CN115340376A - Ceramic substrate for LTCC (Low temperature Co-fired ceramic), and preparation method and application thereof - Google Patents
Ceramic substrate for LTCC (Low temperature Co-fired ceramic), and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a ceramic substrate for LTCC (low temperature co-fired ceramic), and a preparation method and application thereof 2 、SiO 2 ZnO and B 2 O 3 ；ZrO 2 And SiO 2 The mass ratio of (A) to (B) is 2-10: 1; znO and B 2 O 3 The mass ratio of (1): 1 to 5; siO 2 2 And ZnO in a mass ratio of 2.5 to 4. The slurry prepared from the preparation raw materials in the proportion can meet the requirements of 3D printing on the slurry, so that the ceramic substrate for the LTCC with accurate size and complex structure can be prepared by means of a 3D printing method. The invention also provides a preparation method and application of the ceramic substrate for the LTCC.
Description
Technical Field
The invention relates to the technical field of LTCC (low temperature co-fired ceramic), in particular to a ceramic substrate for LTCC and a preparation method and application thereof.
Background
With the rapid development of modern information technology, increasingly high requirements are put forward on the aspects of miniaturization, portability, multifunction, high reliability, low cost and the like of electronic products.
Low Temperature Co-fired Ceramic (LTCC) is a compelling multi-disciplinary cross integrated component technology that has emerged in recent years, and simply speaking, this technology is an electronic packaging technology for realizing Low cost, high integration, and high performance by firing electrode materials, substrates, electronic devices, and the like at 900 ℃ or less at one time according to a pre-designed structure. Because of its excellent electronic and thermo-mechanical properties, it has become the first choice for future integration and modularization of electronic devices.
However, the conventional ceramic substrate for LTCC has poor dimensional accuracy, and it is more difficult to obtain a ceramic substrate having a complicated structure.
The ceramic substrate for LTCC adopts thick film materials, and simultaneously, direct writing printing is taken as one of 3D printing forms, so that the method is suitable for the development of new materials and new structures, and is an important method for printing multi-component composite materials. At present, the intelligent materials and structures, soft robots, flexible electronics and the like prepared by the method are widely applied, but the traditional ceramic substrate for the LTCC cannot be directly used for 3D printing, and further the ceramic substrate for the LTCC with accurate size and complex structure cannot be formed by means of 3D printing.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides the ceramic substrate for the LTCC, and the preparation raw materials of the ceramic substrate for the LTCC can meet the requirements of 3D printing on the raw materials, so that the ceramic substrate for the LTCC with accurate size and complex structure can be prepared by a 3D printing method.
The invention also discloses a preparation method of the ceramic substrate for the LTCC.
The invention also discloses application of the ceramic substrate for the LTCC.
According to an embodiment of the first aspect of the present invention, a ceramic substrate for LTCC is provided, wherein the raw material for the preparation of the ceramic substrate for LTCC comprises ZrO 2 、SiO 2 ZnO and B 2 O 3 ；
The ZrO 2 And SiO 2 The mass ratio of (A) to (B) is 2-10: 1;
the ZnO and B 2 O 3 The mass ratio of (1): 1 to 5;
the SiO 2 And ZnO in a mass ratio of 2.5 to 4.0.
The ceramic substrate for the LTCC provided by the embodiment of the invention has at least the following beneficial effects:
(1) The ceramic substrate for the LTCC provided by the invention can be prepared by a 3D printing method (stable slurry can be formed, and the printed ceramic substrate for the LTCC has good performance) by adopting the preparation raw materials in a specific proportion, and the size precision of the obtained ceramic substrate for the LTCC is high (less than or equal to 100 mu m); and a complicated pattern can be formed on the ceramic substrate for LTCC.
(2) The melting point of metal oxides such as ZnO and the like is high, the ceramic substrate for LTCC is difficult to form in the preparation process, and a certain amount of B is added into the preparation raw materials adopted by the invention 2 O 3 The method has the function of improving the processing performance of the prepared raw materials.
(3) In the preparation raw material adopted by the invention, zrO 2 The photocuring efficiency of subsequent 3D printing can be effectively improved, so that the printed green body can be effectively cured, the change of the size is avoided, and the mechanical property of the obtained ceramic substrate for LTCC can be improved; siO 2 2 The strength of the obtained ceramic substrate for the LTCC can be effectively improved; znO and B 2 O 3 The dielectric property of the ceramic substrate for LTCC can be effectively improved;
the preparation raw materials are combined for use, so that the LTCC ceramic substrate with accurate size, high strength and excellent dielectric property can be obtained.
According to some embodiments of the invention, the ZrO 2 And SiO 2 The mass ratio of (A) to (B) is 4-6: 1.
according to some embodiments of the invention, the ZnO and B 2 O 3 The mass ratio of (1): 2 to 4.
According to some embodiments of the invention, the SiO 2 And ZnO in a mass ratio of about 2.8 to 3.2.
According to some embodiments of the invention, the ceramic substrate for LTCC has a pattern.
According to some embodiments of the invention, the pattern comprises at least one of holes, grooves, protrusions. Thus, the ceramic substrate for LTCC can be used for designing integrated electronic components with higher precision.
According to an embodiment of the second aspect of the present invention, there is provided a method for manufacturing the ceramic substrate for LTCC, the method comprising the steps of:
s1, preparing the ZrO 2 And SiO 2 Mixing, grinding and roasting to obtain a pre-sintered material;
the ZnO and B are mixed 2 O 3 Mixing and melting to obtain an additive;
s2, mixing a solvent with the pre-sintered material and the additive to obtain slurry;
s3, preparing a blank by using the slurry as a raw material and adopting a 3D printing method;
and S4, sintering the green body.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects:
the traditional process needs to prepare a flat-plate-shaped LTCC ceramic substrate without special patterns, and if special patterns are needed, the flat-plate-shaped LTCC ceramic substrate needs to be prepared in later processing, so that the working hours are long, and the size precision of the obtained LTCC ceramic substrate is difficult to guarantee.
The invention can accurately control the size of the printed blank by combining the film-free direct-writing 3D printing technology, and can conveniently design and print a hole structure or a special structure, thereby avoiding subsequent processes such as drilling, surface processing and the like; meanwhile, the size precision of the ceramic substrate can be ensured, and the performance of the obtained ceramic substrate for LTCC can be improved. Meanwhile, the preparation method provided by the invention adopts an industrially mature 3D printing technology, is simple to operate and is convenient for commercial application.
According to some embodiments of the invention, the method of hybrid milling is wet milling.
According to some embodiments of the invention, the wet grinding is performed in a ball mill.
According to some embodiments of the invention, the solvent used for wet milling comprises DMF.
According to some embodiments of the invention, the solvent accounts for 10wt% to 20wt% of the wet-ground material in the wet grinding.
According to some embodiments of the invention, the wet-milled ball mill has a rotation speed of 400rpm to 500rpm.
According to some embodiments of the invention, the wet grinding time is 1h to 2h.
According to some embodiments of the invention, in step S1, after the mixed grinding, the particle size of the obtained material is less than or equal to 100 μm.
And after the mixing and grinding, directly roasting without drying.
According to some embodiments of the invention, in the step S1, the constant temperature of the simmering is 700-1000 ℃.
According to some preferred embodiments of the present invention, in step S1, the constant temperature of the simmering is 800-900 ℃.
According to some embodiments of the invention, in the step S1, the constant temperature duration of the simmering is 1h to 10h.
According to some preferred embodiments of the present invention, in step S1, the constant temperature duration of the simmering is 1 to 5 hours.
According to some embodiments of the invention, in step S1, the simmering is performed under an air atmosphere.
In the roasting process, due to the action of surface energy, the material tends to be homogenized, namely small particles grow larger and large particles become smaller, and agglomeration does not occur in the temperature range, so that an additional crushing step is not needed, and impurities introduced in the mixing and grinding process can be volatilized in a high-temperature environment.
In conclusion, the roasting can improve the uniformity of the obtained pre-sintered material, refine particles, eliminate agglomeration and eliminate impurities, and is favorable for preparing the slurry in the step S2.
According to some embodiments of the invention, in the step S1, the constant temperature of the melting is 1000 ℃ to 1600 ℃.
According to some preferred embodiments of the present invention, in step S1, the constant temperature of the melting is 1300 ℃ to 1500 ℃.
In the above range of melting conditions, uniform fusion between the additive components can be ensured to the maximum extent, and agglomeration among particles can be avoided to the maximum extent.
According to some embodiments of the invention, in step S1, the constant temperature duration of the melting is 2h to 10h.
According to some preferred embodiments of the present invention, in step S1, the constant temperature time for melting is 3 to 7 hours.
According to some embodiments of the invention, step S1 further comprises cooling the resulting molten product after said melting;
preferably, the cooling period is about 30min.
Further preferably, the temperature of the material obtained after cooling is 10-40 ℃; it is understood that the specific temperature may be about 30 ℃.
According to some embodiments of the invention, the method of preparing further comprises crushing the additive.
According to some embodiments of the invention, the method of fragmenting comprises ball milling.
According to some embodiments of the invention, the ball milling time is 0.5h to 10h.
According to some preferred embodiments of the present invention, the ball milling time is 2 to 5 hours.
According to some embodiments of the invention, the particle size of the additive after crushing is less than or equal to 100 μm.
According to some embodiments of the invention, in step S2, the solvent comprises at least one of DMF (N, N-dimethylformamide) and ethyl acetate.
According to some embodiments of the invention, the mixing time in step S2 is 1h to 10h.
According to some embodiments of the invention, in step S2, the mixing is performed by means of mechanical stirring; preferably, the rotation speed of the mechanical stirring is 80-150 rpm; further preferably, in the apparatus for mechanical stirring, the diameter of the dispersion plate is 25cm (equivalent to a stirring paddle), the diameter of the mixing cylinder is 35cm (container),
according to some embodiments of the invention, in step S2, the solid content of the slurry is 78wt% to 85wt%.
According to some embodiments of the invention, the slurry has a solids content of about 80wt% in step S2.
According to some embodiments of the invention, the method of preparing further comprises performing digital modeling of the 3D printing prior to step S3.
According to some embodiments of the present invention, the digital modeling may be implemented by commercial mapping software, and mainly functions to define the structure of the product obtained by 3D printing, such as the length, width, height, and pattern structure, and more specifically, the moving track of the printer nozzle in 3D printing.
According to some embodiments of the invention, in step S3, the 3D printing method is a modulo-free direct write 3D printing method; preferably, the instrument employed is a modeless direct write 3D printing device.
According to some embodiments of the invention, the modeless direct write 3D printing apparatus employs a servo stepper motor; therefore, the repeated positioning precision is less than or equal to 100 mu m, the XY line width motion resolution precision is less than or equal to 10 mu m, and the layer thickness resolution is less than or equal to 20 mu m, so that the printing precision is fully ensured; the dimensional accuracy of the obtained ceramic substrate for LTCC was further confirmed.
According to some embodiments of the invention, in step S4, the sintering comprises a first stage sintering and a second stage sintering.
According to some embodiments of the invention, the constant temperature of the first stage sintering is 400-600 ℃.
According to some preferred embodiments of the present invention, the constant temperature of the first stage sintering is 500-600 ℃.
According to some embodiments of the invention, the constant temperature duration of the first stage sintering is between 0.5h and 5h.
According to some preferred embodiments of the invention, the constant temperature time of the first stage sintering is 1h to 3h.
According to some embodiments of the invention, the constant temperature of the second sintering stage is 600 ℃ to 850 ℃.
According to some preferred embodiments of the invention, the constant temperature of the second stage sintering is 700-800 ℃.
According to some embodiments of the invention, the constant temperature duration of the second stage sintering is 1h to 10h.
According to some preferred embodiments of the invention, the constant temperature duration of the second sintering stage is 2 to 5 hours.
According to some embodiments of the invention, in step S4, the sintering is performed under an air atmosphere.
Under the condition of above-mentioned sintering, LTCC uses the ceramic substrate size with the size of body is the almost the same, promptly the sintering process is right LTCC uses the ceramic substrate size has almost not influenced, and this has further guaranteed the size precision of gained ceramic substrate for LTCC.
According to some embodiments of the invention, the preparation method further comprises grinding the sintered product after step S4.
According to the third aspect of the embodiment of the invention, the application of the ceramic substrate for LTCC in the preparation of electronic components is provided.
Since the application adopts all the technical solutions of the ceramic substrate for LTCC of the above embodiments, at least all the advantageous effects brought by the technical solutions of the above embodiments are obtained.
Unless otherwise specified, "about" in the present invention means a tolerance of ± 2%, for example, about 100 actually means 100 ± 2% × 100, i.e., 98 to 102.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 shows the appearance of the ceramic substrate green body for LTCC obtained in step D4 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 reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention and are not to be construed as limiting the present invention.
In the description of the present invention, if there are first, second, etc. described, it is only for the purpose of distinguishing technical features, and it is not understood that relative importance is indicated or implied or that the number of indicated technical features is implicitly indicated or that the precedence of the indicated technical features is implicitly indicated.
In the description of the present invention, it should be understood that the orientation or positional relationship referred to, for example, the upper, lower, etc., is indicated based on the orientation or positional relationship shown in the drawings, and is only for convenience of description and simplification of description, but does not indicate or imply that the device or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention.
Example 1
The ceramic substrate for the LTCC is prepared by the embodiment, and the specific preparation method comprises the following steps:
D1. preparing a pre-sintering material: weighing ZrO 2 1400g and SiO 2 600g is ground in a ball mill for 1.5h in a wet process, wherein the solvent DMF: zrO (zirconium oxide) 2 +SiO 2 17 (mass ratio), the rotating speed of the ball mill is 450rpm, ball milling beads made of stainless steel are arranged in a ball milling tank, the particle size of the mixture after grinding is less than or equal to 100 mu m, drying is not needed, and the mixture is directly roasted at 840 ℃ for 2.0h to prepare a pre-sintering material;
preparation of the additive: weighing ZnO 200g and B 2 O 3 800g, mixing, and then melting at high temperature, wherein the constant temperature of the high-temperature melting is 1000 ℃, and the constant temperature heat preservation time is as follows: 4.5h;
annealing for 30min after the constant temperature heat preservation time is finished, specifically placing in the air, naturally cooling, and after 30min, the material temperature is about 30 ℃;
ball milling treatment is carried out on the product obtained by annealing, the ball milling time is 3h, and the particle size of the added material after ball milling is less than or equal to 100 mu m.
D2. Preparing a mixture: d1, mixing the pre-sintered material and the additive obtained in the step D1 with 700g of DMF (dimethyl formamide) and 78g of ethyl acetate, and then fully mixing for 2.5 hours (mechanical stirring at the rotating speed of 100rpm, the diameter of a dispersion disc in a stirrer is 20cm, and the diameter of a charging barrel is 30 cm) to prepare mixed slurry for die-free direct writing 3D printing;
D3. adding the mixed slurry obtained in the step D2 into a charging barrel of a film-free direct-writing 3D printer;
3D print program settings (digital modeling): setting a 3D printing program, mainly setting the length and width of a blank to be printed to be 100mm x 2.5mm, then setting a special double-ring structure on the surface, wherein a unit of a periodic structure is a sunken double ring, the outer diameter of a large ring is 22mm, the inner diameter of the large ring is 18mm, the outer diameter of a small ring is 14mm, the inner diameter of the small ring is 10mm, the depth of the small ring is 1mm, and then setting a printing path;
D4. printing: starting a film-free direct-writing 3D printer to print layer by layer, and printing a blank body, wherein the appearance of the obtained blank body is shown in figure 1;
D5. sintering the green body obtained in the step D4 at the temperature of 600 ℃ for 1 hour, and then sintering at the temperature of 750 ℃ for 2.0 hours;
D6. and (3) preparing a finished product: and D5, grinding and polishing the surface of the component obtained in the step D5 to obtain the LTCC ceramic substrate.
In the present example, the sizes of the green body obtained in step D4 and the sintered product obtained in step D5 were also measured by a level meter measurement method; the results show that the sintering process of step D5 has little effect on the size of the ceramic substrate for LTCC.
The ceramic substrate for LTCC produced in this example had a sintering shrinkage of about 1.0%. The specific test method comprises the following steps: testing the length of the LTCC substrate,The width varied before and after sintering. Substitution formula for calculating sintering | L 1 -L 0 /L 0 * Calculation is made 100% |, taking the maximum of two values, where the value after sintering is indicated by the angle 1, and the value before sintering is indicated by the angle 0, e.g. length and width are both 20cm before sintering and 19.8cm after sintering, the shrinkage is 0.2/20=1%;
from the above results, the preparation process of the invention has little influence on the size of the LTCC ceramic substrate, and the LTCC ceramic substrate with higher size precision can be obtained by means of a 3D printing method.
The ceramic substrate for LTCC prepared in this example has a plane warpage of 0.8%. Specifically, a tabulation measurement method is adopted: the method is to put the measured part and the micrometer on the standard flat plate, and to measure the part point by point or along several straight lines by the micrometer along the actual surface with the standard flat plate as the measuring reference surface.
Therefore, the warping degree of the component is hardly affected in the sintering process in the step D5, which further increases the dimensional accuracy of the ceramic substrate for LTCC manufactured by the present invention.
The flexural strength of the ceramic substrate for LTCC obtained in this example was 73MPa. Specifically, flexural strength testing was performed on an Instron1195 universal materials testing machine, english. The loading rate was 0.5mm/min as measured by three-point bending. Each data was tested on 5 bars and then averaged.
The dielectric constant and the dielectric loss of the ceramic substrate for the LTCC obtained in the embodiment are measured by adopting a coaxial line method and the tested frequency range is 1-18Ghz, and the specific results are as follows: the dielectric constant is 3-5.6; dielectric loss of 1.1-1.4X 10 -3 。
Comparative example 1
The ceramic substrate for the LTCC is prepared by the specific preparation method, which comprises the following steps:
D1. preparing a pre-sintering material: as FeO and SiO 2 Weighing FeO 1400g and SiO as raw materials 2 600g of the mixture is ground in a grinding machine by a wet method, and roasted at 900 ℃ for 3.5 hours after being ground to prepare a pre-sintered material;
preparation of the additive: weighing ZrO 2 200g and Al 2 O 3 800g, and carrying out high-temperature melting after mixing, wherein the constant temperature of the high-temperature melting is 750 ℃; keeping the temperature for 3h;
annealing for 40min after constant temperature heat preservation;
performing ball milling treatment on the product obtained by annealing, wherein the ball milling time is 2 hours;
D2. preparing a mixture: mixing the pre-sintered material and the additive obtained in the step D1 with a mixed solvent formed by 700g of DMF and 78g of ethyl acetate, and then fully mixing for 2.5 hours to prepare a mixture;
D3. adding the mixed slurry obtained in the step D2 into a charging barrel of a film-free direct-writing 3D printer;
3D print program settings (digital modeling): setting a 3D printing program, mainly setting the length, width and height of a blank to be printed to be 20mm-0.4mm, and then setting a printing path;
D4. printing: starting a DLP 3D printer to print layer by layer, and printing a blank;
D5. sintering the blank obtained in the step D4 at the temperature of 800 ℃ for 1h, and then sintering at 950 ℃ for 2h; the surface appearance is rough after sintering and has certain warping;
D6. and (3) preparing a finished product: and D, grinding and polishing the surface of the part obtained in the step D5 to obtain the ceramic substrate for the LTCC.
With reference to the test method of example 1, the ceramic substrate for LTCC obtained in this comparative example was measured to have:
sintering shrinkage of about 1.2%;
the plane warp is about 0.8%;
the bending strength is about 75MPa;
the dielectric constant is 2-4.5;
dielectric loss of 1.2-1.9X 10 -3 (ii) a The dielectric properties of which are inferior to those of ZrO of the same mass fraction 2 -Si0 2 -ZnO-B 2 0 3 A material system.
As can be seen from comparison between the results of example 1 and comparative example 1, on the basis that the size of the LTCC substrate obtained in example 1 is significantly higher than that of comparative example 1, the sintering shrinkage rate and the warpage are lower than those of comparative example 1, which indicates that the raw material system used in example 1 has higher dimensional accuracy than that of comparative example 1; as can be seen from the comparison of the dielectric constant and the dielectric loss, the example had more excellent dielectric properties than the comparative example 1.
According to the results, the invention is suitable for the 3D printing technology by adjusting the types and the proportion of the preparation raw materials, and the obtained ceramic substrate for the LTCC has higher dimensional precision and very abundant surface patterns after sintering and other steps, so that the ceramic substrate is more suitable for the preparation of integrated electronic elements.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (10)
1. The ceramic substrate for LTCC is characterized in that the raw material for preparing the ceramic substrate for LTCC comprises ZrO 2 、SiO 2 ZnO and B 2 O 3 ；
The ZrO 2 And SiO 2 The mass ratio of (A) to (B) is 2-10: 1;
the ZnO and B 2 O 3 The mass ratio of (1): 1 to 5;
the SiO 2 And ZnO in a mass ratio of 2.5 to 4.0.
2. The ceramic substrate of claim 1, wherein the ZrO 2 is 2 And SiO 2 The mass ratio of (A) to (B) is 4-6: 1.
3. the ceramic substrate for LTCC according to claim 1, wherein said ZnO and B 2 O 3 The mass ratio of (1): 2 to 4.
4. A method for preparing a ceramic substrate for LTCC according to any one of claims 1 to 3, comprising the steps of:
s1, preparing the ZrO 2 And SiO 2 Mixing, grinding and roasting to obtain a pre-sintered material;
the ZnO and B are mixed 2 O 3 Mixing and melting to obtain an additive;
s2, mixing a solvent with the pre-sintered material and the additive to obtain slurry;
s3, preparing a blank by using the slurry as a raw material and adopting a 3D printing method;
and S4, sintering the green body.
5. The preparation method according to claim 4, wherein in the step S1, the constant temperature of the simmering is 700-1000 ℃; preferably, the constant temperature duration of the simmering is 1-10 h.
6. The preparation method according to claim 4, wherein in the step S1, the constant temperature of the melting is 1000 to 1600 ℃; preferably, the constant temperature time of the melting is 2-10 h.
7. The method of claim 4, further comprising breaking the additive.
8. The method of manufacturing according to claim 4, further comprising performing digital modeling of the 3D printing prior to step S3.
9. The method according to claim 4, wherein in step S4, the sintering includes a first stage sintering and a second stage sintering; preferably, the constant temperature of the first-stage sintering is 400-600 ℃; preferably, the constant temperature of the second-stage sintering is 600-850 ℃.
10. Use of the ceramic substrate for LTCC according to any one of claims 1 to 3 in the preparation of an electronic component.
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