CN101717245A - Low-temperature co-fired ceramic substrate material and preparation method thereof - Google Patents

Abstract

The invention discloses a low-temperature co-fired ceramic substance material and a preparation method thereof. The ceramic substance material comprises a substrate material and a ceramic phase, wherein the substrate material accounts for 45 to 80 mass percent, and the balance is the ceramic phase; the ceramic phase adopts alpha-Al2O3; and the substrate material is ZnO-B2O3-Al2O3 glass consisting of 70 molar percent of ZnO, 30 to 65 molar percent of B2O3 and 0 to 10 molar percent of Al2O3. The preparation method comprises the following steps: firstly preparing the ZnO-B2O3-Al2O3 glass powder; then mixing the alpha-Al2O3 powder and the glass powder, adding deionized water, performing ball milling and drying; and granulating, tabletting, and sintering. The material has the characteristics of wide sintering temperature range and good capability; and the method has simple process and low cost.

Description

A kind of low-temperature co-fired ceramic substrate material and preparation method thereof

Technical field

The invention belongs to the electric substrate technical field of composite materials, a kind of low-temperature co-fired ceramic substrate material and preparation method thereof particularly is provided.

Background technology

Enter 21 century, along with military complete electronic set, communication class electronic product and consumer electronics product develop to weak point, little, light, thin direction rapidly, and the function of terminal systems such as mobile phone, PDA, MP3, notebook computer is more and more many, volume is more and more little, and the circuit packing density is more and more high.If the part passive element can be integrated in the substrate, then not only help the miniaturization of system, improve the packing density of circuit, also help the reliability of raising system.At present, numerous experts and engineering circle are all thought, the best mode of realizing the complete machine or the system integration is to adopt mcm (MCM) technology, and multilayer chip element (chip ceramic capacitor etc. that comprises chip microwave dielectric resonator, wave filter, microwave-medium antenna and have good high frequency use properties) is the effective way that realizes this purpose.The chip type of microwave device needs microwave dielectric material to burn altogether with the metal electrode of high conductivity such as Pt, Pd, Au, Cu, Ag etc.Consider from economy and environmental, use fusing point lower Ag (961 ℃) or Cu metals such as (1064 ℃) ideal as electrode materials.Therefore, require microwave dielectric ceramic materials to have sintering temperature and low, burn altogether with Ag or Cu (Sun Hui duckweed .LTCC hangs down Jie's high frequency microwave dielectric material [master thesis]. Hangzhou: Zhejiang University's material and chemical engineering institute, 2004.).

LTCC Technology (Low temperature co-fired ceramics, write a Chinese character in simplified form LTCC) be in the type material technology of nineteen eighty-two Hughes Electronics's exploitation, be that the low-temperature sintered ceramics powder is made the accurate and fine and close green band of thickness, on the green band, utilize laser boring, micropore slip casting, technologies such as accurate conductor paste printing are made the circuitry needed figure, and with a plurality of passive blocks (as low appearance value electric capacity, resistance, wave filter, impedance transducer, coupling mechanism etc.) imbed in the multilayer ceramic substrate, overlap together then, internal and external electrode can use silver respectively, copper, metals such as gold, at 900 ℃ of following sintering, make the non-interfering high-density circuit of three-dimensional space, also can be made into the three-dimensional circuit substrate of built-in passive element, can mount IC and active part on its surface, make passive/active integrated functional module, can be further with circuit miniaturization and densification, be particularly suitable for high frequency communication assembly (Wang Yuehui, relieve, Cui Xuemin, Deng. the progress of LTCC (LTCC) technology on materialogy. Journal of Inorganic Materials, 2006,21 (02): 267～276.).

The low dielectric constant microwave dielectric material is good because of its microwave dielectric property, and high-frequency loss is little, is fit to the design and the manufacturing of high frequency chip components and parts such as Ba Lun, wave filter, antenna, module, begins to be subjected to people's common concern.For the research of low-k LTCC material, mainly concentrate in the application of ltcc substrate material at present.Concerning microwave circuit, the ltcc substrate material should have low-dielectric loss, low-k and high insulation resistance and dielectric strength.For baseplate material, must reduce the ε of baseplate material _rThe research and development specific inductivity is less than 10, even lower ltcc substrate material with satisfy high frequency and high speed require be the challenge how adapting to frequency applications of LTCC material (research [master thesis] of yellow brave .LTCC glass ceramic material. Chengdu: material system of University of Electronic Science and Technology, 2005.).

Summary of the invention

The object of the present invention is to provide a kind of low-temperature co-fired ceramic substrate material, this material has the advantages that sintering range is wide, performance is high; The present invention also provides the preparation method of this low-temperature co-fired ceramic substrate material, and this method technology is simple, and cost is low.

Low-temperature co-fired ceramic substrate material of the present invention is characterized in that, this ceramic substrate material comprises substrate material and ceramic phase, and wherein, the mass percent of substrate material is 45%～80%, and surplus is a ceramic phase, and ceramic phase adopts α-Al ₂O ₃

Substrate material is ZnO, B ₂O ₃And Al ₂O ₃The ZnO-B that constitutes ₂O ₃-Al ₂O ₃Glass, the molar percentage of each component in substrate material is:

Zinc oxide (ZnO) 30～70%

Boron oxide (B ₂O ₃) 30～65%

Aluminum oxide (Al ₂O ₃) 0～10%.

The preparation method of above-mentioned low-temperature co-fired ceramic substrate material is characterized in that, this preparation method comprises the steps:

The 1st step preparation ZnO-B ₂O ₃-Al ₂O ₃Glass powder, its process is:

(1.1) with ZnO, H ₃BO ₃And Al ₂O ₃Mix in proportion;

(1.2) above-mentioned mixed material is put into High Temperature Furnaces Heating Apparatus, be warming up to 300～350 ℃ with 1～5 ℃/minute, be warming up to 1100～1350 ℃ with 3～8 ℃/minute again, be incubated 1～2 hour, with the glass metal shrend, obtain chopped glass then from room temperature;

(1.3),, obtain glass powder through screening with the chopped glass fragmentation;

(1.4) glass powder mixes with deionized water and put into the planetary ball mill ball milling 2～6 hours, and it is standby to obtain glass powder after the oven dry;

The 2nd step is with α-Al ₂O ₃Powder and ZnO-B ₂O ₃-Al ₂O ₃Glass powder is mixed in proportion respectively, adds deionized water, ball milling, oven dry;

The 3rd step adopt massfraction be 6～8% polyvinyl alcohol solution as binding agent, granulation;

Sintering behind the 4th step compressing tablet.

In the present invention's prescription, adopt α-Al ₂O ₃As ceramic phase, ZnO-B ₂O ₃-Al ₂O ₃Glass is as matrix, and in 650～950 ℃ of temperature ranges, glass has certain fluidity, simultaneously can with α-Al ₂O ₃Reaction, thus α-Al better soaked into ₂O ₃Particle furthers particle mutually, realizes low-temperature sintering.In addition, glassy phase also can crystallization, thereby reduces the glassy phase content in the baseplate material that obtains, and improves dielectric properties.

Baseplate material of the present invention can be realized burning altogether under 850～950 ℃ with high conductivity metal Cu, Ag, Au etc., and baseplate material has excellent dielectric properties: and low specific inductivity (under 7GHz, 3.5～5.5) and dielectric loss (under 7GHz, 5.0 * 10 ^-3～8.7 * 10 ^-4), Q * f (2000～9000GHz) and temperature coefficient of resonance frequency (30～-50ppm/K).

Low-temperature co-fired ceramic substrate of the present invention has the following advantages:

(1) baseplate material of the present invention has superior dielectric properties, and specific inductivity is low, and the dielectric loss under the high frequency is little, can satisfy the dielectric properties requirement of high-frequency high-speed circuit to baseplate material.

(2) raw material of the present invention's employing is cheap oxide compound, and technology is simple, greatly reduces the cost of product, and sintering range is wide simultaneously, is fit to suitability for industrialized production.

(3) brought into play the advantage of LTCC Technology, can realize burning altogether the loss when greatly reducing the Circuits System operation with the metal of high conductivity.By adjusting glass ingredient prescription and α-Al ₂O ₃With the ratio of glass, the performance of baseplate material in very large range, thus satisfy the needs of circuit layout.

Embodiment

For example the present invention is described in further detail below, but embodiments of the present invention are not limited thereto.

Example 1:

1, ZnO-B ₂O ₃-Al ₂O ₃The preparation of glass powder:

(1) with ZnO, H ₃BO ₃And Al ₂O ₃Press the prescription batching in the table 1, total mass is 400 grams, grinds about 1 hour to mixing in agate mortar, contains in the 500ml corundum crucible.

The Al of indication among the present invention ₂O ₃Crystal formation is not had special qualification, can comprise α-Al ₂O ₃And/or γ-Al ₂O ₃Crystal formation.

(2) corundum crucible that oxide raw material will be housed is put into the bell-type smelting furnace, is warming up to 300 ℃ from room temperature with 1 ℃/minute, is warming up to 1150 ℃ with 5 ℃/minute again, is incubated 1 hour, with the glass metal shrend, obtains chopped glass then.

(3) chopped glass is crossed 40 mesh sieves through coarse crushing, obtains glass powder.

(4) glass powder that obtains in the step (3) is mixed with deionized water put into the planetary ball mill ball milling 3 hours, it is standby to make glass powder after the oven dry.

2, α-Al ₂O ₃/ ZnO-B ₂O ₃-Al ₂O ₃The preparation of series low-temperature co-burning baseplate material sample:

(1) with α-Al ₂O ₃Powder and ZnO-B ₂O ₃-Al ₂O ₃The prescription that glass powder is pressed respectively in the table 3 mixes, and total mass is 50 grams, adds deionized water, places the planetary ball mill ball milling 1 hour, oven dry.

(2) adopt massfraction be 8% polyvinyl alcohol solution as binding agent, granulation.

(3) compressing tablet.Slice, thin piece diameter 25mm, height 14～17mm, pressure is 110Mpa, pressurize 1 minute.

(4) sintering adopts the normal sintering method, is warming up to 600 ℃ from room temperature with 3 ℃/minute, is incubated 0.5 hour, and the organism in the material is got rid of fully, is warming up to 900 ℃ with 5 ℃/minute then, and is incubated 2 hours, adopts air atmosphere, cools to room temperature with the furnace.

The prescription of each raw material of example 2-6 is as shown in table 1, its preparation method such as example 1.

Among the present invention, α-Al ₂O ₃/ ZnO-B ₂O ₃-Al ₂O ₃The prescription that is the low-temp ceramics baseplate material is as shown in table 1.

Table 1 baseplate material prescription

Example 7～12:

Example 7～12 all adopts the prescription of example 2, and the processing parameter in the preparation process of example 7～12 is as shown in table 2.

The processing parameter of table 2 example 7～12

	Heat-up rate (℃/minute)	Holding temperature (℃)	Soaking time (hour)
				Example 7	??3	??900	??2
Example 8	??5	??900	??2
				Example 9	??3	??850	??4
Example 10	??3	??950	??4
				Example 11	??5	??950	??6
Example 12	??5	??900	??6

(remarks: heat-up rate refers to 600 ℃ of heat-up rates to the temperature range of holding temperature)

Adopt ADVANTEST R3767C type network analyzer to measure the dielectric properties of above-mentioned sample, the result is as shown in table 3.

The dielectric properties of table 3 laboratory sample

Among the present invention, compressing tablet and sintering all can adopt conventional processing method.Be warming up to 600 ℃ from room temperature with 3 ℃/minute, be incubated 0.5 hour, the organism in the material is got rid of fully, be warming up to 850～950 ℃ with 5 ℃/minute then, and be incubated 2～6 hours, adopt air atmosphere, cool to room temperature with the furnace.

The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment.So everyly do not break away from the equivalence of finishing under the spirit disclosed in this invention or revise, all fall into the scope of protection of the invention.

Claims (2)

1. a low-temperature co-fired ceramic substrate material is characterized in that, this ceramic substrate material comprises substrate material and ceramic phase, and wherein, the mass percent of substrate material is 45%～80%, and surplus is a ceramic phase, and ceramic phase adopts α-Al ₂O ₃

Substrate material is ZnO, B ₂O ₃And Al ₂O ₃The ZnO-B that constitutes ₂O ₃-Al ₂O ₃Glass, the molar percentage of each component in substrate material is:

ZnO??30～70％

B ₂O ₃?30～65％

Al ₂O ₃?0～10％。

2. the preparation method of the described low-temperature co-fired ceramic substrate material of claim 1 is characterized in that, this preparation method comprises the steps:

The 1st step preparation ZnO-B ₂O ₃-Al ₂O ₃Glass powder, its process is:

(1.1) with ZnO, H ₃BO ₃And Al ₂O ₃Mix in proportion;

(1.2) above-mentioned mixed material is put into High Temperature Furnaces Heating Apparatus, be warming up to 300～350 ℃ with 1～5 ℃/minute, be warming up to 1100～1350 ℃ with 3～8 ℃/minute again, be incubated 1～2 hour, with the glass metal shrend, obtain chopped glass then from room temperature;

(1.3),, obtain glass powder through screening with the chopped glass fragmentation;

(1.4) glass powder mixes with deionized water and put into the planetary ball mill ball milling 2～6 hours, and it is standby to obtain glass powder after the oven dry;

The 2nd step is with α-Al ₂O ₃Powder and ZnO-B ₂O ₃-Al ₂O ₃Glass powder is mixed in proportion respectively, adds deionized water, ball milling, oven dry;

The 3rd step adopt massfraction be 6～8% polyvinyl alcohol solution as binding agent, granulation;

Sintering behind the 4th step compressing tablet.