JPH06350154A - Piezoelectric thin film element - Google Patents
Piezoelectric thin film elementInfo
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- JPH06350154A JPH06350154A JP5137892A JP13789293A JPH06350154A JP H06350154 A JPH06350154 A JP H06350154A JP 5137892 A JP5137892 A JP 5137892A JP 13789293 A JP13789293 A JP 13789293A JP H06350154 A JPH06350154 A JP H06350154A
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- film
- pzt
- thin film
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は薄膜圧電振動子、液体噴
射装置等の圧電素子、半導体記憶装置、焦電型赤外線検
出器等に用いられる強誘電体薄膜装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin film piezoelectric vibrator, a piezoelectric element such as a liquid ejecting device, a semiconductor memory device, a ferroelectric thin film device used in a pyroelectric infrared detector and the like.
【０００２】[0002]
【従来の技術】本発明にかかわる従来技術は、例えば、
特開昭６２−２５２００５が開示されている。2. Description of the Related Art The prior art relating to the present invention is, for example,
JP-A-62-252005 is disclosed.
【０００３】前記従来技術によると、化学式がＰｂ1+Y
（ＺｒXＴｉ1-X）Ｏ3+Yの場合において、組成比が、０
≦Ｘ＜０．５５、Ｙ＝０の範囲に限定されており、バル
クの多結晶体のチタン酸ジルコン酸鉛（ＰＺＴ）に於い
て、結晶構造が正方晶系の化学量論的組成に限定されて
いた。According to the above prior art, the chemical formula is Pb 1 + Y
In the case of (Zr X Ti 1-X ) O 3 + Y , the composition ratio is 0
≤X <0.55, Y = 0, and in bulk polycrystalline lead zirconate titanate (PZT), the crystal structure is limited to a tetragonal stoichiometric composition. It had been.
【０００４】更に、Ｚｒ組成比Ｘが０から０．５５の範
囲に限られており、ＰＺＴの結晶粒の中のドメインの自
発分極の７５％以上が一方向を向いていた。Further, the Zr composition ratio X is limited to the range of 0 to 0.55, and more than 75% of the spontaneous polarization of the domain in the crystal grains of PZT is directed in one direction.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、前記従
来技術を用いた強誘電体薄膜素子には以下に示す問題点
が存在する。However, the ferroelectric thin film element using the above conventional technique has the following problems.
【０００６】ＰＺＴのＰｂ組成比がＰｂ／（Ｚｒ＋Ｔ
ｉ）＝１と化学量論的組成であるため、製造方法が困難
である。The Pb composition ratio of PZT is Pb / (Zr + T
Since i) = 1 and the stoichiometric composition, the manufacturing method is difficult.
【０００７】特に、Ｐｂを含む化合物の場合、焼成、焼
結、またはスパッタ法等の成膜時の高温処理時にＰｂＯ
の形で、Ｐｂが抜けやすく、化学量論的組成に制御する
ことは、非常に困難である。Particularly, in the case of a compound containing Pb, PbO is used at the time of high temperature treatment during film formation such as firing, sintering, or sputtering.
In the form of, Pb is easily released, and it is very difficult to control the stoichiometric composition.
【０００８】更に、ほとんどの圧電素子、半導体記憶装
置、焦電型赤外線検出器素子においては、成膜後に分極
処理をする事が許されるため、Ｚｒ組成比Ｘが０≦Ｘ＜
０．５５の範囲に限られる必要がない。Furthermore, in most piezoelectric elements, semiconductor memory devices, and pyroelectric infrared detector elements, polarization processing is allowed after film formation, so that the Zr composition ratio X is 0 ≦ X <.
It need not be limited to the range of 0.55.
【０００９】そこで、本発明はこのような課題を解決す
るもので、その目的とするところは、最適な結晶配向性
及び組成を持ったＰＺＴ薄膜を用いて、圧電特性、強誘
電体特性、焦電特性を向上することである。Therefore, the present invention is intended to solve such a problem, and an object of the present invention is to use a PZT thin film having an optimum crystal orientation and composition to obtain piezoelectric characteristics, ferroelectric characteristics, and focal characteristics. It is to improve electric characteristics.
【００１０】[0010]
【課題を解決するための手段】上記問題点を解決するた
めに、 （１）本発明の圧電体薄膜素子は、金属膜が形成された
基板上に、化学式がＰｂ1+Y（ＺｒXＴｉ1-X）Ｏ3+Yで、
組成比が、０≦Ｘ＜０．５５、０≦Ｙ≦０．５の範囲に
あり、結晶構造が菱面体晶系のチタン酸ジルコン酸鉛膜
であって、前記基板の主面垂直方向に対して、前記チタ
ン酸ジルコン酸鉛膜の＜１１１＞配向度が７０％以上で
あることを特徴とする。In order to solve the above problems, (1) the piezoelectric thin film element of the present invention has a chemical formula of Pb 1 + Y (Zr X Ti on a substrate on which a metal film is formed. 1-X ) O 3 + Y ,
A lead zirconate titanate film having a composition ratio of 0 ≦ X <0.55 and 0 ≦ Y ≦ 0.5 and a crystal structure of a rhombohedral system, which is perpendicular to the main surface of the substrate. In contrast, the degree of <111> orientation of the lead zirconate titanate film is 70% or more.
【００１１】（２）更に、上記金属膜が、白金（Ｐ
ｔ）、金（Ａｕ）または、ＰｔまたはＡｕを主成分とす
る膜であって、前記基板の主面垂直方向に対して、＜１
１１＞配向膜であることが望ましい。(2) Further, the metal film is platinum (P
t), gold (Au), or a film containing Pt or Au as a main component, and <1 with respect to the direction perpendicular to the main surface of the substrate.
11> It is desirable that the alignment film.
【００１２】あるいは、（３）本発明の圧電体薄膜素子
は、金属膜が形成された基板上に、化学式がＰｂ
1+Y（ＺｒXＴｉ1-X）Ｏ3+Yで、組成比が、０．５５≦Ｘ
＜１、０≦Ｙ≦０．５の範囲にあり、結晶構造が正方晶
系のチタン酸ジルコン酸鉛膜であって、前記基板の主面
垂直方向に対して、前記チタン酸ジルコン酸鉛膜の＜０
０１＞配向度が７０％以上であることを特徴とする。Alternatively, (3) the piezoelectric thin film element of the present invention has a chemical formula of Pb on a substrate on which a metal film is formed.
1 + Y (Zr X Ti 1-X ) O 3 + Y with a composition ratio of 0.55 ≦ X
A lead zirconate titanate film having a tetragonal crystal structure in the range of <1, 0 ≦ Y ≦ 0.5, the lead zirconate titanate film being perpendicular to the main surface of the substrate. <0
01> The degree of orientation is 70% or more.
【００１３】（４）更に、上記金属膜が、白金（Ｐ
ｔ）、金（Ａｕ）または、ＰｔまたはＡｕを主成分とす
る膜であって、前記基板の主面垂直方向に対して、＜１
００＞配向膜であることが望ましい。(4) Further, the metal film is platinum (P
t), gold (Au), or a film containing Pt or Au as a main component, and <1 with respect to the direction perpendicular to the main surface of the substrate.
00> alignment film is desirable.
【００１４】[0014]
【実施例】（実施例１）以下、本発明の実施例を図面に
基づいて説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS (Embodiment 1) An embodiment of the present invention will be described below with reference to the drawings.
【００１５】図１は、本発明に従って作成した強誘電体
薄膜素子の第１の実施例である薄膜圧電振動子の断面図
である。FIG. 1 is a sectional view of a thin film piezoelectric vibrator which is a first embodiment of a ferroelectric thin film element prepared according to the present invention.
【００１６】（１００）面単結晶Ｓｉ基板１０１に、熱
酸化を行い、１μｍのＳｉＯ2膜１０２を形成する。A (100) plane single crystal Si substrate 101 is thermally oxidized to form a 1 μm SiO 2 film 102.
【００１７】前記ＳｉＯ2膜１０２上に、膜厚５０Ａの
Ｔｉ層１０３と膜厚３０００ＡのＰｔ下部電極１０４を
直流スパッタリングにより形成した。A Ti layer 103 having a film thickness of 50 A and a Pt lower electrode 104 having a film thickness of 3000 A were formed on the SiO 2 film 102 by DC sputtering.
【００１８】スパッタは、Ａｒ雰囲気、２００℃の基板
温度で行った。The sputtering was performed in an Ar atmosphere at a substrate temperature of 200 ° C.
【００１９】Ｐｔ下部電極１０４は、Ｓｉ基板１０１の
主面垂直方向に対して、＜１１１＞配向している。The Pt lower electrode 104 is <111> oriented with respect to the direction perpendicular to the main surface of the Si substrate 101.
【００２０】次にＰＺＴ膜１０５を２μｍ、高周波スパ
ッタ法により形成した。Next, a PZT film 105 having a thickness of 2 μm was formed by a high frequency sputtering method.
【００２１】スパッタは、ＡｒとＯ2雰囲気、２００℃
の基板温度で行った。Sputtering was carried out in Ar and O 2 atmosphere at 200 ° C.
Was performed at the substrate temperature of.
【００２２】スパッタリングターゲットには、Ｐｂ1+Y
（ＺｒXＴｉ1-X）Ｏ3+Yを用いた。For the sputtering target, Pb 1 + Y
Using (Zr X Ti 1-X) O 3 + Y.
【００２３】ここで、Ｙ＝０．３、Ｘ＝０．５である。Here, Y = 0.3 and X = 0.5.
【００２４】次いで、ペロブスカイト結晶構造のＰＺＴ
を得るために、Ｏ2雰囲気中、６００℃で、３時間熱処
理を行った。Next, PZT having a perovskite crystal structure
In order to obtain the above, heat treatment was performed at 600 ° C. for 3 hours in an O 2 atmosphere.
【００２５】次いで、ＰＺＴ膜上に膜厚１００ＡのＴｉ
層１０６、及び膜厚２０００ＡのＡｕ電極１０７を順次
蒸着し、最後に、ＰＺＴ膜１０５の下部に於ける単結晶
Ｓｉ基板１０１にＳｉＯ2膜１０２に至るまで開口部１
０８を設け、強誘電体薄膜素子を作成した。Then, a Ti film having a thickness of 100 A is formed on the PZT film.
A layer 106 and an Au electrode 107 having a thickness of 2000 A are sequentially deposited, and finally, an opening 1 is formed on the single crystal Si substrate 101 below the PZT film 105 up to the SiO 2 film 102.
No. 08 was provided to prepare a ferroelectric thin film element.
【００２６】図２に、代表的なＰＺＴ薄膜のＸ線回折パ
ターンを示す。FIG. 2 shows an X-ray diffraction pattern of a typical PZT thin film.
【００２７】Ｓｉ基板の反射ピークとＰｔ下部電極の反
射ピーク以外は、ペロブスカイト構造のＰＺＴの反射ピ
ークである。Except for the reflection peak of the Si substrate and the reflection peak of the Pt lower electrode, there are reflection peaks of PZT having a perovskite structure.
【００２８】図２に示された本実施例の過剰鉛組成比Ｙ
は、０．０５、Ｚｒ組成比Ｘは、０．５０であり、＜１
１１＞配向度は、８０％であった。The excess lead composition ratio Y of this embodiment shown in FIG.
Is 0.05, the Zr composition ratio X is 0.50, and <1
11> The degree of orientation was 80%.
【００２９】ここで、＜１１１＞配向度Ｐ（１１１）
は、Ｐ（１１１）＝Ｉ（１１１）／ΣＩ（ｈｋｌ）で表
す。Here, the <111> orientation degree P (111)
Is represented by P (111) = I (111) / ΣI (hkl).
【００３０】ΣＩ（ｈｋｌ）は、Ｘ線回折（ＸＲＤ）法
の高角反射法で、波長にＣｕＫα線を用いたときの２θ
が２０度〜８０度のＰＺＴの全回折強度の和を表す。ΣI (hkl) is a high-angle reflection method of the X-ray diffraction (XRD) method, and 2θ when CuKα rays are used for the wavelength.
Represents the sum of all diffraction intensities of PZT from 20 degrees to 80 degrees.
【００３１】具体的には、（１００）、（１１０）、
（１１１）、（２１０）、（２１１）、（２２１）、
（３１０）結晶面反射強度の総和である。Specifically, (100), (110),
(111), (210), (211), (221),
(310) This is the sum of the crystal plane reflection intensities.
【００３２】Ｉ（１１１）は、同じくＰＺＴの（１１
１）結晶面反射強度を表す。I (111) is the same as (11) of PZT.
1) Represents crystal plane reflection intensity.
【００３３】図３は＜１１１＞方向に７０から１００％
配向した膜厚２μｍのＰＺＴ薄膜の圧電定数ｄ31のＺｒ
組成比Ｘ依存性を示す。FIG. 3 shows 70 to 100% in the <111> direction.
Zr of piezoelectric constant d 31 of oriented PZT thin film of 2 μm thickness
The composition ratio X dependence is shown.
【００３４】ＰｂＯ過剰組成比Ｙは、０．０５である。The PbO excess composition ratio Y is 0.05.
【００３５】図３中に比較のため、バルクＰＺＴの圧電
定数も示した。For comparison, the piezoelectric constant of bulk PZT is also shown in FIG.
【００３６】図３に示すように、全組成範囲に於いて、
バルクのＰＺＴの圧電定数より、７０から１００％＜１
１１＞配向したＰＺＴ薄膜の圧電定数は、大きな値を示
した。As shown in FIG. 3, in the entire composition range,
From the piezoelectric constant of bulk PZT, 70 to 100% <1
The piezoelectric constant of the 11> -oriented PZT thin film showed a large value.
【００３７】特に、Ｚｒ組成比Ｘが、０から０．５５の
範囲に於いて、バルクＰＺＴに比較して、飛躍的に大き
い値を示した。Particularly, when the Zr composition ratio X was in the range of 0 to 0.55, it showed a remarkably large value as compared with the bulk PZT.
【００３８】これは、バルクＰＺＴの結晶構造が、この
組成範囲で、正方晶系で有るのに対して、配向薄膜の場
合は、菱面体晶系となることによると考えられる。It is considered that this is because the crystal structure of bulk PZT is tetragonal in this composition range, whereas that of oriented thin film is rhombohedral.
【００３９】すなわち、バルクＰＺＴの菱面体晶系組成
の範囲、すなわちＺｒ組成比Ｘが０．５５から１の範囲
では、組成比Ｘが小さいほど圧電定数が大きくなるが、
薄膜の場合には、更にＸが０から０．５５の範囲まで及
んであるためだろう。That is, in the rhombohedral composition range of bulk PZT, that is, in the range where the Zr composition ratio X is 0.55 to 1, the smaller the composition ratio X, the larger the piezoelectric constant.
In the case of a thin film, it may be because X further ranges from 0 to 0.55.
【００４０】図４には、Ｚｒ組成比Ｘ＝０．４５に固定
した場合の圧電定数ｄ31のＰｂＯ過剰組成比Ｙ依存性を
示す。FIG. 4 shows the dependency of the piezoelectric constant d 31 on the PbO excess composition ratio Y when the Zr composition ratio X is fixed at 0.45.
【００４１】ＰＺＴ薄膜の膜厚は、同じく２μｍ、＜１
１１＞配向度は、７０から１００％である。The film thickness of the PZT thin film is 2 μm, <1.
11> The degree of orientation is 70 to 100%.
【００４２】図４に示すように、圧電定数ｄ31は、Ｐｂ
Ｏの過剰分Ｙに大きく依存しており、Ｙが０より小さい
と急激に低下し、Ｙ＝０．５より大では、バルクＰＺＴ
並みまで低下する。As shown in FIG. 4, the piezoelectric constant d 31 is Pb.
It largely depends on the excess Y of O, and decreases sharply when Y is smaller than 0, and bulk PZT when Y is larger than 0.5.
Falls to the average.
【００４３】Ｙが０．５より大きくなると圧電定数31が
小さくなる理由としては、粒界へのＰｂＯの析出である
ことがわかった。It was found that the reason why the piezoelectric constant 31 becomes smaller when Y exceeds 0.5 is the precipitation of PbO at the grain boundaries.
【００４４】従って、Ｙの範囲は、０以上０．５以下で
あることが望ましい。Therefore, it is desirable that the range of Y is 0 or more and 0.5 or less.
【００４５】以上実施例１に於いて、下部電極として、
＜１１１＞配向Ｐｔを用いて説明したが、ＰＺＴ薄膜の
＜１１１＞配向度が、７０％以上となれば良く、Ａｕ、
Ｐｔ−Ｉｒ、Ｐｔ−Ｐｄ、Ｐｔ−Ｎｉ、Ｐｔ−Ｔｉ等他
の金属膜でも良い。In the above Example 1, as the lower electrode,
Although the description has been made by using the <111> orientation Pt, it is sufficient that the degree of the <111> orientation of the PZT thin film is 70% or more.
Other metal films such as Pt-Ir, Pt-Pd, Pt-Ni, and Pt-Ti may be used.
【００４６】更に、実施例１では、薄膜圧電振動子を例
に取り説明したが、液体噴射装置、半導体記憶装置、焦
電型赤外線検出器等にもそのまま応用できることは自明
である。Further, in the first embodiment, the thin film piezoelectric vibrator is described as an example, but it is obvious that the invention can be directly applied to a liquid ejecting apparatus, a semiconductor memory device, a pyroelectric infrared detector and the like.
【００４７】（実施例２）以下、本発明の実施例を図面
に基づいて説明する。(Embodiment 2) An embodiment of the present invention will be described below with reference to the drawings.
【００４８】図５は、本発明に従って作成した強誘電体
薄膜素子の第２の実施例の断面図である。FIG. 5 is a sectional view of a second embodiment of a ferroelectric thin film element manufactured according to the present invention.
【００４９】（１００）面単結晶ＭｇＯ基板２０１に、
高周波スパッタ法により、ＭｇＯ基板２０１の主面方向
に対して＜１００＞配向のＰｔ下部電極２０２を形成す
る。On the (100) plane single crystal MgO substrate 201,
A Pt lower electrode 202 having a <100> orientation with respect to the main surface direction of the MgO substrate 201 is formed by a high frequency sputtering method.
【００５０】スパッタは、Ａｒ／Ｏ2＝８／２の雰囲気
中、２００℃の基板温度で行った。Sputtering was performed at a substrate temperature of 200 ° C. in an atmosphere of Ar / O 2 = 8/2.
【００５１】次にＰＺＴ膜２０３を２μｍ、高周波スパ
ッタ法により形成した。Next, a PZT film 203 having a thickness of 2 μm was formed by a high frequency sputtering method.
【００５２】スパッタは、ＡｒとＯ2雰囲気、７００℃
の基板温度で行った。Sputtering was performed in an Ar and O 2 atmosphere at 700 ° C.
Was performed at the substrate temperature of.
【００５３】スパッタリングターゲットには、Ｐｂ1+Y
（ＺｒXＴｉ1-X）Ｏ3+Yを用いた。For the sputtering target, Pb 1 + Y
Using (Zr X Ti 1-X) O 3 + Y.
【００５４】ここで、Ｙ＝０．５、Ｘ＝０．６である。Here, Y = 0.5 and X = 0.6.
【００５５】高温スパッタにより、アズ−スパッタで、
ペロブスカイト結晶構造のＰＺＴを得ることができた。By high temperature sputtering, as-sputtering,
It was possible to obtain PZT having a perovskite crystal structure.
【００５６】次いで、ＰＺＴ膜上に膜厚１００ＡのＴｉ
層２０４、及び膜厚２０００ＡのＡｕ電極２０５を順次
蒸着し、特性を評価した。Then, a Ti film having a film thickness of 100 A is formed on the PZT film.
A layer 204 and an Au electrode 205 having a film thickness of 2000 A were sequentially deposited, and the characteristics were evaluated.
【００５７】図６に、代表的なＰＺＴ薄膜のＸ線回折パ
ターンを示す。FIG. 6 shows an X-ray diffraction pattern of a typical PZT thin film.
【００５８】ＭｇＯ単結晶基板の反射ピークとＰｔ電極
の反射ピーク以外は、ペロブスカイト構造のＰＺＴの反
射ピークである。Except for the reflection peak of the MgO single crystal substrate and the reflection peak of the Pt electrode, there are reflection peaks of PZT having a perovskite structure.
【００５９】図６に示された本実施例の過剰鉛組成比Ｙ
は、０．１０、Ｚｒ組成比Ｘは、０．６０であり、＜０
０１＞配向度は、９８％であった。Excess lead composition ratio Y of this embodiment shown in FIG.
Is 0.10, the Zr composition ratio X is 0.60, and <0
The 01> orientation degree was 98%.
【００６０】ここで、＜００１＞配向度Ｐ（００１）
は、Ｐ（００１）＝Ｉ（００１）／ΣＩ（ｈｋｌ）で表
す。Here, <001> degree of orientation P (001)
Is represented by P (001) = I (001) / ΣI (hkl).
【００６１】図７は＜００１＞方向に７０から１００％
配向した膜厚２μｍのＰＺＴ薄膜の比誘電率εのＺｒ組
成比Ｘ依存性を示す。FIG. 7 shows 70% to 100% in the <001> direction.
3 shows the Zr composition ratio X dependence of the relative permittivity ε of the oriented PZT thin film having a film thickness of 2 μm.
【００６２】ここで示す比誘電率εは、膜厚方向に分極
処理した後の膜厚方向の比誘電率である。The relative permittivity ε shown here is the relative permittivity in the film thickness direction after polarization in the film thickness direction.
【００６３】ＰｂＯ過剰組成比Ｙは、０．１０である。The PbO excess composition ratio Y is 0.10.
【００６４】図７中に比較のため、バルクＰＺＴの比誘
電率εも示した。For comparison, the relative permittivity ε of bulk PZT is also shown in FIG.
【００６５】図７に示すように、全組成範囲に於いて、
バルクのＰＺＴの比誘電率εより、７０から１００％＜
００１＞配向したＰＺＴ薄膜の比誘電率εは、大きな値
を示した。As shown in FIG. 7, in the entire composition range,
From the relative permittivity ε of bulk PZT, 70 to 100% <
The relative permittivity ε of the 001> oriented PZT thin film showed a large value.
【００６６】特に、Ｚｒ組成比Ｘが、０．５５から１の
範囲に於いて、バルクＰＺＴに比較して、飛躍的に大き
い値を示した。Particularly, when the Zr composition ratio X was in the range of 0.55 to 1, it showed a remarkably large value as compared with the bulk PZT.
【００６７】これは、バルクＰＺＴの結晶構造が、この
組成範囲で、菱面体晶系で有るのに対して、配向薄膜の
場合は、正方晶系となることによると考えられる。It is considered that this is because the crystal structure of bulk PZT is rhombohedral in this composition range, whereas it is tetragonal in the case of an oriented thin film.
【００６８】すなわち、バルクＰＺＴの正方晶系組成の
範囲、すなわちＺｒ組成比Ｘが０から０．５５の範囲で
は、組成比Ｘが大きいほど比誘電率が大きくなるが、薄
膜の場合には、更にＸが０．５５から１の範囲まで及ん
であるためだろう。That is, in the range of the tetragonal composition of bulk PZT, that is, in the range of Zr composition ratio X from 0 to 0.55, the relative permittivity increases as the composition ratio X increases, but in the case of a thin film, It is probably because X ranges from 0.55 to 1.
【００６９】図８に、Ｚｒ組成比Ｘ＝０．６０に固定し
た場合の比誘電率εのＰｂＯ過剰組成比Ｙ依存性を示
す。FIG. 8 shows the dependence of the relative permittivity ε on the PbO excess composition ratio Y when the Zr composition ratio X is fixed at 0.6 = 0.60.
【００７０】ＰＺＴ薄膜の膜厚は、同じく２μｍ、＜０
０１＞配向度は、９５から１００％である。The film thickness of the PZT thin film was 2 μm, <0.
The 01> orientation degree is 95 to 100%.
【００７１】比較のためバルクＰＺＴの比誘電率も示
す。For comparison, the relative permittivity of bulk PZT is also shown.
【００７２】図８に示すように、比誘電率εは、ＰｂＯ
の過剰分Ｙに大きく依存しており、Ｙが０より小さいと
急激に低下し、Ｙ＝０．５より大では、バルクＰＺＴ並
みまたは、それ以下まで低下する。As shown in FIG. 8, the relative permittivity ε is PbO.
It largely depends on the excess Y of Y. When Y is smaller than 0, it sharply drops, and when Y is larger than 0.5, it drops to the level of bulk PZT or less.
【００７３】従って、Ｙの範囲は、０以上０．５以下で
あることが望ましい。Therefore, it is desirable that the range of Y is 0 or more and 0.5 or less.
【００７４】以上実施例２に於いて、下部電極として、
＜１００＞配向Ｐｔを用いて説明したが、ＰＺＴ薄膜の
＜００１＞配向度が、７０％以上となれば良く、Ａｕ、
Ｐｔ−Ｉｒ、Ｐｔ−Ｐｄ、Ｐｔ−Ｎｉ、Ｐｔ−Ｔｉ等他
の金属膜でも良い。In the above second embodiment, as the lower electrode,
Although the description has been made using the <100> -oriented Pt, it is sufficient that the degree of <001> orientation of the PZT thin film is 70% or more.
Other metal films such as Pt-Ir, Pt-Pd, Pt-Ni, and Pt-Ti may be used.
【００７５】以上上記実施例１、２に於いて、圧電膜と
して、純粋な組成のＰＺＴ薄膜を用いて説明したが、勿
論若干の不純物が混入されていてもさしつかえない。In the above-mentioned Examples 1 and 2, the PZT thin film having a pure composition was used as the piezoelectric film, but of course, a slight amount of impurities may be mixed.
【００７６】不純物としては、一般的に圧電性を向上す
るものとして、Ｎｂ、Ｌａ、Ｔａ、Ｎｄ、Ｗ、Ｍｏ、、
Ｍｎ、、Ｂａ、Ｓｒ、Ｃａ、Ｂｉ等があり、１５モル％
以下を加えることは可能である。As the impurities, Nb, La, Ta, Nd, W, Mo, ...
There are Mn, Ba, Sr, Ca, Bi, etc., and 15 mol%
It is possible to add:
【００７７】[0077]
【発明の効果】以上述べてきたように本発明の圧電体薄
膜素子は、以下のような効果を有する。 最適な結晶配
向性及び組成を持ったＰＺＴ薄膜を用いることにより、
バルクのＰＺＴに比較して飛躍的に、圧電特性、強誘電
体特性、焦電特性を向上することができ、更に薄膜であ
るため、スパッタ法や化学気相成長法等で製造できるの
で、作成が容易であり、薄膜圧電振動子、液体噴射装置
等の圧電素子、半導体記憶装置、焦電型赤外線検出器等
に応用することができる。As described above, the piezoelectric thin film element of the present invention has the following effects. By using a PZT thin film having an optimum crystal orientation and composition,
Compared with bulk PZT, it can dramatically improve piezoelectric characteristics, ferroelectric characteristics, and pyroelectric characteristics. Furthermore, since it is a thin film, it can be manufactured by sputtering or chemical vapor deposition. It can be easily applied to a thin film piezoelectric vibrator, a piezoelectric element such as a liquid ejecting apparatus, a semiconductor memory device, a pyroelectric infrared detector, and the like.
【図１】本発明の実施例における薄膜圧電振動子の断面
図。FIG. 1 is a sectional view of a thin film piezoelectric vibrator according to an embodiment of the invention.
【図２】本発明の実施例における、ＰＺＴ薄膜のＸ線回
折パターンの図。FIG. 2 is a diagram showing an X-ray diffraction pattern of a PZT thin film in an example of the present invention.
【図３】本発明の実施例及び従来のＰＺＴ薄膜の圧電定
数ｄ31のＺｒ組成比Ｘ依存性を示す図。FIG. 3 is a diagram showing the Zr composition ratio X dependence of the piezoelectric constant d 31 of an example of the present invention and a conventional PZT thin film.
【図４】本発明の実施例及び従来のＰＺＴ薄膜の、Ｚｒ
組成比Ｘ＝０．４５に固定した場合の圧電定数ｄ31のＰ
ｂＯ過剰組成比Ｙ依存性を示す図。FIG. 4 is a graph showing Zr of an example of the present invention and a conventional PZT thin film.
P of the piezoelectric constant d 31 when the composition ratio X is fixed at 0.45
The figure which shows bO excess composition ratio Y dependence.
【図５】本発明の実施例における強誘電体薄膜素子の断
面図。FIG. 5 is a sectional view of a ferroelectric thin film element in an example of the present invention.
【図６】本発明の実施例における、ＰＺＴ薄膜のＸ線回
折パターンの図。FIG. 6 is a diagram showing an X-ray diffraction pattern of a PZT thin film in an example of the present invention.
【図７】本発明の実施例及び従来のＰＺＴ薄膜の比誘電
率εのＺｒ組成比Ｘ依存性を示す図。FIG. 7 is a diagram showing the Zr composition ratio X dependence of the relative permittivity ε of the example of the present invention and the conventional PZT thin film.
【図８】本発明の実施例及び従来のＰＺＴ薄膜の、Ｚｒ
組成比Ｘ＝０．６０に固定した場合の比誘電率εのＰｂ
Ｏ過剰組成比Ｙ依存性を示す図。FIG. 8 is a graph showing Zr of an example of the present invention and a conventional PZT thin film.
Pb of relative permittivity ε when composition ratio X is fixed at 0.60
The figure which shows O excess composition ratio Y dependence.
１０１・・・単結晶Ｓｉ基板 １０２・・・ＳｉＯ2膜 １０３・・・Ｔｉ層 １０４・・・Ｐｔ下部電極 １０５・・・ＰＺＴ膜 １０６・・・Ｔｉ層 １０７・・・Ａｕ電極 １０８・・・開口部 ２０１・・・単結晶ＭｇＯ基板 ２０２・・・Ｐｔ下部電極 ２０３・・・ＰＺＴ膜 ２０４・・・Ｔｉ層 ２０５・・・Ａｕ電極101 ... Single crystal Si substrate 102 ... SiO 2 film 103 ... Ti layer 104 ... Pt lower electrode 105 ... PZT film 106 ... Ti layer 107 ... Au electrode 108 ... Opening 201 ... Single crystal MgO substrate 202 ... Pt lower electrode 203 ... PZT film 204 ... Ti layer 205 ... Au electrode
Claims (4)
Ｐｂ1+Y（ＺｒXＴｉ1-X）Ｏ3+Yで、組成比が、０≦Ｘ＜
０．５５、０≦Ｙ≦０．５の範囲にあり、結晶構造が菱
面体晶系のチタン酸ジルコン酸鉛膜であって、前記基板
の主面垂直方向に対して、前記チタン酸ジルコン酸鉛膜
の＜１１１＞配向度が７０％以上であることを特徴とす
る圧電体薄膜素子。1. A substrate having a metal film formed thereon has a chemical formula of Pb 1 + Y (Zr X Ti 1-X ) O 3 + Y and a composition ratio of 0 ≦ X <
0.55, a range of 0 ≦ Y ≦ 0.5, and a rhombohedral lead zirconate titanate film having a crystal structure, wherein the zirconate titanate is perpendicular to the main surface of the substrate. A piezoelectric thin film element, wherein the degree of <111> orientation of the lead film is 70% or more.
たは、ＰｔまたはＡｕを主成分とする膜であって、前記
基板の主面垂直方向に対して、＜１１１＞配向膜である
ことを特徴とする請求項１記載の圧電体薄膜素子。2. The metal film is platinum (Pt), gold (Au), or a film containing Pt or Au as a main component, and a <111> orientation film with respect to a direction perpendicular to the main surface of the substrate. The piezoelectric thin film element according to claim 1, wherein the piezoelectric thin film element is present.
Ｐｂ1+Y（ＺｒXＴｉ1-X）Ｏ3+Yで、組成比が、０．５５
≦Ｘ＜１、０≦Ｙ≦０．５の範囲にあり、結晶構造が正
方晶系のチタン酸ジルコン酸鉛膜であって、前記基板の
主面垂直方向に対して、前記チタン酸ジルコン酸鉛膜の
＜００１＞配向度が７０％以上であることを特徴とする
圧電体薄膜素子。3. A substrate having a metal film formed thereon has a chemical formula of Pb 1 + Y (Zr X Ti 1-X ) O 3 + Y and a composition ratio of 0.55.
A lead zirconate titanate film having a tetragonal crystal structure in the range of ≦ X <1, 0 ≦ Y ≦ 0.5, wherein the zirconate titanate is perpendicular to the main surface of the substrate. A piezoelectric thin film element, wherein the <001> orientation degree of the lead film is 70% or more.
たは、ＰｔまたはＡｕを主成分とする膜であって、前記
基板の主面垂直方向に対して、＜１００＞配向膜である
ことを特徴とする請求項３記載の圧電体薄膜素子。4. The metal film is platinum (Pt), gold (Au), or a film containing Pt or Au as a main component, and a <100> orientation film with respect to a direction perpendicular to the main surface of the substrate. The piezoelectric thin film element according to claim 3, wherein the piezoelectric thin film element is present.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13789293A JP3341357B2 (en) | 1993-06-08 | 1993-06-08 | Piezoelectric thin film element |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13789293A JP3341357B2 (en) | 1993-06-08 | 1993-06-08 | Piezoelectric thin film element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06350154A true JPH06350154A (en) | 1994-12-22 |
| JP3341357B2 JP3341357B2 (en) | 2002-11-05 |
Family
ID=15209121
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13789293A Expired - Lifetime JP3341357B2 (en) | 1993-06-08 | 1993-06-08 | Piezoelectric thin film element |
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| Country | Link |
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| JP2011249649A (en) * | 2010-05-28 | 2011-12-08 | Toshiba Corp | Semiconductor device |
| JP2014199265A (en) * | 2014-07-30 | 2014-10-23 | セイコーエプソン株式会社 | Pyroelectric photodetector, pyroelectric photodetection device, and electronic apparatus |
| US11295770B2 (en) | 2015-12-03 | 2022-04-05 | Sae Magnetics (H.K.) Ltd. | Thin-film piezoelectric material substrate, thin-film piezoelectric material element, head gimbal assembly, ink jet head and method of manufacturing the thin-film piezoelectric |
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| JP3341357B2 (en) | 2002-11-05 |
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