Flat packaged piezoelectric device using glass-ceramic composite material comprising forsterite

Abstract: In a crystal oscillator unit which serves as a flat packaged piezoelectric device and which comprises a base member (1), a quarts piece (2), and a cap member (3) sealed air-tight to the base member to enclose the quartz piece in cooperation with the base member, each of the base and the cap members is made of a glass-ceramic composite material in which 30 to 70% by weight of forsterite is dispersed in glass of a thermal expansion coefficient between 100 and 150 x 10⁻⁷/°C. The glass consists, in percent by weight, essentially of 50 to 70% of SiO₂, 3 to 15% of Al₂O₃, 0 to 10% of ZnO, 0 to 8% of B₂O₃, 7 to 25% of at least one member of CaO, SrO, and BaO, and 13 to 27% of at least one member of Na₂O, K₂O, and Li₂O. The glass and the forsterite are pulverized to an average particle diameter of 1 to 3 microns, mixed together with addition of fine powder of an average particle diameter of 0.1 to 1 micron of 0 to 5% by weight of at least one member of ZrO₂, TiO₂, SnO₂, P₂O₅, and MoO₃, and sintered at a temperature between 800°C and 1000°C.

Description: Background of the Invention: This invention relates to a glass-ceramic composite material for use in a flat packaged piezoelectric device. This invention relates also to the flat packaged piezoelectric device. A flat packaged piezoelectric device of the type described is, for example, a crystal oscillator unit or an SAW (surface acoustic wave) resonator unit and is for use in surface mounting. A conventional flat packaged piezoelectric device comprises a base member, a pair of electrode pad parts formed on the base member, and a piezoelectric oscillator piece of, for example, quartz. A pair of electrodes are formed on both surfaces of the piezoelectric oscillator piece and have parts fixed to the electrode pad parts. A cap member is sealed air-tight to the base member to enclose the piezoelectric oscillator piece in cooperation with the base member. As will later be described, the piezoelectric oscillator piece and the base and the cap members have different thermal expansion coefficients. This gives rise to a strain after cooling down from a raised temperature which results in a variation in the resonant frequency of the crystal oscillator unit and makes it impossible to attain a desired frequency characteristic. Moreover, the use of a resilient supporter as an intermediary for connecting the piezoelectric oscillator piece to the base and the cap members to solve the above-described problem, results in other problems, such as an increased manufacturing cost and a thicker thickness of the flat packaged piezoelectric device as will also later be described. Still further, alumina (Al 2 O 3 ) for use as a principal material of each of the base and the cap members must be sintered at a temperature of 1500 to 1600°C. As a consequence, internal conductors for wiring in the flat packaged piezoelectric device must be made of tungsten (W), molybdenum (Mo), or a like metal having a high melting point if the conductors are concurrently to be sintered. Such a high melting point metal has a low electric conductivity and is not adapted to soldering. Nickel (Ni) plating and/or gold (Au) plating are therefore indispensable. As a result, great amounts of process and cost are necessary on manufacture. Chemical Abstracts, vol. 112, No. 16, 16.04.90, abstract No. 144490p and Japanese patent application JP-A-1-179741 describe a glass-ceramic composite composition containing 35 to 95 wt.% glass powder (average particle size 0.5 to 4 micrometres), 5 to 65 wt.% ceramic powder (average particle size 0.1 to 5 micrometres), 0 to 10 wt.% of an oxidiser (CeO 2 , SnO 2 , TiO 2 , BaO 2 , Cr 2 O 3 , and CoO) and O.O5 to 10 wt% Nb oxide. The glass contains 35 to 65 wt.% SiO 2 , 1 to 20 wt.% Al 2 O 3 , 1 to 30 wt.% MgO + CaO + BaO, 0 to 15 wt.% Li 2 O + Na 2 O + K 2 O, 1.5 to 55 wt.% PbO, 0 to 10 wt.% ZnO, 0 to 10 wt.% ZrO 2 + TiO 2 , and 0 to 0.9 wt.% B 2 O 3 . The ceramic is preferably Al 2 O 3 , α-quartz, cordierite, forsterite, mullite and ZrO 2 . Summary of the Invention: The invention provides a flat-packaged piezoelectric device as defined in the appendent independent claim. Preferred features of the invention are defined in dependent subclaims. A flat packaged piezoelectric device to which this invention is applicable comprises a base member, a pair of electrode pad parts formed on the base member, a piezoelectric oscillator piece, a pair of electrodes formed on both surfaces of the piezoelectric oscillator piece and having parts fixed to the electrode pad parts, and a cap member sealed air-tight to the base member to enclose the piezoelectric oscillator piece in cooperation with the base member. Each of the base and the cap members is made of a glass-ceramic composite material comprising a glass component and a ceramic component. The glass component has a thermal expansion coefficient between 100 x 10 -7 /°C and 150 x 10 -7 /°C, both inclusive. The ceramic component is 30 to 70% by weight of forsterite (2MgO·SiO 2 ) which is dispersed in the glass component. This invention is characterised by selection, for the base and the cap members, of a material having a thermal expansion coefficient similar to that of a piezoelectric oscillator piece, such as a quartz piece, so that the piezoelectric oscillator piece may be fixed directly to the package without an intermediate supporting member. The invention may thus advantageously provide a flat packaged piezoelectric device which can attain a desired frequency characteristic and has a decreased manufacturing cost. In addition, the glass-ceramic composite material described allows the device to be manufactured using a reduced number of processes and at a low cost. The glass component preferably consists essentially of 50 to 70% by weight of SiO 2 , 3 to 15% by weight of Al 2 0 3 , 0 to 10% by weight of ZnO, 7 to 25% by weight of RO (where RO represents at least one member of CaO, SrO and BaO), 0 to 8% by weight of B 2 O 3 , and 13 to 27% by weight of R 2 O (where R 2 O represents at least one member of Na 2 O, K 2 O, and Li 2 O). To improve the bend breakage strength of the glass-ceramic composite to a desired value, the glass component and the forsterite are preferably pulverised into sufficiently fine powder of an average particle diameter between 1 and 3 micrometres. For further improvement of the bend breakage strength, 0 to 5% by weight of at least one member of ZrO 2 , TiO 2 , SnO 2 , P 2 O 5 , and MoO 3 can be mixed so that the glass is caused to at least partly crystallize during sintering or firing. As a result of the foregoing, the thermal expansion coefficient of the material of the base and the cap members matches that of the piezoelectric oscillator piece. Residual strain after cooling down the device from a raised temperature is thus reduced and variation in the resonant frequency is suppressed. Moreover, a sufficient bend breakage strength is achieved. It is possible to lower the sintering temperature of the package and to use Ag, Ag/Pd, Ag/Au, or like metal of a low melting point even if the internal conductors are simultaneously sintered. These metal materials have high electric conductivity. Selection of a component ratio in the internal conductors enables soldering to be carried out and eliminates the need for plating processes. As a consequence, a flat packaged piezoelectric device may be provided in which a piezoelectric oscillator piece is subject to less variation in its resonance frequency and which is thinner in thickness and more highly reliable than ever. In addition, it is possible to reduce the cost of manufacture and to shorten manufacturing time. Brief Description of the Drawings: Fig. 1 is an exploded perspective view of a conventional crystal oscillator unit; Fig. 2 is an exploded perspective view of another conventional crystal oscillator unit; Fig. 3 is an exploded perspective view of a crystal oscillator unit according to a first embodiment of this invention; Fig. 4 is a diagram illustrative of a degree of influence which is caused by the temperature of heat treatment on the resonance frequency of the crystal oscillator units illustrated in Figs. 1 and 3; and Fig. 5 is an exploded perspective view of a crystal oscillator unit according to a second embodiment of this invention. Description of the Preferred Embodiments: Referring to Fig. 1, a conventional crystal oscillator unit which serves as a flat packaged piezoelectric device, will first be described for a better understanding of this invention. In Fig. 1, the crystal oscillator unit is for use in surface mounting and comprises a quartz piece 2 fixed to a base member 1 made principally of alumina. Subsequently, a cap member 3, made principally of alumina, is used as a cover and an air-tight seal is achieved by a sealing part 4 of glass of a low melting point. A sealed package 5 is mounted on a circuit base board (not shown) by reflow soldering or a similar method. On sealing the package and mounting it onto the circuit base board, the package is heated to a raised temperature. It is to be noted in this connection that the package 5 and the quartz piece 2 have different thermal expansion coefficients. This results in a strain in the quartz piece 2 after it is cooled down from a raised temperature, which gives rise to a variation in the resonance frequency of the quartz piece 2 and makes it impossible to attain a desired frequency characteristic. As a countermeasure, a periodical published in the Japanese language under the title of "Electronics Update", 1990.4, teaches on pages 83 to 88, the structure illustrated in Fig. 1, in which the quartz piece 2 is fixed to the base member 2 by the intermediary of a resilient supporter 6 before the subsequent air-tight seal is made. As depicted in Fig. 2, another conventional crystal oscillator unit is proposed in JP-A-2-105 710 of 1990 as follows. Electrode lead parts 7 for the quartz piece 2 are led from a common end of the quartz piece 2 with the quartz piece 2 fixed, without intermediary of a supporter, directly to electrode pad parts 8 formed on the base member 1. Being fixed to the electrode pad parts 8 only at the common end, the quartz piece 2 has a free end and is not subjected to strain. In the crystal oscillator units illustrated in Figs. 1 and 2, the package 5 and the quartz piece 2 have different thermal expansion coefficients. This gives rise to a strain after cooling down from a raised temperature which results in a variation in the resonance frequency of the crystal oscillator unit and makes it impossible to attain a desired frequency characteristic as described above. Moreover, use of the resilient supporter 6 as an intermediary for connection of the quartz piece 2 to the package 5, while solving the above-described problem, results in other problems, such as an increased manufacturing cost and a thicker thickness of the package 5 as also described above. Still further, alumina (Al 2 O 3 ) for use as a principal material of the package 5 must be sintered at a temperature of 1500 to 1600°C. As a consequence, internal conductors for wiring in the package 5 must be made of tungsten (W), molybdenum (Mo), or a like metal having a high melting point so that the conductors can concurrently be sintered. Such a high melting point metal has a low electrical conductivity and is not adapted to soldering. Nickel (Ni) plating and/or gold (Au) plating are therefore indispensable. As a result, great amounts of processing and costs are necessary during manufacture as also mentioned before. Embodiments and examples of this invention will now be described in detail by referring to Tables 1 and 2 and to Figs. 3 through 5. In the glass compositions of Tables 1 and 2, RO represents at least one oxide selected from CaO, SrO, and BaO. R 2 O represents at least one oxide selected from Na 2 O, K 2 O, and Li 2 O. Glass, ceramics (forsterite), and an additive (zirconia) as specified in Table 1 were first ground and mixed in a wet ball mill, dried to have an average particle diameter between 1 and 3 µm, machine-pestled, powder-mould pressed, and sintered or fired at a temperature between 800°C and 1000°C. With a rectangular parallelopiped thereafter cut out, the bend breakage strength and the thermal expansion coefficient were measured. The results are given in Table 1 and prove that a large thermal expansion coefficient of about 100 to 140 x 10 -7 /°C was achieved by a mixture of a fine powder of glass and forsterite according to preferred embodiments of this invention and that addition of zirconia raises the bend breakage strength to more than 2200 kg/cm 2 and, depending on the composition, even more than 3000 kg/cm 2 . It has been confirmed by results of differential thermal analysis and X-ray diffraction that a material sintered with addition of zirconia was partially crystallized. It appears that zirconia serves as an agent for providing seeds of crystallization. In order next to study characteristics of packages for use as crystal oscillator units, crystal oscillator units were manufactured to have the structure depicted in Fig. 3 as a first embodiment of this invention by using material powder given in Example 1 or Example 1(A) of Table 1 and by manufacturing processes specified in the following. (a) A slurry was prepared by mixing the above-mentioned material, a binder of, for example, polyvinyl butyral, and a solvent of, for example, 2-methoxyethanol. A first green sheet of a thickness between 100 and 300 µm was manufactured by the doctor blade method. (b) Through-holes (not shown) were formed through the first green sheet of (a). Silver (Ag) paste was screen printed to fill the through-holes and to provide internal conductors (not shown). (c) Ag/Pd paste was screen printed on a second green sheet to provide electrode lead-out parts (not shown). (d) Sets of rectangular holes were punched through the second green sheet, each set as a cavity for the quartz piece 2. (e) In the manner which will presently be described, the first and the second green sheets and a dummy green sheet were stacked and hot-pressed at 100°C and under a pressure between 100 and 200 kg/cm 2 . (f) The above-mentioned laminate was debindered and then sintered at a temperature between 800°C and 1000°C. (g) The sintered laminate was cut into pieces, each for use as a base member 1 of a package 50 shown in Fig. 3. (h) Mixed powder, used for the base member 1, was shaped by powder pressing and sintered at 800°C to 1000°C to provide a cap member 3 of the package 50. (i) A sealing part 4 was preliminarily formed on the base member 1 by using known glass of a low melting point. Into the structure depicted in Fig. 3, electrode pad parts 80 formed on the base member 1 and electrode lead parts 7 of the quartz piece 2 were fixed to the base member 1 by a known electrically conductive adhesive. Subsequently, the cap member 3 was sealed by using the sealing part 4 to complete a flat packaged crystal oscillator unit. In order to make a comparison with prior-art manufacture, this crystal oscillator unit was tested to assess how the resonance frequency was dependent on the temperature of thermal treatment. Forty crystal oscillator units were manufactured. First, their resonance frequency (f0) was measured by a spectrum analyzer. Next, ten-unit sets were subjected to heat treatment at 100°C, 200°C, 300°C, and 400°C for thirty minutes and then cooled down to room temperature. Their resonance frequencies (f(T)) were measured. Equation 1 was used to calculate Δf/f0. Δf/f0 = (f(T) - f0)/f0, namely, (the resonance frequency after the heat treatment minus the resonance frequency before the heat treatment)/(the resonance frequency before the heat treatment). Results of these measurements are depicted in Fig. 4. Similar results are also depicted in Fig. 4 for crystal oscillator units sealed in packages made principally of alumina according to prior art. This shows that the heat treatment resulted in a variation in the resonance frequency, which was about a quarter of that in units made by prior-type manufacturing methods. Next, similar packages 50 for crystal oscillator units were manufactured using material powders listed in Table 1 and Table 2 as Example 2 or 2(A), Example 3 or 3(A), Example 4 or 4(A), Example 5 or 5(A), and Example 6 or 6(A) and in accordance with the processes specified in conjunction with Example 1 or 1(A). With a quartz piece 2 put in place, each crystal oscillator unit was completed. Evaluation was carried out on the dependency of the resonance frequency on the temperature of heat treatment of such crystal oscillator units in comparison with prior-art units. The results were substantially similar to those for units made of the composite materials of Examples 1 and 1(A) as depicted in Fig. 4. Using material powder given in Example 1 or 1(A) of Table 1, packages 10 were manufactured in accordance with the above described processes for use as crystal oscillator units having the structure depicted in Fig. 5, according to a second embodiment of this invention. With an IC 9 for an oscillator circuit and the quartz piece 2 placed in each package 10, such crystal oscillator units were tested in comparison with prior-art units as regards the dependency of resonance frequency on the temperature of thermal treatment. Results were substantially similar to those described in connection with Examples 1 and (1A) depicted in Fig. 4. Similar results were obtained when fine powder of TiO 2 , SnO 2 , P 2 O 5 , and MoO 3 was singly or jointly used in addition to fine powder of zirconia (ZrO 2 ) used in the above-described examples in the manner listed in Tables 1 and 2 as Examples 1(B) through 1(D), 2(B) through 2(D), 3(B) through 3(D), 4(B) through 4(D), 5(B) through 5(D), and 6(B) through 6(D). Preferably, the fine powder is given an average particle diameter between 0.1 and 1 µm. Results of evaluation are given in Tables 1 and 2. Inasmuch as the thermal expansion coefficient of a piezoelectric oscillator piece, such as the quartz piece, matches the thermal expansion coefficient of the package, it is possible to make the crystal oscillator unit or the like have a frequency characteristic hardly susceptible to thermal treatment during and after sealing of the piezoelectric oscillator piece in the package and to give a high reliability to the crystal oscillator units and other piezoelectric devices for surface mounting. It is possible to reduce the cost as well. This invention is widely applicable, for example to packages for surface mounting SAW resonator units and similar piezoelectric devices, besides the crystal oscillator unit. Moreover, it is no longer necessary to use a resilient support member for absorbing strain resulting from thermal treatment. This makes it possible to give a thin thickness to the package. Furthermore, it is possible to lower the sintering temperature of the package. This reduces the cost of manufacture. In addition, this renders it unnecessary to plate the electrode lead-out parts and thereby shortens the hours of manufacture. Advantageously, the package of this invention has a high bend breakage strength. Use of fine powder of the ceramics and the glass raises the bend breakage strength. Addition of an additive or additives can further raise the bend breakage strength.

Claims: A flat-packaged piezoelectric device comprising a base member (1), a pair of electrode pad parts (80) formed on said base member, a piezoelectric oscillator piece (2), a pair of electrodes (7) formed on both surfaces of said piezoelectric oscillator piece and having parts fixed to said electrode pad parts, and a cap member (3) sealed air-tight to said base member to enclose said piezoelectric oscillator piece in cooperation with said base member, wherein each of said base and said cap members is made of a glass-ceramic composite material comprising a glass component and a ceramic component, said glass component having a thermal expansion coefficient between 100 x 10 -7 /°C and 150 x 10 -7 /°C, both inclusive, and said ceramic component comprising 30 to 70% by weight of forsterite (2MgO.SiO 2 ) which is dispersed in said glass component. A flat-packaged piezoelectric device as claimed in claim 1, wherein said glass component consists, in percent by weight, essentially of 50 to 70% of SiO 2 , 3 to 15% of Al 2 O 3 , 0 to 10% of ZnO, 0 to 8% of B 2 O 3 , 7 to 25% of at least one of CaO, SrO, and BaO, and 13 to 27% of at least one of Na 2 O, K 2 O, and Li 2 O. A flat-packaged piezoelectric device as claimed in Claim 1 or 2, wherein said glass-ceramic composite material is composed of a sintered pulverised mixture of particles of said glass component and said forsterite having an average diameter of 1 to 3 micrometres, and 0 to 5% by weight of a fine powder of an average particle diameter of 0.1 to 1 micrometre of at least one of ZrO 2 , TiO 2 , SnO 2 , P 2 O 5 and MoO 3 . A flat-packaged piezoelectric device as claimed in Claim 1, 2 or 3, further comprising an oscillator integrated circuit connected to said electrodes and enclosed by said base and said cap members.

Inventors: GOTOH YOSHIHIRO, MIKAZUKI YOSHINOBU, MORISAKI YASUTOSHI, GOTOH, YOSHIHIRO, MIKAZUKI, YOSHINOBU, MORISAKI, YASUTOSHI, GOTOH, YOSHIHIRO, NEC KANSAI, LTD., MIKAZUKI, YOSHINOBU, NEC KANSAI, LTD., MORISAKI, YASUTOSHI, NEC KANSAI, LTD.
Applicants: NIPPON ELECTRIC CO, NEC CORPORATION
Application year: 1993
Main classification: C03C14
IPC codes: H01L41, C03C14, C03C10, C04B35, H03H9