Background technology
Microwave dielectric ceramic refers to and is applied in microwave frequency band (being mainly UHF and SHF frequency range) circuit as dielectric material and completes the pottery of one or more functions, in modern communication, be widely used as the components and parts such as resonator, wave filter, dielectric substrate and medium guided wave loop, it is the key foundation material of modern communication technology, at aspects such as portable mobile phone, automobile telephone, cordless telephone, telestar susceptor and military radars, there is very important application, in the miniaturization of modern communication instrument, integrated process, just bringing into play increasing effect.
Be applied to the dielectric ceramic of microwave frequency band, should meet the requirement of following dielectric characteristics: (1) seriation DIELECTRIC CONSTANT ε
rto adapt to the requirement of different frequency and different application occasion; (2) high quality factor q value or dielectric loss tan δ are to reduce noise, general requirement Qf>=3000 GHz; (3) the temperature factor τ of resonant frequency
?the as far as possible little thermostability to guarantee that device has had, general requirement-10/ ℃≤τ
?≤+10 ppm/ ℃.From late 1930s, just someone attempts dielectric substance to be applied to microwave technology in the world.
According to relative permittivity ε
rsize from use the different of frequency range, conventionally the microwave-medium ceramics being developed He developing can be divided into 4 classes.
(1) ultralow dielectric microwave dielectric ceramic, main representative is Al
2o
3-TiO
2, Y
2baCuO
5, MgAl
2o
4and Mg
2siO
4deng, its ε
r≤ 20, quality factor q * f>=50000GHz, τ
?≤ 10 ppm/ ° C.Be mainly used in microwave base plate and high-end microwave device.
(2) low ε
rwith the microwave dielectric ceramic of high Q value, be mainly BaO-MgO-Ta
2o
5, BaO-ZnO-Ta
2o
5or BaO-MgO-Nb
2o
5, BaO-ZnO-Nb
2o
5system or the composite system MWDC material between them.Its ε
r=25~30, Q=(1~2) * 10
4(under the GHz of f>=10), τ
?≈ 0.Be mainly used in the microwave communication equipments such as direct broadcasting satellite of f >=8 GHz as dielectric resonance device.
(3) medium ε
rwith the microwave dielectric ceramic of Q value, be mainly with BaTi
4o
9, Ba
2ti
9o
20(Zr, Sn) TiO
4deng the MWDC material that is base, its ε
r=35 ~ 40, Q=(6~9) * 10
3(under f=3~-4GHz), τ
?≤ 5 ppm/ ° C.Be mainly used in microwave military radar in 4~8 GHz range of frequency and communication system as dielectric resonance device.
(4) high ε
rand the lower microwave dielectric ceramic of Q value is mainly used in civilian mobile communcations system in 0.8~4GHz range of frequency, this is also the emphasis of microwave dielectric ceramic research.Since the eighties, the people such as Kolar, Kato find and have studied perovskite-like tungsten bronze type BaO-Ln in succession
2o
3-TiO
2series (Ln=La, Sm, Nd or Pr etc. are called for short BLT system), complex perovskite structure CaO-Li
2o-Ln
2o
3-TiO
2series, lead base series material, Ca
1-xln
2x/3tiO
3be contour ε
rmicrowave dielectric ceramic, the wherein BaO-Nd of BLT system
2o
3-TiO
2material dielectric constant reaches 90, lead base series (Pb, Ca) ZrO
3specific inductivity reaches 105.
The sintering temperature of these material systems is generally higher than 1300 ° of C above, can not be directly and the low melting point metal such as Ag and Cu burn altogether formation laminated ceramic capacitor.In recent years, along with LTCC Technology (Low Temperature Co-fired Ceramics, the requirement of development LTCC) and the development of microwave multilayer device, researchist both domestic and external has carried out exploring widely and studying to some low fever's system materials, mainly to adopt devitrified glass or glass-ceramic composite system, because low melting glass has relatively high dielectric loss mutually, the existence of glassy phase has improved the dielectric loss of material greatly.Therefore development is the emphasis of current research without the low fired microwave dielectric ceramic material of glassy phase.
Explore with development of new can the process of low fired microwave dielectric ceramic materials in, the material systems such as the Li based compound that intrinsic sintering temperature is low, Bi based compound, tungstate architecture compound and tellurate architecture compound get the attention and study, wherein a large amount of exploratory developments concentrates on Li base binary or ternary compound, and has developed as Li
2tiO
3, Li
2moO
4and Li
2mTi
3o
8serial well behaved microwave-medium ceramics such as (M=Mg or Zn) etc., but microwave-medium ceramics system that can low fever is still more limited, and the τ of the low single-phase microwave dielectric ceramic of intrinsic sintering temperature
?conventionally larger, can not meet the requirement of device thermostability, this has limited the development of low temperature co-fired technology and microwave multilayer device to a great extent.
We find Li
2zn
3wO
7pottery has excellent comprehensive microwave dielectric property while sintering temperature lower than 800
°c, can be widely used in the manufacture of the microwave devices such as various medium substrates, can meet the Technology Need of low temperature co-fired technology and microwave multilayer device.
Summary of the invention
The object of this invention is to provide a kind of have low-loss and good thermostability, simultaneously low temperature sintering microwave dielectric ceramic material and preparation method thereof.
The chemical constitution of microwave dielectric ceramic material of the present invention is Li
2zn
3wO
7.
Preparation method's step of this microwave dielectric ceramic material is:
(1) by purity, be more than 99.9% Li
2cO
3, ZnO and WO
3starting powder press Li
2zn
3wO
7composition weigh batching.
(2) step (1) raw material wet ball-milling is mixed 12 hours, ball-milling medium is distilled water, pre-burning 6 hours in 700 ℃ of air atmosphere after oven dry.
(3) in the powder making in step (2), add after binding agent granulation, then compression moulding, finally sintering 4 hours in 750 ~ 780 ℃ of air atmosphere; Described binding agent adopts the polyvinyl alcohol solution that mass concentration is 5%, and polyvinyl alcohol addition accounts for 3% of powder total mass.
Useful technique effect of the present invention: ceramic sintering temperature is low, 750 ~ 780 ℃ of sintering are good; Its dielectric properties are excellent, and especially temperature coefficient of resonance frequency is closely zero, can meet the thermostability requirement of device; Quality factor q f value is up to 69000-81000GHz, industrial, has a great using value.