CN101671169B - Low temperature sintering microwave medium ceramic material and preparation method thereof - Google Patents

Abstract

The invention discloses a low temperature sintering microwave medium ceramic material and a preparation method thereof. The material comprises the following compositions by weight percent: 92-99 percent of Ba4MTi11O27 and 1-8 percent of BaCu (B2O5), wherein the M is one of Zn and Mg, and the material can be prepared through solid-phase reaction. The prepared low temperature sintering LTCC microwave medium ceramic has low sintering temperature (about 900 DEG C) and excellent microwave performance, i.e. the dielectric constant (epsilonr) is that x is about more than 27 and not more than 36, the value of Q multiplied by f is high, and tauf is small; the low temperature sintering LTCC microwave medium ceramic is not reacted with silver (Ag); and pure silver can be adopted as an electrode to carry out co-firing, thus being capable of greatly lowering the manufacture cost of a device and being used for manufacturing microwave devices such as low temperature co-firing ceramic systems (LTCC), multi-layer medium resonators, microwave antennas, wave filters and the like.

Description

A kind of low-temperature sintered microwave dielectric ceramic material and preparation method thereof

Technical field

The invention belongs to electronic ceramics and manufacturing field thereof, relate to a kind of microwave dielectric ceramic materials, especially a kind of low-temperature sintered microwave dielectric ceramic material and preparation method thereof.

Background technology

Along with electronic information technology constantly develops to high frequencyization and digitizing direction,, integrated so that modular requirement is also more and more urgent to the miniaturized of components and parts.LTCC LTCC (Low TemperatureCo-fired Ceramics) is with its excellent electricity, machinery, calorifics and operational characteristic; Become one of major technique of electronic-component moduleization; Reach the Taiwan fast development abroad, formed the industry taper.In the past few years, the global LTCC element market output value is at mobile phone, and the promotion of radio communication products such as bluetooth and WLAN increases down fast, estimates the future market performance and also will continue beautiful.Good this technology of at present domestic existing how tame manufacturer and actively dropping into, however because upstream materials and correlation technique by external control, make the manufacturer of a large amount of shipment still in minority.Because domestic passive device manufacturer still appears loath to part from each otherly with Japanese trader's dragsaw for many years at present, whether might be continued dragsaw to widen future by the Japanese trader, and the development effect of domestic LTCC is the significant effects factor.

Realize the integrated of passive element; Modularization; Must develop the LTCC material new system that makes new advances, the LTCC porcelain of especially middle and high specific inductivity does not at home and abroad still well solve and is commercial, is badly in need of the LTCC microwave dielectric ceramic materials of differing dielectric constants such as research low K (low-k), middle K and high K simultaneously in the module design with in making; Must research and solve simultaneously between the different K values material and with the common burning compatibling problem of silver electrode, copper electrode; Abroad the colleague has done number of research projects in this respect, and ripe the production also of the LTCC raw material band of low K value has several big international suppliers such as Du Pont, Ferro and Hereus, and the domestic present external research that only is confined to follow the tracks of; Rest on the development low-K material and make its phase of localization, most LTCC products depend on from external imported L TCC raw material band.Therefore, want to break away to the depending on of external LTCC porcelain and device, it is extremely urgent to develop LTCC material and device with independent intellecture property.

The common burning temperature of LTCC system (LTCC) is generally between 800 ℃～950 ℃.Because sintering temperature is low; The low metal of available resistivity is as the conductor material of multilayer wiring; Can improve packing density, signaling rate; And can in be embedded in the various laminar microwave electronic devices of multilager base plate once-firing, therefore extensively be used in high-speed and high-density and interconnect among the polynary ceramic component (MCM).Because altogether burning technology has the packing density height, dielectric loss is low, can be used for high microwave frequency band, and monolithic structure high reliability and IC heat such as match at characteristics; Therefore extremely wide application prospect is arranged, wherein first-elected again LTCC technology because it not only sintering temperature is low; But also be to adopt the metal electrode Au of high conductivity, Ag, Cu etc.; The wiring good conductivity, and with the Cu electrode time, cost also can be very low.

Usually the method that reduces the sintering temperature of microwave dielectric material has, and adds oxide compound or low melting glass sintering aid, introduce chemical synthesis process, and superfine powder is made raw material etc.Chemical process is synthetic to be made raw material with superfine powder and can cause complex technical process, and manufacturing cost and cycle can rise.Comparatively speaking, add an amount of low melting point oxide or glassy phase, though possibly cause the decline of a little microwave dielectric property, its technology is simple, is easy to the material mass production.

In sum, along with the fast development of microwave communication, new requirement has been proposed for portable, the microminiaturization of microwave device.Microwave resonator with the high-dielectric constant microwave material prepn can greatly reduce the microwave circuit size, but further microminiaturized outlet is the development of MCM.When making MCM with the multilayer Mulitilayer circuit board, the LTCC technology demonstrates peculiar advantage, so has obtained paying attention to widely and studying with multilayered medium device and material that the LTCC technology adapts.Be applicable to LTCC technology, microwave property excellent, can with silver electrode altogether the simple novel microwave dielectric ceramic material of burning, chemical constitution and preparation technology be one type of novel material that has application prospect.

Summary of the invention

The objective of the invention is to overcome the deficiency of LTCC in the above-mentioned prior art, a kind of low-temperature sintered microwave dielectric ceramic material and preparation method thereof is provided, this low-temperature sintered microwave dielectric ceramic material is from the low temperature co-fired angle of LTCC, at Ba ₄MTi ₁₁O ₂₇(M=Zn Mg) passes through a spot of lower melting point sintering aid BaCu (B that mixes in the system ₂O ₅), its sintering temperature can successfully be reduced to about 900 ℃, keeps excellent microwave property simultaneously.

The low-temperature sintering medium dielectric constant microwave medium microwave dielectric ceramic materials that the present invention relates to is 92～99% Ba by weight percent ₄MTi ₁₁O ₂₇With weight percent be 1～8% BaCu (B ₂O ₅) form; Wherein M is a kind of among Zn and the Mg.

The step for preparing above-mentioned low-temperature sintering medium dielectric constant microwave medium microwave dielectric ceramic materials is following:

(1) at first with BaCO ₃, MO and TiO ₂Ba in molar ratio ₄MTi ₁₁O ₂₇Be mixed with main powder, wherein M is a kind of among Zn and the Mg;

(2) the main powder that step (1) is prepared mixes, and is to main powder in to add alcohol at 1: 1 according to the weight ratio of main powder and alcohol, adopts wet milling process to mix 4～8 hours; Take out the back 120～140 ℃ of oven dry down; Sieve with 80 purpose screen clothes, be pressed into bulk after sieving, the block main powder that will suppress with the temperature rise rate of 5 ℃/min then rises to 1000 ℃～1100 ℃ and under this temperature, be incubated 2～6h by room temperature; Process the burning piece, promptly synthetic principal crystalline phase;

(3) the burning piece of step (2) being processed is pulverized, and carries out 4～5 hours secondary ball milling, and adding weight percent in oven dry back is 1～8% BaCu (B ₂O ₅), be made into powder, be to powder in to add alcohol at 1: 2 according to the weight ratio of powder and alcohol; Ball milling took out after 4～8 hours; Put into baker 120～140 ℃ of oven dry down, be pressed into sequin after the granulation, in 500～600 ℃ of binder removals; Obtain porcelain behind the furnace cooling, again porcelain can be obtained microwave dielectric ceramic materials at 850～950 ℃ of following sintering 2～4h.

Phase composite after above-mentioned low-temperature sintered LTCC microwave dielectric ceramics material burns till is Ba ₄ZnTi ₁₁O ₂₇Perhaps Ba ₄MgTi ₁₁O ₂₇

The present invention is with Ba ₄MTi ₁₁O ₂₇(M=Zn, Mg) series microwave dielectric ceramic is the basis, adopts homemade lower melting point BaCu (B ₂O ₅) as sintering aid, successfully its sintering temperature is reduced to about 900 ℃, keep excellent microwave property simultaneously, thereby make this material to burn altogether with silver electrode.This low-temperature sintering medium dielectric constant microwave medium microwave dielectric ceramic materials chemical constitution and preparation technology are all fairly simple, can be widely used in the manufacturing of microwave devices such as LTCC system (LTCC), multilayered medium resonator, microwave antenna, wave filter.

Embodiment

Embodiment 1:

(1) at first with chemical feedstocks BaCO ₃, ZnO and TiO ₂BaCO in molar ratio ₃: ZnO: TiO ₂=4: be mixed with main powder at 1: 11;

(2) the main powder that step (1) is prepared mixes; According to the mass ratio of main powder and alcohol is to main powder in to add alcohol at 1: 1, adopts wet milling process to mix 4 hours, and levigate back is 120～140 ℃ of oven dry down; Sieve with 80 purpose screen clothes; Be pressed into bulk after sieving, the block raw material that will suppress with the temperature rise rate of 5 ℃/min then rises to 1050 ℃ and under this temperature, be incubated 4h by room temperature, processes the burning piece;

(3) the burning piece of step (2) being processed is pulverized; According to the mass ratio of powder and alcohol is to powder in to add alcohol at 1: 1, puts into nylon jar ball milling and takes out after 4 hours, puts into baker 120～140 ℃ of oven dry down; Be pressed into sequin after the granulation; In 500～600 ℃ of binder removals, obtain porcelain behind the furnace cooling, again porcelain can be obtained microwave dielectric ceramic materials at 1175 ℃ of following sintering 2h.The microwave property of this material is: ε _r=36.8, Q * f=16500GHz, τ _f=18ppm/ ℃.

Embodiment 2:

(1) at first with chemical feedstocks BaCO ₃, ZnO and TiO ₂BaCO in molar ratio ₃: ZnO: TiO ₂=4: be mixed with main powder at 1: 11;

(2) the main powder that step (1) is prepared mixes; According to the mass ratio of main powder and alcohol is to main powder in to add alcohol at 1: 1, adopts wet milling process to mix 8 hours, and levigate back is 120～140 ℃ of oven dry down; Sieve with 80 purpose screen clothes; Be pressed into bulk after sieving, the block raw material that will suppress with the temperature rise rate of 5 ℃/min then rises to 1050 ℃ and under this temperature, be incubated 4h by room temperature, processes the burning piece;

(3) the burning piece of step (2) being processed is pulverized, and carries out 4 hours secondary ball milling, and putting into baker oven dry back adding weight percent is the BaCu (B of 1wt% ₂O ₅), be made into powder, be to powder in to add alcohol at 1: 2 according to the volume ratio of powder and alcohol; Putting into nylon jar ball milling took out after 8 hours; Put into baker 120～140 ℃ of oven dry down, be pressed into sequin after the granulation, in 500～600 ℃ of binder removals; Obtain porcelain behind the furnace cooling, again porcelain can be obtained low-temperature sintering medium dielectric constant microwave medium microwave dielectric ceramic materials at 925 ℃ of following sintering 3h.The microwave property of this material is: ε _r=27.6, Q * f=10545GHz, τ _f=12ppm/ ℃.Can find out the BaCu (B of doping 1% ₂O ₅) after sample can realize low-temperature sintering well, and temperature coefficient of resonance frequency has obtained good improvement.

Embodiment 3:

(1) at first with chemical feedstocks BaCO ₃, ZnO and TiO ₂BaCO in molar ratio ₃: ZnO: TiO ₂=4: be mixed with main powder at 1: 11;

(2) the main powder that step (1) is prepared mixes; According to the mass ratio of main powder and alcohol is to main powder in to add alcohol at 1: 1, adopts wet milling process to mix 8 hours, and levigate back is 120～140 ℃ of oven dry down; Sieve with 80 purpose screen clothes; Be pressed into bulk after sieving, the block raw material that will suppress with the temperature rise rate of 5 ℃/min then rises to 1050 ℃ and under this temperature, be incubated 4h by room temperature, processes the burning piece;

(3) the burning piece of step (2) being processed is pulverized, and carries out 4 hours secondary ball milling, and putting into baker oven dry back adding weight percent is the BaCu (B of 2wt% ₂O ₅), be made into powder, be to powder in to add alcohol at 1: 2 according to the volume ratio of powder and alcohol; Putting into nylon jar ball milling took out after 8 hours; Put into baker 120～140 ℃ of oven dry down, be pressed into sequin after the granulation, in 500～600 ℃ of binder removals; Obtain porcelain behind the furnace cooling, again porcelain can be obtained low-temperature sintering medium dielectric constant microwave medium microwave dielectric ceramic materials at 925 ℃ of following sintering 3h.The microwave property of this material is: ε _r=30.8, Q * f=11240GHz, τ _f=10ppm/ ℃.Can find out the BaCu (B of doping 2% ₂O ₅) after sample can realize low-temperature sintering well, and temperature coefficient of resonance frequency has obtained good improvement.

Embodiment 4:

(1) at first with chemical feedstocks BaCO ₃, ZnO and TiO ₂BaCO in molar ratio ₃: ZnO: TiO ₂=4: be mixed with main powder at 1: 11;

(2) the main powder that step (1) is prepared mixes; According to the mass ratio of main powder and alcohol is to main powder in to add alcohol at 1: 1, adopts wet milling process to mix 8 hours, and levigate back is 120～140 ℃ of oven dry down; Sieve with 80 purpose screen clothes; Be pressed into bulk after sieving, the block raw material that will suppress with the temperature rise rate of 5 ℃/min then rises to 1050 ℃ and under this temperature, be incubated 4h by room temperature, processes the burning piece;

(3) the burning piece of step (2) being processed is pulverized, and carries out 4 hours secondary ball milling, and putting into baker oven dry back adding weight percent is the BaCu (B of 4wt% ₂O ₅), be made into powder, be to powder in to add alcohol at 1: 2 according to the volume ratio of powder and alcohol; Putting into nylon jar ball milling took out after 8 hours; Put into baker 120～140 ℃ of oven dry down, be pressed into sequin after the granulation, in 500～600 ℃ of binder removals; Obtain porcelain behind the furnace cooling, again porcelain can be obtained low-temperature sintering medium dielectric constant microwave medium microwave dielectric ceramic materials at 925 ℃ of following sintering 3h.The microwave property of this material is: ε _r=33.8, Q * f=12180GHz, τ _f=7ppm/ ℃.Can find out the BaCu (B of doping 4% ₂O ₅) after sample can realize low-temperature sintering well, and temperature coefficient of resonance frequency has obtained good improvement.After the cooling powder can be well and the compatible (see figure 1) of silver electrode.

Embodiment 5:

(1) at first with chemical feedstocks BaCO ₃, MgO and TiO ₂BaCO in molar ratio ₃: MgO: TiO ₂=4: be mixed with main powder at 1: 11;

(2) the main powder that step (1) is prepared mixes; According to the mass ratio of main powder and alcohol is to main powder in to add alcohol at 1: 1, adopts wet milling process to mix 4 hours, and levigate back is 120～140 ℃ of oven dry down; Sieve with 80 purpose screen clothes; Be pressed into bulk after sieving, the block raw material that will suppress with the temperature rise rate of 5 ℃/min then rises to 1150 ℃ and under this temperature, be incubated 4h by room temperature, processes the burning piece;

(3) the burning piece of step (2) being processed is pulverized; According to the mass ratio of powder and alcohol is to powder in to add alcohol at 1: 1, puts into nylon jar ball milling and takes out after 4 hours, puts into baker 120～140 ℃ of oven dry down; Be pressed into sequin after the granulation; In 500～600 ℃ of binder removals, obtain porcelain behind the furnace cooling, again porcelain can be obtained microwave dielectric ceramic materials at 1275 ℃ of following sintering 2h.The microwave property of this material is: ε _r=36.1, Q * f=19625GHz, τ _f=14.9ppm/ ℃.

Embodiment 6:

(1) at first with chemical feedstocks BaCO ₃, MgO and TiO ₂BaCO in molar ratio ₃: MgO: TiO ₂=4: be mixed with main powder at 1: 11;

(2) the main powder that step (1) is prepared mixes; According to the mass ratio of main powder and alcohol is to main powder in to add alcohol at 1: 1, adopts wet milling process to mix 8 hours, and levigate back is 120～140 ℃ of oven dry down; Sieve with 80 purpose screen clothes; Be pressed into bulk after sieving, the block raw material that will suppress with the temperature rise rate of 5 ℃/min then rises to 1150 ℃ and under this temperature, be incubated 4h by room temperature, processes the burning piece;

(3) the burning piece of step (2) being processed is pulverized, and carries out 4 hours secondary ball milling, and putting into baker oven dry back adding weight percent is the BaCu (B of 4wt% ₂O ₅), be made into powder, be to powder in to add alcohol at 1: 2 according to the volume ratio of powder and alcohol; Putting into nylon jar ball milling took out after 8 hours; Put into baker 120～140 ℃ of oven dry down, be pressed into sequin after the granulation, in 500～600 ℃ of binder removals; Obtain porcelain behind the furnace cooling, again porcelain can be obtained low-temperature sintering medium dielectric constant microwave medium microwave dielectric ceramic materials at 925 ℃ of following sintering 3h.The microwave property of this material is: ε _r=27.3, Q * f=11200GHz, τ _f=9ppm/ ℃.Can find out the BaCu (B of doping 4% ₂O ₅) after sample can realize low-temperature sintering well, and temperature coefficient of resonance frequency has obtained good improvement.

Embodiment 7:

(1) at first with chemical feedstocks BaCO ₃, MgO and TiO ₂BaCO in molar ratio ₃: MgO: TiO ₂=4: be mixed with main powder at 1: 11;

(2) the main powder that step (1) is prepared mixes; According to the mass ratio of main powder and alcohol is to main powder in to add alcohol at 1: 1, adopts wet milling process to mix 8 hours, and levigate back is 120～140 ℃ of oven dry down; Sieve with 80 purpose screen clothes; Be pressed into bulk after sieving, the block raw material that will suppress with the temperature rise rate of 5 ℃/min then rises to 1150 ℃ and under this temperature, be incubated 4h by room temperature, processes the burning piece;

(3) the burning piece of step (2) being processed is pulverized, and carries out 4 hours secondary ball milling, and putting into baker oven dry back adding weight percent is the BaCu (B of 5wt% ₂O ₅), be made into powder, be to powder in to add alcohol at 1: 2 according to the volume ratio of powder and alcohol; Putting into nylon jar ball milling took out after 8 hours; Put into baker 120～140 ℃ of oven dry down, be pressed into sequin after the granulation, in 500～600 ℃ of binder removals; Obtain porcelain behind the furnace cooling, again porcelain can be obtained low-temperature sintering medium dielectric constant microwave medium microwave dielectric ceramic materials at 925 ℃ of following sintering 3h.The microwave property of this material is: ε _r=29.27, Q * f=12890GHz, τ _f=6ppm/ ℃.Can find out the BaCu (B of doping 5% ₂O ₅) after sample can realize low-temperature sintering well, and temperature coefficient of resonance frequency has obtained good improvement.

Embodiment 8:

(1) at first with chemical feedstocks BaCO ₃, MgO and TiO ₂BaCO in molar ratio ₃: MgO: TiO ₂=4: be mixed with main powder at 1: 11;

(2) the main powder that step (1) is prepared mixes; According to the mass ratio of main powder and alcohol is to main powder in to add alcohol at 1: 1, adopts wet milling process to mix 8 hours, and levigate back is 120～140 ℃ of oven dry down; Sieve with 80 purpose screen clothes; Be pressed into bulk after sieving, the block raw material that will suppress with the temperature rise rate of 5 ℃/min then rises to 1050 ℃ and under this temperature, be incubated 4h by room temperature, processes the burning piece;

(3) the burning piece of step (2) being processed is pulverized, and carries out 4 hours secondary ball milling, and putting into baker oven dry back adding weight percent is the BaCu (B of 8wt% ₂O ₅), be made into powder, be to powder in to add alcohol at 1: 2 according to the volume ratio of powder and alcohol; Putting into nylon jar ball milling took out after 8 hours; Put into baker 120～140 ℃ of oven dry down, be pressed into sequin after the granulation, in 500～600 ℃ of binder removals; Obtain porcelain behind the furnace cooling, again porcelain can be obtained low-temperature sintering medium dielectric constant microwave medium microwave dielectric ceramic materials at 925 ℃ of following sintering 3h.The microwave property of this material is: ε _r=30.6, Q * f=12560GHz, τ _f=3ppm/ ℃.Can find out the BaCu (B of doping 8% ₂O ₅) after sample can realize low-temperature sintering well, and temperature coefficient of resonance frequency has obtained good improvement.After the cooling powder can be well and the compatible (see figure 2) of silver electrode

It is pointed out that according to technical scheme of the present invention, the foregoing description can also be enumerated many, prove,, all can reach the object of the invention in the scope that claims of the present invention proposed according to applicant's lot of experiment results.

Claims (1)

1. the preparation method of a microwave dielectric ceramic materials is characterized in that microwave dielectric ceramic materials is 92～99% Ba by weight percent ₄MTi ₁₁O ₂₇With weight percent be 1～8% BaCu (B ₂O ₅) form, wherein M is a kind of among Zn and the Mg;

Preparing method's concrete steps of described microwave dielectric ceramic materials are:

(1) at first with BaCO ₃, MO and TiO ₂Ba in molar ratio ₄MTi ₁₁O ₂₇Be mixed with main powder, wherein M is a kind of among Zn and the Mg;

(2) the main powder that step (1) is prepared mixes, and is to main powder in to add alcohol at 1: 1 according to the weight ratio of main powder and alcohol, adopts wet milling process to mix 4～8 hours; Take out the back 120～140 ℃ of oven dry down; Sieve with 80 purpose screen clothes, be pressed into bulk after sieving, the block main powder that will suppress with the temperature rise rate of 5 ℃/min then rises to 1000 ℃～1100 ℃ and under this temperature, be incubated 2～6h by room temperature; Process the burning piece, promptly synthetic principal crystalline phase;

(3) the burning piece of step (2) being processed is pulverized, and carries out 4～5 hours secondary ball milling, and adding weight percent in oven dry back is 1～8% BaCu (B ₂O ₅), be made into powder, be to powder in to add alcohol at 1: 2 according to the weight ratio of powder and alcohol; Ball milling took out after 4～8 hours; Put into baker 120～140 ℃ of oven dry down, be pressed into sequin after the granulation, in 500～600 ℃ of binder removals; Obtain porcelain behind the furnace cooling, again porcelain can be obtained microwave dielectric ceramic materials at 850～950 ℃ of following sintering 2～4h.