CN113045305B - LTCC raw material belt material, substrate and preparation method - Google Patents
LTCC raw material belt material, substrate and preparation method Download PDFInfo
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Abstract
The invention provides an LTCC raw material belt material, a substrate and a preparation method, wherein Li-based ceramics with relatively low sintering temperature are adopted in inorganic material components, so that the dielectric constant of the mixture can be effectively adjusted in the sintering process, and the LTCC raw material belt material can play a role in combustion assistance; in the organic material components, the solvent is selected from alcohol-ketone mixed solvent which has lower boiling point, is volatile and has better solubility with the binder, so that the tape casting effect is better, and the LTCC raw material belt material with smooth surface and uniform thickness is formed; the invention can prepare the material with dielectric constant of 40-80 and dielectric loss of 1.0 multiplied by 10 ‑3 ～2×10 ‑3 The LTCC green tape material and the LTCC substrate with the medium and high dielectric constant have good co-firing performance matched with the low-melting-point metal slurry.
Description
Technical Field
The invention belongs to the field of electronic ceramic materials and manufacturing thereof, and particularly relates to an LTCC raw material belt material, a substrate and a preparation method thereof.
Background
LTCC (Low Temperature sintered Co-fired Ceramics) material is a Low Temperature Co-fired ceramic material, which is a novel material technology developed by Houss corporation in 1982, Low Temperature sintered ceramic powder is made into a raw material belt with precise and compact thickness, a required circuit pattern is made on the raw material belt by using the processes of laser punching, micropore grouting, printing of precise conductor paste and the like, a plurality of passive components (such as Low capacitance value capacitors, resistors, filters, impedance converters, couplers and the like) are embedded into a multilayer ceramic substrate and then laminated together, the inner electrode and the outer electrode can be respectively made of metals such as silver, copper, gold and the like and sintered at 800-900 ℃ to make a high density circuit without three-dimensional space interference, and also can be made into a three-dimensional circuit substrate with built-in passive elements, ICs and active devices can be pasted on the surface to make a passive/active integrated functional module, the miniaturization and high density of the circuit can be further realized, is particularly suitable for high-frequency communication components.
In recent years, no matter general electronic complete machines, communication equipment or electronic products of civil consumption type are rapidly developed towards miniaturization, light weight, multiple functions and high reliability, and the development of LTCC technology in electronic components such as patch filters, resonators, couplers, LED display modules, Bluetooth modules, inductors, capacitors and the like is promoted. In the resonant dielectric, the wavelength λ of the microwave is inversely proportional to the square root of the dielectric constant ∈ r, and the size of the microwave device is generally an integral multiple of the wavelength, and therefore, to reduce the size of the microwave device, a material having a higher dielectric constant must be used.
CaTiO 3 The dielectric constant of the ceramic is about 164 and the dielectric loss is 5 x 10 -4 About, the ceramic is a microwave dielectric ceramic with better performance, but the sintering temperature is about 1350 ℃, and the ceramic cannot be directly co-sintered with low-melting-point metals such as Ag, Au and the like, so that the ceramic does not meet the requirements of practical application.
Therefore, it is necessary to provide a LTCC green tape material, a substrate and a preparation method thereof.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides a green LTCC tape material, a substrate and a method for manufacturing the same, which are used to solve the problem that the green LTCC tape material with medium and high dielectric constant is difficult to co-fire with low melting point metal in the prior art.
To achieve the above and other related objects, the present invention provides a raw LTCC tape material, comprising:
52 to 55 percent of inorganic material component and 45 to 48 percent of inorganic material component% of organic material components, wherein the inorganic material comprises, by mass percent, 60% -85% of main materials, 10% -35% of auxiliary materials and 3% -25% of sintering aids, wherein the main materials comprise CaTiO 3 Ceramics, the sub-materials comprising Li 2 MgTi 3 O 8 Ceramics, Li 2 ZnTi 3 O 8 Ceramics and Li 2 MgSiO 4 At least one of ceramics, the sintering aid comprises BaO-B 2 O 3 -ZnO-SiO 2 Glass and ZnO-B 2 O 3 -SiO 2 At least one of glass.
Optionally, with said BaO-B 2 O 3 -ZnO-SiO 2 The mass percent of the glass is BaO-B 2 O 3 -ZnO-SiO 2 The glass comprises 28 to 33 percent of BaO and 30 to 34 percent of B 2 O 3 18 to 22 percent of ZnO and 17 to 22 percent of SiO 2 (ii) a With said ZnO-B 2 O 3 -SiO 2 The ZnO-B is calculated by the mass percent of the glass 2 O 3 -SiO 2 The glass comprises 47 to 54 percent of ZnO and 37 to 41 percent of B 2 O 3 8% -12% of SiO 2 And 1% -3% of Na 2 O。
Optionally, the dielectric constant of the green LTCC tape material is 40-80, and the dielectric loss of the green LTCC tape material is 1.0 x 10 -3 ～2×10 -3 。
The invention also provides a preparation method of the LTCC raw material belt material, which comprises the following steps:
preparation of CaTiO 3 A ceramic to provide a main material of inorganic material components;
preparation of Li 2 MgTi 3 O 8 Ceramics, Li 2 ZnTi 3 O 8 Ceramics and Li 2 MgSiO 4 At least one of a ceramic to provide a sub-charge of the inorganic material component;
preparation of BaO-B 2 O 3 -ZnO-SiO 2 Glass and ZnO-B 2 O 3 -SiO 2 At least one of glass to provide firing of the inorganic material componentA coalescing agent;
taking 60% -85% of the main material, 10% -35% of the auxiliary material and 3% -25% of the sintering aid by mass percentage of the inorganic material component to provide the inorganic material component in the LTCC raw material belt material, wherein the inorganic material component is 52% -55% by mass percentage of the LTCC raw material belt material; wherein the sub-material comprises the Li 2 MgTi 3 O 8 Ceramics, Li 2 ZnTi 3 O 8 Ceramics and Li 2 MgSiO 4 At least one of ceramics, the sintering aid comprising BaO-B 2 O 3 -ZnO-SiO 2 Glass and ZnO-B 2 O 3 -SiO 2 At least one of glass;
providing organic material components, adding the organic material components into the inorganic material components, and mixing, wherein the organic material components account for 45-48% of the LTCC raw material tape material in percentage by mass;
and carrying out vacuum defoaming and tape casting molding to prepare the LTCC raw material tape material.
Optionally, preparing the CaTiO 3 The step of ceramic comprises:
mixing CaCO 3 、TiO 2 Prepared according to the calculated mass, and the mixture is presintered for 4 to 8 hours at 1100 to 1200 ℃ to form CaTiO 3 Pre-firing ceramic materials;
controlling the granularity D50 to be 1.0-2.0 mu m by a sand mill and taking water as a ball milling medium;
drying in an oven at 120-170 ℃;
sieving by using a 40-mesh sieve to prepare the CaTiO 3 And (3) ceramic.
Optionally, the step of preparing the regrind comprises:
mixing Li 2 CO 3 、ZnO、TiO 2 、MgO、SiO 2 Preparing according to the calculated mass;
pre-burning the mixture for 4-8 h at 900-1000 ℃ to form Li 2 MgTi 3 O 8 Ceramic pre-sinter, Li 2 ZnTi 3 O 8 Ceramic pre-sinter and Li 2 MgSiO 4 At least one of ceramic pre-sinter;
controlling the granularity D50 to be 1.0-2.0 mu m by a sand mill and taking water as a ball milling medium;
drying in an oven at 120-170 ℃;
sieving by using a 40-mesh sieve to prepare the Li 2 MgTi 3 O 8 Ceramics, Li 2 ZnTi 3 O 8 Ceramics and Li 2 MgSiO 4 At least one of ceramics.
Optionally, the step of preparing the sintering aid comprises:
mixing BaCO 3 、Na 2 CO 3 、H 3 BO 3 、ZnO、SiO 2 Preparing according to the calculated mass;
melting the mixture to form molten glass, and quenching the molten glass into glass blocks;
using absolute ethyl alcohol as a ball milling medium through a sand mill, and controlling the granularity D50 to be 2.0-2.2 mu m;
drying in an oven at 100-120 ℃;
sieving by a 40-mesh sieve to prepare the BaO-B 2 O 3 -ZnO-SiO 2 Glass or ZnO-B 2 O 3 -SiO 2 And (3) glass.
Optionally, the BaO-B 2 O 3 -ZnO-SiO 2 The mixture ratio of the mixture in the glass is 28-33 percent of BaO and 30-34 percent of B 2 O 3 18 to 22 percent of ZnO and 17 to 22 percent of SiO 2 Melting at 1100-1200 ℃ for 2-4 h; the ZnO-B 2 O 3 -SiO 2 The mixture ratio of the mixture in the glass is 47 to 54 percent of ZnO and 37 to 41 percent of B 2 O 3 8% -12% of SiO 2 And 1% -3% of Na 2 O, melting at 1200-1300 ℃ for 2-4 h; the BaO-B 2 O 3 -ZnO-SiO 2 Glass and ZnO-B 2 O 3 -SiO 2 The glass transition temperature of the glass is 600-650 ℃.
Optionally, the organic material components comprise a solvent, a dispersant, a plasticizer and a binder, and when the organic material components are added for ball milling, the steps of adding the solvent and the dispersant, ball milling and mixing for 2 h-4 h are performed, adding the plasticizer and the binder after uniform mixing, and ball milling and mixing for 2 h-4 h; the solvent includes an alcohol-ketone mixed solvent.
The invention also provides an LTCC substrate which comprises any one of the LTCC green tape materials.
The invention also provides a preparation method of the LTCC substrate, which comprises the steps of preparing the LTCC raw material belt material by adopting any one method, overlapping the LTCC raw material belt material to prepare a biscuit, heating to 500 ℃ at the room temperature at the heating rate of 1 ℃/min, preserving heat for 3h at 500 ℃ to remove the adhesive, heating to 890-920 ℃ at the heating rate of 5 ℃/min after the adhesive is removed, preserving heat for 2-4 h, and completing sintering to prepare the LTCC substrate.
As described above, in the LTCC green tape material, the substrate and the preparation method thereof, the Li-based ceramic with relatively low sintering temperature is adopted in the inorganic material component, so that the dielectric constant of the mixed material can be effectively adjusted in the sintering process, and the LTCC green tape material and the substrate can play a role in sintering assistance; in the organic material components, the solvent is selected from alcohol-ketone mixed solvent which has lower boiling point, is volatile and has better solubility with the binder, so that the tape casting effect is better, and the LTCC raw material belt material with smooth surface and uniform thickness is formed; the invention can prepare the material with dielectric constant of 40-80 and dielectric loss of 1.0 multiplied by 10 -3 ～2×10 -3 The LTCC green tape material and the LTCC substrate with the medium and high dielectric constant have good co-firing performance matched with the low-melting-point metal slurry.
Drawings
Fig. 1 is a schematic flow chart of a process for preparing an LTCC green tape material according to an embodiment of the present invention.
FIG. 2 is an SEM image of a cross section of a sintered LTCC green tape material in an embodiment of the invention.
FIG. 3 is an SEM image of a cross section of a ceramic chip after co-firing of LTCC green tape material and silver electrode in an embodiment of the invention.
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.
As in the detailed description of the embodiments of the present invention, the cross-sectional views illustrating the device structures are not partially enlarged in general scale for convenience of illustration, and the schematic views are only examples, which should not limit the scope of the present invention. In addition, the three-dimensional dimensions of length, width and depth should be included in the actual fabrication.
For convenience in description, spatial relational terms such as "below," "beneath," "below," "under," "over," "upper," and the like may be used herein to describe one element or feature's relationship to another element or feature as illustrated in the figures. It will be understood that these terms of spatial relationship are intended to encompass other orientations of the device in use or operation in addition to the orientation depicted in the figures. Further, when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present. As used herein, "between … …" is meant to include both values.
In the context of this application, a structure described as having a first feature "on" a second feature may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which additional features are formed in between the first and second features, such that the first and second features may not be in direct contact.
It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the drawings only show the components related to the present invention rather than being drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of each component in actual implementation may be changed freely, and the layout of the components may be more complicated.
Example one
This embodiment provides an LTCC green tape material, in which the LTCC green tape material includes, by mass percent, 52% to 55% of an inorganic material component and 45% to 48% of an organic material component, wherein the LTCC green tape material includes, by mass percent, 60% to 85% of a main material, 10% to 35% of an auxiliary material, and 3% to 25% of a sintering aid, and the main material includes CaTiO 3 (CT) ceramics, the sub-material comprising Li 2 MgTi 3 O 8 (LMT) ceramics, Li 2 ZnTi 3 O 8 (LZT) ceramics and Li 2 MgSiO 4 At least one of (LMS) ceramics, said sintering aid comprising BaO-B 2 O 3 -ZnO-SiO 2 (BBZS) glass and ZnO-B 2 O 3 -SiO 2 (ZBS) glass.
Specifically, the inorganic material composition may include values in any range of 52%, 53%, 54%, 55%, etc., and the organic material composition may include values in any range of 45%, 46%, 47%, 48%, etc. The main material of the CT ceramic may include values in any ranges of 60%, 65%, 70%, 80%, 85%, etc., the auxiliary material may include values in any ranges of 10%, 15%, 20%, 25%, 30%, 35%, etc., and the sintering aid may include values in any ranges of 3%, 5%, 8%, 10%, 15%, 20%, 25%, etc., and may be specifically adjusted as required. The auxiliary material can be one or a combination of the LMT ceramic, the LTZ ceramic and the LMS ceramic, and Li-based ceramic with relatively low sintering temperature is used as the auxiliary material in the inorganic material, so that the dielectric constant of the mixed material can be effectively adjusted in the sintering process, and the sintering aid can also play a role, wherein the dielectric constant of the LMS ceramic is about 6.0, the dielectric constant of the LZT ceramic is about 25, and the dielectric constant of the LMT ceramic is about 25.
For example, the mass percent of the BBZS glass isThe BBZS glass comprises 28-33% of BaO and 30-34% of B in percentage by weight 2 O 3 18 to 22 percent of ZnO and 17 to 22 percent of SiO 2 (ii) a Based on the mass percent of the ZBS glass, the ZBS glass comprises 47-54 percent of ZnO and 37-41 percent of B 2 O 3 8% -12% of SiO 2 And 1% -3% of Na 2 O。
Specifically, in the BBZS glass, the BaO may include a value in any range of 28%, 29%, 30%, 31%, 32%, 33%, etc., in terms of mass percentage of the BBZS glass, and the B may include B 2 O 3 May include values in any range of 30%, 31%, 32%, 33%, 34%, etc., the ZnO may include values in any range of 18%, 19%, 20%, 21%, 22%, etc., the SiO 2 Values within any range of 17%, 18%, 19%, 20%, 21%, 22%, etc. may be included. In the ZBS glass, the ZnO may include a value in any range of 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, etc., the B, in percentage by mass of the ZBS glass 2 O 3 Can include values in any range of 37%, 38%, 39%, 40%, 41%, etc., the SiO 2 May include values in any range of 8%, 9%, 10%, 11%, 12%, etc., the Na 2 O may comprise values in any range of 1%, 2%, 3%, etc.
By way of example, the organic materials include solvents, dispersants, plasticizers, and binders; the solvent includes an alcohol-ketone mixed solvent.
Specifically, when the LTCC raw material tape material is prepared, in the tape casting slurry of the LTCC raw material tape material, preferably, the solvent is an alcohol-ketone mixed solvent which has a relatively low boiling point, is volatile, has relatively good solubility with the binder, and has a relatively good tape casting effect, so that after tape casting, the LTCC raw material tape has a smooth surface and uniform thickness, and is convenient for the subsequent preparation of the LTCC substrate.
By way of example, the dielectric constant of the LTCC green tape material is 40-80, and the dielectric loss of the LTCC green tape material is 1.0 x 10 -3 ～2×10 -3 。
Specifically, the mass ratio of the CT ceramic, the LZT ceramic, the LMT ceramic, the LMS glass, the BBZS glass and the ZBS glass is selected and adjusted, and sintering densification is carried out at 890-920 ℃, so that the dielectric constant of the prepared LTCC raw material belt material can be changed between 40-80, such as 40, 50, 60, 70, 80 and the like; the dielectric loss can be 1.0 x 10 -3 ～2×10 -3 In a fluctuation of 1.0X 10, for example -3 、1.2×10 -3 、1.5×10 -3 、2.0×10 -3 And the like, so that the prepared LTCC raw material belt material can be matched with low-melting-point metal slurry for co-firing, such as silver electrode slurry, so as to realize good performance. FIG. 2 is a SEM photograph of a cross section of a sintered ceramic tile made of the LTCC green tape material of the present embodiment; FIG. 3 is an SEM image of a cross section of a green LTCC tape material according to this embodiment after co-firing with silver electrodes.
Referring to fig. 1, this embodiment also provides a method for preparing raw LTCC tape material, which can be used to prepare the raw LTCC tape material, but the method for preparing raw LTCC tape material is not limited thereto. The method specifically comprises the following steps:
preparation of CaTiO 3 (CT) a ceramic to provide a main material of inorganic material components;
preparation of Li 2 MgTi 3 O 8 (LMT) ceramics, Li 2 ZnTi 3 O 8 (LZT) ceramics and Li 2 MgSiO 4 At least one of (LMS) ceramics to provide a side-stream of said inorganic material composition;
preparation of BaO-B 2 O 3 -ZnO-SiO 2 (BBZS) glass and ZnO-B 2 O 3 -SiO 2 (ZBS) at least one of a glass to provide a sintering aid for the inorganic material component;
taking 60% -85% of the main material, 10% -35% of the auxiliary material and 3% -25% of the sintering aid by mass percentage of the inorganic material component to provide the inorganic material component in the LTCC raw material belt material, wherein the inorganic material component is 52% -55% by mass percentage of the LTCC raw material belt material; wherein the auxiliary material comprises at least one of LMT ceramic, LZT ceramic and LMS ceramic, and the sintering aid comprises at least one of BBZS glass and ZBS glass;
providing organic material components, adding the organic material components into the inorganic material components, and mixing, wherein the organic material components account for 45-48% of the LTCC raw material tape material in percentage by mass;
and carrying out vacuum defoaming and tape casting molding to prepare the LTCC raw material tape material.
Wherein the inorganic material composition may include values in any range of 52%, 53%, 54%, 55%, etc., and the organic material composition may include values in any range of 45%, 46%, 47%, 48%, etc. The main material of the CT ceramic may include values in any ranges of 60%, 65%, 70%, 80%, 85%, etc., the auxiliary material may include values in any ranges of 10%, 15%, 20%, 25%, 30%, 35%, etc., and the sintering aid may include values in any ranges of 3%, 5%, 8%, 10%, 15%, 20%, 25%, etc., and may be specifically adjusted as required.
Specifically, the sequence of the above steps may be adjusted according to needs, and is not limited herein, and specifically, the steps may include:
firstly, preparing the CT ceramic and the auxiliary material.
As an example, the step of preparing the CT ceramic may include:
mixing CaCO 3 、TiO 2 Preparing according to the calculated mass, and pre-sintering the mixture for 4-8 h at 1100-1200 ℃ to form a CT ceramic pre-sintered material;
controlling the granularity D50 to be 1.0-2.0 mu m by a sand mill and taking water as a ball milling medium;
drying in an oven at 120-170 ℃;
and sieving the mixture by using a 40-mesh sieve to prepare the CT ceramic.
As an example, the step of preparing the regrind comprises:
mixing Li 2 CO 3 、ZnO、TiO 2 、MgO、SiO 2 According to calculated qualityPreparing quantity;
pre-burning the mixture for 4-8 h at 900-1000 ℃ to form at least one of LMT ceramic pre-burning material, LZT ceramic pre-burning material and LMS ceramic pre-burning material;
controlling the granularity D50 to be 1.0-2.0 mu m by a sand mill and taking water as a ball milling medium;
drying in an oven at 120-170 ℃;
and screening by using a 40-mesh screen to prepare at least one of the LMT ceramic, the LZT ceramic and the LMS ceramic.
Specifically, CaCO can be used in the synthesis of the CT ceramic pre-sintered material 3 、TiO 2 Preparing according to the calculated mass, and pre-sintering the mixture at 1100-1200 ℃ for 4-8 h, wherein the pre-sintering temperature can include values in any range of 1100 ℃, 1150 ℃, 1200 ℃ and the like, and the pre-sintering time can include values in any range of 4h, 5h, 6h, 7h, 8h and the like; when synthesizing the LMT ceramic pre-sintering material, Li can be added 2 CO 3 、MgO、TiO 2 According to the calculated mass, Li can be added when the LZT ceramic pre-sintering material is synthesized 2 CO 3 、ZnO、TiO 2 When the LMS ceramic pre-sintering material is synthesized according to the calculated mass preparation, Li can be added 2 CO 3 、MgO、SiO 2 Preparing according to the calculated mass, and then pre-sintering the corresponding mixture for 4-8 h at 900-1000 ℃, for example, the pre-sintering temperature can include values in any range of 900 ℃, 950 ℃, 1000 ℃ and the like, and the pre-sintering time can include values in any range of 4h, 5h, 6h, 7h, 8h and the like, so as to prepare the corresponding ceramic pre-sintering material.
And then feeding the CT ceramic pre-sintering material and at least one of the LMT ceramic pre-sintering material, the LZT ceramic pre-sintering material and the LMS ceramic pre-sintering material into a sand mill, using water as a ball milling medium, controlling the granularity D50 of the ceramic pre-sintering material to be between 1.0 mu m and 2.0 mu m, such as values in any ranges of 1.0 mu m, 1.1 mu m, 1.2 mu m, 1.3 mu m, 1.4 mu m, 1.5 mu m, 1.6 mu m, 1.7 mu m, 1.8 mu m, 1.9 mu m and 2.0 mu m, further drying in an oven at 120-170 ℃, such as values in any ranges of 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ and the like, and sieving by adopting a 40-mesh sieve to obtain corresponding powder of the CT ceramic, LMT, LZT and LMS ceramic.
Then, preparing the sintering aid, including:
mixing BaCO 3 、Na 2 CO 3 、H 3 BO 3 、ZnO、SiO 2 Preparing according to the calculated mass;
melting the mixture to form molten glass, and quenching the molten glass into glass blocks;
using absolute ethyl alcohol as a ball milling medium through a sand mill, and controlling the granularity D50 to be 2.0-2.2 mu m;
drying in an oven at 100-120 ℃;
the BBZS glass or ZBS glass is prepared by sieving with a 40-mesh sieve.
For example, the mixture ratio of the mixture in the BBZS glass is 28-33% of BaO and 30-34% of B 2 O 3 18 to 22 percent of ZnO and 17 to 22 percent of SiO 2 Melting at 1100-1200 ℃ for 2-4 h; the mixture ratio of the mixture in the ZBS glass is 47-54 percent of ZnO and 37-41 percent of B 2 O 3 8% -12% of SiO 2 And 1% -3% of Na 2 O, melting at 1200-1300 ℃ for 2-4 h; the glass transition temperature of the BBZS glass and the ZBS glass is 600-650 ℃.
Specifically, in the BBZS glass, the BaO may include a value in any range of 28%, 29%, 30%, 31%, 32%, 33%, etc., in terms of mass percentage of the BBZS glass, and the B may include B 2 O 3 May comprise values in any range of 30%, 31%, 32%, 33%, 34%, etc., the ZnO may comprise values in any range of 17%, 18%, 19%, 20%, 21%, 22%, etc., the SiO 2 Values in any range of 17%, 18%, 19%, 20%, 21%, 22%, etc. may be included. In the ZBS glass, the ZnO may include a value in any range of 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, etc., the B, in percentage by mass of the ZBS glass 2 O 3 Can include values in any range of 37%, 38%, 39%, 40%, 41%, etc., the SiO 2 May include values in any range of 8%, 9%, 10%, 11%, 12%, etc., the Na 2 O may comprise values in any range of 1%, 2%, 3%, etc.
When preparing the BBZS glass, BaCO is added 3 、H 3 BO 3 、ZnO、SiO 2 Weighing raw materials according to a ratio, mixing, drying, sieving, melting the mixed powder for 2 h-4 h at 1100-1200 ℃, such as melting to values in any range of 1100 ℃, 1150 ℃, 1200 ℃ and the like, melting for any range of 2h, 3h, 4h and the like, melting into glass liquid, quenching into glass blocks by water, grinding by a sand mill by taking absolute ethyl alcohol as a ball milling medium, controlling the glass granularity D50 to be 2.0-2.2 μm, such as values in any range of 2.0 μm, 2.1 μm, 2.2 μm and the like, drying in an oven at 100-120 ℃, such as values in any range of 100 ℃, 110 ℃, 120 ℃ and the like, and sieving by a 40-mesh sieve to prepare the BBZS glass powder. When preparing the ZBS glass, ZnO and H are added 3 BO 3 、SiO 2 、Na 2 CO 3 Weighing and mixing raw materials according to a ratio, melting the mixed powder for 2-4 h at 1200-1300 ℃, such as the melting is a value in any range of 1200 ℃, 1250 ℃, 1300 ℃ and the like, the melting time comprises a value in any range of 2h, 3h, 4h and the like, melting into glass liquid, quenching into glass blocks by water, grinding by a sand mill by taking absolute ethyl alcohol as a ball milling medium, controlling the glass particle size D50 to be 2.0-2.2 μm, such as a value in any range of 2.0 μm, 2.1 μm, 2.2 μm and the like, drying in an oven at 100-120 ℃, such as a value in any range of 100 ℃, 110 ℃, 120 ℃ and the like, and sieving by a 40-mesh sieve to prepare the ZBS glass powder.
Wherein, the glass transition temperature of the BBZS glass can be 600-650 ℃, such as 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃ and the like; the glass transition temperature of the ZBS glass can be 600-650 ℃, such as 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃ and the like; thereby effectively reducing the sintering temperature of the mixture.
And then, providing the organic material component, adding the organic material component into the inorganic material component, and mixing, wherein the organic material component accounts for 45-48% of the LTCC raw material tape material by mass percent.
As an example, the organic material components comprise a solvent, a dispersant, a plasticizer and a binder, and when the organic material components are added for ball milling, the solvent and the dispersant are added firstly, the ball milling and mixing are carried out for 2 to 4 hours, after the uniform mixing, the plasticizer and the binder are added, and the ball milling and mixing are carried out for 2 to 4 hours; the solvent includes an alcohol-ketone mixed solvent.
Specifically, 10-35% of LZT ceramic powder, LMT ceramic powder, LMS ceramic powder, 3-25% of BBZS glass powder and ZBS glass powder are sequentially added into a ball milling tank with a certain amount of zirconium balls in percentage by mass, then the solvent and the dispersing agent are added, ball milling and mixing are carried out for 2-4 h, such as values within any range of 2h, 3h, 4h and the like, and after the mixture is uniformly mixed, the plasticizer and the binding agent are added, so that the casting slurry has cohesiveness and toughness. Then, ball milling and mixing for 2 h-4 h, such as 2h, 3h and 4 h. Wherein, the ball milling tank can adopt a nylon tank filled with zirconia balls, but the ball milling equipment is not limited to the above.
And finally, carrying out vacuum defoamation, and carrying out tape casting to obtain the LTCC raw material belt material.
Example two
This embodiment provides an LTCC substrate comprising the green LTCC tape material of the first embodiment, which will not be described herein.
The embodiment also provides a preparation method of the LTCC substrate, which includes the steps of preparing the LTCC raw material tape material by using the method in the first embodiment, overlapping the LTCC raw material tape material to prepare a green body, heating to 500 ℃ at a heating rate of 1 ℃/min at room temperature, keeping the temperature at 500 ℃ for 3 hours to remove the adhesive, heating to 890-920 ℃ at a heating rate of 5 ℃/min after the adhesive is removed, and keeping the temperature for 2-4 hours to complete sintering, so as to prepare the LTCC substrate.
Specifically, the LTCC raw material tape material can be cut into a desired size, for example, a size of 100mm × 100mm, cross lamination of 10 layers, 8 layers, and the like is performed, vacuum pumping is performed, isostatic pressing is performed to form a green body, the green body is further placed into a sintering furnace, the temperature is raised to 500 ℃ at a heating rate of 1 ℃/min at room temperature, the temperature is maintained for 3 hours at 500 ℃, glue is discharged, after the glue discharge is completed, the temperature is raised to 890-920 ℃ at a heating rate of 5 ℃/min, for example, 890 ℃, 900 ℃, 910 ℃, and 920 ℃, the temperature is maintained for 2 hours to 4 hours, for example, 2 hours, 3 hours, and 4 hours, and sintering is completed to prepare the LTCC substrate. The LTCC substrate manufacturing process is not limited thereto.
The following tests were carried out on the performance of the prepared LTCC substrate by means of specific examples:
the formulations in table 1 below are formulations of only a part of the green LTCC tape material, i.e. the formulations of the green LTCC tape material are not limited thereto.
Table 1 (mass ratio):
| serial number | CT | LZT | LMT | LMS | BBZS-1 | BBZS-2 | ZBS-1 | ZBS-2 |
| 1 | 60 | 35 | 5 | |||||
| 2 | 60 | 15 | 25 | |||||
| 3 | 60 | 30 | 5 | 5 | ||||
| 4 | 60 | 10 | 20 | 5 | 5 | |||
| 5 | 60 | 10 | 10 | 10 | 5 | 5 | ||
| 6 | 65 | 20 | 10 | 5 | ||||
| 7 | 65 | 10 | 10 | 10 | 5 | |||
| 8 | 70 | 10 | 5 | 10 | 5 | |||
| 9 | 70 | 10 | 10 | 10 | ||||
| 10 | 70 | 20 | 10 | |||||
| 11 | 75 | 15 | 5 | 5 | ||||
| 12 | 75 | 15 | 5 | 5 | ||||
| 13 | 80 | 15 | 5 | |||||
| 14 | 80 | 10 | 10 | |||||
| 15 | 85 | 10 | 5 |
In Table 1, BBZS-1 glass contains, as essential components, 30 wt% of BaO and 30 wt% of B 2 O 3 18 wt% of ZnO, 22 wt% of SiO 2 The melting temperature is 1200 ℃; BBZS-2 glass mainly comprises 33 wt% of BaO and 32 wt% of B 2 O 3 18 wt% of ZnO, 17 wt% of SiO 2 The melting temperature is 1130 ℃. ZBS-1 glass mainly comprising 49 wt% of ZnO and 37 wt% of B 2 O 3 12% by weight of SiO 2 2 wt% of Na 2 O, the melting temperature is 1250 ℃; ZBS-2 glass mainly comprising 50 wt% of ZnO and 41 wt% of B 2 O 3 8% by weight of SiO 2 1 wt% of Na 2 O, the melting temperature is 1200 ℃.
In table 1, the mass ratio of the organic material in the casting slurry is 52% to 55%, and the LTCC raw material belt material with smooth appearance, no cracking and good toughness can be prepared by adjusting the ratio of the organic material in the casting slurry.
The LTCC raw material belt material is cut into the required size of 100mm multiplied by 100mm, 10 layers are crossed and stacked, vacuumized and formed into a biscuit in an isostatic pressing mode, then the biscuit is placed into a sintering furnace, the temperature is increased to 500 ℃ at room temperature at the heating rate of 1 ℃/min, the temperature is kept at 500 ℃ for 3h for glue discharging, after the glue discharging is completed, the temperature is increased to 890-920 ℃ at the heating rate of 5 ℃/min, the heat is kept for 2 h-4 h, and the LTCC substrate is formed after sintering. The dielectric constant and dielectric loss of the LTCC substrate were measured at 4.9GHz, and 3 samples were taken from each formulation, and the average was taken as the final test data, as shown in table 2 below.
Table 2:
| serial number | Dielectric constant | Dielectric loss | Sintering temperature |
| 1 | 40.5 | 1.35×10 -3 | 920℃-4h |
| 2 | 52.7 | 1.97×10 -3 | 890℃-2h |
| 3 | 42.3 | 1.52×10 -3 | 900℃-3h |
| 4 | 47.8 | 1.65×10 -3 | 900℃-3h |
| 5 | 51.4 | 1.67×10 -3 | 900℃-3h |
| 6 | 50.9 | 1.77×10 -3 | 900℃-2h |
| 7 | 52.1 | 1.72×10 -3 | 900℃-2h |
| 8 | 55.9 | 1.55×10 -3 | 910℃-3h |
| 9 | 58.3 | 1.43×10 -3 | 910℃-3h |
| 10 | 62.6 | 1.57×10 -3 | 910℃-3h |
| 11 | 66.9 | 1.53×10 -3 | 910℃-3h |
| 12 | 54.4 | 1.36×10 -3 | 920℃-3h |
| 13 | 72.7 | 1.78×10 -3 | 920℃-4h |
| 14 | 63.9 | 1.44×10 -3 | 910℃-3h |
| 15 | 78.4 | 1.82×10 -3 | 920℃-4h |
Wherein the dielectric constant of the LTCC green tape material is 40-80, and the dielectric loss of the LTCC green tape material is 1.0 multiplied by 10 -3 ～2×10 -3 So that the ceramic material can be co-fired with low-melting-point metal slurry in a matching way and has good performance.
In conclusion, in the LTCC green tape material, the substrate and the preparation method, the Li-based ceramic with relatively low sintering temperature is adopted in the inorganic material component, so that the dielectric constant of the mixed material can be effectively adjusted in the sintering process, and the sintering assisting effect can be realized; in the organic material components, the solvent is selected from alcohol-ketone mixed solvent which has lower boiling point, is volatile and has better solubility with the binder, so that the tape casting effect is better, and the LTCC raw material belt material with smooth surface and uniform thickness is formed; the invention can prepare the material with dielectric constant of 40-80 and dielectric loss of 1.0 x 10 -3 ～2×10 -3 The LTCC green tape material and the LTCC substrate with the medium and high dielectric constant have good co-firing performance matched with the low-melting-point metal slurry.
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 (10)
1. An LTCC green tape material, wherein the LTCC green tape material comprises:
52-55% of inorganic material components and 45-48% of organic material components in percentage by mass, wherein the inorganic material comprises 60-85% of main material, 10-35% of auxiliary material and 3-25% of sintering aid in percentage by mass, and the main material is CaTiO 3 Ceramics, the sub-materials comprising Li 2 MgTi 3 O 8 Ceramics, Li 2 ZnTi 3 O 8 Ceramics and Li 2 MgSiO 4 At least one of ceramics, the sintering aid comprising BaO-B 2 O 3 -ZnO-SiO 2 Glass and ZnO-B 2 O 3 -SiO 2 At least one of glass; wherein the sintering temperature of the LTCC raw material belt material is 890-920 ℃, the dielectric constant is 40-80, and the dielectric loss is 1.0 multiplied by 10 -3 ~2×10 -3 。
2. A green LTCC tape material as claimed in claim 1, wherein: with said BaO-B 2 O 3 -ZnO-SiO 2 The mass percent of the glass is BaO-B 2 O 3 -ZnO-SiO 2 The glass comprises 28-33% of BaO and 30-34% of B 2 O 3 18% -22% of ZnO and 17% -22% of SiO 2 (ii) a With said ZnO-B 2 O 3 -SiO 2 The ZnO-B is calculated by the mass percent of the glass 2 O 3 -SiO 2 The glass comprises 47% -54% of ZnO and 37% -41% of B 2 O 3 8% -12% of SiO 2 And 1% -3% of Na 2 O。
3. The preparation method of the LTCC raw material belt material is characterized by comprising the following steps:
preparation of CaTiO 3 A ceramic to provide a main material of inorganic material components;
preparation of Li 2 MgTi 3 O 8 Ceramics, Li 2 ZnTi 3 O 8 Ceramics and Li 2 MgSiO 4 At least one of the ceramics is selected from the group consisting of,to provide a sub-charge of the inorganic material composition;
preparation of BaO-B 2 O 3 -ZnO-SiO 2 Glass and ZnO-B 2 O 3 -SiO 2 At least one of glass to provide a sintering aid for the inorganic material component;
taking 60% -85% of the main material, 10% -35% of the auxiliary material and 3% -25% of the sintering aid by mass percentage of the inorganic material components to provide the inorganic material components in the LTCC raw material belt material, wherein the inorganic material components are 52% -55% by mass percentage of the LTCC raw material belt material; wherein the sub-material comprises the Li 2 MgTi 3 O 8 Ceramics, Li 2 ZnTi 3 O 8 Ceramics and Li 2 MgSiO 4 At least one of ceramics, the sintering aid comprises BaO-B 2 O 3 -ZnO-SiO 2 Glass and ZnO-B 2 O 3 -SiO 2 At least one of glass;
providing organic material components, adding the organic material components into the inorganic material components, and mixing, wherein the organic material components account for 45-48% of the LTCC raw material tape material in percentage by mass;
and carrying out vacuum defoaming and tape casting to prepare the LTCC raw material tape material, wherein the sintering temperature of the LTCC raw material tape material is 890-920 ℃, the dielectric constant is 40-80, and the dielectric loss is 1.0 multiplied by 10 -3 ~2×10 -3 。
4. A method of producing a green LTCC tape material as claimed in claim 3, wherein: preparation of the CaTiO 3 The step of ceramic comprises:
mixing CaCO 3 、TiO 2 Preparing according to the calculated mass, and pre-sintering the mixture at 1100-1200 ℃ for 4-8 h to form CaTiO 3 Pre-firing ceramic materials;
controlling the granularity D50 to be 1.0-2.0 mu m by using water as a ball milling medium through a sand mill;
drying in an oven at the temperature of 120-170 ℃;
sieving by using a 40-mesh sieve to prepare the CaTiO 3 A ceramic.
5. A method of producing a green LTCC tape material as claimed in claim 3, wherein: the step of preparing the secondary material comprises:
mixing Li 2 CO 3 、ZnO、TiO 2 、MgO、SiO 2 Preparing according to the calculated mass;
pre-burning the mixture for 4-8 h at 900-1000 ℃ to form Li 2 MgTi 3 O 8 Ceramic pre-sinter, Li 2 ZnTi 3 O 8 Ceramic pre-sinter and Li 2 MgSiO 4 At least one of ceramic pre-sinter;
controlling the granularity D50 to be 1.0-2.0 mu m by using water as a ball milling medium through a sand mill;
drying in an oven at the temperature of 120-170 ℃;
sieving by using a 40-mesh sieve to prepare the Li 2 MgTi 3 O 8 Ceramics, Li 2 ZnTi 3 O 8 Ceramics and Li 2 MgSiO 4 At least one of ceramics.
6. A method of producing a green LTCC tape material as claimed in claim 3, wherein: the step of preparing the sintering aid comprises:
mixing BaCO 3 、Na 2 CO 3 、H 3 BO 3 、ZnO、SiO 2 Preparing according to the calculated mass;
melting the mixture to form glass liquid, and quenching the glass liquid into glass blocks;
controlling the particle size D50 to be 2.0-2.2 mu m by using absolute ethyl alcohol as a ball milling medium through a sand mill;
drying in an oven at 100-120 ℃;
sieving by a 40-mesh sieve to prepare the BaO-B 2 O 3 -ZnO-SiO 2 Glass or ZnO-B 2 O 3 -SiO 2 And (3) glass.
7. The method of manufacturing green LTCC tape material according to claim 6, wherein: the BaO-B 2 O 3 -ZnO-SiO 2 The mixture ratio of the mixture in the glass is 28-33% of BaO and 30-34% of B 2 O 3 18% -22% of ZnO and 17% -22% of SiO 2 Melting at 1100-1200 ℃ for 2-4 h; the ZnO-B 2 O 3 -SiO 2 The mixture ratio of the glass mixture is 47-54% of ZnO and 37-41% of B 2 O 3 8 to 12 percent of SiO 2 And 1% -3% of Na 2 O, melting at 1200-1300 ℃ for 2-4 h; the BaO-B 2 O 3 -ZnO-SiO 2 Glass and ZnO-B 2 O 3 -SiO 2 The glass transition temperature of the glass is 600-650 ℃.
8. A method of producing a green LTCC tape material as claimed in claim 3, wherein: the organic material components comprise a solvent, a dispersing agent, a plasticizer and a binder, and when the organic material components are added for ball milling, the solvent and the dispersing agent are firstly added, the ball milling and mixing are carried out for 2 to 4 hours, after the uniform mixing, the plasticizer and the binder are added, and the ball milling and mixing are carried out for 2 to 4 hours; the solvent includes an alcohol-ketone mixed solvent.
9. An LTCC substrate, characterized in that: the LTCC substrate comprises the green LTCC tape material as claimed in any one of claims 1 to 2.
10. A preparation method of an LTCC substrate is characterized by comprising the following steps: the method comprises the steps of preparing the LTCC green tape material by adopting any one of the methods of claims 3-8, overlapping the LTCC green tape material to prepare a biscuit, heating to 500 ℃ at a heating rate of 1 ℃/min at room temperature, keeping the temperature at 500 ℃ for 3 hours to remove the adhesive, heating to 890-920 ℃ at a heating rate of 5 ℃/min after the adhesive is removed, keeping the temperature for 2-4 hours, and completing sintering to prepare the LTCC substrate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050078073A (en) * | 2004-01-30 | 2005-08-04 | 한국과학기술연구원 | Low-fire high-permittivity dielectric compositions with adjustable temperature coefficient |
| CN102701730A (en) * | 2012-06-25 | 2012-10-03 | 景德镇陶瓷学院 | Calcium strontium lithium samarium titanium system microwave dielectric ceramic water-base tape-casting slurry and method for preparing ceramic diaphragm |
| CN107176834A (en) * | 2016-03-11 | 2017-09-19 | 上海卡翱投资管理合伙企业（有限合伙） | LTCC ceramic materials of middle high-k and preparation method thereof |
| CN112225547A (en) * | 2020-10-19 | 2021-01-15 | 上海晶材新材料科技有限公司 | LTCC material, substrate and preparation method |
-
2021
- 2021-04-15 CN CN202110407356.7A patent/CN113045305B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050078073A (en) * | 2004-01-30 | 2005-08-04 | 한국과학기술연구원 | Low-fire high-permittivity dielectric compositions with adjustable temperature coefficient |
| CN102701730A (en) * | 2012-06-25 | 2012-10-03 | 景德镇陶瓷学院 | Calcium strontium lithium samarium titanium system microwave dielectric ceramic water-base tape-casting slurry and method for preparing ceramic diaphragm |
| CN107176834A (en) * | 2016-03-11 | 2017-09-19 | 上海卡翱投资管理合伙企业（有限合伙） | LTCC ceramic materials of middle high-k and preparation method thereof |
| CN112225547A (en) * | 2020-10-19 | 2021-01-15 | 上海晶材新材料科技有限公司 | LTCC material, substrate and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| Li2ZnTi3O8 掺杂对 0.7CaTiO3-0.3NdAlO3 微波介质陶瓷低温烧结及介电性能的影响;占丽娜 等;《中国陶瓷》;20190715;第55卷(第7期);第42-47+53页 * |
| 复合助烧剂对0.4CaTiO3-0.6(Li1/2Nd1/2)TiO3陶瓷的低温烧结及性能的影响;王应 等;《电子元件与材料》;20110405;第30卷(第4期);第6-9页 * |
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