JPS63238799A - Manufacture of piezo-electric type vibrator - Google Patents
Manufacture of piezo-electric type vibratorInfo
- Publication number
- JPS63238799A JPS63238799A JP61295951A JP29595186A JPS63238799A JP S63238799 A JPS63238799 A JP S63238799A JP 61295951 A JP61295951 A JP 61295951A JP 29595186 A JP29595186 A JP 29595186A JP S63238799 A JPS63238799 A JP S63238799A
- Authority
- JP
- Japan
- Prior art keywords
- piezoelectric
- diaphragm
- film
- frequency
- thin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000004544 sputter deposition Methods 0.000 claims abstract description 23
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 239000010409 thin film Substances 0.000 claims description 32
- 239000010408 film Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910020276 Pb(Zr,Ti) O3 Inorganic materials 0.000 abstract 1
- 238000003384 imaging method Methods 0.000 description 17
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 244000236655 Diospyros kaki Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、センサ用途に用いる圧電薄型撮動子の製造
方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method of manufacturing a thin piezoelectric sensor used for sensor applications.
圧電素子に外部より周波電圧を印加すると、素子形状に
よって決定される固有の共振周波数で圧電素子は伸縮運
動を起こす。かかる圧電素子の特徴を活用したものがい
わゆる圧電振動子であり。When a frequency voltage is externally applied to a piezoelectric element, the piezoelectric element causes expansion and contraction at a unique resonance frequency determined by the shape of the element. A so-called piezoelectric vibrator utilizes the characteristics of such a piezoelectric element.
その具体的な応用としては超音波発生装置、圧１イ１ブ
ザー令圧電スピーカなどの発音体、各種セ〉・すなどが
ある。これらのいずれの用途においても、通常金属薄板
からなる振動基板の片面あるいは両面に圧電素子を何ら
かの接着もしくは接合方法によって貼り合せる必要があ
る。Specific applications include ultrasonic generators, sounding bodies such as piezoelectric speakers, and various speakers. In any of these applications, it is necessary to attach a piezoelectric element to one or both sides of a vibrating substrate, which is usually made of a thin metal plate, by some adhesive or bonding method.
本発明においては、とくに空気などの気体の流量測定と
その制御などに用いられる密度センサを例にとって、振
動板と圧電素子の接着すなわち圧電振動子の製造方法に
ついて説明する。密１ｆセンサの構造は第１図のごとく
であり、）”ｅ−Ｎｉ合金あるいはステンレス鋼などの
金属薄板からなる系動板ｌの両面には、その表裏面にＡ
ｇ′α極を有する圧型素子２が貼り合わされていわゆる
圧電撮動子となっている。そして振動板１の端部は金属
製のハウジング３で固定された構造となっている。この
構造において、圧電素子２に外部より電圧を印加すると
、それに応じて撮動板は駆動する。そして。In the present invention, a method for bonding a diaphragm and a piezoelectric element, that is, a method for manufacturing a piezoelectric vibrator, will be described by taking a density sensor used for measuring and controlling the flow rate of a gas such as air as an example. The structure of the dense 1f sensor is as shown in Figure 1.) The system moving plate l, which is made of a thin metal plate such as e-Ni alloy or stainless steel, has A on both sides.
Piezo elements 2 having g'α poles are bonded together to form a so-called piezoelectric sensor. The end of the diaphragm 1 is fixed with a metal housing 3. In this structure, when a voltage is applied to the piezoelectric element 2 from the outside, the imaging plate is driven accordingly. and.
一定電圧印加状態で駆動する振動板は、ホーン部分４の
流体（空気）の流量が変化するとそれに応じて振動板１
の等価窟看がホーン部分の質量分増加するので、密度に
より撮動板１の共握周波数（ｆ「）が変化する。この関
係は下式で示される。The diaphragm that is driven with a constant voltage applied changes the diaphragm 1 according to the change in the flow rate of the fluid (air) in the horn portion 4.
Since the equivalent capacitor increases by the mass of the horn portion, the joint frequency (f') of the imaging plate 1 changes depending on the density. This relationship is expressed by the following equation.
Ｍｍ＝機械系實量
Ｍａ−音響系質＋＝−（−密度）
Ｋｍｍ二接系バネ定数
また、この煽動糸の電気的な等価回路は第２図のように
なり、振動板の共温周波数でπ／２だけ位相が進む特性
をもっている。したがって、この位相差を補正して正帰
還することにより撮動板は自振の共釡６周波数で発振す
るので、発振周波数から密度を計測することができるこ
とになる。Mm = Mechanical system quantity Ma - Acoustic system quality + = - (- density) Kmm Bilateral spring constant Also, the electrical equivalent circuit of this stirring thread is as shown in Figure 2, and the resonant frequency of the diaphragm is It has the characteristic that the phase advances by π/2. Therefore, by correcting this phase difference and providing positive feedback, the imaging plate oscillates at the self-oscillating resonance 6 frequency, so that the density can be measured from the oscillation frequency.
かかる原理で駆動する密度センサの圧電撮動子において
は、以下の特性を具備することが望まれる。A piezoelectric sensor of a density sensor driven on this principle is desired to have the following characteristics.
（１）感度が大であること。(1) High sensitivity.
（２）動作温度の幅が広いこと（望ましくは−５０”Ｃ
〜＋１２０℃で使用可能なこと）。(2) Wide operating temperature range (preferably -50"C)
(Can be used at temperatures up to +120°C).
（３１共振周波数の温度変化がほぼ直線的で、温度履歴
によるヒステリシスの小さいこと。(31) The temperature change of the resonance frequency is almost linear, and the hysteresis due to temperature history is small.
（４１耐振性、耐冷熱性（ヒートサイクル）、耐湿性。(41 Vibration resistance, cold and heat resistance (heat cycle), moisture resistance.
耐汚損性などに優れていること。Must have excellent stain resistance.
ところで、従来の密度センサの製造においては、撮動板
と圧電素子は有機系接層剤もしくはノ・ンダ（ｐｂ−８
ｎ系）を用いて接合し圧電振動子を構成していた。有機
系接層剤を用いる方法はその接着剤が低密度（軽ｔ）で
あり、常温付近で接層作業が可能であるという利点をも
っている。しかし、剛性（ヤング率）が低くさらにその
温度依存性が大であるため、高ｍ （１００℃前後）で
の共握周波数の変化が直線性から逸脱し、温度履歴によ
るヒステリシスも太きい。また、耐湿性にも劣るという
欠点がある。一方、ハンダを用いて構成した圧電振動子
は共握周波数の温度依存性が良好でヒステリシスも小さ
いが、ハンダの密度が大きいためその影響によって感度
を低下させやすいという欠点がある。By the way, in the production of conventional density sensors, the imaging plate and the piezoelectric element are coated with an organic adhesive or non-diamond (PB-8).
n series) to form a piezoelectric vibrator. The method using an organic adhesive has the advantage that the adhesive has a low density (light t) and can be used at room temperature. However, since the stiffness (Young's modulus) is low and its temperature dependence is large, the change in the co-grip frequency deviates from linearity at high m (around 100° C.), and the hysteresis due to temperature history is also large. It also has the disadvantage of poor moisture resistance. On the other hand, a piezoelectric vibrator constructed using solder has good temperature dependence of the co-grip frequency and small hysteresis, but has the disadvantage that sensitivity tends to decrease due to the influence of the high solder density.
なお、以上の方式とは別に撮動板に高周波スバッ・タリ
ンクによって圧電薄膜を直接的に形成せしめて圧電撮動
子とする方法も提案されている。この方法は、高周波ス
パッタリング装置のチャンバー内に配設されたアノード
電極側に振動板を固定し、カソード電極側にはターゲッ
トとなる圧電体を配置させ、チャンバー内をアルゴンと
酸素の混合ガスで充満したのち、アノードとカソード電
極間に高周波電圧を印加することにより撮動板表面に圧
電性結晶をもった薄膜を付着させ、さらにその薄膜上に
電極を形成させることにより圧電撮動子を得るものであ
る。この方法による圧電振動子は接層層が存在していな
いので、共珈周波数の温度依存性が良好でヒステリシス
も小さくかつ感度が大であるという利点をもっている。In addition to the above-mentioned method, a method has also been proposed in which a piezoelectric thin film is directly formed on an imaging plate by high-frequency sputtering to form a piezoelectric sensor. In this method, a diaphragm is fixed to the anode electrode side placed in the chamber of a high-frequency sputtering device, a piezoelectric material serving as a target is placed on the cathode electrode side, and the chamber is filled with a mixed gas of argon and oxygen. Then, by applying a high frequency voltage between the anode and cathode electrodes, a thin film with piezoelectric crystals is attached to the surface of the imaging plate, and electrodes are further formed on the thin film to obtain a piezoelectric sensor. It is. Since the piezoelectric vibrator manufactured by this method does not have a contact layer, it has the advantage that the temperature dependence of the resonant frequency is good, the hysteresis is small, and the sensitivity is high.
しかし、製造上においては以下の問題点がある。However, there are the following problems in manufacturing.
（１１アノード電極側に設置した振動板をある温度以上
に加熱しておかないと圧電性結晶をもった薄膜が得られ
にくい。(11) It is difficult to obtain a thin film with piezoelectric crystals unless the diaphragm placed on the anode electrode side is heated above a certain temperature.
（２）シかし、振動板を加熱すると酸素が含まれた雰囲
であるため、振動板が酸化してその表面にＦｅ２Ｏ３、
Ｃｒ２Ｏ３、ＮｉＯなどの酸化皮膜が生成し、薄膜との
密着性が低下する。(2) However, when the diaphragm is heated, the atmosphere contains oxygen, so the diaphragm oxidizes and the surface becomes Fe2O3.
An oxide film of Cr2O3, NiO, etc. is formed, and the adhesion with the thin film is reduced.
（３）振動板を加熱しないで、圧電体をスパッタするこ
とにより形成した圧電薄膜は非晶質の状態になりやすい
。この非晶質の薄膜も、大気中で５００°〜９００°Ｃ
の範囲で加熱処理すれば圧電性を有する結晶にすること
ができる。しかし、大気中での加熱であるので撮動板が
酸化してしまい。(3) A piezoelectric thin film formed by sputtering a piezoelectric material without heating the diaphragm tends to be in an amorphous state. This amorphous thin film can also be heated at temperatures of 500° to 900°C in the atmosphere.
A piezoelectric crystal can be obtained by heat treatment within the range of . However, since it was heated in the atmosphere, the photographic plate oxidized.
圧電薄膜が脱落しやすい。The piezoelectric thin film easily falls off.
したがって、振動板に高周波スパッタリングによって圧
電薄膜を形成して圧電撮動子を構造する方法においては
、撮動板の酸化防止および圧電薄膜と振動板の密着性の
向上が望まれている。Therefore, in a method of constructing a piezoelectric sensor by forming a piezoelectric thin film on a diaphragm by high-frequency sputtering, it is desired to prevent oxidation of the diaphragm and to improve the adhesion between the piezoelectric thin film and the diaphragm.
この発明は、前記した圧電体を高周波スパッタリングに
よって振動板に圧電薄膜を付着させ、圧Ｍ、薄型損動子
をル造する方法を改良し共振周波数の温度依存性がほぼ
直線的で温度履歴によるヒステリシスも小さく５さらに
耐湿性にも優れた特性を発揮する密度センサ用途の圧Ｉ
Ｉｔ薄型振動子の提供を目的とする。This invention improves the method of manufacturing a thin loss element by attaching a piezoelectric thin film to the diaphragm of the piezoelectric body by high-frequency sputtering, and the temperature dependence of the resonant frequency is almost linear and depends on the temperature history. Pressure I for density sensor applications with low hysteresis5 and excellent moisture resistance
The purpose is to provide a thin oscillator.
前記の目的は、Ｆｅ−Ｎｉ合金またはステンレス鋼の薄
板からなる振動板の表面にＳｉもしくはＴｉを含むアル
コラート溶液を塗布し加熱焼成するか。The above purpose is to apply an alcoholate solution containing Si or Ti to the surface of a diaphragm made of a thin plate of Fe--Ni alloy or stainless steel, and then heat and bake it.
またはＳ ｉ０２もしくはＴｉ０ｚ ＃細体をターゲッ
トとして高周波スパッタ１１ングによって５ｉｎ２もし
くはＴｉＯ２の皮膜を形成する第１の工程１次いで第１
の工程を経た撮動板にＰｂ （Ｚｒ 、 Ｔｉ ） ０
３を主体とする圧電材をターゲットとして高周波スバッ
７ｊ１）ングを行って圧電薄膜を付着せしめる第２の工
程を経ることにより達成することができる。Or S i02 or Ti0z
Pb (Zr, Ti) 0 on the imaging plate that has gone through the process of
This can be achieved by performing a second step of attaching a piezoelectric thin film by performing high-frequency subbing (7j1) using a piezoelectric material mainly composed of A.3 as a target.
本発明者は、金属裂損動板の酸化防止の手段として、振
動板の表面にあらかじめ圧電薄膜と物理的、熱的に整合
性のある酸化物の薄膜状の皮膜を形成させておけば、振
動板を加熱した状態で高周波スパッタリングが可能とな
り、さらに非晶質の圧電薄膜であっても高周波スパッタ
リング後に大気中での熱処理を実施することで薄膜に圧
電性を付与することができ、圧電薄型振動子の製造歩留
りも向上するであろうと発想した。そして以上の観点か
ら種々の検討した結果５次の条件によって密度センサ用
圧電薄型撮動子の製造が可能であることを確認した。The present inventor has proposed that as a means of preventing oxidation of the metal diaphragm, if a thin oxide film that is physically and thermally compatible with the piezoelectric thin film is formed on the surface of the diaphragm in advance, High-frequency sputtering can be performed while the diaphragm is heated, and even if an amorphous piezoelectric thin film is heat-treated in the atmosphere after high-frequency sputtering, piezoelectricity can be imparted to the thin film. The idea was that the manufacturing yield of resonators would also improve. As a result of various studies from the above viewpoint, it was confirmed that it is possible to manufacture a thin piezoelectric sensor for a density sensor under the fifth-order condition.
（１）撮動板の材質はＦｅ −４２Ｎ ｉ合金もしくは
ステンレス鋼であって、その厚さは２０−５０μｍの範
囲が好ましい。(1) The material of the imaging plate is Fe-42Ni alloy or stainless steel, and its thickness is preferably in the range of 20-50 μm.
（２１振動板の酸化防止のために、その表面に形成する
酸化物は５ｉ０２もしくはＴｉＯ２が最も適している。(5i02 or TiO2 is the most suitable oxide to be formed on the surface of the 21 diaphragm to prevent oxidation.
そして、その形成方法としては次の２つの方法が適して
いる。その一つとしてはＳｉ またはＴｉを含むアルコ
ラート溶液を塗布し、 １５０’〜ＳＯＯ℃の温度で
加熱処理して５ｉ０２ 、 ＴｉＯ２の皮膜を得る方法
およびＳ ｉ０２あるいはＴｉ０ｚ焼結体をターゲット
として高周波スパッタリングでその皮膜を形成する方法
である。振動板の表面に形成させる皮膜の厚さとしては
振動板および圧電薄膜との密着性の関係から１〜５μｍ
の範囲が好ましいものである。金属環振動板に対し酸化
物皮膜は溶射によっても付着形成することができる。し
かし、溶射では緻密質の皮膜が得られず、かつ振動板さ
の密着性も悪く不可でありた。The following two methods are suitable for forming it. One method is to apply an alcoholate solution containing Si or Ti and heat treat it at a temperature of 150' to SOO°C to obtain a 5i02, TiO2 film, and another method is to obtain a 5i02 or TiO2 film by high-frequency sputtering using a Si02 or Ti0z sintered body as a target. This is a method of forming the film. The thickness of the film formed on the surface of the diaphragm is 1 to 5 μm due to the adhesion between the diaphragm and the piezoelectric thin film.
A range of is preferred. The oxide film can also be deposited on the metal ring diaphragm by thermal spraying. However, thermal spraying did not produce a dense film, and the adhesion to the diaphragm was also poor.
（３）圧電薄膜を形成するに用いるターゲットとしての
圧電材の組成は、電気機械結合係数（Ｋｒ）が高く、機
械的品質係数（Ｑｍ ）が小で共振周波数の温度係数の
小さいものが望しい。すなわち。(3) The composition of the piezoelectric material used as a target for forming the piezoelectric thin film is preferably one with a high electromechanical coupling coefficient (Kr), a small mechanical quality factor (Qm), and a small temperature coefficient of resonance frequency. . Namely.
Ｐｂ（Ｚｒ 、Ｔｉ ）Ｏ３−Ｐｂ（Ｓｂ３ＡＮｂ３Ａ
）Ｏ３ 、 Ｐｂ（Ｚｒ 。Pb(Zr,Ti)O3-Pb(Sb3ANb3A
)O3, Pb(Zr.
Ｔｉ ）Ｏ３−Ｐｂ（Ｍｇ３ＡＮｂ％）Ｏ３． ｐｂ
（Ｚｒ 、Ｔｉ）Ｏ３−Ｐｂ（Ｍｇ％Ｗ％）Ｏ３などが
本発明の目的に合致するものである。Ti)O3-Pb(Mg3ANb%)O3. pb
(Zr, Ti)O3-Pb(Mg%W%)O3, etc. meet the purpose of the present invention.
（４）高周波スパッタリングの条件としては、了ノード
電極側に設置する撮動板を４００°〜７００℃に加熱し
た状態で圧電材を高周波スパッタリングすると圧電性結
晶（ペロブスカイト相）を有する圧電薄膜が形成できた
。振動板の保持温度が旬℃以下であると得られた圧電薄
膜は非晶質であった。逆に保持温度が７００”Ｃ以上で
あると薄膜にクラックなどが入りやすく良好な膜質が得
られがたくなる。(4) The conditions for high-frequency sputtering are that when the piezoelectric material is high-frequency sputtered with the imaging plate installed on the node electrode side heated to 400° to 700°C, a piezoelectric thin film having piezoelectric crystals (perovskite phase) is formed. did it. The piezoelectric thin film obtained when the holding temperature of the diaphragm was below 10°C was amorphous. On the other hand, if the holding temperature is 700''C or higher, cracks are likely to occur in the thin film, making it difficult to obtain good film quality.
（５）非晶質であった圧電ｖ−膜も、スパッタリング後
に大気中で５０００〜８５０℃の範囲で０．５〜３時間
の処理を行うことにより圧電性をもつペロブスカイト相
を出現させることができることｔ−Ｘ線的に確認した。(5) Piezoelectric V-films that were amorphous can also be made to have a piezoelectric perovskite phase by performing treatment in the air at a temperature of 5000 to 850°C for 0.5 to 3 hours after sputtering. This was confirmed using t-X-rays.
（６）密度センサ用としての圧電薄型撮動子における圧
を薄膜の厚さは１５〜３０μｍであれば実用可能であっ
た。(6) A piezoelectric thin sensor for use as a density sensor can be practically used if the thickness of the thin film is 15 to 30 μm.
以下に本発明の詳細な実施例を宗す。 Detailed embodiments of the present invention are given below.
（実施例１） 厚さが３０ Ｂｍ （７） Ｆｅ−４２
重ｔ ％ Ｎ ｉで作られたｉ％が′２Ｓ＋Ｉ１１のツ
バ付き振動板を、シリコンアルコラート溶液ＣＳ＋ （
Ｕ、Ｃ５Ｈｔ□）４〕に浸漬して振動板表面に溶液を均
一に塗布せしめたのち、大気中で３５０℃× １時間の
熱処理を行って厚さ１．５μｍのＳ ｉ０２の皮膜を形
成させた。その後、 ５ｉ０２皮膜付きの撮動板を高
周波スパッタリング装置のアノード電極側に配置し、こ
のアノード電極部に配設されている加熱ヒータにより撮
動板を５５０℃に加熱した。この状翌において、厚さ３
龍で直径５０ｆｉｌの組成がｐｂ （Ｚｒ 、 Ｔｉ
） ０３ Ｐｂ （Ｓｂ％ Ｎｂ５Ａ％）３の圧電
体をターゲットとして所定の条件で高周波スパッタ１１
ングを行い、撮動板の表裏面に厚さｎμｍの圧ａ薄膜を
炸裂した。この圧電薄膜をＸ線回析したところ、光全な
ペロブスカイト相であることが確認された。以上の工程
で得られた圧電薄型振動子を用いて第１図と同様な構成
である密度センサを農作した。本発明品に対する比較品
としては、前記と同一形状の撮動板に組成がＰｂ （Ｚ
ｒ 。(Example 1) Thickness: 30 Bm (7) Fe-42
A flanged diaphragm with an i% of '2S+I11 made of heavy t%Ni was soaked in a silicon alcoholate solution CS+ (
U, C5Ht□)4] to uniformly apply the solution to the surface of the diaphragm, and then heat treated in the air at 350°C for 1 hour to form a Si02 film with a thickness of 1.5 μm. Ta. Thereafter, the imaging plate coated with the 5i02 film was placed on the anode electrode side of the high-frequency sputtering device, and the imaging plate was heated to 550° C. by a heater provided in the anode electrode section. In this situation, the thickness is 3
The composition of a dragon with a diameter of 50fil is pb (Zr, Ti
)03 Pb (Sb% Nb5A%)3 high frequency sputtering 11 under predetermined conditions using a piezoelectric material as a target.
A pressure-a thin film with a thickness of nμm was exploded on the front and back surfaces of the imaging plate. When this piezoelectric thin film was subjected to X-ray diffraction, it was confirmed that the piezoelectric thin film had a completely optical perovskite phase. A density sensor having a configuration similar to that shown in FIG. 1 was produced using the thin piezoelectric vibrator obtained through the above steps. As a comparative product for the product of the present invention, a photographing plate having the same shape as the above but with a composition of Pb (Z
r.
Ｔｉ ）Ｏ３−ｐｂ （Ｓｂ３／２． Ｎｂ％ ） ０
３で、厚さが５０μｍ、直径が２３１である圧１１Ｌ素
子をエポキシ系接着剤によって接着した圧電振動子を用
いた。Ti)O3-pb (Sb3/2.Nb%) 0
In Example 3, a piezoelectric vibrator was used in which a pressure 11L element having a thickness of 50 μm and a diameter of 231 was bonded with an epoxy adhesive.
かかる密度センサの圧’ｉｓ子部に外部より５■の周波
電圧を印加して振動板を駆動させ、そのときの共振周波
数（ｆｒ）の温度依存性および温度履歴によるヒステリ
シスを測定した。温度サイクルは頷℃→−（９）℃→ｍ
℃→１００℃→頷℃の順とした。A frequency voltage of 5 cm was externally applied to the indentation part of the density sensor to drive the diaphragm, and the temperature dependence of the resonance frequency (fr) at that time and the hysteresis due to temperature history were measured. The temperature cycle is nod ℃→-(9)℃→m
The order was ℃ → 100℃ → nod ℃.
第３図は一３０’Ｃから１００℃の範囲における共振周
波数と温度の関係を示したものである。実線１１で示し
た本発明品の共振周波数は低温側で増加し高温になると
減少してくるが、温度に対する変化はほぼ直線的である
。これに対し、実線１２で示すエポキシ系接着剤を用い
た比較品は囮℃前後になると共振周波数の減少が大とな
ってその直線性が悪化している。また、２０℃（ｆｒｌ
）→−（資）℃→２０”Ｃ→１００℃→２０”Ｃ（ｆｒ
２ ）の温度履歴をうけた場合の共振周波数のヒステリ
シス（ｆｒ２〜ｆｒ １／ｆｌ ｓ Ｘ １００）を算
出すると本発明品は十〇、ＯＳ％、比較品は＋０．７８
％となり、本発明品はヒステリシスも小さいことを示し
た。一方、別に実施した塩水噴霧試験および一４０℃と
１２０℃の間を閣サイクル繰返す耐冷熱試験でも、本発
明品は従来の有機系接着剤、ハンダを用いた密度センサ
と比べて何の不具合も認められなかった。FIG. 3 shows the relationship between resonance frequency and temperature in the range of -30'C to 100C. The resonant frequency of the product of the present invention, indicated by the solid line 11, increases at low temperatures and decreases at high temperatures, but the change with respect to temperature is almost linear. On the other hand, in the comparative product using the epoxy adhesive shown by the solid line 12, the resonance frequency decreases greatly and its linearity deteriorates when the temperature is around 10°C. Also, 20℃ (frl
)→-(capital)℃→20”C→100℃→20”C(fr
2) Calculating the resonant frequency hysteresis (fr2~fr1/fl s x 100) when subjected to the temperature history, the inventive product is 10, OS% is +0.78 for the comparative product.
%, indicating that the product of the present invention also has small hysteresis. On the other hand, in a separate salt spray test and a cold/heat resistance test that repeated temperature cycles between -40°C and 120°C, the product of the present invention showed no problems compared to conventional density sensors using organic adhesives and solders. I was not able to admit.
（実施例２） 実施例１と同様な部材を用い、アノード
電極側に配置した撮動板を加熱しない状態で高周波スパ
ッタリングを行い、振動板の表裏面に厚さ５μｍの圧電
薄膜を付着せしめた。これをＸ線回折したが、非晶質で
圧電性を示す結晶の存在は認められなかった。これに大
気中で６５０℃×１時間の熱処理を施し、再度Ｘ線回折
を行ったところ、圧電性を発現するペロブスカイト相の
生成していることが確認された。なお、熱処理の際に振
動板と圧電薄膜が剥離するような現象は一切認められな
かった。(Example 2) Using the same members as in Example 1, high-frequency sputtering was performed without heating the imaging plate placed on the anode electrode side, and a piezoelectric thin film with a thickness of 5 μm was attached to the front and back surfaces of the diaphragm. . When this was subjected to X-ray diffraction, the presence of amorphous crystals exhibiting piezoelectricity was not observed. When this was subjected to heat treatment at 650° C. for 1 hour in the air and X-ray diffraction was performed again, it was confirmed that a perovskite phase exhibiting piezoelectricity had been generated. It should be noted that no phenomenon of peeling between the diaphragm and the piezoelectric thin film was observed during the heat treatment.
以上の圧電薄型振動子を用いて密度センサを構成し、実
施例１と同様の実験を行い、゛共振周波数の温度依存性
と温度履歴によるヒステリシスを測定した。その結果、
本発明品の特性は実施例１に示した発明品のそれと同等
であることを確認された。A density sensor was constructed using the piezoelectric thin vibrator described above, and the same experiment as in Example 1 was conducted to measure the temperature dependence of the resonance frequency and the hysteresis due to temperature history. the result,
It was confirmed that the characteristics of the product of the present invention are equivalent to those of the product of the invention shown in Example 1.
（実施例３）実施例１と同様な撮動板を用い、これにＳ
ｉＯ焼結体をターゲットにして高周波スパッタ１１ング
を行い、厚さ１．３μｍの皮膜を付着せしめた。これを
、さらにアノード電極側に設置し、湖℃に加熱した状態
テＰｂ （Ｚｒ 、 Ｔｉ ）Ｏ３−Ｐｂ （Ｓｂ％。(Example 3) Using the same imaging board as in Example 1,
High frequency sputtering was performed using the iO sintered body as a target to deposit a film with a thickness of 1.3 μm. This was further installed on the anode electrode side and heated to a temperature of 10°C.
Ｎｂ局）Ｏ３をターゲットとして高周波スパッタリング
を行い、厚さ四μｍの圧電薄膜を形成した。この圧電薄
膜はＸ線回折により、ペロブスカイト相であることを確
認された。そして、これを用いた密度センサは従来品以
上のすぐれた特性をもっていることを実験的に確認した
。High frequency sputtering was performed using O3 as a target to form a piezoelectric thin film with a thickness of 4 μm. This piezoelectric thin film was confirmed to have a perovskite phase by X-ray diffraction. It has been experimentally confirmed that a density sensor using this material has superior characteristics over conventional products.
なお、撮動板に対し前記と同様の方法でＴ ｉ ０２の
皮膜を付着せしめ、これに圧電体をターゲットにして高
周波スパッタリングで圧電薄膜を形成して炸裂した圧電
薄型振動子も密度センサ用として優れた特性を具備して
いることを確認した。A thin piezoelectric vibrator is also used for density sensors, in which a T i 02 film is attached to the imaging plate in the same manner as described above, and a piezoelectric thin film is formed by high-frequency sputtering using a piezoelectric material as a target. It was confirmed that it has excellent properties.
以上説明したように本発明は、表面に５ｉ０２もしくは
ＴｉＯ２の皮膜が形成された金属製薄板撮動板にｐｂ
（Ｚｒ 、 Ｔｉ ）Ｏ３を主体とする圧電体をターゲ
ットトシて高周波スパッタ１１ングによって圧電薄膜を
形成する方法であるので、振動板を酸化性雰囲気で加熱
しても酸化せず、振動板を加熱した状態で高周波スパッ
タリングが可能であり、さらに高周波スパッタリング後
に大気中の熱処理によって非晶質であったＨ膜に圧電性
結晶性を付与することも可能となり振動板との密着性に
すぐれた圧電薄膜を提供できる。そして、本発明の方伝
であるならば、従来のように有機系接着剤あるいはハン
ダなどの接合材を用いないでも圧電薄型振動子を作製で
きるので、密度センサに用いた場合に共振周波数の温度
特性が直線的であって、温度履歴によって生ずるヒステ
１１シスも小さく、さらに耐湿性、耐汚損性、耐冷熱性
などにも優れているので、高感度で信頼性の高い密度セ
ンサを提供できるという効果を有する。なお１本発明の
方法は密度センサにかぎらず微細で精密な機能部品の圧
電薄型振動子として適用できるという利点をもっている
。As explained above, the present invention provides a thin metal imaging plate with a 5i02 or TiO2 film formed on the surface of the pbb film.
This method uses a piezoelectric material mainly composed of (Zr, Ti)O3 as a target and forms a piezoelectric thin film by high-frequency sputtering, so even if the diaphragm is heated in an oxidizing atmosphere, it will not oxidize, and the diaphragm will not be heated. High-frequency sputtering is possible in this state, and it is also possible to impart piezoelectric crystallinity to the amorphous H film by heat treatment in the atmosphere after high-frequency sputtering, creating a piezoelectric thin film with excellent adhesion to the diaphragm. can be provided. In addition, if it is a derivative of the present invention, it is possible to produce a thin piezoelectric vibrator without using conventional bonding materials such as organic adhesive or solder, so when used in a density sensor, the temperature at the resonant frequency The characteristics are linear, the hysteresis caused by temperature history is small, and it also has excellent moisture resistance, stain resistance, cold heat resistance, etc., so it has the advantage of being able to provide a highly sensitive and reliable density sensor. has. Note that the method of the present invention has the advantage that it can be applied not only to density sensors but also to thin piezoelectric vibrators of fine and precise functional parts.
第１図は密度センサの構造断面図、第２図は密度センサ
の等価回路図、第３図は密度センサで測定した共振周波
数と温度の関係を示したグラフである。
１：撮動板、２：圧電素子、３：ハウジング、４：ホー
ン、１１：発明品の共振周波数一温度曲線、１２：比較
品の共振周波数一温度曲線。
／″１−
代、ヱ、い連子 山 口 巌 ゛くミ（’ＨＧ、’
、’；Ｍφ十Ｍ仄 、２に補
Ｃす、 Ｃｐ ：恥勧糧、柿３荀７婢電客号第２ 区
云ｊ辰問浪書ズ（Ｈｚ）FIG. 1 is a cross-sectional view of the structure of the density sensor, FIG. 2 is an equivalent circuit diagram of the density sensor, and FIG. 3 is a graph showing the relationship between the resonance frequency and temperature measured by the density sensor. 1: Imaging plate, 2: Piezoelectric element, 3: Housing, 4: Horn, 11: Resonant frequency vs. temperature curve of the invention product, 12: Resonant frequency vs. temperature curve of the comparative product. /″1- Generation, E, Irenko Yamaguchi Iwao ゛Kumi ('HG,'
,';Mφ1M 组 、Additional C to 2、Cp: Shameful offering, persimmon 3x7 婢电语 2 GU 云辑辰行書zu (Hz)
Claims (1)
る金属製振動板にＰｂ（Ｚｒ、Ｔｉ）Ｏ＿３を主体とす
る圧電体をターゲットとして高周波スパッタリングによ
って圧電薄膜を形成することを特徴とする圧電薄型圧電
振動子の製造方法。 ２）特許請求の範囲第１項記載の圧電薄型振動子におい
て、金属製振動板にＳｉもしくはＴｉを含むアルコラー
ト溶液を塗布し、加熱焼成してＳｉＯ＿２あるいはＴｉ
Ｏ＿２の皮膜を形成したことを特徴とする圧電薄型振動
子の製造方法。 ３）特許請求の範囲第１項記載の圧電振動子において、
金属製振動板にＳｉＯ＿２もしくはＴｉＯ＿２焼結体を
ターゲットとして、高周波スパッタリングによってＳｉ
Ｏ＿２あるいはＴｉＯ＿２の皮膜を形成したことを特徴
とする圧電薄型振動子の製造方法。[Claims] 1) A piezoelectric thin film is formed on a metal diaphragm having a SiO_2 or TiO_2 film on its surface by high-frequency sputtering using a piezoelectric material mainly composed of Pb(Zr, Ti)O_3 as a target. A method for manufacturing a thin piezoelectric vibrator. 2) In the piezoelectric thin vibrator according to claim 1, a metal diaphragm is coated with an alcoholate solution containing Si or Ti, and heated and fired to form an SiO_2 or Ti
A method for manufacturing a thin piezoelectric vibrator, characterized in that a film of O_2 is formed. 3) In the piezoelectric vibrator according to claim 1,
Si is applied to a metal diaphragm by high-frequency sputtering using SiO_2 or TiO_2 sintered body as a target.
A method for manufacturing a thin piezoelectric vibrator, characterized in that a film of O_2 or TiO_2 is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61295951A JPS63238799A (en) | 1986-12-12 | 1986-12-12 | Manufacture of piezo-electric type vibrator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61295951A JPS63238799A (en) | 1986-12-12 | 1986-12-12 | Manufacture of piezo-electric type vibrator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63238799A true JPS63238799A (en) | 1988-10-04 |
Family
ID=17827211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61295951A Pending JPS63238799A (en) | 1986-12-12 | 1986-12-12 | Manufacture of piezo-electric type vibrator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63238799A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996020503A1 (en) * | 1994-12-27 | 1996-07-04 | Seiko Epson Corporation | Thin-film piezoelectric element, process for preparing the same, and ink jet recording head made by using said element |
-
1986
- 1986-12-12 JP JP61295951A patent/JPS63238799A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996020503A1 (en) * | 1994-12-27 | 1996-07-04 | Seiko Epson Corporation | Thin-film piezoelectric element, process for preparing the same, and ink jet recording head made by using said element |
| US5814923A (en) * | 1994-12-27 | 1998-09-29 | Seiko Epson Corporation | Piezoelectric thin-film device, process for producing the same, and ink jet recording head using said device |
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