceramic oxide powder, size distribution is less than 150um;
B, adding the dispersion agent that mass concentration is 5wt% in nano level MnFeNi base ceramic oxide powder is polyvinyl butyral acetal alcoholic solution (quality of polyvinyl butyral acetal being pressed to 5wt% forms the polyvinyl butyral acetal alcoholic solution than stirring and dissolving in dehydrated alcohol), add again the excessive dehydrated alcohol of 10 times of quality to form mixed solution, the beaker that mixed solution is housed is put into to supersonic cleaning machine, ultrasonic dispersion 60min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, crossing 500 orders after powder is ground all just sieves, obtain the uniform nano level MnFeNi of granulation base ceramic oxide powder,
C, by the uniform ceramic oxide powder of granulation, adding organic solvent, be propyl carbinol, adopting planetary high-energy ball mill to carry out ball milling sizes mixing, in mechanical milling process, the ball mill frequency is 45HZ, Ball-milling Time is 35min, obtain the ceramic oxide slurry, wherein the mass ratio of oxide powder and organic solvent is 8:2;
D, adopt conventional method for printing screen, regulate steel wire half tone specification 100 orders, screen cloth tension force is 25N, and subtegulum 2 surfaces that step c ceramic oxide slurry evenly are coated in to the steel wire half tone are on the smooth silicon chip of atomic level, the ceramic sheet 1 that formation thickness is 30um;
E, silk-screen gained ceramic sheet 1 is placed in to dry 20 hours of the constant temperature oven of 100 ℃ of temperature, make subtegulum 2 surfaces fully curing for the ceramic sheet 1 of the smooth silicon chip surface of atomic level, the ceramic sheet of completion of cure 1 and subtegulum 2 surfaces are taken out together with the smooth silicon chip of atomic level, press substrate 3 surfaces at the ceramic surface lid and form interlayer for the smooth resistant to elevated temperatures silicon chip of atomic level, adopt Vacuum Package that the ceramic sheet 1 clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film, vacuum tightness is 10E
-3pa;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 200MPa, pressurize 1min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper substrate 3 surfaces for the smooth silicon chip of atomic level slowly level push open, ceramic sheet 1 is peeled off and is taken off, making it is smooth complete separation of resistant to elevated temperatures silicon chip of atomic level with subtegulum 2 surfaces, the unsupported ceramic sheet 4 that acquisition thickness is 30um;
G, will be placed on lower alumina ceramic plate 5 without supporting micron order ceramic sheet 4, at the placed around pad 6 without supporting micron order ceramic sheet 4, it is resistant to elevated temperatures quartzy flag, again upper alumina ceramic plate 7 is placed on to pad 6 on resistant to elevated temperatures quartz plate, form a gap between two alumina plates, again unsupported ceramic sheet 4 is carried out to sintering, sintering temperature is 950 ℃, can obtain without supporting micron order ultra-thin ceramic sheet.
Embodiment 12
A, according to molar ratio weighing raw acetic acid manganese, ironic acetate, the venus crystals of 46:33:23, adopt indoor temperature solid phase method ball milling 20h that raw material is mixed and react to abundant, generate the MnFeCu base oxide, again by the MnFeCu base oxide constant temperature pre-burning 1h under 500 ℃ of conditions of temperature generated, obtain stable nano level MnFeCu base ceramic oxide powder, size distribution is less than 150um;
B, the dispersion agent that to add mass concentration in nano level MnFeCu base ceramic oxide powder be 5wt% is polyvinyl alcohol water solution (quality of polyvinyl alcohol press to 5wt% is the aqueous solution to formation polyvinyl alcohol in deionized water than stirring and dissolving), add again the excessive dehydrated alcohol of 5 times of quality to form mixed solution, the beaker that mixed solution is housed is put into to supersonic cleaning machine, ultrasonic dispersion 40min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, crossing 500 orders after powder is ground all just sieves, obtain the uniform nano level MnFeCu of granulation base ceramic oxide powder,
C, by the uniform ceramic oxide powder of granulation, adding organic solvent, be ethanol, adopting planetary high-energy ball mill to carry out ball milling sizes mixing, in mechanical milling process, the ball mill frequency is 30HZ, Ball-milling Time is 35min, obtain the ceramic oxide slurry, wherein the mass ratio of oxide powder and organic solvent is 7:3;
D, adopt conventional method for printing screen, regulate steel wire half tone specification 150 orders, screen cloth tension force is 20N, and subtegulum 2 surfaces that step c ceramic oxide slurry evenly are coated in to the steel wire half tone are on the smooth silicon chip of atomic level, the ceramic sheet 1 that formation thickness is 20um;
E, silk-screen gained ceramic sheet 1 is placed in to dry 18 hours of the constant temperature oven of 100 ℃ of temperature, make subtegulum 2 surfaces fully curing for the ceramic sheet 1 of the smooth silicon chip surface of atomic level, the ceramic sheet of completion of cure 1 and subtegulum surface is taken out together with the smooth silicon chip of atomic level, press substrate 3 surfaces at the ceramic surface lid and form interlayer for the smooth resistant to elevated temperatures silicon chip of atomic level, adopt Vacuum Package that the ceramic sheet 1 clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film, vacuum tightness is 10E
-3pa;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 400MPa, pressurize 2min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper substrate 3 surfaces for the smooth silicon chip of atomic level slowly level push open, ceramic sheet 1 is peeled off and is taken off, making it is smooth complete separation of resistant to elevated temperatures silicon chip of atomic level with subtegulum 2 surfaces, the unsupported ceramic sheet 4 that acquisition thickness is 20um;
G, will be placed on lower alumina ceramic plate 5 without supporting micron order ceramic sheet 4, at the placed around pad 6 without supporting micron order ceramic sheet 4, it is resistant to elevated temperatures quartzy flag, again upper alumina ceramic plate 7 is placed on to pad 6 on resistant to elevated temperatures quartz plate, form a gap between two alumina plates, again unsupported ceramic sheet 4 is carried out to sintering, sintering temperature is 1150 ℃, can obtain without supporting micron order ultra-thin ceramic sheet.
Claims (7)
1. one kind without the preparation method who supports micron order ultra-thin ceramic sheet, it is characterized in that the device related in the method is comprised of ceramic sheet (1), ceramic sheet (4), subtegulum (2), upper substrate (3), lower alumina ceramic plate (5), upper alumina ceramic plate (7) and pad (6), concrete operations follow these steps to carry out:
A, by raw material, be three kinds in manganese, cobalt, nickel, copper and ferroelectric metal oxide or metal-salt, adopt the indoor temperature solid phase method mixed grinding to reacting completely, constant temperature pre-burning 1h under temperature 500-700 ℃ condition, obtain the nanometer scale ceramics oxide powder of stable and uniform;
B, by adding the dispersion agent that mass concentration is 4-6 wt% in the nanometer scale ceramics oxide powder of step a gained, be polyvinyl alcohol water solution or polyvinyl butyral acetal alcoholic solution, add again the excessive dehydrated alcohol of 5-10 times of quality to form mixed solution, the vessel that mixed solution is housed are put into to supersonic cleaning machine, ultrasonic dispersion 40-60min, after being uniformly dispersed, mixed solution is placed in to the constant temperature oven drying treatment of 80 ℃ of temperature, grind again, cross the 400-500 order and all just sieve, obtain the uniform ceramic oxide powder of granulation;
C, by the uniform ceramic oxide powder of step b granulation, adding organic solvent, be Terpineol 350, ethanol, ethylene glycol or glycerol, adopting planetary high-energy ball mill to carry out ball milling sizes mixing, in mechanical milling process, the ball mill frequency is 30-45HZ, Ball-milling Time is 10-60min, obtain the ceramic oxide slurry, wherein the mass ratio of oxide powder and organic solvent is 6-8:2-4;
D, adopt conventional method for printing screen, regulate the silk-screen plate specification, the subtegulum (2) that ceramic oxide slurry in step c evenly is coated in to silk-screen plate is upper, the ceramic sheet (1) that to form thickness be 5-35um;
E, silk screen printing gained ceramic sheet (1) is placed in to the dry 10-30 hour of constant temperature oven of 100 ℃ of temperature, the ceramic sheet (1) on subtegulum (2) surface is fully solidified, the ceramic sheet of completion of cure (1) is taken out together with subtegulum (2), on the ceramic surface lid is pressed one, substrate (3) forms interlayer, adopt Vacuum Package that the ceramic sheet (1) clipped is encapsulated, encapsulated layer is one deck aluminium foil at least, two-layer transparent plastic film;
F, packaged sample is carried out to isostatic cool pressing, pressure setting is 100-400 MPa, pressurize 1-5 min, after isostatic cool pressing, slowly cut off packaging bag, with tweezers, interlayer is slowly taken out, be placed on steady table top, by upper strata substrate (3) slowly level push open, ceramic sheet (1) is peeled off and is taken off, make itself and subtegulum (2) complete separation, the unsupported ceramic sheet (4) that to obtain thickness be 5-35um;
G, will be placed on lower alumina ceramic plate (5) without supporting micron order ceramic sheet (4), at the placed around pad (6) without supporting micron order ceramic sheet (4), again upper alumina ceramic plate (7) is placed on pad (6), make between two alumina plates to form a gap, again unsupported ceramic sheet (4) is carried out to sintering, sintering temperature is 900-1200 ℃, after sintering, can obtain without supporting micron order ultra-thin ceramic sheet.
2. method according to claim 1, the metal oxide that it is characterized in that manganese, cobalt, nickel, copper and iron in step a is manganese oxide, cobalt oxide, nickel oxide, cupric oxide, ferric oxide; Metal-salt is manganous sulfate, rose vitriol, single nickel salt, copper sulfate, ferric sulfate, manganous acetate, ironic acetate, nickelous acetate, cobaltous acetate and venus crystals.
3. method according to claim 1, is characterized in that the particle diameter of the described nanometer oxide powder of step a is less than 150nm.
4. method according to claim 1, is characterized in that the silk-screen plate specification described in steps d is that half tone order number is the 100-400 order, and screen cloth tension force is 18-25N, and the half tone material is steel wire half tone, nylon half tone or spun silk half tone.
5. method according to claim 1, is characterized in that the subtegulum described in steps d (2), upper substrate (3) surface are smooth silicon chip, sapphire sheet or the quartz plate of atomic level.
6. method according to claim 1, is characterized in that in step e, vacuum tightness is 10
-5-10
-2pa.
7. method according to claim 1, is characterized in that step g Intermediate gasket (6) is resistant to elevated temperatures silicon chip, sapphire sheet or quartz plate.
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| CN108893723A (en) * | 2018-06-28 | 2018-11-27 | 武汉工程大学 | A method of quickly preparing ultra-thin ceramic piece |
| CN114725461A (en) * | 2020-12-21 | 2022-07-08 | 宁波材料所杭州湾研究院 | Low-temperature sintered densified samarium-neodymium-doped cerium oxide-based barrier layer, preparation method thereof and solid oxide fuel cell |
| CN116120064A (en) * | 2022-11-30 | 2023-05-16 | 北京核力同创科技有限公司 | Preparation method and application of accelerator irradiation target ceramic wafer |
| CN116164878A (en) * | 2023-02-01 | 2023-05-26 | 上海恒脉陶瓷技术有限公司 | Ceramic single-cavity capacitive differential pressure sensor and preparation method thereof |
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