CN111499394A - Low-temperature co-fired ceramic raw material belt and preparation method thereof - Google Patents
Low-temperature co-fired ceramic raw material belt and preparation method thereof Download PDFInfo
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Abstract
The invention provides a low-temperature co-fired ceramic green tape and a preparation method thereof, wherein the preparation method comprises the steps of mixing first ceramic powder and BS glass powder to obtain ceramic-glass mixed powder, preparing ceramic-glass mixed slurry based on the ceramic-glass mixed powder, preparing ceramic slurry based on second ceramic powder, forming a lower material layer on the surface of a base film based on the ceramic-glass mixed slurry, forming an intermediate material layer on the surface of the lower material layer based on the ceramic slurry, and forming an upper material layer on the surface of the intermediate material layer based on the ceramic-glass mixed slurry to prepare the green tape.
Description
Technical Field
The invention relates to the field of low-temperature co-fired ceramics, in particular to a low-temperature co-fired ceramic raw material belt and a preparation method thereof.
Background
A low-temp. co-fired ceramic (L ow-temperature fired ceramic, L TCC) technology is that low-temp. sintered ceramic powder is made into raw material band with precise and compact thickness as the material of circuit substrate, the required circuit pattern is made on the raw material band by using laser punching, micropore grouting, printing with precise conductor paste and other processes, and multiple passive elements are buried in it, then they are laminated together and sintered to make passive integrated assembly of three-dimensional circuit network or three-dimensional circuit substrate with built-in passive elements, and passive/active integrated functional module is made by sticking IC and active devices on its surface.
The major difficulty of the low-temperature co-fired ceramic substrate manufacturing technology is that the shrinkage rate of X, Y axial dimension of the conventional L TCC raw material tape material after sintering generally exceeds 10%, and the unevenness of the dimensional shrinkage generally reaches at least +/-0.3% - +/-0.4%, which affects the co-firing matching of the metal slurry and the ceramic substrate, thereby causing that circuit patterns (interconnection through holes, conductive strips and the like) of each substrate in the same batch and each substrate in different batches of the same product are difficult to accurately control, and making the manufacturing of ultra-high density mixed type ceramic multi-chip components, thick-thin film multi-chip components and precise microwave transmission lines extremely difficult.
Disclosure of Invention
In view of the above drawbacks of the prior art, an object of the present invention is to provide a low-temperature co-fired ceramic green tape and a preparation method thereof, which are used to solve the problem that the sintering shrinkage rate of the conventional L TCC green tape material in the X, Y axial direction is large after sintering.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing a low-temperature co-fired ceramic green tape, the method comprising:
mixing the first ceramic powder and BS glass powder to obtain ceramic-glass mixed powder, and preparing ceramic-glass mixed slurry based on the ceramic-glass mixed powder;
preparing ceramic slurry based on the second ceramic powder;
forming a lower material layer on the surface of a base film based on the ceramic glass mixed slurry, forming an intermediate material layer on the surface of the lower material layer based on the ceramic slurry, and forming an upper material layer on the surface of the intermediate material layer based on the ceramic glass mixed slurry to prepare the raw material tape.
Optionally, the preparation method further comprises: sintering the raw material tape; wherein the sintering temperature is 850-900 ℃.
Optionally, the preparation method of the first ceramic powder includes: grinding first ceramic particles into first ceramic powder by a sand mill; the first ceramic powder is one or two of alumina powder, silicon oxide powder and zirconia powder, and the granularity D50 of the first ceramic powder is 2.0-2.2 mu m;
the preparation method of the BS glass powder comprises the following steps:
the BS glass powder comprises the following components in percentage by mass: 67% -69% of B2O327% -30% of SiO21% -2% of L iO21% -2% of Na2O, 1-2% TiO2；
Weighing the components according to the proportion, mixing, loading into a crucible, melting into glass liquid at 1500-1550 ℃, quenching into glass blocks, and grinding into the BS glass powder by a sand mill; wherein the granularity D50 of the BS glass powder is 2.0-2.2 μm.
Optionally, the preparation method of the second ceramic powder includes: grinding second ceramic particles into second ceramic powder by a sand mill; the second ceramic powder is silicon oxide powder, and the granularity D50 of the second ceramic powder is 2.0-2.2 μm.
Optionally, the method for preparing the ceramic glass mixed slurry based on the ceramic glass mixed powder comprises the following steps: mixing the ceramic glass mixed powder, a first solvent and a first dispersing agent, adding a first resin and a first plasticizer, and mixing to prepare ceramic glass mixed slurry;
the method for preparing the ceramic slurry based on the second ceramic powder comprises the following steps: and mixing the second ceramic powder, the second solvent and the second dispersing agent, adding a second resin and a second plasticizer, and mixing to prepare the ceramic slurry.
Optionally, the mass ratio of the first ceramic powder to the BS glass powder in the ceramic-glass mixed powder is (43:57) - (52: 48).
The invention also provides a low-temperature co-fired ceramic raw material belt which is formed on the surface of the base film, and the raw material belt sequentially comprises the following components from bottom to top: a lower material layer, an intermediate material layer and an upper material layer; the lower material layer is made of ceramic glass mixed slurry prepared from first ceramic powder and BS glass powder, the middle material layer is made of ceramic slurry prepared from ceramic powder, and the upper material layer is made of ceramic glass mixed slurry prepared from first ceramic powder and BS glass powder.
Optionally, the mass ratio of the first ceramic powder to the BS glass powder in the ceramic-glass mixed slurry is (43:57) - (52: 48).
Optionally, the first ceramic powder is one or two of alumina powder, silica powder and zirconia powder, and the particle size D50 of the first ceramic powder is 2.0 μm to 2.2 μm; the BS glass powder comprises the following components in percentage by mass: 67% -69% of B2O327% -30% of SiO21% -2% of L iO21% -2% of Na2O, 1-2% TiO2(ii) a Wherein the granularity D50 of the BS glass powder is 2.0-2.2 μm.
Optionally, the second ceramic powder is silicon oxide powder, and the particle size D50 of the second ceramic powder is 2.0 μm to 2.2 μm.
Optionally, after sintering at 850-900 ℃, the lower material layer takes the first ceramic as a lower skeleton structure, and the lower skeleton structure is filled with molten BS glass; the intermediate material layer takes second ceramic as an intermediate layer skeleton structure, and meanwhile molten BS glass is filled in the intermediate layer skeleton structure; the upper material layer takes first ceramic as an upper-layer skeleton structure, and meanwhile molten BS glass is filled in the upper-layer skeleton structure.
Optionally, the raw material tape has a sintering shrinkage of less than 0.4% in the X, Y axis direction, a sintering shrinkage of 35% to 40% in the Z axis direction, a dielectric constant of 4.5 to 5.7, and a loss tangent of less than 0.004 at room temperature and a test frequency of 9GHz to 11 GHz.
As mentioned above, the invention provides a low-temperature co-fired ceramic raw material tape and a preparation method thereof, and provides a raw material tape which is sintered compactly at 850-900 ℃ under an unconstrained condition, wherein the sintering shrinkage rate of the raw material tape in the X, Y axis direction is less than 0.4%, the sintering shrinkage rate in the Z axis direction is 35-40%, the dielectric constant is 4.5-5.7, and the loss tangent is less than 0.004; the sintering shrinkage rate of the raw material tape in the direction of the X, Y axis is very small and is approximately zero, so that the raw material tape is better in matching with metal slurry, the flatness of a substrate prepared by the raw material tape is less than 3 mu m/mm, and the size stability rate of a finished product exceeds 95%.
Drawings
Fig. 1 is a flowchart illustrating a method for manufacturing a raw material tape according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of the raw material tape according to the second embodiment of the present invention.
Description of the element reference numerals
100 base film
200 layers of material
300 intermediate material layer
400 upper material layer
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1-2. It should be noted that the drawings provided in the present embodiment are only schematic and illustrate the basic idea of the present invention, and although the drawings only show the components related to the present invention and are not drawn according to the number, shape and size of the components in actual implementation, the form, quantity and proportion of the components in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
Example one
As shown in fig. 1, this embodiment provides a method for preparing a low-temperature co-fired ceramic green tape, where the method includes:
step 1) mixing the first ceramic powder and the BS glass powder to obtain ceramic-glass mixed powder, and preparing ceramic-glass mixed slurry based on the ceramic-glass mixed powder.
As an example, the method for preparing the first ceramic powder includes: grinding first ceramic particles into first ceramic powder by a sand mill; the first ceramic powder is one or two of alumina powder, silicon oxide powder and zirconia powder, and the granularity D50 of the first ceramic powder is 2.0-2.2 μm. In this example, the first ceramic particles are water-sanded using a sand mill to sand-grind the first ceramic particles into the first ceramic powder.
As an example, the method for preparing the BS glass powder includes:
the BS glass powder comprises the following components in percentage by mass: 67% -69% of B2O327% -30% of SiO21% -2% of L iO21% -2% of Na2O, 1-2% TiO2；
Weighing the components according to the proportion, mixing, loading into a crucible, melting into glass liquid at 1500-1550 ℃, quenching into glass blocks, and grinding into the BS glass powder by a sand mill; wherein the granularity D50 of the BS glass powder is 2.0-2.2 μm.
Specifically, before the raw materials for forming the BS glass powder are charged into the crucible, the method for producing the BS glass powder further includes: and drying and sieving the mixed raw materials.
Specifically, after each mixed raw material for forming the BS glass powder is filled into a crucible, the mixed raw material is melted for 1h-3h at 1500 ℃ -1550 ℃ so as to melt the mixed raw material into glass liquid; quenching the glass liquid by adopting water to quench the glass liquid into a glass block; and finally, sanding the glass blocks by using alcohol through a sand mill to sand the glass blocks into the BS glass powder. Alternatively, in this example, the melting time is 2 h. It should be noted that, when quenching the molten glass with water, the temperature of the water may be selected according to actual needs, and this example is not limited thereto.
As an example, the method of preparing the ceramic glass mixed slurry based on the ceramic glass mixed powder includes: and mixing the ceramic glass mixed powder, a first solvent and a first dispersing agent, adding a first resin and a first plasticizer, and mixing to prepare the ceramic glass mixed slurry. Optionally, in this example, the ceramic-glass mixed slurry is prepared by using a rapid ball milling and mixing device; the method specifically comprises the following steps: adding the ceramic glass mixed powder, a first solvent and a first dispersing agent into a rapid ball-milling mixing device for rapid ball-milling mixing, then adding a first resin and a first plasticizer into the rapid ball-milling mixing device for rapid ball-milling mixing again, thereby preparing the ceramic glass mixed slurry.
Specifically, the mass ratio of the first ceramic powder to the BS glass powder in the ceramic-glass mixed powder is (43:57) - (52: 48). In the example, the dielectric constant of the sintered raw material tape and the sintering shrinkage rate of the sintered raw material tape in the Z-axis direction are controlled by controlling the mass ratio of the first ceramic powder to the BS glass powder in the ceramic-glass mixed powder.
Specifically, the first solvent comprises ethanol or acetone, the first dispersing agent comprises one or two of castor oil, fish oil and polyvinyl alcohol, the first resin comprises polyvinyl butyral, and the first plasticizer comprises dibutyl phthalate.
Specifically, the first resin in the ceramic-glass mixed slurry accounts for 10 wt% -11 wt% of the total weight of the ceramic-glass mixed slurry, so that the ceramic-glass mixed powder can be effectively coated by the first resin, and the upper material layer and the lower material layer formed based on the ceramic-glass mixed slurry are not prone to cracking in the drying process when the green tape is formed subsequently.
Specifically, the organic material in the ceramic-glass mixed slurry accounts for 43 wt% -45 wt% of the total weight of the ceramic-glass mixed slurry. It should be noted that, the organic material herein means the first solvent, the first dispersant, the first resin and the first plasticizer except for the ceramic glass mixed powder in the ceramic glass mixed slurry, that is, the sum of the first solvent, the first dispersant, the first resin and the first plasticizer accounts for 43 wt% to 45 wt% of the total weight of the ceramic glass mixed slurry.
And 2) preparing ceramic slurry based on the second ceramic powder. It is to be noted that the order of execution of step 1) and step 2) may be reversed, i.e. step 2) is performed before step 1); of course, step 1) and step 2) can also be performed simultaneously, which does not affect the preparation method described in this example.
As an example, the method for preparing the second ceramic powder includes: grinding second ceramic particles into second ceramic powder by a sand mill; the second ceramic powder is silicon oxide powder, and the granularity D50 of the second ceramic powder is 2.0-2.2 μm. In this example, the second ceramic particles are water-sanded with a sander to sand-grind the second ceramic particles into the second ceramic powder.
As an example, the method of preparing the ceramic slurry based on the second ceramic powder includes: and mixing the second ceramic powder, the second solvent and the second dispersing agent, adding a second resin and a second plasticizer, and mixing to prepare the ceramic slurry. Optionally, in this example, the ceramic slurry is prepared using a rapid ball milling mixing apparatus; the method specifically comprises the following steps: adding the second ceramic powder, the second solvent and the second dispersing agent into a rapid ball-milling mixing device for rapid ball-milling mixing, then adding the second resin and the second plasticizer into the rapid ball-milling mixing device for rapid ball-milling mixing again, thereby preparing the ceramic slurry.
Specifically, the second solvent comprises ethanol or acetone, the second dispersing agent comprises one or two of castor oil, fish oil and polyvinyl alcohol, the second resin comprises polyvinyl butyral, and the second plasticizer comprises dibutyl phthalate. Optionally, in this example, the first solvent is the same as the second solvent, the first dispersant is the same as the second dispersant, the first resin is the same as the second resin, and the first plasticizer is the same as the second plasticizer, so that when the green tape is subsequently formed, the layers are tightly bonded to each other, and delamination is avoided.
Specifically, the second resin in the ceramic slurry accounts for 10 wt% -11 wt% of the total weight of the ceramic slurry, so that the second ceramic powder can be effectively coated by the second resin, and the intermediate material layer formed based on the ceramic slurry is not easy to crack in the drying process when the raw material tape is formed subsequently.
Specifically, the organic material in the ceramic slurry accounts for 43 wt% -45 wt% of the total weight of the ceramic slurry. It should be noted that, the organic material herein refers to the second solvent, the second dispersant, the second resin and the second plasticizer except for the second ceramic powder in the ceramic slurry, that is, the sum of the second solvent, the second dispersant, the second resin and the second plasticizer accounts for 43 wt% to 45 wt% of the total weight of the ceramic slurry.
And 3) forming a lower material layer on the surface of the base film based on the ceramic glass mixed slurry, forming an intermediate material layer on the surface of the lower material layer based on the ceramic slurry, and forming an upper material layer on the surface of the intermediate material layer based on the ceramic glass mixed slurry to prepare the raw material tape.
As an example, the lower material layer, the intermediate material layer, and the upper material layer are sequentially formed using a tape casting process, or the lower material layer, the intermediate material layer, and the upper material layer are sequentially formed using a screen printing process. Optionally, in this example, the lower material layer, the intermediate material layer, and the upper material layer are sequentially formed by a tape casting process.
Specifically, the method for preparing the raw material tape by adopting the tape casting process comprises the following steps: providing two casting machines, placing the ceramic glass mixed slurry into a first casting machine, and placing the ceramic slurry into a second casting machine; providing a base film, casting a layer of ceramic glass mixed slurry on the surface of the base film through the first casting machine, and drying to obtain a lower material layer; casting a layer of the ceramic slurry on the surface of the lower material layer through the second casting machine, and drying to obtain the intermediate material layer; and casting a layer of the ceramic-glass mixed slurry on the surface of the intermediate material layer through the first casting machine, and drying to obtain the upper material layer. When the lower material layer, the intermediate material layer and the upper material layer are formed by adopting a tape casting process, the thicknesses of the formed lower material layer, intermediate material layer and upper material layer can be respectively regulated and controlled by adjusting the height of a tape casting knife of the tape casting machine. Optionally, in this example, the thickness of the lower material layer is 40 μm, the thickness of the middle material layer is 30 μm, and the thickness of the upper material layer is 40 μm.
Specifically, the method for preparing the raw material tape by adopting the tape casting process further comprises the following steps: and rolling the prepared raw material tape.
Wherein the base film comprises a PET film; of course, other materials that can be used as the base film are also applicable to the present example, and the material of the base film is not limited in the present example.
Step 4), the preparation method further comprises the following steps: sintering the raw material tape; wherein the sintering temperature is 850-900 ℃.
In this example, when the raw material tape is sintered, when the temperature reaches about 450 ℃, organic materials in the lower material layer, the intermediate material layer and the upper material layer (the organic materials refer to materials except for powder in each layer) are all volatilized, and the lower material layer, the intermediate material layer and the upper material layer all form a porous structure; when the temperature rises to 750-800 ℃, the BS glass powder in the lower material layer and the BS glass powder in the upper material layer are gradually melted into molten glass and partially permeate into the porous structure of the intermediate material layer, the BS glass powder in the lower material layer and the BS glass powder in the upper material layer are melted and shrunk to press the intermediate material layer, so that the intermediate material layer is shrunk in the Z-axis direction, and meanwhile, the pores in the porous structure of the intermediate material layer are reduced, but the shrinkage is hardly performed because the ceramic of the intermediate material layer is used as a support in the X, Y-axis direction; when the temperature continues to rise and reaches the sintering temperature (850 ℃ -900 ℃), sintering densification is realized because the molten BS glass is tightly combined with the three-layer porous structure. It should be noted that, since the melting temperature of the silica ceramic is about 1723 ℃, the ceramic porous structure of the intermediate material layer does not change during the whole sintering process. Specifically, after sintering at 850-900 ℃, the lower material layer takes first ceramic as a lower skeleton structure, and meanwhile, molten BS glass is filled in the lower skeleton structure; the intermediate material layer takes second ceramic as an intermediate layer skeleton structure, and meanwhile molten BS glass is filled in the intermediate layer skeleton structure; the upper material layer takes first ceramic as an upper-layer skeleton structure, and meanwhile molten BS glass is filled in the upper-layer skeleton structure. At the moment, the sintered raw material tape is tested, and the sintering shrinkage rate of the raw material tape in the X, Y axis direction is less than 0.4 percent, the sintering shrinkage rate of the raw material tape in the Z axis direction is 35-40 percent, the dielectric constant is 4.5-5.7, and the loss tangent is less than 0.004 at room temperature and the test frequency of 9GHz-11 GHz.
The properties of the green tape prepared by the preparation method of this embodiment are described below by controlling the type of the first ceramic powder in the upper and lower material layers and the mass ratio of the first ceramic powder to the BS glass powder.
Firstly, respectively preparing alumina ceramic powder, silica ceramic powder, zirconia ceramic powder and BS glass powder according to the preparation methods of the powders;
then, the types of the first ceramic powder and the mass ratio of the first ceramic powder to the BS glass powder shown in the table 1 are configured, and ceramic glass mixed slurry corresponding to different sample numbers is prepared according to the slurry preparation method;
TABLE 1
Then, preparing ceramic slurry of silicon oxide according to the slurry preparation method;
then, based on the prepared No. 1-11 ceramic glass mixed slurry and the ceramic slurry of silicon oxide, preparing by adopting a tape casting process according to the preparation method of the raw material tape to obtain 11 different raw material tapes;
then, 8 sheets of each raw material tape are respectively laminated together to prepare eight layers of raw blanks, 11 eight layers of raw blanks are prepared in total, then the 11 eight layers of raw blanks are sintered at 850-900 ℃ according to the sintering method, the sintered raw material tapes are tested at room temperature and the testing frequency of 9GHz-11GHz by a strip line method, and the tested sintering shrinkage rate in the X, Y axis direction, the sintering shrinkage rate in the Z axis direction, the dielectric constant and the loss tangent (dielectric loss) data are shown in table 2;
finally, 2 sheets of each raw material tape are respectively laminated together to prepare two layers of green blanks, 11 layers of green blanks are prepared, silver layers with the thickness of 10 microns are printed on the surfaces of the green blanks, 11 structures are sintered at 850-900 ℃, and the flatness data measured by GB/T4677-2002 are shown in Table 2.
TABLE 2
It can be seen that the green tape prepared by the preparation method of the present example has a sintering shrinkage rate of less than 0.4% in the X, Y axis direction, a sintering shrinkage rate of 35% to 40% in the Z axis direction, a dielectric constant of 4.5 to 5.7, a loss tangent (dielectric loss) of less than 0.004, and a flatness of less than 3 μm/mm at room temperature and a test frequency of 9GHz to 11GHz, thereby achieving optimization of the properties of the green tape.
Example two
As shown in fig. 2, the embodiment provides a low-temperature co-fired ceramic raw material tape formed on a surface of a base film 100, the raw material tape sequentially includes, from bottom to top: a lower material layer 200, an intermediate material layer 300, and an upper material layer 400; the lower material layer 200 is made of a ceramic glass mixed slurry made of a first ceramic powder and a BS glass powder, the intermediate material layer 300 is made of a ceramic slurry made of a ceramic powder, and the upper material layer 400 is made of a ceramic glass mixed slurry made of a first ceramic powder and a BS glass powder.
In this example, the base film 100 includes a PET film; of course, other materials that can be used as the base film are also applicable to the present example, and the material of the base film is not limited in the present example.
As an example, a ceramic glass mixing paste prepared based on a first ceramic powder and a BS glass powder includes: the adhesive comprises first ceramic powder, BS glass powder, a first solvent, a first dispersing agent, a first resin and a first plasticizer.
Specifically, the first ceramic powder is one or two of alumina powder, silica powder and zirconia powder, and the granularity D50 of the first ceramic powder is 2.0-2.2 μm.
Specifically, the BS glass powder comprises the following components in percentage by mass: 67% -69% of B2O327% -30% of SiO21% -2% of L iO21% -2% of Na2O, 1-2% TiO2(ii) a Wherein the granularity D50 of the BS glass powder is 2.0-2.2 μm.
Specifically, the first solvent comprises ethanol or acetone, the first dispersing agent comprises one or two of castor oil, fish oil and polyvinyl alcohol, the first resin comprises polyvinyl butyral, and the first plasticizer comprises dibutyl phthalate.
Specifically, the mass ratio of the first ceramic powder to the BS glass powder in the ceramic glass mixed slurry is (43:57) - (52: 48). In the example, the dielectric constant of the sintered raw material tape and the sintering shrinkage rate of the sintered raw material tape in the Z-axis direction are controlled by controlling the mass ratio of the CBS microcrystalline glass powder to the BBZ glass powder in the glass mixed powder.
Specifically, the first resin in the ceramic-glass mixed slurry accounts for 10 wt% -11 wt% of the total weight of the ceramic-glass mixed slurry, so that the ceramic-glass mixed powder can be effectively coated by the first resin, and the upper material layer and the lower material layer formed based on the ceramic-glass mixed slurry are not prone to cracking in the drying process when the green tape is formed subsequently.
Specifically, the organic material in the ceramic-glass mixed slurry accounts for 43 wt% -45 wt% of the total weight of the ceramic-glass mixed slurry. It should be noted that, the organic material herein means the first solvent, the first dispersant, the first resin and the first plasticizer except for the ceramic glass mixed powder in the ceramic glass mixed slurry, that is, the sum of the first solvent, the first dispersant, the first resin and the first plasticizer accounts for 43 wt% to 45 wt% of the total weight of the ceramic glass mixed slurry.
As an example, a ceramic slurry prepared based on a ceramic powder includes: the ceramic powder comprises a second ceramic powder body, a second solvent, a second dispersing agent, a second resin and a second plasticizer.
Specifically, the second ceramic powder is silicon oxide powder, and the particle size D50 of the second ceramic powder is 2.0-2.2 μm.
Specifically, the second solvent comprises ethanol or acetone, the second dispersing agent comprises one or two of castor oil, fish oil and polyvinyl alcohol, the second resin comprises polyvinyl butyral, and the second plasticizer comprises dibutyl phthalate. Optionally, in this example, the second solvent is the same as the first solvent, the second dispersant is the same as the first dispersant, the second resin is the same as the first resin, and the second plasticizer is the same as the first plasticizer, so that when the green tape is subsequently formed, the layers are tightly bonded to each other, and delamination is avoided.
Specifically, the second resin in the ceramic slurry accounts for 10 wt% -11 wt% of the total weight of the ceramic slurry, so that the second ceramic powder can be effectively coated by the second resin, and the intermediate material layer formed based on the ceramic slurry is not easy to crack in the drying process when the raw material tape is formed subsequently.
Specifically, the organic material in the ceramic slurry accounts for 43 wt% -45 wt% of the total weight of the ceramic slurry. It should be noted that, the organic material herein refers to the second solvent, the second dispersant, the second resin and the second plasticizer except for the second ceramic powder in the ceramic slurry, that is, the sum of the second solvent, the second dispersant, the second resin and the second plasticizer accounts for 43 wt% to 45 wt% of the total weight of the ceramic slurry.
As an example, the thickness of the lower material layer is 40 μm, the thickness of the intermediate material layer is 30 μm, and the thickness of the upper material layer is 40 μm.
As an example, after sintering at 850-900 ℃, the lower material layer takes the first ceramic as a lower skeleton structure, and the lower skeleton structure is filled with molten BS glass; the intermediate material layer takes second ceramic as an intermediate layer skeleton structure, and meanwhile molten BS glass is filled in the intermediate layer skeleton structure; the upper material layer takes first ceramic as an upper-layer skeleton structure, and meanwhile molten BS glass is filled in the upper-layer skeleton structure. Specifically, the sintering shrinkage of the sintered raw material tape in the X, Y axis direction is less than 0.4%, the sintering shrinkage of the sintered raw material tape in the Z axis direction is 35-40%, the dielectric constant is 4.5-5.7, and the loss tangent is less than 0.004 at room temperature and at a test frequency of 9GHz-11 GHz.
In conclusion, the invention provides a low-temperature co-fired ceramic raw material tape and a preparation method thereof, and provides a raw material tape which is sintered compactly at 850-900 ℃ under an unconstrained condition, wherein the sintering shrinkage rate of the raw material tape in the X, Y axis direction is less than 0.4%, the sintering shrinkage rate in the Z axis direction is 35-40%, the dielectric constant is 4.5-5.7, and the loss tangent is less than 0.004; the sintering shrinkage rate of the raw material tape in the direction of the X, Y axis is very small and is approximately zero, so that the raw material tape is better in matching with metal slurry, the flatness of a substrate prepared by the raw material tape is less than 3 mu m/mm, and the size stability rate of a finished product exceeds 95%. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (12)
1. A preparation method of a low-temperature co-fired ceramic raw material belt is characterized by comprising the following steps:
mixing the first ceramic powder and BS glass powder to obtain ceramic-glass mixed powder, and preparing ceramic-glass mixed slurry based on the ceramic-glass mixed powder;
preparing ceramic slurry based on the second ceramic powder;
forming a lower material layer on the surface of a base film based on the ceramic glass mixed slurry, forming an intermediate material layer on the surface of the lower material layer based on the ceramic slurry, and forming an upper material layer on the surface of the intermediate material layer based on the ceramic glass mixed slurry to prepare the raw material tape.
2. The method for preparing the low-temperature co-fired ceramic green tape according to claim 1, further comprising the following steps: sintering the raw material tape; wherein the sintering temperature is 850-900 ℃.
3. The method for preparing the low-temperature co-fired ceramic green tape according to claim 1, wherein the method for preparing the first ceramic powder comprises the following steps: grinding first ceramic particles into first ceramic powder by a sand mill; the first ceramic powder is one or two of alumina powder, silicon oxide powder and zirconia powder, and the granularity D50 of the first ceramic powder is 2.0-2.2 mu m;
the preparation method of the BS glass powder comprises the following steps:
the BS glass powder comprises the following components in percentage by mass: 67% -69% of B2O327% -30% of SiO21% -2% of L iO21% -2% of Na2O, 1-2% TiO2；
Weighing the components according to the proportion, mixing, loading into a crucible, melting into glass liquid at 1500-1550 ℃, quenching into glass blocks, and grinding into the BS glass powder by a sand mill; wherein the granularity D50 of the BS glass powder is 2.0-2.2 μm.
4. The method for preparing the low-temperature co-fired ceramic green tape according to claim 1, wherein the method for preparing the second ceramic powder comprises the following steps: grinding second ceramic particles into second ceramic powder by a sand mill; the second ceramic powder is silicon oxide powder, and the granularity D50 of the second ceramic powder is 2.0-2.2 μm.
5. The method for preparing the low-temperature co-fired ceramic green tape according to claim 1, wherein the method for preparing the ceramic glass mixed slurry based on the ceramic glass mixed powder comprises the following steps: mixing the ceramic glass mixed powder, a first solvent and a first dispersing agent, adding a first resin and a first plasticizer, and mixing to prepare ceramic glass mixed slurry;
the method for preparing the ceramic slurry based on the second ceramic powder comprises the following steps: and mixing the second ceramic powder, the second solvent and the second dispersing agent, adding a second resin and a second plasticizer, and mixing to prepare the ceramic slurry.
6. The method for preparing the low-temperature co-fired ceramic green tape according to claim 1 or 5, wherein the mass ratio of the first ceramic powder to the BS glass powder in the ceramic glass mixed powder is (43:57) - (52: 48).
7. The utility model provides a low temperature burns pottery thread seal area altogether, is formed at the base film surface, its characterized in that, the thread seal area by supreme down including in proper order: a lower material layer, an intermediate material layer and an upper material layer; the lower material layer is made of ceramic glass mixed slurry prepared from first ceramic powder and BS glass powder, the middle material layer is made of ceramic slurry prepared from ceramic powder, and the upper material layer is made of ceramic glass mixed slurry prepared from first ceramic powder and BS glass powder.
8. The low-temperature co-fired ceramic green tape according to claim 7, wherein the mass ratio of the first ceramic powder to the BS glass powder in the ceramic glass mixed slurry is (43:57) - (52: 48).
9. The low-temperature co-fired ceramic green tape according to claim 7, wherein the first ceramic powder is one or two of alumina powder, silica powder and zirconia powder, and the particle size D50 of the first ceramic powder is 2.0 μm to 2.2 μm; the BS glass powder comprises the following components in percentage by mass: 67% -69% of B2O327% -30% of SiO21% -2% of L iO21% -2% of Na2O, 1-2% TiO2(ii) a Wherein the granularity D50 of the BS glass powder is 2.0-2.2 μm.
10. The low-temperature co-fired ceramic green tape according to claim 7, wherein the second ceramic powder is silicon oxide powder, and the particle size D50 of the second ceramic powder is 2.0 μm-2.2 μm.
11. The low-temperature co-fired ceramic green tape according to any one of claims 7 to 10, wherein after sintering at 850 ℃ -900 ℃, the lower material layer takes the first ceramic as a lower skeleton structure, and the lower skeleton structure is filled with molten BS glass; the intermediate material layer takes second ceramic as an intermediate layer skeleton structure, and meanwhile molten BS glass is filled in the intermediate layer skeleton structure; the upper material layer takes first ceramic as an upper-layer skeleton structure, and meanwhile molten BS glass is filled in the upper-layer skeleton structure.
12. The low-temperature co-fired ceramic green tape according to claim 11, wherein the green tape has a sintering shrinkage of less than 0.4% in the X, Y axis direction, a sintering shrinkage of 35% to 40% in the Z axis direction, a dielectric constant of 4.5 to 5.7, and a loss tangent of less than 0.004 at room temperature and a test frequency of 9GHz to 11 GHz.
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