JP3992962B2 - Piezoelectric vibrator - Google Patents

Piezoelectric vibrator Download PDF

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Publication number
JP3992962B2
JP3992962B2 JP2001330270A JP2001330270A JP3992962B2 JP 3992962 B2 JP3992962 B2 JP 3992962B2 JP 2001330270 A JP2001330270 A JP 2001330270A JP 2001330270 A JP2001330270 A JP 2001330270A JP 3992962 B2 JP3992962 B2 JP 3992962B2
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Prior art keywords
piezoelectric
piezoelectric vibrator
silicon dioxide
metal film
silicate
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JP2003133884A (en
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政良 白石
安広 野原
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Seiko Instruments Inc
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Seiko Instruments Inc
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Description

【０００１】
【発明の属する技術分野】
この発明は、携帯情報端末の発振回路に用いられる圧電振動子に関する。
【０００２】
【発明が解決しようとする課題】
従来の圧電振動子は、一つの容器に一つの振動片を配置し、接続する方法が用いられていた。そこで、生産効率を高めるために、振動子片と容器を含めてウエハー単位の製造が検討され、振動子片にシリコンからなる容器を陽極接合で直接接合する方法や、振動子片に低融点金属を介して容器を接合する方法が考案されていた。
【０００３】
しかし、前者の方法では、振動子片とシリコンの熱膨張係数の差が大きいため、振動子片に応力が加わり、振動特性が低下する課題があった。また、後者の方法では、低融点金属の耐食性が低く、十分な耐環境性が得にくい課題があった。
【０００４】
【課題を解決する手段】
この発明では、ウエハー内に形成された圧電振動片の上下面に、それぞれ金属層を介して蓋１０と容器１２を接合し、圧電振動片を切断分離した後、断面から露出した金属層の表面及びその金属層と容器１２や蓋１０の界面を被うようにガラス層１５を形成した圧電振動子とした。
【０００５】
このように形成された圧電振動子では、従来側面部に露出していた金属層の表面に、比較的低温で緻密な保護膜として機能するガラス層１５が形成されるため、金属層の腐食や酸化が起こらず、かつ、特に蓋や容器がガラスの場合は熱膨張による歪の発生が少ないため耐環境性と振動特性に優れた圧電振動子を得ることが出来る。
【０００６】
またこの発明では、圧電材料からなるウエハー内に圧電振動片を形成し、圧電振動片の周囲の上面と下面に金属層を形成し、圧電振動片が振動可能なように上面と下に、空間のある蓋１０と容器１２を、圧電振動片を囲むように陽極接合し、圧電振動片を蓋１０と容器１２と共に切断、分離し側面に露出した金属層に水ガラスを塗布し、焼成しガラス層１５を形成する。
【０００７】
【発明の実施の形態】
この発明では、一対の電極を有する圧電振動片と圧電振動片の基部に接続され圧電振動片の外周を囲み圧電振動片と一体に形成された枠とからなる圧電振動基板１１と、圧電振動片の上面と離間し、枠の上面に第１の金属膜１３を介して接合された蓋１０と、圧電振動片の下面と離間し、枠の下面に第２の金属膜１４を介して接合され、かつ底部に電極と接続された一対の外部電極を有する容器１２と、第１の金属膜１３と第２の金属膜１４の露出部を覆うガラス層１５からなる圧電振動子とした。
【０００８】
また、一対の電極を有する圧電振動片と圧電振動片の基部に接続され圧電振動片の外周を囲み圧電振動片と一体に形成された枠とからなる圧電振動基板１１と、圧電振動片の上面と離間し、枠の上面に形成された第１の金属膜１３を介し陽極接合された蓋１０と、圧電振動片の下面と離間し、枠の下面に形成された第２の金属膜１４を介して陽極接合され、底部に電極と接続された一対の外部電極を有する容器１２と、第１の金属膜１３と第２の金属膜１４の露出部を覆うガラス層１５からなる圧電振動子とした。
【０００９】
ここで、ガラス層１５は珪酸ソーダまたは珪酸カリまたは珪酸リチウムが好ましく、ガラス層１５の膜厚としては１μｍから１０μｍが好ましい。ガラス層の膜厚が１μｍより薄いと、金属膜の耐食性を確保することが困難であり、また１０μｍを越すとガラス層の密着力が低下する。
【００１０】
そして、珪酸カリの酸化カリに対する二酸化ケイ素のモル比が１．８から３．７が好ましい。このモル比にすることにより、ガラス層形成時の粘度が好適な値となり、作業性が高くなる。
【００１１】
また、珪酸カリの酸化カリに対する二酸化ケイ素のモル比が１．８から２．２が好ましい。
【００１２】
または、珪酸カリの酸化カリに対する二酸化ケイ素のモル比が２．５から２．７が好ましい。
【００１３】
または、珪酸カリの酸化カリに対する二酸化ケイ素のモル比が２．７から３．０が好ましい。
【００１４】
または、前記珪酸カリの酸化カリに対する二酸化ケイ素のモル比が２．９から３．２が好ましい。
【００１５】
または、珪酸カリの酸化カリに対する二酸化ケイ素のモル比が３．４から３．７が好ましい。
【００１６】
また、珪酸カリの二酸化ケイ素が２７．５から２９ｗｔ％、酸化カリが２１から２３ｗｔ％が好ましい。その組成範囲では、好適な粘度が得られ、ガラス層の形成が容易になる。
【００１７】
また、珪酸カリの二酸化ケイ素が２８から３０ｗｔ％、酸化カリが１７から１８ｗｔ％が好ましい。
【００１８】
また、珪酸カリの二酸化ケイ素が２６から２９ｗｔ％、酸化カリが１３から１６ｗｔ％が好ましい。
【００１９】
また、珪酸カリの二酸化ケイ素が２５．５から２７．５ｗｔ％、酸化カリが１２．５から１４．５ｗｔ％が好ましい。
【００２０】
また、珪酸カリの二酸化ケイ素が１９．５から２１．５ｗｔ％、酸化カリが８．５から９．５ｗｔ％が好ましい。
【００２１】
ここで、珪酸ソーダは、テトラソディウムモノシリケート、ヘキサソディウムジシリケート、ジソディウムモノシリケートが使用可能である
また、珪酸ソーダは、ジソディウムジシリケート、テトラソディウムペンタシリケート、ジソディウムトリシリケート、ジソディウムテトラシリケートが使用可能である。
【００２２】
ここで、珪酸ソーダが、二酸化珪素３５から３８ｗｔ％、酸化ナトリウム１７から１９ｗｔ％であることが好ましい。
【００２３】
ここで、珪酸ソーダが、二酸化珪素３４から３６ｗｔ％、酸化ナトリウム１４から１５ｗｔ％であることが好ましい。
【００２４】
ここで、珪酸ソーダが、二酸化珪素２８から３０ｗｔ％、酸化ナトリウム９から１０ｗｔ％であることが好ましい。
【００２５】
ここで、珪酸ソーダの酸化ナトリウムに対する二酸化ケイ素のモル比が、２．００から３．９０であることが好ましい。
【００２６】
また、珪酸ソーダの酸化ナトリウムに対する二酸化ケイ素のモル比が、３．００から３．３０であることが好ましい。
【００２７】
【実施例】
図１に本発明による一実施例を示す。
図１に示す圧電振動子は以下のように形成される。従来の技術の応用により、ウエハー内に形成された圧電振動片の上下面に、それぞれ金属層を介して蓋１０と容器１２を接合し、外部電極１６をスパッタリングや蒸着または電解メッキや無電解メッキなどにより形成する。
【００２８】
次に、圧電振動片を切断し電気的に分離する。電気的に分離するとは、隣接する圧電振動片が金属層にて電気的に接続していないことを示す。接合された圧電振動片と蓋１０と容器１２の全てを切断分離しても良いし、圧電振動片と容器１２について切断し、蓋１０については若干の切り込みが入る位に切断をしても良い。
【００２９】
そして、断面から露出した金属層及び金属層と容器１２や蓋１０の界面を被うように表面にガラス層１５を形成する。この際には、圧電振動子を実装する際に接合部となる外部電極１６の底部については、少なくともガラス層１５を形成しない。
【００３０】
このように形成された圧電振動子では、従来側面部に露出していた金属層の表面に、比較的低温で緻密な保護膜として機能するガラス層１５が形成されるため、金属層の腐食や酸化が起こらず、かつ、特に蓋や容器がガラスの場合は熱膨張による歪の発生が少ないため耐環境性と振動特性に優れた圧電振動子を得ることが出来る。
【００３１】
次に、ガラス層１５を珪酸ソーダ水溶液にて形成する場合について説明する。珪酸ソーダは空気中に放置または脱水することにより強固な皮膜を形成する。また、皮膜を短時間に形成するには加熱処理が有効である。例えば、８５℃の雰囲気中では３０分以内で十分な皮膜を得ることができる。
【００３２】
モル比の高い濃厚熱溶液はアルミニウムやその合金などを侵食するが、その際に金属表面に珪酸または金属酸化物の皮膜を形成し、これにより耐食性が向上する。
【００３３】
また、珪酸カリ溶液は物理的にも化学的にも珪酸ソーダとほぼ同等の性質を示し、皮膜を形成する条件についても、その皮膜についても上述した珪酸ソーダと同等である。
【００３４】
【発明の効果】
本発明によれば、薄い圧電振動基板を薄い蓋と容器で挟み、それぞれの層間を金属薄膜で接合した圧電振動子を形成することができるので、振動子全体の厚みを極めて小さくすることができる。
【図面の簡単な説明】
【図１】本発明における圧電振動子の一実施例
【符号の説明】
１０ 蓋
１１ 圧電振動基板
１２ 容器
１３ 第１の金属膜
１４ 第２の金属膜
１５ ガラス層
１６ 外部電極[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a piezoelectric vibrator used in an oscillation circuit of a portable information terminal.
[0002]
[Problems to be solved by the invention]
In the conventional piezoelectric vibrator, a method of arranging and connecting one vibrating piece in one container has been used. Therefore, in order to increase production efficiency, manufacturing of wafer units including a vibrator piece and a container has been studied, and a method of directly joining a container made of silicon to the vibrator piece by anodic bonding or a low melting point metal to the vibrator piece. There has been devised a method for joining containers through the.
[0003]
However, in the former method, since the difference in thermal expansion coefficient between the vibrator piece and silicon is large, there is a problem that stress is applied to the vibrator piece and vibration characteristics are deteriorated. In the latter method, the low-melting point metal has a low corrosion resistance, and it is difficult to obtain sufficient environmental resistance.
[0004]
[Means for solving the problems]
In this invention, the surface of the metal layer exposed from the cross section after joining the lid 10 and the container 12 to the upper and lower surfaces of the piezoelectric vibrating piece formed in the wafer via the metal layer, cutting and separating the piezoelectric vibrating piece, respectively. In addition, the piezoelectric vibrator in which the glass layer 15 is formed so as to cover the interface between the metal layer and the container 12 or the lid 10 is obtained.
[0005]
In the piezoelectric vibrator formed in this way, the glass layer 15 that functions as a dense protective film at a relatively low temperature is formed on the surface of the metal layer that has been exposed to the side surface in the related art. In the case where oxidation does not occur and the lid and the container are made of glass, in particular, the occurrence of distortion due to thermal expansion is small, so that a piezoelectric vibrator excellent in environmental resistance and vibration characteristics can be obtained.
[0006]
In the present invention, the piezoelectric vibrating piece is formed in the wafer made of the piezoelectric material, the metal layer is formed on the upper surface and the lower surface around the piezoelectric vibrating piece, and the upper and lower surfaces are provided so that the piezoelectric vibrating piece can vibrate. The lid 10 and the container 12 having an anode are anodically bonded so as to surround the piezoelectric vibrating piece, and the piezoelectric vibrating piece is cut together with the lid 10 and the container 12 and separated, and water glass is applied to the metal layer exposed on the side surface, followed by baking and glass. Layer 15 is formed.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In this invention, a piezoelectric vibration substrate 11 comprising a piezoelectric vibration piece having a pair of electrodes, a frame connected to the base of the piezoelectric vibration piece and surrounding the outer periphery of the piezoelectric vibration piece and formed integrally with the piezoelectric vibration piece, and the piezoelectric vibration piece The lid 10 is separated from the upper surface of the frame and joined to the upper surface of the frame via the first metal film 13, and is separated from the lower surface of the piezoelectric vibrating piece, and is joined to the lower surface of the frame via the second metal film 14. The piezoelectric vibrator is composed of a container 12 having a pair of external electrodes connected to electrodes at the bottom, and a glass layer 15 covering the exposed portions of the first metal film 13 and the second metal film 14.
[0008]
In addition, a piezoelectric vibrating substrate 11 including a piezoelectric vibrating piece having a pair of electrodes, a frame connected to the base of the piezoelectric vibrating piece and surrounding the outer periphery of the piezoelectric vibrating piece and formed integrally with the piezoelectric vibrating piece, and an upper surface of the piezoelectric vibrating piece The lid 10 anodically bonded via the first metal film 13 formed on the upper surface of the frame and the second metal film 14 formed on the lower surface of the frame, separated from the lower surface of the piezoelectric vibrating piece. And a piezoelectric vibrator comprising a glass layer 15 covering the exposed portions of the first metal film 13 and the second metal film 14, and a container 12 having a pair of external electrodes connected to the electrodes at the bottom. did.
[0009]
Here, the glass layer 15 is preferably sodium silicate, potassium silicate, or lithium silicate, and the thickness of the glass layer 15 is preferably 1 μm to 10 μm. When the film thickness of the glass layer is thinner than 1 μm, it is difficult to ensure the corrosion resistance of the metal film, and when it exceeds 10 μm, the adhesion of the glass layer decreases.
[0010]
The molar ratio of silicon dioxide to potassium oxide of potassium silicate is preferably 1.8 to 3.7. By setting this molar ratio, the viscosity at the time of forming the glass layer becomes a suitable value, and workability is improved.
[0011]
The molar ratio of silicon dioxide to potassium oxide of potassium silicate is preferably 1.8 to 2.2.
[0012]
Alternatively, the molar ratio of silicon dioxide to potassium oxide of potassium silicate is preferably 2.5 to 2.7.
[0013]
Alternatively, the molar ratio of silicon dioxide to potassium oxide of potassium silicate is preferably 2.7 to 3.0.
[0014]
Alternatively, the molar ratio of silicon dioxide to potassium oxide of silicate is preferably 2.9 to 3.2.
[0015]
Alternatively, the molar ratio of silicon dioxide to potassium oxide of potassium silicate is preferably 3.4 to 3.7.
[0016]
Further, it is preferable that silicon dioxide of potassium silicate is 27.5 to 29 wt% and potassium oxide is 21 to 23 wt%. In the composition range, a suitable viscosity can be obtained and the glass layer can be easily formed.
[0017]
Further, it is preferable that silicon dioxide of potassium silicate is 28 to 30 wt% and potassium oxide is 17 to 18 wt%.
[0018]
Further, potassium silicate is preferably 26 to 29 wt%, and potassium oxide is preferably 13 to 16 wt%.
[0019]
Moreover, 25.5 to 27.5 wt% of silicon dioxide of potassium silicate and 12.5 to 14.5 wt% of potassium oxide are preferable.
[0020]
Moreover, 19.5 to 21.5 wt% of silicon dioxide of potassium silicate and 8.5 to 9.5 wt% of potassium oxide are preferable.
[0021]
Here, sodium silicate can be tetrasodium monosilicate, hexasodium disilicate, and disodium monosilicate. Sodium silicate is disodium disilicate, tetrasodium pentasilicate, disodium trisilicate, disodium tetra Silicate can be used.
[0022]
Here, it is preferable that sodium silicate is 35 to 38 wt% of silicon dioxide and 17 to 19 wt% of sodium oxide.
[0023]
Here, it is preferable that sodium silicate is 34 to 36 wt% of silicon dioxide and 14 to 15 wt% of sodium oxide.
[0024]
Here, it is preferable that sodium silicate is 28 to 30 wt% of silicon dioxide and 9 to 10 wt% of sodium oxide.
[0025]
Here, the molar ratio of silicon dioxide to sodium oxide of sodium silicate is preferably 2.00 to 3.90.
[0026]
Moreover, it is preferable that the molar ratio of the silicon dioxide with respect to sodium oxide of a sodium silicate is 3.00 to 3.30.
[0027]
【Example】
FIG. 1 shows an embodiment according to the present invention.
The piezoelectric vibrator shown in FIG. 1 is formed as follows. By applying the conventional technology, the lid 10 and the container 12 are joined to the upper and lower surfaces of the piezoelectric vibrating piece formed in the wafer through the metal layers, respectively, and the external electrode 16 is sputtered, vapor-deposited, electroplated or electrolessly plated. And so on.
[0028]
Next, the piezoelectric vibrating piece is cut and electrically separated. The term “electrically separated” means that adjacent piezoelectric vibrating pieces are not electrically connected by a metal layer. The bonded piezoelectric vibrating piece, the lid 10 and the container 12 may all be cut and separated, or the piezoelectric vibrating piece and the container 12 may be cut, and the lid 10 may be cut to a point where a slight cut is made. .
[0029]
And the glass layer 15 is formed in the surface so that the interface of the metal layer exposed from the cross section and a metal layer, and the container 12 or the lid | cover 10 may be covered. In this case, at least the glass layer 15 is not formed on the bottom of the external electrode 16 that becomes a joint when the piezoelectric vibrator is mounted.
[0030]
In the piezoelectric vibrator formed in this way, the glass layer 15 that functions as a dense protective film at a relatively low temperature is formed on the surface of the metal layer that has been exposed to the side surface in the related art. In the case where oxidation does not occur and the lid and the container are made of glass, in particular, the occurrence of distortion due to thermal expansion is small, so that a piezoelectric vibrator excellent in environmental resistance and vibration characteristics can be obtained.
[0031]
Next, the case where the glass layer 15 is formed with a sodium silicate aqueous solution will be described. Sodium silicate forms a strong film by being left in the air or dehydrated. In addition, heat treatment is effective for forming a film in a short time. For example, a sufficient film can be obtained within 30 minutes in an atmosphere at 85 ° C.
[0032]
A concentrated hot solution having a high molar ratio corrodes aluminum or its alloy, and at that time, a film of silicic acid or a metal oxide is formed on the metal surface, thereby improving the corrosion resistance.
[0033]
In addition, the potassium silicate solution exhibits almost the same physical and chemical properties as sodium silicate, and the conditions for forming the film are the same as the above-described sodium silicate.
[0034]
【The invention's effect】
According to the present invention, it is possible to form a piezoelectric vibrator in which a thin piezoelectric vibration substrate is sandwiched between a thin lid and a container and the respective layers are joined with a metal thin film, so that the thickness of the whole vibrator can be extremely reduced. .
[Brief description of the drawings]
FIG. 1 shows an embodiment of a piezoelectric vibrator according to the present invention.
10 Lid 11 Piezoelectric Vibration Substrate 12 Container 13 First Metal Film 14 Second Metal Film 15 Glass Layer 16 External Electrode

Claims (22)

一対の電極を有する圧電振動片と前記圧電振動片の基部に接続され前記圧電振動片の外周を囲み前記圧電振動片と一体に形成された枠とからなる圧電振動基板（１１）と、
前記圧電振動片の上面と離間し、前記枠の上面に第１の金属膜（１３）を介して接合された蓋（１０）と、
前記圧電振動片の下面と離間し、前記枠の下面に第２の金属膜（１４）を介して接合され、かつ底部に前記電極と接続された一対の外部電極を有する容器（１２）と、
前記第１の金属膜（１３）と前記第２の金属膜（１４）の露出部を覆うガラス層（１５）からなり、
前記ガラス層（１５）が珪酸ソーダ、珪酸カリ、珪酸リチウムから選ばれる少なくとも一種である圧電振動子。A piezoelectric vibrating substrate (11) comprising a piezoelectric vibrating piece having a pair of electrodes and a frame connected to a base of the piezoelectric vibrating piece and surrounding an outer periphery of the piezoelectric vibrating piece and formed integrally with the piezoelectric vibrating piece;
A lid (10) spaced apart from the upper surface of the piezoelectric vibrating piece and bonded to the upper surface of the frame via a first metal film (13);
A container (12) having a pair of external electrodes spaced apart from the lower surface of the piezoelectric vibrating piece, joined to the lower surface of the frame via a second metal film (14), and connected to the electrodes at the bottom;
The first glass layer (15) covering the exposed portion of the metal film (13) and said second metal film (14) Tona is,
The piezoelectric vibrator in which the glass layer (15) is at least one selected from sodium silicate, potassium silicate, and lithium silicate . 一対の電極を有する圧電振動片と前記圧電振動片の基部に接続され前記圧電振動片の外周を囲み前記圧電振動片と一体に形成された枠とからなる圧電振動基板（１１）と、
前記圧電振動片の上面と離間し、前記枠の上面に形成された第１の金属膜（１３）を介し陽極接合された蓋（１０）と、
前記圧電振動片の下面と離間し、前記枠の下面に形成された第２の金属膜（１４）を介して陽極接合され、底部に前記電極と接続された一対の外部電極を有する容器（１２）と、
前記第１の金属膜（１３）と前記第２の金属膜（１４）の露出部を覆うガラス層（１５）からなり、
前記ガラス層（１５）が珪酸ソーダ、珪酸カリ、珪酸リチウムから選ばれる少なくとも一種である圧電振動子。
圧電振動子。A piezoelectric vibrating substrate (11) comprising a piezoelectric vibrating piece having a pair of electrodes and a frame connected to a base of the piezoelectric vibrating piece and surrounding an outer periphery of the piezoelectric vibrating piece and formed integrally with the piezoelectric vibrating piece;
A lid (10) which is separated from the upper surface of the piezoelectric vibrating piece and is anodically bonded via a first metal film (13) formed on the upper surface of the frame;
A container (12) having a pair of external electrodes spaced apart from the lower surface of the piezoelectric vibrating piece, anodically bonded via a second metal film (14) formed on the lower surface of the frame, and connected to the electrodes at the bottom. )When,
The first glass layer (15) covering the exposed portion of the metal film (13) and said second metal film (14) Tona is,
The piezoelectric vibrator in which the glass layer (15) is at least one selected from sodium silicate, potassium silicate, and lithium silicate .
Piezoelectric vibrator. 前記珪酸カリの酸化カリに対する二酸化ケイ素のモル比が１．８から３．７である請求項１または２に記載の圧電振動子。 3. The piezoelectric vibrator according to claim 1, wherein a molar ratio of silicon dioxide to potassium oxide in the potassium silicate is 1.8 to 3.7. 前記珪酸カリの酸化カリに対する二酸化ケイ素のモル比が１．８から２．２である請求項３記載の圧電振動子。  The piezoelectric vibrator according to claim 3, wherein a molar ratio of silicon dioxide to potassium oxide in the potassium silicate is 1.8 to 2.2. 前記珪酸カリの酸化カリに対する二酸化ケイ素のモル比が２．５から２．７である請求項１または２に記載の圧電振動子。 3. The piezoelectric vibrator according to claim 1, wherein a molar ratio of silicon dioxide to potassium oxide in the potassium silicate is 2.5 to 2.7. 前記珪酸カリの酸化カリに対する二酸化ケイ素のモル比が２．７から３．０である請求項１または２に記載の圧電振動子。The piezoelectric vibrator according to claim 1 or 2, wherein a molar ratio of silicon dioxide to potassium oxide in the potassium silicate is 2.7 to 3.0. 前記珪酸カリの酸化カリに対する二酸化ケイ素のモル比が２．９から３．２である請求項１または２に記載の圧電振動子。The piezoelectric vibrator according to claim 1 or 2, wherein a molar ratio of silicon dioxide to potassium oxide in the potassium silicate is 2.9 to 3.2. 前記珪酸カリの酸化カリに対する二酸化ケイ素のモル比が３．４から３．７である請求項１または２に記載の圧電振動子。 3. The piezoelectric vibrator according to claim 1, wherein a molar ratio of silicon dioxide to potassium oxide in the potassium silicate is 3.4 to 3.7. 前記珪酸カリの二酸化ケイ素が２７．５から２９ｗｔ％、酸化カリが２１から２３ｗｔ％である請求項３記載の圧電振動子。  4. The piezoelectric vibrator according to claim 3, wherein silicon dioxide of the potassium silicate is 27.5 to 29 wt% and potassium oxide is 21 to 23 wt%. 前記珪酸カリの二酸化ケイ素が２８から３０ｗｔ％、酸化カリが１７から１８ｗｔ％である請求項１または２に記載の圧電振動子。 3. The piezoelectric vibrator according to claim 1, wherein silicon dioxide of the potassium silicate is 28 to 30 wt% and potassium oxide is 17 to 18 wt%. 前記珪酸カリの二酸化ケイ素が２６から２９ｗｔ％、酸化カリが１３から１６ｗｔ％である請求項１または２に記載の圧電振動子。 3. The piezoelectric vibrator according to claim 1, wherein silicon dioxide of the potassium silicate is 26 to 29 wt% and potassium oxide is 13 to 16 wt%. 前記珪酸カリの二酸化ケイ素が２５．５から２７．５ｗｔ％、酸化カリが１２．５から１４．５ｗｔ％である請求項１または２に記載の圧電振動子。3. The piezoelectric vibrator according to claim 1, wherein silicon dioxide of the potassium silicate is 25.5 to 27.5 wt% and potassium oxide is 12.5 to 14.5 wt%. 前記珪酸カリの二酸化ケイ素が１９．５から２１．５ｗｔ％、酸化カリが８．５から９．５ｗｔ％である請求項１または２に記載の圧電振動子。3. The piezoelectric vibrator according to claim 1, wherein silicon dioxide of the potassium silicate is 19.5 to 21.5 wt% and potassium oxide is 8.5 to 9.5 wt%. 前記珪酸ソーダが、テトラソディウムモノシリケート、ヘキサソディウムジシリケート、ジソディウムモノシリケートから選ばれる請求項１または２に記載の圧電振動子。The piezoelectric vibrator according to claim 1 or 2, wherein the sodium silicate is selected from tetrasodium monosilicate, hexasodium disilicate, and disodium monosilicate. 前記珪酸ソーダが、ジソディウムジシリケート、テトラソディウムペンタシリケート、ジソディウムトリシリケート、ジソディウムテトラシリケートから選ばれる請求項１または２に記載の圧電振動子。The piezoelectric vibrator according to claim 1 or 2, wherein the sodium silicate is selected from disodium disilicate, tetrasodium pentasilicate, disodium trisilicate, and disodium tetrasilicate. 前記珪酸ソーダが、二酸化珪素３５から３８ｗｔ％、酸化ナトリウム１７から１９ｗｔ％である請求項１または２に記載の圧電振動子。3. The piezoelectric vibrator according to claim 1, wherein the sodium silicate is 35 to 38 wt% silicon dioxide and 17 to 19 wt% sodium oxide. 前記珪酸ソーダが、二酸化珪素３４から３６ｗｔ％、酸化ナトリウム１４から１５ｗｔ％である請求項１または２に記載の圧電振動子。3. The piezoelectric vibrator according to claim 1, wherein the sodium silicate is 34 to 36 wt% silicon dioxide and 14 to 15 wt% sodium oxide. 前記珪酸ソーダが、二酸化珪素２８から３０ｗｔ％、酸化ナトリウム９から１０ｗｔ％である請求項１または２に記載の圧電振動子。 3. The piezoelectric vibrator according to claim 1, wherein the sodium silicate is 28 to 30 wt% silicon dioxide and 9 to 10 wt% sodium oxide. 前記珪酸ソーダの酸化ナトリウムに対する二酸化ケイ素のモル比が、２．００から３．９０である請求項１または２に記載の圧電振動子。 3. The piezoelectric vibrator according to claim 1, wherein a molar ratio of silicon dioxide to sodium oxide in the sodium silicate is 2.00 to 3.90. 前記珪酸ソーダの酸化ナトリウムに対する二酸化ケイ素のモル比が、３．００から３．３０である請求項１または２に記載の圧電振動子。 3. The piezoelectric vibrator according to claim 1, wherein a molar ratio of silicon dioxide to sodium oxide in the sodium silicate is 3.00 to 3.30. 圧電振動片と前記圧電振動片の基部に接続され前記圧電振動片の外周を囲み前記圧電振動片と一体に形成された枠とからなる圧電振動基板と、  A piezoelectric vibration substrate comprising a piezoelectric vibration piece and a frame connected to a base of the piezoelectric vibration piece and surrounding an outer periphery of the piezoelectric vibration piece and formed integrally with the piezoelectric vibration piece;
前記枠の上面に形成された第１の金属膜と、  A first metal film formed on the upper surface of the frame;
前記第１の金属膜を介して接合された蓋と、  A lid joined via the first metal film;
前記枠の下面に形成された第２の金属膜と、  A second metal film formed on the lower surface of the frame;
前記第２の金属膜を介して接合された容器と、  A container joined via the second metal film;
前記第１の金属膜と前記枠及び前記蓋の接合部分の境界を含む前記第１の金属膜の露出部と、前記第２の金属膜と前記枠及び前記容器の接合部分の境界を含む前記第２の金属膜の露出部を全周に渡って覆うガラス層と、からなる圧電振動子。  The exposed portion of the first metal film including the boundary between the first metal film and the joint portion of the frame and the lid, and the boundary of the joint portion between the second metal film, the frame and the container. A piezoelectric vibrator comprising a glass layer covering the exposed portion of the second metal film over the entire circumference. 前記ガラス層が１〜１０μｍである請求項２１に記載の圧電振動子。  The piezoelectric vibrator according to claim 21, wherein the glass layer is 1 to 10 μm.
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