CN112299825A - Preparation method of low dielectric low temperature co-fired ceramic material - Google Patents
Preparation method of low dielectric low temperature co-fired ceramic material Download PDFInfo
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Abstract
The invention belongs to the technical field of microwave dielectric materials, and discloses a preparation method of a low-dielectric low-temperature co-fired ceramic material, which comprises the following steps: s1: mixing Al2O3Ceramic powder and glass powder of LCBS glass according to xAl2O3Mixing (100-x) LCBS in a nominal stoichiometric proportion, adding a binder for granulation, and performing compression molding to obtain a blank, wherein x is more than or equal to 50 and less than or equal to 65; the LCBS glass has the following composition in mole percent: (5-10) mol% of La2O3，(20‑28)mol％CaO，(45‑65)mol％B2O3，(5‑25)mol％SiO2(ii) a S2: sintering the blank at 800-900 ℃ for 0.5-1 hour to obtain xAl2O3- (100-x) LCBS low-dielectric low-temperature co-fired ceramic material. According to the invention, through optimizing and improving the components of the microcrystalline glass, the LCBS glass with specific components is compounded with the microwave dielectric ceramic with good microwave dielectric property, so that the obtained composite material can meet the sintering requirement below 900 ℃, the sintering treatment time requirement can be effectively reduced, and the correspondingly obtained low-temperature co-fired ceramic material has excellent dielectric property, thermal property and mechanical property.
Description
Technical Field
The invention belongs to the technical field of microwave dielectric materials, and particularly relates to a preparation method of a low-dielectric low-temperature co-fired ceramic material.
Background
The microwave dielectric ceramic is a ceramic material which is used as a medium in a microwave frequency band (300 MHz-30 GHz) circuit. With the development of 5G technology, electronic components are developed towards the direction of ultra-thin, high-performance, high-reliability and high-integration, and Low Temperature Co-fired ceramic (LTCC) technology is the mainstream technology for realizing high-integration and high-performance electronic packaging at present due to the advantages of unique Low-Temperature multi-layer Co-firing characteristic, Low cost and good repeatability. The continuous improvement of the operating frequency of the communication equipment can make the signal delay phenomenon more obvious, the system loss and the heat productivity increase, and the system stability gradually becomes worse. By the formula
(where v is the signal transmission speed, c is the speed of light,. epsilon.)rIs a baseDielectric constant of the plate), lowering the dielectric constant of the substrate can increase the transmission rate of electrical signals, and lower dielectric constant (epsilon)r<15) The mutual coupling loss between the material and the electrode can be reduced, and the energy loss is reduced. Therefore, in order to adapt to the development of 5G technology, the research on the LTCC substrate material with low dielectric constant is particularly important. In addition, as LTCC substrate materials, there is a need to satisfy: (1) chemical compatibility: can be co-fired with Ag electrodes; good acid resistance, and realizes the compatibility of chemical gold plating on the surface of the silver conductor; (2) mechanical properties: higher mechanical strength (>160MPa), the supporting and protecting effect on the chip is realized; (3) electrical properties: high electrical resistivity: (>1012Ω · cm), avoiding mutual crosstalk of signals in the electronic system; (4) good thermal properties: the high thermal conductivity facilitates dissipation of heat in highly integrated circuits; the coefficient of thermal expansion is matched with that of the Si chip (3.5 ppm/DEG C), and thermal compatibility with the Si chip is realized.
Therefore, in order to meet the requirements of electronic materials in practical application, it is very important to develop a low dielectric constant temperature co-fired ceramic (LTCC) material with excellent dielectric properties, mechanical properties and thermal properties.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention aims to provide a preparation method of a low-dielectric and low-temperature co-fired ceramic material, which is characterized in that the components of microcrystalline glass are optimized and improved, LCBS glass with specific components is compounded with microwave dielectric ceramic with good microwave dielectric property, so that the obtained composite material can meet the sintering requirement below 900 ℃, meanwhile, the sintering treatment time requirement can be effectively reduced, and the correspondingly obtained low-temperature co-fired ceramic material has excellent dielectric property, thermal property and mechanical property, and can be directly applied to various industrial application scenes of the low-temperature co-fired ceramic material.
In order to achieve the above object, according to the present invention, there is provided a method for preparing a low dielectric low temperature co-fired ceramic material, comprising the steps of:
s1: mixing Al2O3Ceramic powder and glass powder of LCBS glass according to xAl2O3Mixing (100-x) LCBS with nominal stoichiometric proportion, adding binder, and granulatingPressing and forming to obtain a blank; wherein x satisfies: x% represents xAl2O3Al in (100-x) LCBS2O3The percentage of the component (100-x)% represents xAl2O3- (100-x) the LCBS glass in the LCBS by mass percent, wherein x is any real number which is more than or equal to 50 and less than or equal to 65;
the LCBS glass is La2O3-CaO-B2O3-SiO2The quaternary system glass comprises the following components in percentage by mole: (5-10) mol% of La2O3，(20-28)mol％CaO，(45-65)mol％B2O3，(5-25)mol％SiO2；
S2: sintering the blank obtained in the step S1 at 800-900 ℃ for 0.5-1 hour to obtain xAl2O3- (100-x) LCBS low-dielectric low-temperature co-fired ceramic material, the dielectric constant of the low-temperature co-fired ceramic material is 6-7.
As a further preferred aspect of the present invention, in step S1, the method for preparing the glass frit for LCBS glass includes the steps of:
(1) according to La: ca: b: si molar ratio (10-20): (20-28): (90-130): (5-25) mixing a La source, a Ca source, a B source and a Si source, or the La source, the Ca source and the B source, which are used as raw material powder, to obtain a raw material mixture;
(2) and melting the raw material mixture, and then performing water quenching, crushing, drying and sieving to obtain the glass powder of the LCBS glass.
As a further preferred aspect of the present invention, the La source is La2O3The Ca source is CaCO3The B source is H3BO3Or B2O3The Si source is SiO2(ii) a The purity of these La, Ca, B and Si sources was greater than 99.0%.
In a further preferred embodiment of the present invention, the La source, the Ca source, the B source, and the Si source are dried to remove moisture in advance; preferably, the drying to remove water is carried out at 300 ℃ for 2 h.
As a further preference of the invention, the melting temperature is 1150-1400 ℃ and the time is 1.0-4.0 hours.
As a further preferred aspect of the present invention, the binder is an aqueous PVA solution having a solute mass percentage of 6.0 to 10.0%.
As a further preferred aspect of the present invention, in the step S1, the LCBS glass has the following components in mol percentage: 7 mol% of La2O3，28mol％CaO，55mol％B2O3，10mol％SiO2。
Through the technical scheme of the invention, compared with the prior art, the LCBS glass with specific components is utilized, and the LCBS glass component comprises (5-10) mol% of La2O3、(20-28)mol％CaO、(45-65)mol％B2O3And (5-25) mol% SiO2The ceramic material is compounded with microwave dielectric ceramic with good microwave dielectric property, so that the obtained composite material can meet the sintering requirement below 900 ℃, meanwhile, the sintering treatment time can be effectively reduced, the sintering is only required to be carried out for 0.5-1 hour at 800-900 ℃, and the correspondingly obtained low-temperature co-fired ceramic material has excellent dielectric property, thermal property and mechanical property, and can be directly applied to various industrial application scenes of the low-temperature co-fired ceramic material.
La2O3-CaO-B2O3-SiO2Glass was originally used as a material for shielding X-rays, and the present inventors first applied it to Ca by Lei Wen et al2RE8Si6O26The (RE ═ Nd, Sm, Er) microwave dielectric ceramic is used for preparing a low dielectric constant LTCC material (patent number CN 110563463A) with excellent performance, the dielectric constant is between 11 and 13.1, and the Qxf is between 3410-. For this purpose, the invention further provides La2O3-CaO-B2O3-SiO2The formula of the glass powder is researched and improved, and the LCBS glass with specific components is used for preparing xAl2O3The (100-x) LCBS low-dielectric low-temperature co-fired ceramic material can effectively shorten the sintering treatment time on one hand, and on the other hand, the prepared low-dielectric low-temperature LTCC material has lower dielectric constant and more lossSmall size, simultaneously has excellent mechanical property and thermal property, and can be directly applied to various industrial application scenes of low-temperature co-fired ceramic materials.
The low-temperature co-fired ceramic material prepared by the preparation method has the dielectric constant of 6-7 and the quality factor of>5000GHz with a temperature coefficient of resonance frequency of<-30 ppm/DEG C, flexural strength>260MPa, acid resistance<0.15%, insulation resistance>1012Omega cm, thermal conductivity of 2.4-3.5W/(m.K), and thermal expansion coefficient of 4-6 ppm/deg.C. For example, the low-temperature co-fired ceramic material with a specific mixture ratio obtained by the invention has the dielectric constant of 6.9, Q multiplied by f of 6987GHz (f is 13GHz), the temperature coefficient of resonance frequency is-29 ppm/DEG C, the thermal conductivity is 3.4W/(m.K), the bending strength is 282MPa, and the thermal expansion coefficient is 4.3 ppm/DEG C.
Therefore, the invention can obtain the following beneficial effects:
(1) the LTCC material prepared by the LTCC preparation process and the preparation method thereof have the advantages of low dielectric constant, low dielectric loss, sintering temperature lower than 900 ℃ and short sintering time, and can be co-fired with silver paste at 800-plus-material 900 ℃.
(2) The novel low-temperature microwave dielectric ceramic provided by the invention adopts the traditional glass melting method to prepare LCBS glass powder, adopts the solid phase method to prepare the glass/ceramic composite material, has cheap raw materials and simple preparation process, does not need a special sintering process, is an ideal LTCC preparation process, and can be used for large-scale industrial production of devices such as microwave antennas, filters, substrate packaging and the like.
The preparation method of the low-temperature co-fired ceramic material has the advantages of simple preparation process, cheap raw materials and good repeatability, is suitable for batch production, and is very beneficial to the application of the low-temperature co-fired ceramic material.
In conclusion, the preparation method adopts the LCBS glass with specific components, and the low-temperature co-fired ceramic material obtained correspondingly has short sintering time required by sintering treatment at 800-900 ℃, for example, can be sintered at 800-900 ℃ for 30 minutes for densification. In addition, the sintering temperature and the dielectric constant of the composite material can be regulated and controlled by adjusting the mass percentage of the LCBS glass in the composite material, and the low-temperature co-fired material with excellent dielectric property, mechanical property and thermal property can be obtained.
Drawings
FIG. 1 is an XRD pattern of a sample co-fired with Ag in example 2 of the present invention.
FIG. 2 is a scanning electron micrograph of a Co-fired Ag sample of example 2 according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In general, the invention compounds LCBS glass with specific components and microwave dielectric ceramic with good microwave dielectric property, i.e. towards Al2O3La with specific component proportion is added into ceramic material2O3-CaO-B2O3-SiO2Glass material, and the low dielectric microwave dielectric ceramic composite material is obtained by using the glass material, wherein the chemical composition of the material is xAl2O3- (100-x) LCBS, wherein 50. ltoreq. x.ltoreq.65 (x%, i.e. x percent, representing Al in the system)2O3The mass percentage of the glass is more than or equal to 50 percent and less than or equal to x percent and less than or equal to 65 percent), and the glass comprises (5-10) mol percent of La2O3，(20-28)mol％CaO，(45-65)mol％B2O3，(5-25)mol％SiO2The sum of the mole percentages of all components in the glass is 100 mol%. During preparation, the LCBS glass powder can be prepared by a melting method, and then the prepared glass powder and the ceramic powder are subjected to ball milling, mixing, drying, granulation, dry pressing and molding according to the mass ratio, and sintered at the temperature of 800-plus-material 900 ℃ to prepare the low-temperature co-fired ceramic material.
Example 1
The embodiment specifically comprises the following steps:
(1) press 5La2O3-25CaO-45B2O3-25SiO2The mixture ratio is (mol%) Weighing, adding proper amount of deionized water and ZrO2Ball milling is carried out for 5.0h in a planetary ball mill with the rotating speed of 365 r/min;
(2) drying and sieving the powder obtained in the step (1), placing the powder in a platinum crucible at 1400 ℃ for heat preservation for 4 hours, and then quickly pouring the molten glass into deionized water for quenching to obtain broken glass pieces;
(3) putting the glass fragment material obtained in the step (2) into a nylon tank, and carrying out ball milling for 12.0h in a planetary ball mill with the rotating speed of 365 r/min;
(4) placing the ball-milled glass powder slurry in the step (3) in a constant-temperature drying oven at 100 ℃, drying for 6 hours, and sieving with a 200-mesh sieve after drying to obtain glass powder with the particle size of 2-3 mu m for later use;
(5) mixing the glass powder obtained in the step (4) with 50g of Al2O3Mixing the ceramic powder, and mixing the ceramic powder by 100 g; adding 100g of materials into a zirconia ball and deionized water in a nylon tank, wherein the weight ratio of the materials: ball: water 1: 3: 2 (mass percent) and ball-milling for 5.0h in a planetary ball mill with the rotating speed of 365 r/min; drying in a constant-temperature drying oven at 100 ℃, adding 6% by mass of PVA solution as a binder for granulation, sieving with a 40-mesh sieve, and pressing into a cylinder with the diameter of 12mm and the height of 6mm by using a tablet press under 150 MPa;
(6) and (4) placing the cylinder obtained in the step (5) in a box-type furnace, discharging the glue for 2h at 550 ℃, and carrying out heat preservation sintering for 30 minutes at 900 ℃ in an air atmosphere to prepare the low-temperature co-fired ceramic. And (4) grinding the two sides, and performing ultrasonic cleaning and drying test.
(7) And (3) performing performance test on the sample obtained in the step (6) to obtain a sample with the dielectric constant of 6.5, the Q multiplied by f is 5848GHz (f is 12.88Hz), the temperature coefficient of the resonance frequency is-35 ppm/DEG C, the bending strength is 262MPa, the acid resistance is 0.12% (GB/T4738-14Omega cm, thermal conductivity 2.6W/(m.K), coefficient of thermal expansion 5.4 ppm/DEG C.
Example 2
The embodiment specifically comprises the following steps:
(1) press 10La2O3-20CaO-65B2O3-5SiO2The proportion (mol%) of the glass is weighed,adding proper amount of deionized water and ZrO2Ball milling is carried out for 5.0h in a planetary ball mill with the rotating speed of 365 r/min;
(2) drying and sieving the powder obtained in the step (1), placing the powder in a platinum crucible at 1300 ℃ for heat preservation for 2 hours, and then quickly pouring the molten glass into deionized water for quenching to obtain broken glass pieces;
(3) putting the glass fragment material obtained in the step (2) into a nylon tank, and carrying out ball milling for 12.0h in a planetary ball mill with the rotating speed of 365 r/min;
(4) placing the ball-milled glass powder slurry in the step (3) in a constant-temperature drying oven at 100 ℃, drying for 6 hours, and sieving with a 200-mesh sieve after drying to obtain glass powder with the particle size of 2-3 mu m for later use;
(5) mixing a part of the glass powder obtained in the step (4) with 55g of Al2O3The ceramic powder was mixed together to give 100g, and the other part was mixed with 55g of Al2O3Mixing the ceramic powder and 20g of Ag powder, wherein the total amount is 120g, adding the mixture into zirconia balls and deionized water in a nylon tank, and mixing: ball: water 1: 3: 2 (mass percent) and ball-milling for 5.0h in a planetary ball mill with the rotating speed of 365 r/min; drying in a constant-temperature drying oven at 100 ℃, adding 8% by mass of PVA solution as a binder for granulation, sieving with a 40-mesh sieve, and pressing into a cylinder with the diameter of 12mm and the height of 6mm by using a tablet press under 150 MPa;
(6) and (4) placing the cylinder obtained in the step (5) in a box-type furnace, removing the glue for 2h at 550 ℃, and carrying out heat preservation sintering for 60 minutes at 800 ℃ in an air atmosphere to prepare the low-temperature co-fired ceramic.
(7) And (3) performing XRD and SEM performance tests on the sample co-fired with Ag obtained in the step (6), wherein the obtained result is shown in figures 1 and 2, and the sample can be co-fired with Ag. The other part of the samples had dielectric constant of 6.7, Q × f 6542GHz (f 13.001Hz), temperature coefficient of resonance frequency of-42 ppm/DEG C, bending strength of 275MPa, acid resistance of 0.13% (GB/T4738-14Omega cm, thermal conductivity 2.9W/(m.K), coefficient of thermal expansion 5.9 ppm/DEG C.
Example 3
The embodiment specifically comprises the following steps:
(1) press 7La2O3-28CaO-55B2O3-10SiO2Weighing glass according to the proportion (mol percent), adding a proper amount of deionized water and ZrO2Ball milling is carried out for 5.0h in a planetary ball mill with the rotating speed of 365 r/min;
(2) drying and sieving the powder obtained in the step (1), placing the powder in a platinum crucible at 1150 ℃ for heat preservation for 1h, and then quickly pouring the molten glass into deionized water for quenching to obtain broken glass pieces;
(3) putting the glass fragment material obtained in the step (2) into a nylon tank, and carrying out ball milling for 12.0h in a planetary ball mill with the rotating speed of 365 r/min;
(4) placing the ball-milled glass powder slurry in the step (3) in a constant-temperature drying oven at 100 ℃, drying for 6 hours, and sieving with a 200-mesh sieve after drying to obtain glass powder with the particle size of 2-3 mu m for later use;
(5) mixing the glass powder obtained in the step (4) with 65g of Al2O3Mixing the ceramic powder, and mixing the ceramic powder by 100 g; adding 100g of materials into a zirconia ball and deionized water in a nylon tank, wherein the weight ratio of the materials: ball: water 1: 3: 2 (mass percent) and ball-milling for 5.0h in a planetary ball mill with the rotating speed of 365 r/min; drying in a constant-temperature drying oven at 100 ℃, adding 10% by mass of PVA solution as a binder for granulation, sieving with a 40-mesh sieve, and pressing into a cylinder with the diameter of 12mm and the height of 6mm by using a tablet press under 150 MPa;
(6) and (4) placing the cylinder obtained in the step (5) in a box-type furnace, removing the glue for 2h at 550 ℃, and carrying out heat preservation sintering for 30 minutes at 850 ℃ in an air atmosphere to prepare the low-temperature co-fired ceramic. And (4) grinding the two sides, and performing ultrasonic cleaning and drying test.
(7) The ceramic sample obtained in the step (6) has a dielectric constant of 6.9, Q × f is 6987GHz (f is 13GHz), a temperature coefficient of resonance frequency of-32 ppm/DEG C, bending strength of 282MPa, acid resistance of 0.11% (GB/T4738-14Omega cm, thermal conductivity 3.4W/(m.K), coefficient of thermal expansion 4.3 ppm/DEG C.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A preparation method of a low dielectric low temperature co-fired ceramic material is characterized by comprising the following steps:
s1: mixing Al2O3Ceramic powder and glass powder of LCBS glass according to xAl2O3Mixing (100-x) LCBS in a nominal stoichiometric proportion, adding a binder for granulation, and performing compression molding to obtain a blank; wherein x satisfies: x% represents xAl2O3Al in (100-x) LCBS2O3The percentage of the component (100-x)% represents xAl2O3- (100-x) the LCBS glass in the LCBS by mass percent, wherein x is any real number which is more than or equal to 50 and less than or equal to 65;
the LCBS glass is La2O3-CaO-B2O3-SiO2The quaternary system glass comprises the following components in percentage by mole: (5-10) mol% of La2O3，(20-28)mol％CaO，(45-65)mol％B2O3，(5-25)mol％SiO2；
S2: sintering the blank obtained in the step S1 at 800-900 ℃ for 0.5-1 hour to obtain xAl2O3- (100-x) LCBS low-dielectric low-temperature co-fired ceramic material, the dielectric constant of the low-temperature co-fired ceramic material is 6-7.
2. The method according to claim 1, wherein in step S1, the method for preparing the glass frit of the LCBS glass comprises the steps of:
(1) according to La: ca: b: si molar ratio (10-20): (20-28): (90-130): (5-25) mixing a La source, a Ca source, a B source and a Si source, or the La source, the Ca source and the B source, which are used as raw material powder, to obtain a raw material mixture;
(2) and melting the raw material mixture, and then performing water quenching, crushing, drying and sieving to obtain the glass powder of the LCBS glass.
3. The method of claim 2, wherein the La source is La2O3The Ca source is CaCO3The B source is H3BO3Or B2O3The Si source is SiO2(ii) a The purity of these La, Ca, B and Si sources was greater than 99.0%.
4. The method according to claim 2, wherein the La source, the Ca source, the B source and the Si source are dried to remove moisture in advance; preferably, the drying to remove water is carried out at 300 ℃ for 2 h.
5. The method of claim 2, wherein the melting is performed at a temperature of 1150 ℃ to 1400 ℃ for 1.0 to 4.0 hours.
6. The method according to claim 1, wherein the binder is an aqueous solution of PVA having a solute mass fraction of 6.0 to 10.0%.
7. The method of claim 1, wherein in step S1, the LCBS glass has a composition in mole percent: 7 mol% of La2O3，28mol％CaO，55mol％B2O3，10mol％SiO2。
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