JPH04308607A - Manufacture of pzt ferroelectric thin film - Google Patents
Manufacture of pzt ferroelectric thin filmInfo
- Publication number
- JPH04308607A JPH04308607A JP3102034A JP10203491A JPH04308607A JP H04308607 A JPH04308607 A JP H04308607A JP 3102034 A JP3102034 A JP 3102034A JP 10203491 A JP10203491 A JP 10203491A JP H04308607 A JPH04308607 A JP H04308607A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- ferroelectric thin
- pzt ferroelectric
- pzt
- compound solution
- 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
- 239000010409 thin film Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000010304 firing Methods 0.000 claims abstract description 8
- 150000002611 lead compounds Chemical class 0.000 claims abstract description 4
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 4
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 11
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 27
- 239000010408 film Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- OFYFURKXMHQOGG-UHFFFAOYSA-J 2-ethylhexanoate;zirconium(4+) Chemical compound [Zr+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O OFYFURKXMHQOGG-UHFFFAOYSA-J 0.000 description 1
- NJLQUTOLTXWLBV-UHFFFAOYSA-N 2-ethylhexanoic acid titanium Chemical compound [Ti].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O NJLQUTOLTXWLBV-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- -1 β-diketone Chemical compound 0.000 description 1
Landscapes
- Inorganic Insulating Materials (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、強誘電体薄膜に係わり
、さらに詳しくは、耐熱基板上に密着して形成された０
．１〜１０μｍの膜厚を有するＰＺＴ強誘電体薄膜およ
びその製造方法に関する。本発明のＰＺＴ強誘電体薄膜
は、優れた誘電特性を有するため、圧電素子の強誘電体
層、積層コンデンサの誘電体層などとして利用できる。[Field of Industrial Application] The present invention relates to a ferroelectric thin film, and more specifically, a ferroelectric thin film formed in close contact with a heat-resistant substrate.
．． The present invention relates to a PZT ferroelectric thin film having a thickness of 1 to 10 μm and a method for manufacturing the same. Since the PZT ferroelectric thin film of the present invention has excellent dielectric properties, it can be used as a ferroelectric layer of a piezoelectric element, a dielectric layer of a multilayer capacitor, and the like.
【０００２】0002
【従来の技術】ＰＺＴ強誘電体は、通常、酸化鉛粉末と
酸化ジルコニウム粉末とチタン粉末との化学量論比の混
合物の圧縮成型体を焼成して製造される。近年、基板上
への金属酸化物薄膜、金属薄膜等の形成に使用されてい
る真空蒸着法、スパッタリング法、ＣＶＤ法等の気相法
を応用して強誘電体薄膜を基板上に形成する試みが種々
検討されている。BACKGROUND OF THE INVENTION PZT ferroelectric materials are usually manufactured by firing a compression molded body of a mixture of lead oxide powder, zirconium oxide powder, and titanium powder in a stoichiometric ratio. Attempts have been made to form ferroelectric thin films on substrates by applying vapor phase methods such as vacuum evaporation, sputtering, and CVD, which have been used in recent years to form metal oxide thin films and metal thin films on substrates. Various methods are being considered.
【０００３】0003
【発明が解決しようとする課題】チタン酸ジルコン酸鉛
（ＰＺＴ）は、代表的な強誘電性セラミックスであり、
種々の圧電性デバイスに広く応用されている。近年、電
子デバイスの高機能化のため、これらの強誘電体を薄膜
化する研究が盛んである。粉末焼結法で製造される（Ｐ
ＺＴ）は、組成のコントロールが比較的に容易であるこ
とから優れた誘電特性を有するが、均一な組成を有する
導通のないミクロン・オーダーの薄膜の製造は極めて困
難であり、注意して製造しても薄膜中の結晶粒径が不揃
いとなる。[Problem to be solved by the invention] Lead zirconate titanate (PZT) is a typical ferroelectric ceramic.
It is widely applied to various piezoelectric devices. In recent years, in order to improve the functionality of electronic devices, research has been actively conducted to reduce the thickness of these ferroelectric materials. Manufactured by powder sintering method (P
ZT) has excellent dielectric properties because its composition is relatively easy to control, but it is extremely difficult to manufacture a micron-order thin film with a uniform composition and no conduction, so it must be manufactured with care. However, the crystal grain size in the thin film becomes uneven.
【０００４】一方、気相法を採用することにより、結晶
粒径が比較的揃ったＰＺＴ薄膜を得ることが期待される
が、多元系における膜組成のターゲット組成からのずれ
などの組成制御の困難さや強誘電相であるペロブスカイ
ト相に結晶化させるためには、５００〜６００゜Ｃ以上
の熱処理が必要であるなど低温で成膜できるというスパ
ッタリング法の特徴を生かせないなどの問題がある。On the other hand, by employing the vapor phase method, it is expected that a PZT thin film with a relatively uniform crystal grain size can be obtained, but it is difficult to control the composition, such as deviation of the film composition from the target composition in a multi-component system. In order to crystallize the perovskite phase, which is a sheath ferroelectric phase, there are problems such as heat treatment at 500 to 600° C. or higher, which prevents the sputtering method from taking advantage of its ability to form a film at low temperatures.
【０００５】本発明は前述の事情に鑑み、組成のコント
ロールされた優れた誘電特性を有するＰＺＴ強誘電体薄
膜を容易に製造できるようにすることをその課題とする
。In view of the above-mentioned circumstances, it is an object of the present invention to enable easy production of a PZT ferroelectric thin film having a controlled composition and excellent dielectric properties.
【０００６】[0006]
【課題を解決するための手段】前記課題を解決するため
に本発明のＰＺＴ強誘電体薄膜の製造方法は、鉛化合物
溶液とジルコニウム化合物溶液とチタン化合物溶液の混
合物に粘度調整剤を添加して粘度調整したＰＺＴ強誘電
体薄膜形成材料層が形成された耐熱基板を５００゜Ｃ以
上で焼成することを特徴とする。鉛化合物溶液、ジルコ
ニウム化合物溶液およびチタン化合物溶液は、鉛および
チタンの有機配位子錯体を含有するペ−ストを使用する
ことができる。有機配位子錯体は、たとえばナフテン酸
などのカルボン酸やβ−ジケトン、安息香酸、２−エチ
ルヘキサン酸を配位子とするものが使用される。前記粘
度調整剤としては、従来公知の増粘剤または希釈剤等を
適当に混合して使用することができる。前記耐熱性基板
はＰＺＴの結晶化温度以上、好ましくは５００゜Ｃ以上
に加熱しても変形や相変化のない基板であれば特に制限
はなく、たとえばホウケイ酸ガラス基板、石英ガラス基
板、アルミナ基板などが、その目的に応じて使用される
。前記耐熱基板にＰＺＴ強誘電体薄膜形成材料層を形成
する方法としては、スクリーン印刷法、ロールコート法
、スピンコート法等の従来公知の種々の厚膜法を採用す
ることができる。前記焼成条件を５００゜Ｃ以上のピ−
ク温度で行うのは５００゜Ｃ以下では強誘電体薄膜の形
成が困難であることによる。前記耐熱基板の加熱法は、
基板温度を所定温度に加熱できる方法であれば特に制限
はない。[Means for Solving the Problems] In order to solve the above problems, the method for producing a PZT ferroelectric thin film of the present invention includes adding a viscosity modifier to a mixture of a lead compound solution, a zirconium compound solution, and a titanium compound solution. The method is characterized in that a heat-resistant substrate on which a viscosity-adjusted PZT ferroelectric thin film forming material layer is formed is fired at 500°C or higher. As the lead compound solution, zirconium compound solution, and titanium compound solution, a paste containing an organic ligand complex of lead and titanium can be used. The organic ligand complex used includes, for example, a carboxylic acid such as naphthenic acid, β-diketone, benzoic acid, or 2-ethylhexanoic acid as a ligand. As the viscosity modifier, conventionally known thickeners, diluents, etc. can be appropriately mixed and used. The heat-resistant substrate is not particularly limited as long as it does not deform or phase change even when heated to a temperature higher than the crystallization temperature of PZT, preferably 500°C or higher, such as a borosilicate glass substrate, a quartz glass substrate, or an alumina substrate. etc. are used depending on the purpose. As a method for forming the PZT ferroelectric thin film forming material layer on the heat-resistant substrate, various conventionally known thick film methods such as screen printing, roll coating, and spin coating can be employed. The firing conditions were changed to a peak temperature of 500°C or higher.
The reason why the process is carried out at a temperature below 500°C is that it is difficult to form a ferroelectric thin film at temperatures below 500°C. The heating method for the heat-resistant substrate is as follows:
There is no particular restriction as long as the method can heat the substrate to a predetermined temperature.
【０００７】[0007]
【作用】前述の本発明のＰＺＴ強誘電体薄膜の製造方法
によれば、薄膜技術で使用されるような大形の製造設備
を必要としない厚膜技術によって、すぐれた特性のＰＺ
Ｔ強誘電体薄膜を形成することができる。本発明により
、耐熱性基板上に密着して形成されたＰＺＴ強誘電体薄
膜は、ＰＺＴの正方晶結晶を主体としており、結晶粒界
にアモルファス相が存在することもあるが、そのアモル
ファス層の存在によっても強誘電体薄膜としての特性に
障害が生じることはない。[Operation] According to the method for manufacturing a PZT ferroelectric thin film of the present invention described above, PZT with excellent characteristics can be produced using thick film technology that does not require large manufacturing equipment as used in thin film technology.
A T ferroelectric thin film can be formed. According to the present invention, the PZT ferroelectric thin film formed in close contact with the heat-resistant substrate is mainly composed of tetragonal PZT crystals, and although an amorphous phase may exist at the grain boundaries, the amorphous layer is Its presence does not impair the properties of the ferroelectric thin film.
【０００８】[0008]
【実施例】次に本発明のＰＺＴ強誘電体薄膜の製造方法
の−実施例を説明する。
（１）レジネ−トの調整
２−エチルヘキサン酸鉛と２−エチルヘキサン酸ジルコ
ニウムと２−エチルヘキサン酸チタンを所望の原子比数
になるように混合する。混合比はＰｂ：Ｚｒ：Ｔｉ＝１
：ｘ：１−ｘ（０≦ｘ≦１）となるような原子比数であ
ればよく、ｘの値によって２００〜１５００の誘電率を
自由に選択することができる。高い比誘電率を得たい場
合にはＰｂ：Ｚｒ：Ｔｉ＝１：Ｏ．５２：０．４８の比
率で混合してやるのが望ましい。この混合物溶液にレジ
ン、セルロ−ス、スキ−ジメジウムなどの増粘剤、ある
いはタ−ピオネ−ルなどの希釈剤を用いて１０００〜１
００００ｃｐｓ程度に粘度調整し、レジネート（ＰＺＴ
強誘電体薄膜形成用材料）を製造する。EXAMPLES Next, examples of the method for manufacturing a PZT ferroelectric thin film of the present invention will be described. (1) Preparation of resinate Lead 2-ethylhexanoate, zirconium 2-ethylhexanoate, and titanium 2-ethylhexanoate are mixed in a desired atomic ratio. The mixing ratio is Pb:Zr:Ti=1
:x:1-x (0≦x≦1), and the dielectric constant can be freely selected from 200 to 1500 depending on the value of x. If you want to obtain a high dielectric constant, Pb:Zr:Ti=1:O. It is desirable to mix at a ratio of 52:0.48. Add a thickener such as resin, cellulose, or ski dimedium, or a diluent such as terpionaire to this mixture solution to
The viscosity was adjusted to about 0,000 cps, and resinate (PZT
ferroelectric thin film forming materials).
【０００９】（２）誘電体膜の形成
前記（１）で調整したレジネ−トを絶縁基板上に印刷し
て、ＰＺＴ強誘電体薄膜形成用材料層が形成された絶縁
基板を製造する。このＰＺＴ強誘電体薄膜形成用材料層
が形成された絶縁基板を焼成してＰＺＴ強誘電体薄膜を
形成する。焼成はベルト赤外炉を用いて８００゜Ｃで３
０分間行う。一回の印刷・焼成で得られる薄膜の厚みは
（１）のレジネ−トの粘度と、スクリ−ン印刷の版の種
類とエマルジョンの厚みを変化させることで自由に変え
ることが出来、一回の印刷・焼成で０．１〜２μｍの膜
厚が得られる。なお前記レジネートの印刷、焼成のプロ
セスを繰り返すことにより０．１〜１０μｍの膜厚のＰ
ＺＴ強誘電体薄膜を得ることができる。(2) Formation of dielectric film The resin prepared in (1) above is printed on an insulating substrate to produce an insulating substrate on which a layer of material for forming a PZT ferroelectric thin film is formed. The insulating substrate on which the PZT ferroelectric thin film forming material layer is formed is fired to form a PZT ferroelectric thin film. Firing was performed at 800°C using a belt infrared furnace.
Do this for 0 minutes. The thickness of the thin film obtained in one printing and firing process can be freely changed by changing the viscosity of the resin in (1), the type of screen printing plate, and the thickness of the emulsion. A film thickness of 0.1 to 2 μm can be obtained by printing and baking. By repeating the resin printing and firing process, P with a film thickness of 0.1 to 10 μm can be obtained.
A ZT ferroelectric thin film can be obtained.
【００１０】図１は、前記実施例のＰＺＴ強誘電体薄膜
形成用材料層の熱重量分析図である。この図１から、Ｐ
ＺＴ強誘電体薄膜が形成される温度（ＰＺＴ強誘電体薄
膜の結晶化温度）は５００゜Ｃ以上であり、５００゜Ｃ
以下では強誘電体薄膜の形成が困難であることがわかる
。したがって、前記焼成条件は５００゜Ｃ以上のピ−ク
温度で行う必要がある。前記実施例により製造された誘
電体体薄膜は図２に示すような誘電特性を持っており、
Ｚｒ：Ｔｉの比率が０．５２：０．４８付近で最大の誘
電率を示す。なお、前記誘電率の測定はＰＺＴ強誘電体
薄膜をＡｕ薄膜でサンドイッチし、２５゜Ｃで１ＭＨｚ
の周波数で測定した。FIG. 1 is a thermogravimetric analysis diagram of the PZT ferroelectric thin film forming material layer of the above example. From this figure 1, P
The temperature at which the ZT ferroelectric thin film is formed (crystallization temperature of the PZT ferroelectric thin film) is 500°C or higher, and 500°C
It can be seen below that it is difficult to form a ferroelectric thin film. Therefore, the firing conditions need to be a peak temperature of 500 DEG C. or higher. The dielectric thin film produced according to the above example has dielectric properties as shown in FIG.
The maximum dielectric constant is exhibited when the ratio of Zr:Ti is around 0.52:0.48. The dielectric constant was measured by sandwiching a PZT ferroelectric thin film with an Au thin film at 25°C and 1MHz.
Measured at the frequency of
【００１１】[0011]
【発明の効果】前述の本発明のＰＺＴ強誘電体薄膜の製
造方法によれば、製造設備が簡素な厚膜技術を用いて、
組成のコントロールされた優れた誘電特性を有するＰＺ
Ｔ強誘電体薄膜を容易に製造することができる。[Effects of the Invention] According to the method for manufacturing a PZT ferroelectric thin film of the present invention described above, thick film technology with simple manufacturing equipment is used, and
PZ with excellent dielectric properties with controlled composition
A T ferroelectric thin film can be easily manufactured.
【図１】 図１は、前記実施例のＰＺＴ強誘電体薄膜
形成用材料層の熱重量分析図である。FIG. 1 is a thermogravimetric analysis diagram of the PZT ferroelectric thin film forming material layer of the above example.
【図２】 図２は本発明のＰＺＴ強誘電体薄膜の製造
方法の−実施例により製造したＰＺＴ強誘電体薄膜の誘
電特性を示す図である。FIG. 2 is a diagram showing the dielectric properties of a PZT ferroelectric thin film manufactured by an example of the method for manufacturing a PZT ferroelectric thin film of the present invention.
Claims (1)
液とチタン化合物溶液の混合物に粘度調整剤を添加して
粘度調整したＰＺＴ強誘電体薄膜形成材料層が形成され
た耐熱基板耐熱基板を５００゜Ｃ以上で焼成することを
特徴とするＰＺＴ強誘電体薄膜の製造方法。Claim 1: A heat-resistant substrate on which a PZT ferroelectric thin film forming material layer is formed, the viscosity of which is adjusted by adding a viscosity modifier to a mixture of a lead compound solution, a zirconium compound solution, and a titanium compound solution, is heated to 500°C or higher. 1. A method for producing a PZT ferroelectric thin film, the method comprising firing the PZT ferroelectric thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3102034A JPH04308607A (en) | 1991-04-06 | 1991-04-06 | Manufacture of pzt ferroelectric thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3102034A JPH04308607A (en) | 1991-04-06 | 1991-04-06 | Manufacture of pzt ferroelectric thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04308607A true JPH04308607A (en) | 1992-10-30 |
Family
ID=14316482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3102034A Pending JPH04308607A (en) | 1991-04-06 | 1991-04-06 | Manufacture of pzt ferroelectric thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04308607A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003095651A (en) * | 2001-09-21 | 2003-04-03 | Ricoh Co Ltd | Precursor sol for forming dielectric film, method for preparing precursor sol, dielectric film and method for forming dielectric film |
| JP2008147682A (en) * | 2007-12-18 | 2008-06-26 | Seiko Epson Corp | Piezoelectric thin-film element and ink jet recording head |
-
1991
- 1991-04-06 JP JP3102034A patent/JPH04308607A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003095651A (en) * | 2001-09-21 | 2003-04-03 | Ricoh Co Ltd | Precursor sol for forming dielectric film, method for preparing precursor sol, dielectric film and method for forming dielectric film |
| JP2008147682A (en) * | 2007-12-18 | 2008-06-26 | Seiko Epson Corp | Piezoelectric thin-film element and ink jet recording head |
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