WO2023286327A1 - 圧電振動子及び圧電振動子の製造方法 - Google Patents

圧電振動子及び圧電振動子の製造方法 Download PDF

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Publication number
WO2023286327A1
WO2023286327A1 PCT/JP2022/008919 JP2022008919W WO2023286327A1 WO 2023286327 A1 WO2023286327 A1 WO 2023286327A1 JP 2022008919 W JP2022008919 W JP 2022008919W WO 2023286327 A1 WO2023286327 A1 WO 2023286327A1
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Prior art keywords
metal layer
crystal
piezoelectric
base member
excitation electrode
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PCT/JP2022/008919
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English (en)
French (fr)
Japanese (ja)
Inventor
光洋 山田
茂夫 尾島
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to JP2023535106A priority Critical patent/JP7733882B2/ja
Publication of WO2023286327A1 publication Critical patent/WO2023286327A1/ja
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    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H3/00—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators
    • H03H3/007—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks
    • H03H3/02—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of piezoelectric or electrostrictive resonators or networks
    • H03H3/04—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of piezoelectric or electrostrictive resonators or networks for obtaining desired frequency or temperature coefficient
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H9/00—Networks comprising electromechanical or electro-acoustic elements; Electromechanical resonators
    • H03H9/15—Constructional features of resonators consisting of piezoelectric or electrostrictive material
    • H03H9/17—Constructional features of resonators consisting of piezoelectric or electrostrictive material having a single resonator
    • H03H9/19—Constructional features of resonators consisting of piezoelectric or electrostrictive material having a single resonator consisting of quartz

Definitions

  • the present invention relates to a piezoelectric vibrator and a method for manufacturing a piezoelectric vibrator.
  • a piezoelectric vibrator used as a reference signal source for oscillators, bandpass filters, etc. is generally known as one of electronic components.
  • a piezoelectric vibrator includes, for example, a piezoelectric vibrating element, a lid member and a base member forming a housing in which the piezoelectric vibrating element is housed, and a bonding material for bonding the lid member and the base member.
  • the piezoelectric vibrating element includes a vibrating reed that is a piezoelectric body, and an excitation electrode provided in a vibrating portion of the vibrating reed.
  • Cited Document 1 a piezoelectric substrate, a pair of conductive electrode layers provided on the upper surface of the piezoelectric substrate, and a material to be oxidized provided on the surface of the electrode layer are disclosed as a method for adjusting the frequency of the vibrating reed.
  • a vibration element having a mass portion is subjected to oxidation treatment to increase the mass of the mass portion by oxidation, thereby adjusting the resonance frequency of the vibration element. Since this method can finely adjust the mass of the layer to be oxidized, it is possible to easily finely adjust the resonance frequency.
  • the piezoelectric element (vibrating element) is oxidized as in the frequency adjustment method of Cited Document 1, after the piezoelectric vibrating element is sealed in the housing, it may be exposed to a high temperature environment or high temperature constant temperature and high humidity. When placed in an environment or the like, the unoxidized material of the material to be oxidized in the mass portion is oxidized over time, and the mass of the vibrating portion of the piezoelectric piece may change. As a result, there is a risk that the resonance frequency of the piezoelectric vibrating element will change over time.
  • the present invention has been made in view of such circumstances, and one of its objects is to provide a piezoelectric vibrator and a method for manufacturing a piezoelectric vibrator that can suppress changes in resonance frequency over time.
  • a piezoelectric vibrator is a piezoelectric vibration element having a base member, a piezoelectric piece held on one surface of the base member, and excitation electrodes provided on both main surfaces of the piezoelectric piece. and the excitation electrode includes a first metal layer and a second metal layer disposed between the first metal layer and the piezoelectric piece, wherein the weight ratio of the second metal layer to the first metal layer is , 0.1% or more and 1.1% or less.
  • a method of manufacturing a piezoelectric vibrator includes steps of preparing a piezoelectric piece, forming first metal layers containing gold as a main component on each of both main surfaces of the piezoelectric piece, and forming the first metal layers on both main surfaces of the piezoelectric piece. and a second metal layer containing chromium as a main component and disposed between the piezoelectric piece and a part of the first metal layer formed on one of the two main surfaces. and removing by trimming, wherein the thickness ratio of the second metal layer to the first metal layer is 0.4% or more and 2.9% or less.
  • FIG. 1 is an exploded perspective view schematically showing the configuration of a crystal resonator according to the first embodiment.
  • FIG. 2 is a cross-sectional view schematically showing the cross-sectional structure of the crystal resonator shown in FIG. 1 along the line II-II.
  • FIG. 3 is an enlarged view of a main part schematically showing an example of the configuration of the side surface along the X-axis of the crystal vibrating element shown in FIGS. 1 and 2.
  • FIG. FIG. 4 is a graph showing changes over time in the resonance frequency of the resonance oscillator of this embodiment and the conventional crystal oscillator.
  • FIG. 5 is a graph showing the relationship between the weight ratio of the second metal layer to the first metal layer and the frequency change rate of the resonance frequency.
  • FIG. 6 is a flow chart showing a method for manufacturing a crystal resonator according to the first embodiment.
  • FIG. 7 is a graph showing the relationship between the thickness of the second metal layer and the frequency change rate of the resonance frequency.
  • FIG. 8 is a graph showing the relationship between the thickness ratio of the second metal layer to the first metal layer and the frequency change rate of the resonance frequency.
  • FIG. 9 is a cross-sectional view schematically showing the cross-sectional structure of the crystal resonator in the second embodiment.
  • the X-axis, Y'-axis and Z'-axis correspond to each other in each drawing.
  • the X-axis, Y'-axis, and Z'-axis respectively correspond to crystallographic axes of the crystal piece 11, which will be described later.
  • the X-axis corresponds to the electric axis (polar axis) of the crystal, the Y-axis to the mechanical axis of the crystal, and the Z-axis to the optical axis of the crystal.
  • the Y'-axis and Z'-axis are obtained by rotating the Y-axis and Z-axis about the X-axis from the Y-axis in the direction of the Z-axis by 35 degrees 15 minutes ⁇ 1 minute 30 seconds.
  • the direction parallel to the X-axis is called the "X-axis direction”
  • the direction parallel to the Y'-axis is called the “Y'-axis direction”
  • the direction parallel to the Z'-axis is called the "Z'-axis direction”.
  • the direction of the tip of the arrow on the X-axis, Y'-axis and Z'-axis is called “positive” or “+ (plus)”
  • the direction opposite to the arrow is called “negative” or "- (minus)”.
  • the +Y′-axis direction is described as the upward direction
  • the ⁇ Y′-axis direction is the downward direction, but the vertical directions of the crystal vibrating element 10 and the crystal oscillator 1 are not limited.
  • a plane specified by the X-axis and the Z'-axis is defined as a Z'X plane, and the same applies to planes specified by the other axes.
  • a piezoelectric oscillator a crystal oscillator (Quartz Crystal Resonator Unit) having a crystal oscillator element (Quartz Crystal Resonator) will be taken as an example.
  • a piezoelectric vibration element a crystal vibration element having a crystal blank will be described as an example.
  • a crystal piece is a type of piezoelectric body (piezoelectric piece) that vibrates in response to an applied voltage.
  • the piezoelectric vibrator is not limited to a crystal vibrator, and may use other piezoelectric materials such as ceramic, lithium tantalate, and lithium niobate.
  • the piezoelectric vibrating element is not limited to a crystal vibrating element, and may use other piezoelectric materials such as ceramics, lithium tantalate, and lithium niobate.
  • FIG. 1 is an exploded perspective view schematically showing the configuration of a crystal resonator 1 according to the first embodiment.
  • FIG. 2 is a cross-sectional view schematically showing the cross-sectional structure of the crystal oscillator 1 shown in FIG. 1 along the line II-II.
  • the crystal resonator 1 includes a crystal resonator element 10, a lid member 20, a base member 30, and a bonding material 40.
  • the lid member 20 and the base member 30 are part of the configuration of a retainer for housing the crystal vibrating element 10 .
  • the crystal unit 1 has external dimensions smaller than, for example, 2.0 ⁇ 1.6 mm (2016 size), 1.6 ⁇ 1.2 mm (1612 size), 1.0 ⁇ 0.8 mm (1008 size). ) is a small crystal oscillator.
  • the crystal vibrating element 10 is an element that vibrates a crystal by a piezoelectric effect and converts electrical energy and mechanical energy.
  • the crystal vibrating element 10 includes, for example, an AT-cut crystal blank 11 .
  • the AT-cut crystal piece 11 has the X-axis, the Y-axis, and the Z-axis, which are the crystal axes of a synthetic quartz crystal.
  • the axes rotated by 35 degrees 15 minutes ⁇ 1 minute 30 seconds are the Y' axis and Z' axis, respectively, the XZ' plane specified by the X axis and Z' axis is cut out as the main surface .
  • the rotation angles of the Y'-axis and Z'-axis in the AT-cut crystal piece 11 may be tilted in the range of 35 degrees 15 minutes to -5 degrees or more and +15 degrees or less. Also, for the cut angle of the crystal piece 11, different cuts other than AT cut, such as BT cut, GT cut, and SC cut, may be applied.
  • a crystal resonator element that uses an AT-cut crystal blank has high frequency stability over a wide temperature range.
  • the AT-cut quartz-crystal vibrating element is excellent in aging characteristics and can be manufactured at a low cost.
  • the AT-cut crystal vibrating element uses a thickness shear vibration mode as the main vibration.
  • the crystal oscillator 10 further includes a set of excitation electrodes. An alternating electric field is applied between the pair of excitation electrodes. As a result, the vibrating portion of the crystal blank 11 vibrates at a predetermined oscillation frequency in the thickness-shear vibration mode, and resonance characteristics associated with the vibration are obtained.
  • the main vibration of the crystal resonator element 10 is the thickness-shear vibration mode, for example, by using an AT-cut crystal blank 11, the crystal resonator 1 that performs thickness-shear vibration at a vibration frequency in the MHz band can be easily manufactured. can be realized.
  • the crystal piece 11 has a first main surface 12a and a second main surface 12b which are XZ' planes and face each other.
  • Crystal blank 11 has a flat plate shape. Therefore, the first main surface 12a and the second main surface 12b of the crystal piece 11 are flat surfaces.
  • the crystal piece 11 is not limited to a flat plate shape, and may have a convex or concave shape at the center, for example.
  • the AT-cut crystal piece 11 has a long side direction in which long sides extend parallel to the X-axis direction, a short side direction in which short sides extend parallel to the Z′-axis direction, and a short side direction parallel to the Y′-axis direction. and a thickness direction in which the thickness extends.
  • the crystal piece 11 has a rectangular shape when the first main surface 12a of the crystal piece 11 is viewed from above (hereinafter simply referred to as "plan view").
  • planar shape of the crystal piece 11 is not limited to a rectangular shape.
  • the planar shape of the crystal piece 11 may be polygonal, circular, elliptical, or a combination thereof.
  • the crystal vibrating element 10 includes a first excitation electrode 14a and a second excitation electrode 14b that constitute a pair of electrodes.
  • the first excitation electrode 14a is provided on the first main surface 12a.
  • the second excitation electrode 14b is provided on the second main surface 12b.
  • the first excitation electrode 14a and the second excitation electrode 14b are provided facing each other with the crystal piece 11 interposed therebetween in regions including the centers of the principal surfaces.
  • the first excitation electrode 14a and the second excitation electrode 14b are arranged so as to substantially overlap with each other on the XZ' plane. The region where the first excitation electrode 14 a and the second excitation electrode 14 b are provided becomes the vibrating portion of the crystal piece 11 .
  • the first excitation electrode 14a and the second excitation electrode 14b each have a long side parallel to the X-axis direction, a short side parallel to the Z'-axis direction, and a thickness parallel to the Y'-axis direction. .
  • the long sides of the first excitation electrode 14a and the second excitation electrode 14b are parallel to the long sides of the crystal piece 11 on the XZ' plane.
  • the short sides of the first excitation electrode 14a and the second excitation electrode 14b are parallel to the short sides of the crystal blank 11, respectively.
  • the long sides of the first excitation electrode 14a and the second excitation electrode 14b are separated from the long sides of the crystal blank 11, respectively.
  • the short sides of the first excitation electrode 14a and the second excitation electrode 14b are separated from the short sides of the crystal blank 11, respectively.
  • the crystal oscillator 10 includes extraction electrodes 15a and 15b and connection electrodes 16a and 16b.
  • the connection electrode 16a is electrically connected to the first excitation electrode 14a through the extraction electrode 15a.
  • the connection electrode 16b is electrically connected to the second excitation electrode 14b through the extraction electrode 15b.
  • the connection electrode 16 a and the connection electrode 16 b are terminals for electrically connecting to the base member 30 .
  • the connection electrode 16a and the connection electrode 16b are provided on the second main surface 12b of the crystal blank 11, respectively.
  • the connection electrodes 16a and the connection electrodes 16b are arranged in the vicinity of the short side of the crystal piece 11 in the negative direction of the X-axis along the direction of the short side.
  • the extraction electrode 15a electrically connects the first excitation electrode 14a and the connection electrode 16a. Specifically, the extraction electrodes 15a extend from the first excitation electrodes 14a on the first main surface 12a in the Z′-axis positive direction and the X-axis negative direction, and extend from the first main surface 12a to the crystal blank 11. It extends through each side surface to reach the second main surface 12b and is electrically connected to the connection electrode 16a on the second main surface 12b. In addition, the extraction electrode 15b electrically connects the second excitation electrode 14b and the connection electrode 16b.
  • the extraction electrode 15b extends from the second excitation electrode 14b on the second main surface 12b in the negative direction of the X-axis, and is electrically connected to the connection electrode 16b on the second main surface 12b. ing.
  • the extraction electrodes 15a and 15b By extending the extraction electrodes 15a and 15b in this manner, the first excitation electrode 14a and the second excitation electrode 14b provided on both the first main surface 12a and the second main surface 12b are electrically connected.
  • the connected connection electrodes 16a and 16b can be arranged on one second main surface 12b.
  • connection electrodes 16a and 16b are electrically connected to electrodes of the base member 30, which will be described later, via conductive holding members 36a and 36b.
  • each of the extraction electrodes 15a and 15b and the connection electrodes 16a and 16b is not particularly limited, but for example, it has a chromium (Cr) layer as a base, and gold (Cr) is added to the surface of the chromium layer. Au) layer. Details of the first excitation electrode 14a and the second excitation electrode 14b will be described later.
  • the crystal resonator element 10 has a configuration including the flat plate-shaped crystal piece 11, but is not limited to this.
  • the crystal blank may adopt a mesa structure in which the vibrating portion including the center of the main surface is thicker than the peripheral portion, or may adopt an inverted mesa structure in which the vibrating portion is thinner than the peripheral portion.
  • the crystal blank may have a convex shape or a bevel shape in which the change in thickness (step) between the vibrating portion and the peripheral portion changes continuously.
  • a different cut other than the AT cut such as the BT cut, may be applied.
  • the quartz crystal vibrating element has, as a base material, a quartz crystal plate cut out at a predetermined angle with respect to the X-axis, Y-axis, and Z-axis that are orthogonal to each other as the crystal axes of the quartz crystal, and has a base and at least a base extending from the base.
  • It may be a tuning-fork type crystal vibrating element including a crystal piece having one vibrating arm and excitation electrodes provided on the vibrating arm so as to cause bending vibration.
  • the crystal vibrating element 10 includes a pair of the first excitation electrode 14a and the second excitation electrode 14b provided on both main surfaces of the crystal piece 11, the vibrating portion vibrates in a predetermined vibration mode.
  • the vibrating element 10 can be easily configured (realized).
  • the lid member 20 and the base member 30 form an internal space 26 that accommodates the crystal vibrating element 10 .
  • the lid member 20 and the base member 30 are joined by a jointing material 40 which will be described later.
  • the lid member 20 has a concave shape, specifically a box shape including an opening, and has an inner surface 24 and an outer surface 25 .
  • the lid member 20 is connected to the top surface portion 21 facing the first main surface 32a of the base member 30 and to the outer edge of the top surface portion 21, and extends in the normal direction to the main surface of the top surface portion 21. and a side wall portion 22 .
  • the lid member 20 has a long side direction in which long sides extend parallel to the X-axis direction, a short side direction in which short sides extend parallel to the Z′-axis direction, and a height direction parallel to the Y′-axis direction. and a direction.
  • the lid member 20 also has a facing surface 23 facing the first main surface 32a of the base member 30 at the edge of the concave opening.
  • the facing surface 23 has a frame shape and extends so as to surround the crystal vibrating element 10 .
  • the lid member 20 is, for example, a member made of metal.
  • the lid member 20 is made of 42 alloy, which is an alloy containing iron (Fe) and nickel (Ni), or Kovar, which is an alloy containing iron (Fe), nickel (Ni), and cobalt (Co). Configured. Both 42 alloy and Kovar are known as metals with low coefficients of thermal expansion.
  • a nickel (Ni) layer or the like formed by plating may be provided on the innermost surface (surface including the inner surface 24 ) of the lid member 20 .
  • a gold (Au) layer or the like may be provided on the outermost surface (surface including the outer surface 25) of the lid member 20 for the purpose of preventing oxidation.
  • the facing surface 23 of the lid member 20 may be provided with a nickel (Ni) layer and a gold (Au) layer formed by plating.
  • the material of the lid member 20 is not limited to metal, and other materials may be used.
  • the lid member 20 that houses the crystal oscillator 10 in the internal space 26 formed between the base member 30 and the crystal oscillator 10
  • the crystal oscillator 10 can be protected from the external environment.
  • the base member 30 supports the crystal vibrating element 10 so that it can vibrate. Specifically, the crystal oscillator 10 is oscillatably held on the first main surface 32a of the base member 30 via the conductive holding members 36a and 36b.
  • the base member 30 has a flat plate shape.
  • the base member 30 has a long side direction in which long sides extend parallel to the X-axis direction, a short side direction in which short sides extend parallel to the Z′-axis direction, and a thickness parallel to the Y′-axis direction. and an extending thickness direction.
  • the base member 30 includes a base 31.
  • the base 31 has a first main surface 32a and a second main surface 32b, which are XZ' planes facing each other.
  • the substrate 31 is, for example, a sintered material such as insulating ceramic (alumina).
  • the substrate 31 may be formed by laminating and sintering a plurality of insulating ceramic sheets.
  • the substrate 31 may be a glass material (for example, a silicate glass or a material having a main component other than a silicate and exhibiting a glass transition phenomenon when heated), a crystal material (for example, an AT-cut crystal), or It may be formed of a glass epoxy resin or the like.
  • Substrate 31 is preferably made of a heat-resistant material.
  • the substrate 31 may be a single layer or a plurality of layers, and in the case of a plurality of layers, the substrate 31 includes an insulating layer formed as the outermost layer of the first major surface 32a.
  • the base member 30 includes electrode pads 33a, 33b provided on the first main surface 32a and external electrodes 35a, 35b, 35c, 35d provided on the second main surface 32b.
  • the electrode pads 33 a and 33 b are terminals for electrical connection with the crystal vibrating element 10 .
  • the external electrodes 35a, 35b, 35c, and 35d are terminals for electrical connection with a circuit board (not shown).
  • the electrode pad 33a is electrically connected to the external electrode 35a via a via electrode 34a extending in the Y'-axis direction
  • the electrode pad 33b is electrically connected to the external electrode 35a via a via electrode 34b extending in the Y'-axis direction. 35b.
  • the via electrodes 34a and 34b are formed in via holes (not shown) penetrating the base 31 in the Y'-axis direction.
  • the electrode pads 33a and 33b are provided near the short side of the base member 30 on the negative side of the X-axis on the first main surface 32a. In the example shown in FIG. 1, the electrode pads 33a and 33b are arranged apart from the short side of the base member 30 and along the short side direction.
  • the electrode pad 33a is connected to the connection electrode 16a of the crystal vibrating element 10 via the conductive holding member 36a. Further, the electrode pad 33b is connected to the connection electrode 16b of the crystal vibrating element 10 via the conductive holding member 36b.
  • a plurality of external electrodes 35a, 35b, 35c, and 35d are provided near respective corners of the second main surface 32b.
  • the external electrodes 35a and 35b are arranged directly below the electrode pads 33a and 33b.
  • the external electrodes 35a and 35b can be electrically connected to the electrode pads 33a and 33b by the via electrodes 34a and 34b extending in the Y'-axis direction.
  • the external electrodes 35a, 35b, 35c, 35d In the example shown in FIG. 1, of the four external electrodes 35a, 35b, 35c, 35d, the external electrodes 35a, 35b arranged near the short side of the base member 30 on the negative side of the X-axis are It is an input/output electrode to which an input/output signal is supplied.
  • the external electrodes 35c and 35d arranged near the short side of the base member 30 in the positive direction of the X-axis are dummy electrodes to which input/output signals of the crystal vibrating element 10 are not supplied.
  • the arrangement relationship between the electrode pads 33a, 33b and the external electrodes 35a, 35b, 35c, 35d is not limited to the example described above.
  • two external electrodes which are input/output electrodes, may be provided diagonally on the second main surface 32b.
  • the four external electrodes may be arranged near the center of each side instead of the corners of the second main surface 32b.
  • the number of external electrodes is not limited to four, and may be, for example, only two external electrodes which are input/output electrodes.
  • the form of electrical connection between the electrode pads and the external electrodes is not limited to via electrodes.
  • electrical connection between the electrode pads or the internal electrodes and the external electrodes may be achieved by drawing out the lead electrodes on the first major surface 32a or the second major surface 32b.
  • the substrate 31 of the base member 30 with a plurality of layers, extending the via electrodes to the intermediate layer, and extracting the extraction electrodes from the intermediate layer, the electrical connection between the electrode pads or the internal electrodes and the external electrodes is achieved. You may try to connect.
  • a sealing frame 37 is provided on the first main surface 32 a of the base 31 .
  • the sealing frame 37 has a frame shape when the first main surface 32a of the base member 30 is viewed from above.
  • Electrode pads 33 a and 33 b are arranged inside the sealing frame 37 and are provided so as to surround the crystal vibrating element 10 .
  • the electrode pads 33a and 33b of the base member 30, the external electrodes 35a, 35b, 35c and 35d, and the sealing frame 37 are all made of metal films.
  • the electrode pads 33a, 33b, the external electrodes 35a, 35b, 35c, 35d, and the sealing frame 37 are each composed of a molybdenum (Mo) layer, a nickel (Ni) layer, and a gold (Au) layer from the lower layer to the upper layer. It is constructed by stacking.
  • the via electrodes 34a and 34b can be formed by filling the via holes of the substrate 31 with a metal material such as molybdenum (Mo).
  • the crystal resonator element 10 is sealed in the internal space 26 surrounded by the lid member 20 and the base member 30 .
  • the pressure in the internal space 26 is preferably a vacuum state lower than the atmospheric pressure.
  • the bonding material 40 is provided over the entire circumferences of the lid member 20 and the base member 30 . Specifically, the bonding material 40 is provided on the sealing frame 37 . By interposing the sealing frame 37 and the bonding material 40 between the facing surface 23 of the side wall portion 22 of the lid member 20 and the first main surface 32 a of the base member 30 , the crystal oscillator 10 is connected to the lid member 20 and the bonding material 40 . It is sealed to the base member 30 .
  • the bonding material 40 is made of a metal material.
  • the bonding material 40 is composed of an alloy composed of a plurality of metals, such as a gold (Au)-tin (Sn) eutectic alloy.
  • the crystal vibrating element 10 can be sealed in the internal space 26 between the base member 30 and the lid member 20 . .
  • an alternating electric field is applied between a pair of the first excitation electrode 14a and the second excitation electrode 14b in the crystal vibrating element 10 via the external electrodes 35a and 35b of the base member 30. be done.
  • the vibrating portion of the crystal blank 11 vibrates in a predetermined vibration mode such as a thickness-shear vibration mode, and resonance characteristics associated with the vibration are obtained.
  • the crystal resonator element 10 has one end in the long side direction of the crystal blank 11 (the end on the side where the electrode pads 33a and 33b are arranged) as a fixed end, and the other end as a fixed end. It is held so as to be a free end.
  • the conductive holding members 36a and 36b are formed on one surface of the electrode pads 33a and 33b (the surface on the Y′-axis positive direction side in FIG. 2).
  • One end of the crystal vibrating element 10 is held on the surfaces of the electrode pads 33a and 33b.
  • This structure can be obtained, for example, by applying a conductive adhesive to one surface of the electrode pads 33a and 33b, and heating and solidifying the conductive adhesive with the crystal vibrating element 10 mounted thereon. can be done.
  • the connection electrodes 16a, 16b of the crystal vibrating element 10 and the electrode pads 33a, 33b of the base member 30 are electrically connected by the solidified conductive holding members 36a, 36b. Further, the crystal vibrating element 10 is mounted so that the second excitation electrode 14b faces the first main surface 32a of the base member 30. As shown in FIG.
  • the position of the fixed end of the crystal oscillator 10 is not particularly limited.
  • the crystal vibrating element 10 may be fixed to the base member 30 at both ends of the crystal blank 11 in the long side direction.
  • each electrode of the crystal oscillator 10 and the base member 30 may be formed in such a manner that the crystal oscillator 10 is fixed at both ends of the crystal blank 11 in the long side direction.
  • the material of the conductive holding members 36a and 36b is preferably an adhesive having conductivity.
  • the crystal oscillator 1 that holds one end of the crystal oscillator 10 on one surface of the electrode pads 33a and 33b while electrically connecting the electrode pads 33a and 33b to the crystal oscillator 10 can be easily configured (realized). can do.
  • FIG. 3 is an enlarged view of a main part schematically showing an example of the configuration of the side surface along the X-axis of the crystal vibrating element 10 shown in FIGS. 1 and 2.
  • FIG. 3 is an enlarged view of a main part schematically showing an example of the configuration of the side surface along the X-axis of the crystal vibrating element 10 shown in FIGS. 1 and 2.
  • FIG. 3 is an enlarged view of a main part schematically showing an example of the configuration of the side surface along the X-axis of the crystal vibrating element 10 shown in FIGS. 1 and 2.
  • the crystal vibrating element 10 includes a crystal blank 11, first excitation electrodes 14a provided on the first main surface 12a of the crystal blank 11, and electrodes provided on the second main surface 12b of the crystal blank 11. and a second excitation electrode 14b.
  • the first excitation electrode 14a and the second excitation electrode 14b include a first metal layer 141 and a second metal layer 142, respectively.
  • the first metal layer 141 is a layer exposed on the surfaces of the first excitation electrode 14a and the second excitation electrode 14b, and serves as an electrode. Therefore, the first metal layer 141 is preferably made of metal with high electrical conductivity.
  • the material of the first metal layer 141 is, for example, metal such as gold (Au) or silver (Ag), and the first metal layer 141 is mainly composed of one of these metals. That is, the first metal layer 141 may contain, for example, the metal of the second metal layer 142 diffused therein, or may contain metal oxides, compounds combined with other elements, or the like.
  • the second metal layer 142 is a layer underlying the first metal layer 141 , and the first metal layer 141 is laminated on the second metal layer 142 . That is, the second metal layer 142 is arranged between the first metal layer 141 and the crystal blank 11, and serves to fix the first metal layer 141 to the crystal blank 11, which is a piezoelectric body.
  • the material of the second metal layer 142 is, for example, a metal such as chromium (Cr) or titanium (Ti), and the second metal layer 142 is mainly composed of one of these metals. That is, the second metal layer 142 may contain, for example, the metal of the first metal layer 141 diffused therein, or may contain metal oxides, compounds combined with other elements, or the like.
  • the thermal expansion coefficient of the second metal layer 142 is preferably close to the thermal expansion coefficient of the contacting piezoelectric piece.
  • the difference in thermal expansion coefficient between the second metal layer 142 and the crystal blank 11 is preferably smaller than the difference in thermal expansion coefficient between the first metal layer 141 and the crystal blank 11 .
  • the second metal layer 142 can function (role) as an adhesion layer that adheres the first metal layer 141 to the crystal piece 11 .
  • the metal of the second metal layer which is the lower layer of the excitation electrode, may diffuse into the first metal layer and be exposed on the surface. For this reason, even when the crystal resonator element is sealed in a housing, the conventional crystal resonator is exposed to the surface of the excitation electrode over time when placed in a high-temperature environment or a high-temperature and high-humidity environment.
  • the metal of the metal layer was oxidized, and the mass of the vibrating portion of the crystal piece was sometimes changed. As a result, there is a possibility that the resonance frequency of the crystal oscillator changes over time.
  • the inventors of the present invention found that when the ratio (percentage) of the first metal layer and the second metal layer in the excitation electrode is within a predetermined range, was found to be able to suppress the diffusion of
  • the ratio of the weight of the second metal layer 142 to the weight of the first metal layer 141 (hereinafter also simply referred to as "the weight ratio of the second metal layer 142") is It is 0.1% or more and 1.1% or less.
  • the thickness of the second metal layer 142 is preferably smaller than the thickness of the first metal layer 141 . More specifically, the thickness of the second metal layer 142 is preferably less than several percent of the thickness of the first metal layer 141, specifically less than about 3%.
  • the material of the first metal layer 141 is gold (Au) and the material of the second metal layer 142 is chromium (Cr). Also, the piezoelectric body (piezoelectric piece) will be described using the aforementioned crystal piece 11 unless otherwise specified.
  • FIG. 4 is a graph showing temporal changes in resonance frequency in the crystal oscillator 1 of this embodiment and a conventional crystal oscillator.
  • FIG. 5 is a graph showing the relationship between the weight ratio of the second metal layer to the first metal layer and the frequency change rate of the resonance frequency.
  • the horizontal axis is time, and the unit is [h].
  • the vertical axis represents the frequency change rate (dF/F) of the resonance frequency, and the unit is [ppm].
  • the horizontal axis represents the weight ratio of the second metal layer to the first metal layer, and the unit is [%].
  • the vertical axis represents the frequency change rate (dF/F) of the resonance frequency, and the unit is [ppm].
  • the conventional crystal oscillator has a temperature of 85 [°C] and a humidity of 85 [%R. H. ], the frequency change rate of the resonance frequency is about -14 [ppm] on average after 500 hours.
  • the conventional crystal oscillator had a thickness of 1820 [nm] at the vibrating portion of the crystal piece, a thickness of 125 [nm] at the first metal layer at each excitation electrode, and The thickness of the second metal layer in the excitation electrode is set to 5 [nm].
  • the weight ratio of the second metal layer to the first metal layer is 1.5[%].
  • the average frequency change rate of the resonance frequency after 500 hours is about -4 [ppm].
  • the crystal resonator 1 of the present embodiment has a thickness of 1820 [nm] at the vibrating portion of the crystal piece 11 and The thickness of the first metal layer 141 is set to 125 [nm], and the thickness of the second metal layer 142 in each excitation electrode is set to 1 [nm].
  • the weight ratio of the second metal layer 142 to the first metal layer 141 is 0.3[%].
  • the conventional crystal unit with a weight ratio of 1.5 [%] has an average frequency change rate of the resonance frequency after 500 hours in the environment described above. is about -14 [ppm].
  • the weight ratio of the second metal layer 142 to the first metal layer 141 in the crystal resonator 1 after 500 hours in the above-described environment is 0.3 [ %]
  • the frequency change rate of the resonance frequency is about ⁇ 4 [ppm] on average.
  • the resonance frequency is about ⁇ 4 [ppm] on average.
  • the resonance frequency is similar. A frequency change rate is obtained.
  • the first excitation electrode 14a and the second excitation electrode 14b each include a first metal layer 141 and a second metal layer 142 arranged between the first metal layer 141 and the crystal piece 11.
  • the weight ratio of the second metal layer 142 to the first metal layer 141 is 0.1% or more and 1.1% or less. Since the weight of the layer 142 is small, diffusion of the metal of the second metal layer 142 into the first metal layer 141 can be suppressed. Therefore, it is possible to reduce the possibility that the metal of the second metal layer 142 is exposed to the surface and oxidized, and it is possible to suppress changes in the resonance frequency over time.
  • the second metal layer 142 since the thickness of the second metal layer 142 is smaller than the thickness of the first metal layer 141, the second metal layer 142 having a small weight ratio to the first metal layer 141 can be easily formed. .
  • FIG. 6 is a flow chart showing the manufacturing method S150 of the crystal unit 1 according to the first embodiment.
  • the crystal piece 11 is prepared (S151).
  • the crystal piece 11 is, for example, an AT-cut crystal piece obtained by cutting artificial quartz at a predetermined angle.
  • a first metal layer 141 and a second metal layer 142 are formed on the first main surface 12a and the second main surface 12b of the crystal piece 11, respectively (S152). Specifically, on each of the first main surface 12a and the second main surface 12b, first, a film of chromium (Cr) is formed on the crystal blank 11 by vapor deposition such as sputtering, and then the second metal layer 142 is formed. Form. Then, a film of gold (Au) is formed on the chromium (Cr) by vapor deposition, sputtering, or the like to form the first metal layer 141 . At this time, for example, the first metal layer 141 formed on the first main surface 12a side is formed thicker than the first metal layer 141 formed on the second main surface 12b side in consideration of removal by trimming, which will be described later. ing.
  • the positions, shapes, dimensions, etc. of the first metal layer 141 and the second metal layer 142 are adjusted by etching or the like.
  • the first excitation electrode 14a and the second excitation electrode 14b are formed on both main surfaces of the crystal blank 11 .
  • lead electrodes 15a and 15b, connection electrodes 16a and 16b, and the like are formed, and the crystal vibrating element 10 is manufactured.
  • the crystal vibrating element 10 having the crystal blank 11, the first excitation electrode 14a and the second excitation electrode 14b is provided on the base member 30 (S153). Specifically, electrode pads 33 a and 33 b are formed on the first main surface 32 a of the base member 30 . Connection electrodes 16a and 16b formed on one end side of the second main surface 12b of the crystal piece 11 are mounted on the electrode pads 33a and 33b via conductive holding members 36a and 36b. As a result, the crystal vibrating element 10 is held on the first main surface 32a of the base member 30 in a cantilevered state. Further, the second excitation electrode 14b of the crystal vibrating element 10 is installed facing the first main surface 32a of the base member 30 .
  • the processing steps of the base member 30 and the forming steps of various electrodes are common, and the configuration of the base member 30 has already been described. Therefore, the description of the step of preparing the base member 30 is omitted.
  • a part of the first excitation electrode 14a formed on the first main surface 12a of the crystal piece 11 is removed by trimming (S154). Specifically, an argon (Ar) ion beam is irradiated onto the entire surface of the first excitation electrode 14a from above the base member 30 on which the crystal vibrating element 10 is provided. As a result, the atoms of the first metal layer 141 exposed on the surface of the first excitation electrode 14a are flipped off by the sputtering phenomenon, and the first metal layer 141 is partly scraped off.
  • the initial thickness of the first metal layer 141 of the first excitation electrode 14a and trimming are performed so that the thickness of the first excitation electrode 14a and the thickness of the second excitation electrode 14b are substantially the same. The thickness to remove is adjusted.
  • the thickness of the crystal blank 11 is 1820 [nm]
  • the thickness of the first metal layer 141 is about 125 [nm]
  • the thickness of the second excitation electrode 14a and the second excitation electrode 14b is about 125 [nm].
  • the thickness of the metal layer 142 is formed to be approximately 1 [nm].
  • the thickness of the crystal blank 11 is usually in the range of about 2000 [nm] at maximum and about 1000 [nm] at minimum. .
  • the thickness of the crystal piece 11 is 1000 [nm]
  • the thickness of the first metal layer 141 is about 68.5 [nm]
  • the thickness of the second metal layer 142 is about 68.5 [nm] in the first excitation electrode 14a and the second excitation electrode 14b. is formed to have a thickness of about 2 [nm].
  • the thickness of the crystal piece 11 is 2000 [nm]
  • the thickness of the first metal layer 141 is about 137 [nm]
  • the thickness of the second metal layer 142 is about 137 [nm] in the first excitation electrode 14a and the second excitation electrode 14b. is formed to have a thickness of about 0.5 [nm].
  • the ratio of the thickness of the second metal layer 142 to the thickness of the first metal layer 141 (hereinafter also simply referred to as the “thickness ratio of the second metal layer 142”) is 0.4% or more. .9% or less.
  • the base member 30 and the lid member 20 are joined by the sealing frame 37 and the joining material 40 (S155).
  • the sealing frame 37 is provided over the entire circumference of the first main surface 32 a of the base member 30 .
  • the sealing frame 37 is provided by screen printing and then heated to be solidified (temporary solidified).
  • the bonding material 40 which is a glass adhesive
  • the lid member 20 are placed on the sealing frame 37 of the base member 30, and heated again to melt the sealing frame 37 and the bonding material 40, and then fired (main firing).
  • main firing main firing
  • the process for processing the lid member 20 is common, and the configuration of the lid member 20 has already been described. Therefore, the description of the step of preparing the lid member 20 is omitted.
  • FIG. 7 is a graph showing the relationship between the thickness of the second metal layer and the frequency change rate of the resonance frequency.
  • FIG. 8 is a graph showing the relationship between the thickness ratio of the second metal layer to the first metal layer and the frequency change rate of the resonance frequency.
  • the horizontal axis represents the thickness of the second metal layer, and the unit is [nm].
  • the vertical axis represents the frequency change rate (dF/F) of the resonance frequency, and the unit is [ppm].
  • the horizontal axis represents the thickness ratio of the second metal layer to the first metal layer, and the unit is [%].
  • the vertical axis represents the frequency change rate (dF/F) of the resonance frequency, and the unit is [ppm].
  • the conventional crystal oscillator with a total thickness of the second metal layer of about 10 [nm] has a temperature of 85 [°C] and a humidity of 85 [%R. H. ] after 500 hours, the frequency change rate of the resonance frequency is about ⁇ 14 [ppm] on average.
  • the crystal unit 1 after 500 hours in the above-described environment has a total thickness of 2 [nm] of the second metal layer 142 , is about -4 [ppm] on average.
  • the frequency change rate of the resonance frequency is -4 [nm] on average. ppm].
  • illustration is omitted, it was found that the frequency change rate of the resonance frequency tends to be saturated as the total thickness of the second metal layer 142 decreases. Therefore, even at 1 [nm], which is the total thickness of the second metal layer when the second metal layer can be stably manufactured and has the smallest thickness (thinest), a similar frequency change rate of the resonance frequency can be obtained. be done.
  • the frequency change rate of the resonance frequency is about ⁇ 14 [ppm] on average.
  • the crystal unit 1 after 500 hours in the above environment has a thickness ratio of the second metal layer 142 to the first metal layer 141 of 0.8. When it is [%], it is about -4 [ppm] on average. Similarly, when the thicknesses of the first metal layer 141 and the second metal layer 142 are changed and the thickness ratio of the second metal layer 142 to the first metal layer 141 is 2.9%, The frequency change rate of the resonance frequency was about -4 [ppm] on average. Furthermore, although illustration is omitted, it was found that the frequency change rate of the resonance frequency tends to saturate as the thickness ratio decreases.
  • the thickness ratio of 0.4 [%] of the second metal layer 142 to the first metal layer 141 when the second metal layer 142 can be manufactured stably is the smallest (thin) is the same. , the frequency change rate of the resonance frequency of is obtained.
  • the thickness ratio of the second metal layer 142 to the first metal layer 141 is 0.4% or more and 2.9% or less. Since the thickness of the second metal layer 142 is smaller than that of the metal layer 141, diffusion of the metal of the second metal layer 142 into the first metal layer 141 can be suppressed. Therefore, it is possible to reduce the possibility that the metal of the second metal layer 142 is exposed to the surface and oxidized, and it is possible to suppress changes in the resonance frequency over time.
  • FIG. 9 is a cross-sectional view schematically showing the cross-sectional configuration of the crystal oscillator 201 in the second embodiment.
  • FIG. 9 is a cross-sectional view corresponding to FIG. 2 in the first embodiment.
  • the configuration example of the second embodiment shown in FIG. 9 differs from that of the first embodiment shown in FIG. It differs from the configuration example of the crystal unit 1 .
  • the base member 230 has an inner bottom surface 238a, a facing surface 238b, and an inner side surface 238c on the lid member 220 side.
  • the inner bottom surface 238 a and the facing surface 238 b face the first main surface 222 a of the lid member 220 .
  • the inner bottom surface 238a is located in the central portion on the lid member 220 side.
  • An electrode pad 233a is provided on the inner bottom surface 238a.
  • the inner side surface 238c is a surface that connects the inner bottom surface 238a and the opposing surface 238b.
  • the facing surface 238b is positioned outside the inner bottom surface 238a when the inner bottom surface 238a is viewed in plan, and has a frame shape.
  • a sealing frame 237 is provided over the entire circumference of the facing surface 238b.
  • the lid member 220 has a first main surface 222a and a second main surface 222b facing each other.
  • a bonding material 240 is provided along the entire circumference of the outer peripheral portion of the second main surface 222b.
  • the bonding material 240 bonds the base member 230 and the lid member 220 to seal the internal space 226 .
  • the internal space 226 accommodates the crystal vibrating element 210 .
  • a conductive holding member 236a is formed on one surface of the electrode pad 233a (the surface on the Y′-axis positive direction side in FIG. 4), and one end of the crystal vibrating element 210 is connected to the electrode by the conductive holding member 236a. It is held on the surface of pad 233a.
  • the crystal vibrating element 210 has a crystal piece 211 and a first excitation electrode 214 a and a second excitation electrode 214 b provided on both main surfaces of the crystal piece 211 .
  • the first excitation electrode 214a and the second excitation electrode 214b respectively include a first metal layer 141 and a second metal layer 142 (not shown) as in the first embodiment.
  • the method for manufacturing the crystal oscillator 210 is substantially the same as the method for manufacturing the crystal unit 1 in the first embodiment described above, so illustration and description thereof will be omitted.
  • the first excitation electrode and the second excitation electrode each include a first metal layer and a second metal layer disposed between the first metal layer and the crystal blank, A weight ratio of the second metal layer to the first metal layer is 0.1% or more and 1.1% or less.
  • the weight of the second metal layer with respect to the first metal layer is smaller than that of the conventional crystal resonator, so that the diffusion of the metal of the second metal layer into the first metal layer can be suppressed. Therefore, it is possible to reduce the possibility that the metal of the second metal layer is exposed to the surface and oxidized, and it is possible to suppress the change in the resonance frequency over time.
  • the thickness of the second metal layer is smaller than the thickness of the first metal layer. This makes it possible to easily form the second metal layer having a small weight ratio with respect to the first metal layer.
  • the difference in thermal expansion coefficient between the second metal layer and the crystal blank is smaller than the difference in thermal expansion coefficient between the first metal layer and the crystal blank.
  • the second metal layer can function (role) as an adhesion layer that adheres the first metal layer to the crystal piece.
  • the material of the first metal layer is gold (Au)
  • the material of the second metal layer is chromium (Cr). This makes it possible to easily configure (realize) a crystal resonator that suppresses changes in the resonance frequency over time.
  • the material of the piezoelectric piece is crystal. This makes it possible to easily configure (realize) a crystal resonator that suppresses changes in the resonance frequency over time.
  • the above-described crystal oscillator further includes a lid member that accommodates the crystal oscillator in an internal space formed between the base member and the crystal oscillator. As a result, the crystal oscillator can be protected from the external environment.
  • the crystal resonator element can be sealed in the internal space between the base member and the lid member.
  • the thickness ratio of the second metal layer to the first metal layer is 0.4% or more and 2.9% or less.
  • the thickness of the second metal layer is smaller than that of the first metal layer as compared with the conventional crystal resonator, so that the diffusion of the metal of the second metal layer into the first metal layer can be suppressed. Therefore, it is possible to reduce the possibility that the metal of the second metal layer is exposed to the surface and oxidized, and it is possible to suppress the change in the resonance frequency over time.

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  • Engineering & Computer Science (AREA)
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  • Piezo-Electric Or Mechanical Vibrators, Or Delay Or Filter Circuits (AREA)
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WO2025192111A1 (ja) * 2024-03-12 2025-09-18 株式会社村田製作所 圧電振動素子

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JP2002057540A (ja) * 2000-08-08 2002-02-22 Seiko Epson Corp 水晶振動片の製造方法及び水晶デバイス
JP2008306594A (ja) * 2007-06-08 2008-12-18 Epson Toyocom Corp メサ型振動片およびメサ型振動デバイス
JP2011160095A (ja) * 2010-01-29 2011-08-18 Daishinku Corp 圧電振動片、圧電振動デバイス、及び圧電振動デバイスの製造方法
JP2014158149A (ja) * 2013-02-15 2014-08-28 Seiko Epson Corp 振動素子、振動子、電子デバイス、電子機器、及び移動体

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JP2002057540A (ja) * 2000-08-08 2002-02-22 Seiko Epson Corp 水晶振動片の製造方法及び水晶デバイス
JP2008306594A (ja) * 2007-06-08 2008-12-18 Epson Toyocom Corp メサ型振動片およびメサ型振動デバイス
JP2011160095A (ja) * 2010-01-29 2011-08-18 Daishinku Corp 圧電振動片、圧電振動デバイス、及び圧電振動デバイスの製造方法
JP2014158149A (ja) * 2013-02-15 2014-08-28 Seiko Epson Corp 振動素子、振動子、電子デバイス、電子機器、及び移動体

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