CN114736005A - Tungsten metallization-multilayer alumina black porcelain substrate and preparation method thereof - Google Patents
Tungsten metallization-multilayer alumina black porcelain substrate and preparation method thereof Download PDFInfo
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- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 72
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 65
- 239000010937 tungsten Substances 0.000 title claims abstract description 65
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000758 substrate Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000010344 co-firing Methods 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005520 cutting process Methods 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims description 43
- 238000010030 laminating Methods 0.000 claims description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 18
- 238000003475 lamination Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 description 18
- 239000010410 layer Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000000462 isostatic pressing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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Abstract
The invention discloses a tungsten metallization-multilayer alumina black porcelain substrate and a preparation method thereof, and the preparation method mainly comprises the following processes: providing a laminated body, wherein the front surface and the back surface of the green porcelain tape on the top layer of the laminated body are printed with tungsten paste; cutting the laminated body to obtain a green body; co-firing the green body at a high temperature, wherein the process of co-firing at the high temperature is specifically that after vacuumizing in reaction equipment, mixed gas of nitrogen and wet hydrogen is introduced, the temperature is raised to 500-fold-600 ℃ at 1-3 ℃/min, and the temperature is kept for 1-3 h; then raising the temperature to 900-1000 ℃ at a speed of 1-3 ℃/min, and preserving the heat for 20-60 min; finally, the temperature is raised to 1650 ℃ at 1-2 ℃/min, the temperature is kept for 1-3h, and the furnace is naturally cooled. Through the process improvement, the warping problem of the prepared tungsten metallization-multilayer alumina black porcelain substrate is obviously improved, and the black porcelain substrate has high flatness.
Description
Technical Field
The invention belongs to the technical field of co-fired ceramics, and particularly relates to a preparation method of a tungsten metallization-multilayer alumina black ceramic substrate, and the tungsten metallization-multilayer alumina black ceramic substrate prepared by the preparation method.
Background
The High-temperature co-fired ceramic (HTCC) of aluminum oxide has excellent material properties, such as High insulation, High strength, High hardness, High temperature resistance and wear resistance, so that the HTCC is widely applied to semiconductor integrated circuits, and meanwhile, the semiconductor integrated circuits have significant photosensitivity, and generally require a packaged ceramic shell to have light-shielding property, so that the preparation research of the tungsten metalized aluminum oxide High-temperature co-fired black ceramic has important significance for the development of the field of semiconductor packaging.
The conventional high-temperature co-fired black ceramic is prepared by printing tungsten paste on a raw ceramic tape, and then performing processes such as laminating, sintering and the like, wherein the adopted alumina raw ceramic is generally 90-95 ceramic (the alumina content is 90-95 wt%), and the ceramic is extremely widely applied to the field of thick film circuits due to the advantage of low cost.
However, in the actual production process, partial sintering defects usually exist in the sintering process of the tungsten metallization-multilayer alumina ceramic, wherein the most common problems are warping problems, mainly including warping caused by the alumina green ceramic itself and warping caused by the mismatching reason of the tungsten slurry and the alumina ceramic, and the warping problems greatly influence the yield of the product.
Disclosure of Invention
In view of the above, the present invention needs to provide a method for preparing a tungsten metalized-multilayer alumina black ceramic substrate, which improves the warpage problem of the prepared tungsten metalized-multilayer alumina black ceramic substrate by process improvement, and the black ceramic substrate has high flatness.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a tungsten metallization-multilayer alumina black porcelain substrate, which comprises the following steps:
providing a laminated body, wherein the laminated body consists of a plurality of layers of alumina green ceramic tapes, and tungsten paste is printed on the front and back surfaces of the green ceramic tape on the top layer of the laminated body;
cutting the laminated body to obtain a green body;
co-firing the green body at a high temperature, wherein the co-firing process at the high temperature is to pump mixed gas of nitrogen and wet hydrogen into reaction equipment after vacuumizing, raise the temperature to 500-600 ℃ at a speed of 1-3 ℃/min, and keep the temperature for 1-3 h; raising the temperature to 900-; finally, the temperature is raised to 1650 ℃ at 1-2 ℃/min, the temperature is kept for 1-3h, and the furnace is naturally cooled.
In a further scheme, the preparation of the laminated body specifically comprises the following steps:
selecting a plurality of aluminum oxide green ceramic belts, uniformly printing tungsten paste on the front side and the back side of one aluminum oxide green ceramic belt, and not performing printing treatment on the other green ceramic belts;
and sequentially laminating the green ceramic tapes to obtain a laminated body, wherein the green ceramic tapes with the front and back surfaces printed with the tungsten paste are positioned on the uppermost layer.
Further, the process conditions of the lamination are 50-70 ℃ and 1500-.
In a further scheme, the vacuum degree of the vacuumizing is less than 1 Pa.
In a further embodiment, the volume ratio of the nitrogen to the wet hydrogen is between 1:1 and 1: 4.
In a further scheme, the content of alumina in the alumina green porcelain strip is between 90 and 95 weight percent.
The invention further provides a tungsten metalized-multilayer alumina black porcelain substrate prepared by the preparation method of any one of the above.
In a further scheme, the warping degree of the tungsten metallization-multilayer alumina black porcelain substrate is less than 0.05 mm.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method, firstly, the tungsten slurry is printed on the front side and the back side of the green porcelain tape, so that mismatching of the tungsten slurry and the green porcelain tape is counteracted, the warping problem is effectively improved, and meanwhile, the tungsten metal and the aluminum oxide are well combined, and the appearance and the performance of a product are not influenced; and secondly, sintering deformation possibly caused by incomplete discharge of colloids in the raw porcelain and the slurry, residual carbon and the like is prevented by strictly controlling a sintering curve in a co-firing stage, and deformation caused by improper internal and external temperatures and inconsistent thermal expansion of the material due to too fast temperature rise is prevented. Through the cooperation of the two aspects, the obtained tungsten metallization-multilayer alumina black porcelain substrate has high flatness.
Drawings
FIG. 1 is a diagram of a green ceramic model after lamination in accordance with some embodiments of the present invention;
FIG. 2 is a schematic diagram of a front surface of a co-fired black ceramic substrate in example 1;
FIG. 3 is a schematic side view of a co-fired black ceramic substrate in example 1;
FIG. 4 is a SEM topographic fracture view of the sintered black ceramic substrate of example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative only and should not be construed as limiting the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a preparation method of a tungsten metallization-multilayer alumina black porcelain substrate, which comprises the following steps:
preparation of laminate
The laminate of the present invention is prepared substantially in accordance with conventional laminate manufacturing processes in the art, i.e., by printing a tungsten paste onto a green ceramic tape and laminating. In the embodiment of the invention, firstly, a plurality of pieces of alumina green porcelain tapes with certain thickness in the same batch are selected, tungsten paste is uniformly printed on the front surface and the back surface of one piece of the alumina green porcelain tape, and the rest green porcelain tapes are not printed; and laminating the raw ceramic tapes after sequentially laminating, wherein the raw ceramic tapes with the front and back surfaces uniformly printed with the tungsten paste are positioned on the uppermost layer. It is understood that "multiple sheets" or "multiple layers" as used herein refers to more than three layers, and the number of layers or sheets can be selected according to the actual substrate requirements; further, the selection of the alumina green tape in the present invention is not particularly limited, and in one or more embodiments of the present invention, the alumina content of the alumina green tape is between 90 to 95 wt%, preferably 92 wt%. The lamination process is not particularly limited, and conventional lamination processes in the art can be used, and in one or more embodiments of the present invention, the lamination temperature is 50-70 ℃ and the pressure is 1500-.
High temperature co-firing
Specifically, the laminate is cut into green sheets according to design requirements, and the specific cutting method is a conventional process in the art and is not specifically described, and in some specific examples of the invention, the green sheets are 200 × 200mm squares. And (2) placing the green body into high-temperature sintering equipment for co-sintering, wherein the specific sintering process comprises the following steps of: vacuumizing the high-temperature sintering furnace, introducing mixed gas of nitrogen and wet hydrogen, raising the temperature to 500-600 ℃ at the speed of 1-3 ℃/min, and preserving the heat for 1-3 h; raising the temperature to 900-; finally, the temperature is raised to 1650 ℃ at 1-2 ℃/min, the temperature is kept for 1-3h, and the furnace is naturally cooled.
Wherein, the mixed gas of nitrogen and wet hydrogen is introduced, and a certain oxygen partial pressure is provided by the wet hydrogen, so that the rubber discharging is more sufficient, and the reduction of the alumina at high temperature is prevented. Before the temperature is 500-600 ℃, various organic colloids in the porcelain body can slowly escape through a slower heating rate of 1-3 ℃/min, wherein the organic colloids comprise solvents, dispersing agents, adhesives, plasticizers and the like; more between 600 ℃ and 1000 ℃ of 500-; the ceramic body begins to be continuously contracted after the temperature is 1000 ℃ from 900-. Because the sintering curve is strictly controlled, sintering deformation possibly caused by incomplete discharge of colloids in the raw porcelain and the slurry and residual carbon and other impurities is prevented, and deformation caused by different internal and external temperatures and different thermal expansions of the material due to too fast temperature rise is prevented; secondly, the mismatching of the slurry and the raw porcelain is counteracted by printing the slurry on the front side and the back side of the raw porcelain belt, generally speaking, when the tungsten slurry is printed on one side of the raw porcelain belt, the tungsten slurry shrinks and Al under high temperature2O3The substrate is not matched, so that the substrate is warped, the upward warping force and the downward warping force are neutralized by printing the tungsten paste on the front side and the back side, the warping problem can be effectively improved, and meanwhile, the tungsten and the aluminum oxide are well combined, so that the appearance and the performance of the product cannot be influenced.
In a second aspect, the invention provides a tungsten metalized-multilayer alumina black porcelain substrate, which is prepared by the preparation method according to any one of the first aspect of the invention, and the warping degree of the substrate is less than 0.05 mm. The tungsten metallization-multilayer alumina black porcelain substrate prepared by the preparation method provided by the invention has the advantages that the warping degree is obviously improved, the flatness is high, the tungsten metal and the alumina are well combined, the appearance and the performance of the product are ensured, and the yield of the product is improved.
The present invention is described below by way of specific examples, which are intended to be illustrative only and not to limit the scope of the present invention in any way, and in addition, unless otherwise specified, the methods without specifying conditions or steps are all conventional methods, and reagents and materials used are commercially available, and the green tape used in the following examples is 92 alumina green.
Example 1
The preparation method of the tungsten metallization-multilayer alumina black porcelain substrate in the embodiment comprises the following specific steps:
printing the raw porcelain: selecting 3 aluminum oxide raw porcelain pieces with the same batch and the thickness of 0.25mm, uniformly printing tungsten paste on the front surface and the back surface of one of the raw porcelain pieces, and not printing the other two raw porcelain pieces;
isostatic pressing of the green porcelain: the three pieces of green porcelain after printing are shown in figure 1 (uppermost layer of Al)2O3Tungsten slurry printed on the front and back sides of the porcelain) are laminated in sequence, and the laminating process conditions are 60 ℃ and 2000 psi;
raw cutting: cutting the laminated green porcelain into square blocks with the size of 200 multiplied by 200 mm;
co-firing: putting the green body into a high-temperature sintering furnace, vacuumizing the furnace chamber at room temperature until the vacuum degree is less than 1Pa, and then introducing nitrogen and wet hydrogen mixed gas (the ratio of nitrogen to wet hydrogen v/v is 1: 3); raising the temperature to 550 ℃ at the speed of 2 ℃/min, and preserving the heat for 2 h; then raising the temperature to 900 ℃ at the speed of 2 ℃/min, and preserving the temperature for 30 min; and finally, heating to 1580 ℃ at the speed of 1.5 ℃/min, preserving the heat for 100min, and naturally cooling along with the furnace.
Tests show that the co-fired aluminum oxide and tungsten are well combined, and the warping degree of the substrate is less than 0.05 mm.
Further, fig. 2 and fig. 3 respectively show a schematic front physical diagram and a schematic side physical diagram of the co-fired black ceramic substrate in the embodiment, and it can be seen by visual inspection that the appearance quality of the substrate is excellent; fig. 4 shows a fracture SEM morphology of the sintered black ceramic substrate in this embodiment, and it can be seen that the thickness of the co-fired tungsten layer is 8 μm, and the co-fired tungsten layer is well bonded with alumina without obvious defects.
Example 2
The preparation method of the tungsten metallization-multilayer alumina black porcelain substrate in the embodiment comprises the following specific steps:
printing the raw porcelain: 3 pieces of alumina raw porcelain with the same batch and the thickness of 0.25mm are selected, tungsten paste is uniformly printed on the front surface and the back surface of one piece of the raw porcelain, and the other two pieces of the raw porcelain are not printed;
isostatic pressing of the green porcelain: laminating the three printed raw porcelains according to the sequence of figure 1, wherein the laminating process conditions are 60 ℃ and 2000 psi;
raw cutting: cutting the laminated green porcelain into squares with the size of 200 multiplied by 200 mm;
co-firing: putting the green body into a high-temperature sintering furnace, vacuumizing the furnace chamber at room temperature until the vacuum degree is less than 1Pa, and then introducing nitrogen and wet hydrogen mixed gas (the ratio of nitrogen to wet hydrogen v/v is 1: 3); raising the temperature to 550 ℃ at the speed of 2 ℃/min, and preserving the heat for 2 h; then raising the temperature to 900 ℃ at the speed of 2 ℃/min, and preserving the temperature for 30 min; and finally, heating to 1580 ℃ at the speed of 1.3 ℃/min, preserving the heat for 100min, and naturally cooling along with the furnace.
Tests show that the co-fired aluminum oxide and tungsten are well combined, and the warping degree of the substrate is less than 0.05 mm.
Example 3
The preparation method of the tungsten metallization-multilayer alumina black porcelain substrate in the embodiment comprises the following specific steps:
printing the raw porcelain: 3 pieces of alumina raw porcelain with the same batch and the thickness of 0.25mm are selected, tungsten paste is uniformly printed on the front surface and the back surface of one piece of the raw porcelain, and the other two pieces of the raw porcelain are not printed;
isostatic pressing of the green porcelain: laminating the three printed raw porcelains according to the sequence of figure 1, wherein the laminating process conditions are 60 ℃ and 2000 psi;
raw cutting: the laminated green porcelain was cut into 200X 200 mm-sized squares.
Co-firing: putting the green body into a high-temperature sintering furnace, vacuumizing the furnace chamber at room temperature until the vacuum degree is less than 1Pa, and then introducing nitrogen and wet hydrogen mixed gas (the ratio of nitrogen to wet hydrogen v/v is 1: 3); raising the temperature to 550 ℃ at the speed of 2 ℃/min, and preserving the heat for 2 h; then raising the temperature to 900 ℃ at the speed of 2 ℃/min, and preserving the temperature for 30 min; and finally, heating to 1580 ℃ at the speed of 1.1 ℃/min, preserving the heat for 100min, and naturally cooling along with the furnace.
Tests show that the co-fired aluminum oxide and tungsten are well combined, and the warping degree of the substrate is less than 0.05 mm.
Example 4
The preparation method of the tungsten metallization-multilayer alumina black porcelain substrate in the embodiment comprises the following specific steps:
printing the raw porcelain: selecting 4 aluminum oxide raw porcelains with the same batch and the thickness of 0.25mm, uniformly printing tungsten paste on the front surface and the back surface of one of the raw porcelains, and not printing the other two raw porcelains;
isostatic pressing of the green porcelain: laminating the four printed green ceramics according to the sequence of figure 1, wherein the laminating process conditions are 50 ℃ and 3500 psi;
raw cutting: the laminated green porcelain was cut into 200X 200mm square blocks.
Co-firing: putting the green body into a high-temperature sintering furnace, vacuumizing the furnace chamber at room temperature until the vacuum degree is less than 1Pa, introducing mixed gas of nitrogen and wet hydrogen (the v/v of the nitrogen/the wet hydrogen is 1: 1), raising the temperature to 500 ℃ at 1.5 ℃/min, and preserving the temperature for 3 h; then heating to 950 ℃ at the speed of 1.5 ℃/min, and preserving the heat for 60 min; finally, the temperature is raised to 1500 ℃ at the speed of 1 ℃/min, the temperature is kept for 3h, and the furnace is naturally cooled.
Tests show that the co-fired aluminum oxide and tungsten are well combined, and the warping degree of the substrate is less than 0.05 mm.
Example 5
The preparation method of the tungsten metallization-multilayer alumina black porcelain substrate in the embodiment comprises the following specific steps:
printing the raw porcelain: selecting 4 aluminum oxide raw porcelains with the same batch and the thickness of 0.25mm, uniformly printing tungsten paste on the front surface and the back surface of one of the raw porcelains, and not printing the other two raw porcelains;
isostatic pressing of green porcelain: laminating the four printed green porcelains according to the sequence of figure 1, wherein the laminating process conditions are 70 ℃ and 1500 psi;
raw cutting: the laminated green porcelain was cut into 200X 200 mm-sized squares.
Co-firing: putting the green body into a high-temperature sintering furnace, vacuumizing the furnace chamber at room temperature until the vacuum degree is less than 1Pa, introducing mixed gas of nitrogen and wet hydrogen (the ratio of the nitrogen to the wet hydrogen is 1: 1), heating to 600 ℃ at the speed of 3 ℃/min, and preserving the heat for 1 h; raising the temperature to 1000 ℃ at a speed of 3 ℃/min, and preserving the heat for 20 min; finally, the temperature is raised to 1650 ℃ at the speed of 2 ℃/min, the temperature is preserved for 1h, and the furnace is naturally cooled.
Tests show that the co-fired aluminum oxide and tungsten are well combined, and the warping degree of the substrate is less than 0.05 mm.
Comparative example 1
The difference between the comparative example and the example 1 is that only the front surface of the surface layer green porcelain tape is printed with tungsten paste, and the back surface is not printed with tungsten paste, and the preparation of the tungsten metallization-multilayer alumina black porcelain substrate in the comparative example comprises the following specific steps:
printing the raw porcelain: selecting 3 aluminum oxide raw porcelains with the same batch and the thickness of 0.25mm, uniformly printing tungsten paste on the front surface of one raw porcelains, not printing the back surface of one raw porcelains, and not printing the other two raw porcelains;
isostatic pressing of the green porcelain: laminating the three printed green porcelains in sequence, wherein the green porcelains with the printed tungsten paste are positioned on the top layer, and the laminating process conditions are 60 ℃ and 2000 psi;
raw cutting: cutting the laminated green porcelain into squares with the size of 200 multiplied by 200 mm;
co-firing: putting the green body into a high-temperature sintering furnace, vacuumizing the furnace chamber at room temperature until the vacuum degree is less than 1Pa, and then introducing nitrogen and wet hydrogen mixed gas (the ratio of nitrogen to wet hydrogen v/v is 1: 3); raising the temperature to 550 ℃ at the speed of 2 ℃/min, and preserving the heat for 2 h; then raising the temperature to 900 ℃ at the speed of 2 ℃/min, and preserving the temperature for 30 min; and finally, heating to 1580 ℃ at the speed of 1.5 ℃/min, preserving the heat for 100min, and naturally cooling along with the furnace.
After testing, the warpage of the substrate after co-firing is more than 0.1 mm.
Comparative example 2
The difference between the comparative example and the example 1 is that the heating rate of the high-temperature section is different, and the preparation of the tungsten metallization-multilayer alumina black porcelain substrate in the comparative example comprises the following specific steps:
printing the raw porcelain: selecting 3 aluminum oxide raw porcelain pieces with the same batch and the thickness of 0.25mm, uniformly printing tungsten paste on the front surface and the back surface of one of the raw porcelain pieces, and not printing the other two raw porcelain pieces;
isostatic pressing of the green porcelain: laminating the three printed green porcelains according to the sequence shown in figure 1, wherein the laminating process conditions are 60 ℃ and 2000 psi;
raw cutting: cutting the laminated green porcelain into squares with the size of 200 multiplied by 200 mm;
co-firing: putting the green body into a high-temperature sintering furnace, vacuumizing the furnace chamber at room temperature until the vacuity is less than 1Pa, and then introducing mixed gas of nitrogen and wet hydrogen (the ratio of nitrogen to wet hydrogen v/v is 1: 3); raising the temperature to 550 ℃ at the speed of 2 ℃/min, and preserving the heat for 2 h; then raising the temperature to 900 ℃ at the speed of 2 ℃/min, and preserving the temperature for 30 min; and finally, heating to 1580 ℃ at the speed of 5 ℃/min, preserving the heat for 100min, and naturally cooling along with the furnace.
After testing, the warpage of the substrate after co-firing is more than 0.1 mm.
TABLE 1 warping degree test results of black porcelain substrates in examples 1 to 5 and comparative examples 1 to 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Degree of warp | <0.05mm | <0.05mm | <0.05mm | <0.05mm | <0.05mm | >0.1mm | >0.1mm |
In the table the warpage test was measured on flat glass panels by means of a standard feeler gauge.
The test results show that the warping degree of the tungsten metallization-multilayer alumina black porcelain substrate prepared by the preparation method is obviously improved, and the tungsten metallization-multilayer alumina black porcelain substrate has high flatness.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A preparation method of a tungsten metallization-multilayer alumina black porcelain substrate is characterized by comprising the following steps:
providing a laminated body, wherein the laminated body consists of a plurality of layers of alumina green ceramic tapes, and tungsten paste is printed on the front and back surfaces of the green ceramic tape on the top layer of the laminated body;
green cutting the laminated body to obtain a green body;
co-firing the green body at a high temperature, wherein the process of co-firing at the high temperature is specifically that after vacuumizing in reaction equipment, mixed gas of nitrogen and wet hydrogen is introduced, the temperature is raised to 500-fold-600 ℃ at 1-3 ℃/min, and the temperature is kept for 1-3 h; raising the temperature to 900-; finally, the temperature is raised to 1650 ℃ at 1-2 ℃/min, the temperature is kept for 1-3h, and the furnace is naturally cooled.
2. The method according to claim 1, wherein the preparation of the laminate specifically comprises:
selecting a plurality of aluminum oxide green ceramic belts, uniformly printing tungsten paste on the front side and the back side of one aluminum oxide green ceramic belt, and not performing printing treatment on the other green ceramic belts;
and sequentially laminating the green ceramic tapes to obtain a laminated body, wherein the green ceramic tapes with the front and back surfaces printed with the tungsten paste are positioned on the uppermost layer.
3. The method of claim 2, wherein the lamination process conditions are 50-70 ℃ and 1500-3500 psi.
4. The method of claim 1, wherein the degree of vacuum applied is less than 1 Pa.
5. The method of claim 1, wherein the volume ratio of nitrogen to wet hydrogen is between 1:1 and 1: 4.
6. The method of any one of claims 1 to 5, wherein the alumina green tape has an alumina content of 90 to 95 wt%.
7. A tungsten-metallized multi-layered alumina black ceramic substrate produced by the production method according to any one of claims 1 to 6.
8. The tungsten-metalized-multi-layered alumina black ceramic substrate of claim 7, wherein the tungsten-metalized-multi-layered alumina black ceramic substrate has a warp of < 0.05 mm.
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