JP3225833B2 - High frequency dielectric composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-frequency dielectric composition effective as a dielectric constituting a device used in a high-frequency circuit.

[0002]

2. Description of the Related Art Multilayer devices are effective for reducing the size and reliability of components such as filters used in high-frequency circuits. In this case, the material for the multilayer device exhibits a relatively high dielectric constant (ε _r = 10 or more) and a high Q (ie, low dielectric loss), and requires co-firing with Cu or Ag / Pd conductor. It is required that firing at a temperature of 1000 ° C. or lower is possible (that is, sufficient densification is achieved by firing at a temperature of 1000 ° C. or lower).

Conventionally, BaO—Al ₂ O ₃ —B ₂ O ₃ —SiO ₂ or Ba has been used as a high frequency dielectric which can be fired at 1000 ° C. or lower.
O-SrO-ZrO ₂ -SiO ₂ -based glass materials Pb-containing perovskite-based material containing Bi-based material ceramics - glass composite materials have been developed and used.

[0004] The above conventional materials have the following problems. That is, in the case of a Pb-containing perovskite-based material or a Bi-containing-based material, a composition shift occurs due to volatilization of components during firing, and stable production is difficult. Also, BaO-Al ₂ O
₃ -B ₂ O ₃ -SiO ₂ or BaO-SrO-ZrO ₂
-In the case of a SiO ₂ glass material or a ceramic-glass composite material, the relative dielectric constants are ε _r = 6 and ε _r = 15, respectively.
And Q is relatively small, about 1000 (1 MHz).

[0005] In order to solve the above-mentioned conventional problems and to be effective as a material for a multi-layer device which is effective for miniaturization and high reliability of an element used in a high-frequency circuit, both dielectric constant and Q are high, and
As a high-frequency dielectric composition that can be fired at 0 ° C. or less, the present applicant has previously made Sr (Ni _1/3 Nb _2/3 ) O ₃ as a main component and added 0.1% to the main component. 50 wt% of the glass, _{preferably, MgO-BaO-B 2 O} 3 -SiO 2
A dielectric composition for high frequency to which a system glass is added has been proposed (Japanese Patent Application No. 7-292750; hereinafter, referred to as "prior application").

Sr (Ni _1/3 Nb _2/3 ) according to the above-mentioned prior application
O ₃ Ceramics _{- (MgO-BaO-B 2} O 3 -Si
O ₂ ) a glass composite material has a high dielectric constant and a high Q, and can be fired at 1000 ° C. or lower.

By the way, in a high-frequency dielectric composition used for a dielectric resonator or the like, the temperature coefficient τ _f of the resonance frequency is set to 0 p.
pm / ° C., while the dielectric constant for high frequency as a capacitor material has a temperature coefficient τε of relative permittivity of −60 ppm / ° C. ≦ τε ≦ 60 ppm / ° C.
(CH characteristics) must be satisfied.

[0008]

However, the above S
r (Ni _1/3 Nb _2/3 ) O ₃ ceramics- (MgO-
_{BaO-B 2 O 3 -SiO 2} ) glass composite material, the temperature coefficient of the resonant frequency is greatly τ _f = -40ppm / ℃ and negative, temperature coefficient of the dielectric constant is that a large positive and τε = 60ppm / ℃ There was a problem.

The present invention relates to the above Sr (Ni _1/3 Nb _2/3 ) O
₃ Ceramics _{- (MgO-BaO-B 2} O 3 -SiO
₂ ) The temperature coefficient τ _{f of the} resonance frequency is 0 pp, which is useful as a material for multilayer devices that solves the problems of glass composite materials and is effective for miniaturization and high reliability of elements used in high-frequency circuits.
m / ° C., and the relative permittivity temperature coefficient τε is −60.
It is an object to provide a high-frequency dielectric composition satisfying ppm / ° C. ≦ τε ≦ 60 ppm / ° C.

[0010]

SUMMARY OF THE INVENTION The dielectric material for high frequency waves according to the present invention
The composition is Sr (Ni_1/3Nb_2/3) O₃And Ba
(M^II _1/3M^V _2/3) O₃(However, M^IIIs N
i, Mg or Zn, M^VRepresents Nb or Ta, and M^VBut
M when Nb^IIIs Ni, Mg or Zn, and M^VBut
M for Ta^IIIs Mg or Zn. ) Consisting of
0.1-50% by weight of glass based on Lamix ingredients
AddedA high frequency dielectric composition, wherein the glass is
MgO-BaO-B having the above composition ₂ O ₃ -SiO ₂ System glass
IsIt is characterized by the following.MgO: 20 to 50% by weight BaO: 5 to 25% by weight B ₂ O ₃ : 15 to 30% by weight SiO ₂ : 10 to 25% by weight

Sr (Ni _1/3 Nb _2/3 ) O ₃ ceramic-glass composite material, especially Sr (Ni _1/3 Nb _2/3 )
O ₃ Ceramics _{- (MgO-BaO-B 2} O 3 -Si
O ₂₎ in the glass composite material, further ^{_{Ba (M II 1/3 M V 2/3}} )
O ₃ (however, M ^II is Ni, Mg or Zn, M ^V is Nb
Or Ta, and when M ^V is Nb, M ^II is Ni, Mg or Zn, and when M ^V is Ta, M ^II is Mg or Zn. ) To form Sr (Ni _1/3 Nb
_2/3) O ₃ ceramics _{- (MgO-BaO-B 2} O 3
-SiO ₂ ) The problem of the glass composite material is solved, the temperature coefficient τ _f of the resonance frequency is close to 0 ppm / ° C., and the temperature coefficient τε of the relative dielectric constant is −60 ppm / ° C. ≦ τε ≦ 60 pp.
A high-performance high-frequency dielectric composition satisfying m / ° C. can be realized.

In the present invention, the ceramic components Sr (Ni _1/3 Nb _2/3 ) O ₃ and Ba (M ^II
_1/3 M ^V _2/3) and _{O 3} in molar ratio Sr (Ni
_1/3 Nb _2/3 ) O ₃ : Ba (M ^II _1/3 MV
_2/3 ) O ₃ = (1-x): x (where 0 <x ≦ 0.
Preferably, the ratio is 8). Further, it is preferable that the glass amount added to the previous SL ceramics component and 1 to 40 wt%.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The dielectric composition for a high frequency wave of the present invention comprises Sr
(Ni _1/3 Nb _2/3 ) O ₃ and Ba (M ^II _1/3
M ^V _{2/3) O 3} ^{(however, M II} is Ni, Mg or Z
n, ^{M V} represents the Nb or Ta, when ^{M V} is Nb M
^II is Ni, Mg or Zn, if ^{M V} is Ta M
^II is Mg or Zn. ) As a ceramic component, and a specific composition of MgO-
The _{BaO-B 2} O 3 -SiO ₂ based glass is obtained by adding 0.1 to 50 wt%.

In the present invention, Sr (Ni _1/3 Nb _2/3 ) O ₃ and Ba (M ^II _1/3 M ^V ) constituting the ceramic component are used.
_2/3 ) O ₃ means that the molar ratio is Sr (Ni _1/3 Nb _2/3 ) O ₃
: Ba (M ^II _1/3 M ^V _2/3 ) O ₃ = (1-x): x (where 0 <x ≦ 0.8), that is, the ceramic component composition is (1-x) Sr (Ni _1/3 Nb _2/3 ) O ₃ x
It is preferably represented by Ba (M ^II _1/3 M ^V _2/3 ) O ₃ (0 <x ≦ 0.8). Here, when x exceeds 0.8,
The proportion of ^{_{Ba (M II 1/3 M V 2/3}} ) O 3 is too many, Sr
_{(Ni 1/3 Nb 2/3) O 3} - Further Ba in glass composite material
(M ^II _1/3 M ^V _2/3) of O _3, the effect of the present invention by be complexed impaired, tau _f, it is impossible to obtain a good value of Tauipushiron. The preferable value of x ^{_{is, Ba (M II 1/3 M V}} 2/3)
The relationship with O ₃ is as follows.

Ba (M ^II _1/3 M ^V _2/3 ) O ₃ is replaced by Ba (Ni
_1/3 Nb _2/3) For _{O 3: 0 <x ≦ 0.8} Ba (M II 1/3 M V 2/3) O 3 is Ba (Mg _1/3 Nb
_2/3 ) O ₃ : 0 <x ≦ 0.34 Ba (M ^II _1/3 M ^V _2/3 ) O ₃ is Ba (Zn _1/3 Nb)
_2/3) For _{O 3: 0 <x ≦ 0.33} Ba (M II 1/3 M V 2/3) O 3 is Ba (Mg _1/3 Ta
_2/3 ) O ₃ : 0 <x ≦ 0.73 Ba (M ^II _1/3 M ^V _2/3 ) O ₃ is Ba (Zn _1/3 Ta)
_2/3 ) O ₃ : 0 <x ≦ 0.76 In the present invention, if the amount of glass added to such a ceramic component is less than 0.1% by weight, the glass is sufficiently densified by firing at 1000 ° C. or lower. And Q is low. 50% by weight of glass added to main component
If it exceeds 300, the content of the ceramic component becomes relatively small, so that the dielectric constant and Q decrease.

In the present invention, when the amount of glass added to the ceramic component is 1 to 40% by weight, particularly 2 to 30% by weight, both the dielectric constant and Q are remarkably high, and τ _f and τε are good. The dielectric composition for use can be obtained.

In the present invention, as the glass,
Using _{MgO-BaO-B 2 O 3} -SiO 2 based glass,
Set formed proportion of the Soviet Union, is as follows.

[0019] _{MgO-BaO-B 2 O 3} -SiO 2 based glass composition (wt%) MgO: 20~50 BaO: 5~25 B 2 O 3: 15~30 SiO 2: high frequency of 10 to 25 the invention The dielectric composition is composed of Sr (Ni _1/3 Nb).
_2/3) oxides or carbonates of O ₃ and ^{_{Ba (M II 1/3 M V 2/3}} ) metal elements constituting the O _3, for example, SrCO _3, B
aCO ₃ , NiO, Nb ₂ O ₅ , MgO, ZnO, Ta
₂ O ₅ is replaced with predetermined Sr (Ni _1/3 Nb _2/3 ) O ₃ , Ba
^{_{(M II 1/3 M V 2/3)}} O 3 mixed in a composition ratio, Sr (Ni _1/3 Nb _2/3) obtained by calcination O _3, Ba (M
The ^{_{II 1/3 M V 2/3) O 3}} , as well as collected at a predetermined molar ratio, this can easily be prepared by admixing a glass of a predetermined ratio, a high frequency of such invention For the dielectric composition, molded by adding an appropriate binder,
By baking at 1000 ° C. or less, for example, at 950 to 980 ° C., it can be easily used.

Incidentally, Sr (Ni _1/3 Nb _2/3 ) O ₃
・ Ba (M ^II _1/3 M ^V _2/3 ) O ₃ ceramic component
The _{M gO-BaO-B 2 O} 3 when adding -SiO ₂ based glass, a carbonate of the oxides or the corresponding amount of the glass component in the same weight ratio _{Sr (Ni 1/3 Nb 2/3) O} 3・ Ba
(M ^II _1/3 M ^V _2/3) was added and mixed in O ₃ ceramics component, but vitrification and the firing and may be performed simultaneously during the heat treatment, it is desirable to add a glass frit previously prepared.

[0021]

The present invention will be described more specifically with reference to the following examples.

Example 1 SrCO ₃ , BaCO ₃ , NiO, Nb ₂ O ₅ , Mg
O, ZnO, Ta ₂ O ₅ are converted to Sr (Ni _1/3 Nb _2/3 ) O ₃
Stoichiometric ratio and ^{_{Ba (M II 1/3 M V 2/3}} ) O 3 ( however, M ^II is Ni, Mg or Zn, M ^V represents the Nb or Ta.) So that the stoichiometric ratio Each was weighed and pulverized in a ball mill for 24 hours using 2-propanol as a dispersion medium.
After mixing, the mixture was dried and then calcined at 1400 ° C. for 4 hours in the atmosphere. The calcined product was pulverized and mixed again with a ball mill for 24 hours using 2-propanol as a dispersion medium.
(Ni _1/3 Nb _2/3) O ₃ and ^{_{Ba (M II 1/3 M V 2/3}} )
O ₃ was synthesized respectively.

The resulting Sr (Ni _1/3 Nb _2/3) a O ₃ and ^{_{Ba (M II 1/3 M V 2/3}} ) O 3 were weighed so that the ceramic composition shown in Table 1, Further, MgO—BaO—B ₂ O ₃ —SiO ₂
Glass (component weight ratio MgO: BaO: B ₂ O ₃ : Si
O ₂ = 45: 15: 25: 15) 10% by weight of frit
20% by weight of a binder (5% by weight aqueous solution of polyvinyl alcohol) was added to the mixture, and a diameter of 15% was added.
It was formed into pellets having a thickness of 1.5 mm and a thickness of 1.5 mm, and fired at 980 ° C. for 1 hour in the atmosphere.

For the obtained sample, the temperature coefficient τ _f of the resonance frequency and the temperature coefficient τε of the relative permittivity were measured, and the results are shown in Table 1.

[0025]

[Table 1]

From Table 1, it can be seen that by mixing Ba (M ^II _1/3 M ^V _2/3 ) O ₃ , the temperature coefficient τ _f of the resonance frequency and the temperature coefficient τε of the relative permittivity become good values. Is evident.

Example 2 In Example 1, 0.8Sr (Ni _1/3 Nb _2/3 ) O
_{3 · 0.2Ba (Ni 1/3 Nb 2/3} ) a glass amount for O ₃ sample was prepared in the same manner except that the proportions shown in Table 2 examine the characteristics of each sample, the results The results are shown in Table 2. The relative permittivity ε _r and Q value were measured at 1 MHz.

[0028]

[Table 2]

From Table 2, it is clear that good properties can be obtained by adding 0.1 to 50% by weight, particularly 1 to 40% by weight of glass to the ceramic component.

[0030]

As described in detail above, the high frequency dielectric composition of the present invention has a high Q and ε, can be fired at 1000 ° C. or less, and has a temperature coefficient τ _{f of} resonance frequency. 0
ppm / ° C, and the temperature coefficient τε of relative permittivity is −
It is a high-performance dielectric composition for high frequency that satisfies 60 ppm / ° C. ≦ τε ≦ 60 ppm / ° C. Therefore, according to the present invention, by forming a dielectric resonator or a high-performance multilayer device as a capacitor material, it is possible to effectively achieve miniaturization and high reliability of an element used in a high-frequency circuit. it can.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshinori Shinohara 2270 Yokoze, Yokoze-cho, Chichibu-gun, Saitama Prefecture Mitsubishi Materials Corporation Electronics Research Laboratory (56) References JP-A-61-191556 (JP, A) JP-A-7-330427 (JP, A) JP-A-5-211006 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C04B 35/42-35/50 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. Sr (Ni_1/3Nb_2/3) O₃as well as
Ba (M^II _1/3M^V _2/3) O₃(However, M^II
Is Ni, Mg or Zn, M^VRepresents Nb or Ta, and M
^VIs M when Nb^IIIs Ni, Mg or Zn, and M
^VM when Ta is^IIIs Mg or Zn. More
0.1-50% by weight of the ceramic component
AddedA dielectric composition for high frequency waves, wherein the glass
Is MgO-BaO-B having the following composition ₂ O ₃ -SiO ₂ System
Is lathA dielectric composition for a high frequency wave, comprising:MgO: 20 to 50% by weight BaO: 5 to 25% by weight B ₂ O ₃ : 15 to 30% by weight SiO ₂ : 10 to 25% by weight 2. The composition according to claim 1, wherein the composition of the ceramic component is (1-x) Sr (Ni _1/3 Nb).
^{_{2/3) O 3 · xBa (M}} II 1/3 M V 2/3) O 3
^{(However, M II} is Ni, Mg or Zn, ^{M V} represents the Nb or Ta, ^{M II} when ^{M V} is Nb is Ni, Mg or Zn, if ^{M V} is Ta ^{M II} is Mg or Zn
It is. x is 0 <x ≦ 0.8. A) a dielectric composition for high frequencies, 3. A composition according to claim 1 or 2, before Symbol
The glass to the ceramic component 1 to 40 wt%
A dielectric composition for high frequency waves, characterized by being added.