JP2008028381A - Method for manufacturing metal oxide film, laminated body and electronic device - Google Patents

Method for manufacturing metal oxide film, laminated body and electronic device Download PDF

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JP2008028381A
JP2008028381A JP2007161753A JP2007161753A JP2008028381A JP 2008028381 A JP2008028381 A JP 2008028381A JP 2007161753 A JP2007161753 A JP 2007161753A JP 2007161753 A JP2007161753 A JP 2007161753A JP 2008028381 A JP2008028381 A JP 2008028381A
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metal oxide
oxide film
film
metal
crystal plane
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JP5126950B2 (en
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Yuki Miyamoto
ゆき 宮本
Tetsuo Tsuchiya
哲男 土屋
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National Institute of Advanced Industrial Science and Technology AIST
TDK Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1283—Control of temperature, e.g. gradual temperature increase, modulation of temperature
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a metal oxide film which can produce the metal oxide film with sufficiently high crystalline orientation easily, at low cost, and almost without damaging the base material and metal oxide film, as well as to provide a laminated body and an electronic device. <P>SOLUTION: The manufacturing method includes a step of forming a metal film 14 having a crystalline plane (111) on a base material 10, a step of forming a metal oxide film 20 on a crystalline plane (111) of the metal film 14, and a step of irradiating ultraviolet rays to the metal oxide film 20 while keeping the temperature of the metal oxide film 20 formed on the crystalline plane (111) of the metal film 14 within the range from 25 to 600°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、金属酸化物膜の製造方法、積層体、及び、電子デバイスに関する。   The present invention relates to a method for manufacturing a metal oxide film, a laminate, and an electronic device.

従来より、電子デバイスの製造等においては、電極膜等の基材上に結晶配向度の高い金属酸化膜を形成することが求められている。金属酸化物としては、例えば、Ｂａ及びＴｉを含む金属酸化物（ＢａＴｉＯ３等）等が例示できる。 Conventionally, in the manufacture of electronic devices and the like, it is required to form a metal oxide film having a high degree of crystal orientation on a substrate such as an electrode film. Examples of the metal oxide include a metal oxide containing Ba and Ti (BaTiO 3 or the like).

基材上に結晶配向度の高い金属酸化物膜を形成する方法としては、単結晶基板上や、結晶配向度の高いバッファ膜や電極膜上に、金属酸化物膜をエピタキシャル成長させる方法（例えば特許文献１〜３、非特許文献１参照）が知られている。また、６００℃以上にされた基材上に金属酸化物をスパッタ法により成膜させる方法も知られている。さらに、ＣＶＤ法やゾルゲル法によって形成した非晶質の金属酸化膜に対して紫外線やレーザ光を照射して結晶化することも知られている（例えば、特許文献４〜６参照）。
特許３６０８４５９号公報 特許２８３４３５５号公報 特許２９１６１１６号公報 特開平６−１４０３８５号公報 特開平９−１５７８５５号公報 特開平５−２４７６５８号公報 J. Appl. Phys., Vol. 65, (1998), pp1666-1670 As a method of forming a metal oxide film having a high degree of crystal orientation on a substrate, a method of epitaxially growing a metal oxide film on a single crystal substrate, a buffer film or an electrode film having a high degree of crystal orientation (for example, a patent) Documents 1 to 3 and Non-Patent Document 1) are known. Also known is a method of forming a metal oxide film on a base material at 600 ° C. or higher by sputtering. Furthermore, it is also known to crystallize an amorphous metal oxide film formed by a CVD method or a sol-gel method by irradiating ultraviolet rays or laser light (for example, see Patent Documents 4 to 6).
Japanese Patent No. 36060859 Japanese Patent No. 2834355 Japanese Patent No. 2916116 JP-A-6-140385 JP-A-9-157855 JP-A-5-247658 J. Appl. Phys., Vol. 65, (1998), pp1666-1670

しかしながら、単結晶基板は高価であり、また、結晶配向度の高い電極膜やバッファ膜を得る事も困難であり、また、６００℃以上の高温下で基材上に金属酸化物を成膜すると基材の酸化や、基材と金属酸化物膜との熱膨張率の差等により基材及び金属酸化物膜を含む積層体にダメージを与えるおそれがあり、基材の選択の幅を狭めることでデバイスの可能性を小さくしてしまっている。さらに、非晶質の金属酸化物膜に紫外線やレーザ光を照射するだけでは、十分に結晶配向度の高い金属酸化物膜を得ることは困難である。   However, a single crystal substrate is expensive, and it is difficult to obtain an electrode film or a buffer film having a high degree of crystal orientation. Further, when a metal oxide is formed on a substrate at a high temperature of 600 ° C. or higher. There is a risk of damaging the laminate including the base material and the metal oxide film due to oxidation of the base material, difference in thermal expansion coefficient between the base material and the metal oxide film, etc., and narrowing the selection range of the base material Has reduced the potential of the device. Furthermore, it is difficult to obtain a metal oxide film having a sufficiently high degree of crystal orientation simply by irradiating an amorphous metal oxide film with ultraviolet rays or laser light.

本発明は上記課題に鑑みてなされたものであり、十分に結晶配向度の高い金属酸化物膜を、簡易、低コスト、かつ、基材及び金属酸化物膜に損傷を殆ど与えずに得ることが可能な金属酸化物膜の製造方法、積層体、及び電子デバイスを提供することを目的とする。   The present invention has been made in view of the above problems, and provides a metal oxide film having a sufficiently high degree of crystal orientation, which is simple, low cost, and hardly damages the substrate and the metal oxide film. An object of the present invention is to provide a method for manufacturing a metal oxide film, a laminate, and an electronic device.

本発明にかかる金属酸化物膜の製造方法は、基材上に（１１１）結晶面を有する金属膜を形成する工程と、金属膜の（１１１）結晶面上に金属酸化物膜を直接形成する工程と、金属酸化物膜の温度を２５〜６００℃に維持し、金属酸化物膜に対して紫外線を照射する工程と、を備える。   The method for producing a metal oxide film according to the present invention includes a step of forming a metal film having a (111) crystal plane on a substrate, and directly forming the metal oxide film on the (111) crystal plane of the metal film. And a step of maintaining the temperature of the metal oxide film at 25 to 600 ° C. and irradiating the metal oxide film with ultraviolet rays.

本発明によれば、基材の種類を問わず金属酸化物膜の結晶配向度を十分に高めることができる。また、温度がそれほど高くないので基材や金属酸化物膜に対して損傷を与えにくい。   According to the present invention, the degree of crystal orientation of the metal oxide film can be sufficiently increased regardless of the type of substrate. Further, since the temperature is not so high, the base material and the metal oxide film are hardly damaged.

ここで、金属酸化物膜がＢａ及びＴｉを含む金属酸化物膜であることが好ましい。特に、ペロブスカイト型金属酸化物膜であることが好ましい。この場合には、金属酸化物膜において、特に（１００）結晶面を膜面と平行に優先配向させることが可能である。   Here, the metal oxide film is preferably a metal oxide film containing Ba and Ti. In particular, a perovskite metal oxide film is preferable. In this case, in the metal oxide film, the (100) crystal plane can be preferentially oriented in parallel with the film plane.

また、紫外線の波長は、１００〜５００ｎｍであることが好ましい。また、紫外線はレーザ光であることが好ましい。特に紫外線が、パルスレーザ光であることが好ましい。   Moreover, it is preferable that the wavelength of an ultraviolet-ray is 100-500 nm. Moreover, it is preferable that an ultraviolet-ray is a laser beam. In particular, the ultraviolet light is preferably pulsed laser light.

そして、パルスレーザ光のエネルギーが、１パルスあたり４０〜４００ｍＪ／ｃｍ２、好ましくは、６０〜３００ｍＪ／ｃｍ２であることが好ましい。 And it is preferable that the energy of a pulse laser beam is 40-400 mJ / cm < 2 > per pulse, Preferably, it is 60-300 mJ / cm < 2 >.

また、パルスレーザ光のパルス周波数は１〜１０００Ｈｚ、好ましくは、１〜１００Ｈｚであることが好ましい。   The pulse frequency of the pulsed laser light is 1-1000 Hz, preferably 1-100 Hz.

本発明に係る積層体は、（１１１）結晶面を有する金属膜と、金属膜の（１１１）結晶面上に直接設けられた金属酸化物膜と、を備え、金属酸化物膜のＸ線回折チャートにおける（１００）結晶面の回折線のピーク強度をＩ（１００）とし、（１１０）結晶面の回折線のピーク強度をＩ（１１０）としたとき、ピーク強度比（Ｉ（１００）／Ｉ（１１０））が２以上、好ましくは２．１以上、より好ましくは２．２以上である。なお、上述のピーク強度比を結晶配向度Ｆとする。   The laminate according to the present invention includes a metal film having a (111) crystal plane and a metal oxide film provided directly on the (111) crystal plane of the metal film, and X-ray diffraction of the metal oxide film When the peak intensity of the diffraction line on the (100) crystal plane in the chart is I (100) and the peak intensity of the diffraction line on the (110) crystal plane is I (110), the peak intensity ratio (I (100) / I (110)) is 2 or more, preferably 2.1 or more, more preferably 2.2 or more. The above-described peak intensity ratio is defined as the degree of crystal orientation F.

このような積層体は上述の製造方法により容易に作製される。   Such a laminate is easily produced by the above-described manufacturing method.

ここで、金属酸化物膜はＢａ及びＴｉを含む金属酸化物膜であることが好ましい。   Here, the metal oxide film is preferably a metal oxide film containing Ba and Ti.

また、本発明に係る電子デバイスは、上述の積層体を有する電子デバイスである。   Moreover, the electronic device which concerns on this invention is an electronic device which has the above-mentioned laminated body.

本発明によれば、十分に結晶配向度の高い金属酸化物膜を、簡易、低コスト、かつ、基材に損傷を殆ど与えずに得ることが可能となる。   According to the present invention, a metal oxide film having a sufficiently high degree of crystal orientation can be obtained simply, at low cost, and with little damage to the substrate.

以下に、図１を参照しつつ、本実施形態に係る金属酸化物膜の製造方法、及び、積層体について説明する。   Below, the manufacturing method of the metal oxide film which concerns on this embodiment, and a laminated body are demonstrated, referring FIG.

まず、基材１０を用意する。基材１０は特に限定されず、単層基材でもよく、多層積層基材でもよい。例えば、単結晶材料、多結晶材料、非晶質材料等の基板が使用できる。基板の組成も特に限定されず、例えば、Ｓｉ、ＧａＡｓ、ＧａＰ、ＩｎＰ、ＳｉＣ等の半導体基板、ＳｉＯ２、Ａｌ２Ｏ３，ＭｇＯ，ＳｒＴｉＯ３等の金属酸化物基板、Ｃｕ，Ｎｉ等の金属基板、ＬＴＣＣ（Ｌｏｗ Ｔｅｍｐｅｒａｔｕｒｅ Ｃｏ−ｆｉｒｅｄ Ｃｅｒａｍｉｃｓ）、アルミナ等のセラミックス基板等が挙げられる。 First, the base material 10 is prepared. The base material 10 is not specifically limited, A single layer base material may be sufficient and a multilayer laminated base material may be sufficient. For example, a substrate made of a single crystal material, a polycrystalline material, an amorphous material, or the like can be used. The composition of the substrate is also not particularly limited. For example, a semiconductor substrate such as Si, GaAs, GaP, InP, or SiC, a metal oxide substrate such as SiO 2 , Al 2 O 3 , MgO, or SrTiO 3, or a metal such as Cu or Ni. Examples include substrates, LTCC (Low Temperature Co-fired Ceramics), ceramic substrates such as alumina, and the like.

また、このような基板に、ＭｇＯ、ＩＴＯ、ＺｎＯ、ＳｎＯ２等の金属酸化物膜、Ａｕ、Ｐｔ、Ａｇ、Ｉｒ、Ｒｕ、Ｃｏ、Ｎｉ、Ｆｅ、Ｃｕ、Ａｌ等の金属膜等の下地膜を１層又は複数層形成した基材１０も使用できる。これらの下地層は、基板自体の酸化や、スパッタ法等により容易に形成できる。 In addition, a base film such as a metal oxide film such as MgO, ITO, ZnO, SnO 2, a metal film such as Au, Pt, Ag, Ir, Ru, Co, Ni, Fe, Cu, Al, etc. It is also possible to use the base material 10 in which one or more layers are formed. These underlayers can be easily formed by oxidation of the substrate itself or sputtering.

具体的には、基材１０としては、例えば、図１に示すように、Ｓｉ等の半導体基板１１上に、バッファ膜として、ＳｉＯ２等の金属酸化物膜１２、及び、ＴｉＯ２等の金属酸化物膜１３を積層したものが好ましい。ＳｉＯ２膜は、Ｓｉ基板を酸化性雰囲気中で高温にすることにより形成できる。また、ＴｉＯ２膜はスパッタ等により形成できる。 Specifically, as the base material 10, for example, as shown in FIG. 1, a metal oxide film 12 such as SiO 2 and a metal such as TiO 2 as a buffer film on a semiconductor substrate 11 such as Si. What laminated | stacked the oxide film 13 is preferable. The SiO 2 film can be formed by raising the temperature of the Si substrate in an oxidizing atmosphere. The TiO 2 film can be formed by sputtering or the like.

続いて、基材１０の表面に、（１１１）結晶面が配向した金属膜１４を形成する。例えば、基材１０の表面に、スパッタ法等により、０．０１〜３０μｍ程度のＰｔ，Ｎｉ，Ｃｕ等の金属膜を形成すると、表面が（１１１）結晶面に配向した金属膜１４を容易に得ることができる。   Subsequently, a metal film 14 having a (111) crystal plane oriented is formed on the surface of the substrate 10. For example, when a metal film of Pt, Ni, Cu or the like of about 0.01 to 30 μm is formed on the surface of the base material 10 by sputtering or the like, the metal film 14 whose surface is oriented to the (111) crystal plane can be easily formed. Obtainable.

続いて、金属膜１４の（１１１）結晶面上に金属酸化物膜２０を直接形成する。金属酸化物の組成は特に限定されないが、例えば、チタン酸バリウム（ＢＴ）、チタン酸バリウムストロンチウム（ＢＳＴ）等のＢａ及びＴｉを含む金属酸化物が好ましい。   Subsequently, the metal oxide film 20 is directly formed on the (111) crystal plane of the metal film 14. The composition of the metal oxide is not particularly limited. For example, a metal oxide containing Ba and Ti such as barium titanate (BT) and barium strontium titanate (BST) is preferable.

金属酸化物膜２０を形成する方法は特に限定されない。例えば、いわゆる化学溶液法、すなわち、金属アルコキシド、金属有機酸塩や無機金属塩等を含む溶液を、例えば、スピンコート法等によって金属膜１４上に塗布し、乾燥により溶媒を蒸発させ、仮焼きにより金属アルコキシド、金属有機酸塩や無機金属塩等を分解することにより金属酸化物膜２０を作成することができる。原料となる金属化合物としては、金属アルコキシド（例えば、Ｔｉ（ＯＣ２Ｈ５）４、Ｂａ（ＯＣ２Ｈ５）２、Ｚｒ（ＯＣ２Ｈ５）４、Ｐｂ（ＯＣ２Ｈ５）２、Ｓｒ（ＯＣ２Ｈ５）２等）、有機酸金属塩（例えば、２−エチルヘキサン酸バリウム、２−エチルヘキサン酸ジルコニル、２−エチルヘキサン酸チタン、２−エチルヘキサン酸鉛、２−エチルヘキサン酸ストロンチウム等、ラウリン酸塩、アセチルアセトナート等）等が挙げられ、無機金属塩としては、金属硝酸塩（例えば、Ｂａ(ＮＯ３)２、Ｓｒ(ＮＯ３)２）、金属酢酸塩（例えば、Ｂａ(ＣＨ３ＣＯＯ)２・H２O、Ｐｂ（ＣＨ３ＣＯＯ））２・３H２O）、金属炭酸塩（ＢａＣＯ３、ＳｒＣＯ３）等が挙げられる。 The method for forming the metal oxide film 20 is not particularly limited. For example, a so-called chemical solution method, that is, a solution containing a metal alkoxide, a metal organic acid salt, an inorganic metal salt, or the like is applied onto the metal film 14 by, for example, a spin coating method, the solvent is evaporated by drying, and calcined Thus, the metal oxide film 20 can be formed by decomposing a metal alkoxide, a metal organic acid salt, an inorganic metal salt, or the like. As a metal compound used as a raw material, metal alkoxide (for example, Ti (OC 2 H 5 ) 4 , Ba (OC 2 H 5 ) 2 , Zr (OC 2 H 5 ) 4 , Pb (OC 2 H 5 ) 2 , Sr (OC 2 H 5) 2, etc.), an organic acid metal salt (e.g., barium 2-ethyl hexanoate, 2-ethylhexanoate, zirconyl 2-ethylhexanoate of titanium, lead 2-ethylhexanoate, 2-ethylhexanoic acid Strontium, laurate, acetylacetonate, etc.), and inorganic metal salts include metal nitrates (for example, Ba (NO 3 ) 2 , Sr (NO 3 ) 2 ), metal acetates (for example, Ba). (CH 3 COO) 2 .H 2 O, Pb (CH 3 COO)) 2 .3H 2 O), metal carbonates (BaCO 3 , SrCO 3 ) and the like.

また、金属酸化物膜２０を、金属酸化物をターゲットとしたスパッタリング法やＣＶＤ、レーザーアブレーション法等のいわゆる気相法により製造することもできる。この場合の成膜温度は室温〜５００℃が好ましい。   The metal oxide film 20 can also be manufactured by a so-called gas phase method such as sputtering, CVD, or laser ablation using a metal oxide as a target. In this case, the film forming temperature is preferably room temperature to 500 ° C.

金属酸化物膜２０の膜厚は、例えば、０．０１〜３０μｍとすることが好ましい。   The thickness of the metal oxide film 20 is preferably 0.01 to 30 μm, for example.

なお、上述のようにして形成された金属酸化物膜２０は結晶配向度が殆ど無い非晶質（アモルファス）状態か、あるいは、結晶配向度があってもその程度は極めて低く、各種電子デバイスの誘電体に対して要求される十分な比抵抗が通常発現しにくい。   Note that the metal oxide film 20 formed as described above is in an amorphous state having almost no crystal orientation, or even if there is a crystal orientation, the degree is extremely low. Sufficient specific resistance required for the dielectric is usually difficult to develop.

続いて、この金属酸化物膜２０を、２５〜６００℃程度、好ましくは、２５〜５００℃程度に維持し、その状態でこの金属酸化物膜２０に対して紫外線を照射する。紫外線の波長は、例えば、１００〜５００ｎｍ、好ましくは、１００〜４００ｎｍである。紫外線としては、ＡｒＦ（１９３ｎｍ）、ＸｅＣｌ（３０８ｎｍ）、ＫｒＦ（２４８ｎｍ）等のレーザ光であることが好ましい。また、レーザ光の中でも、パルスレーザ光が好ましい。１パルスあたりのエネルギーは、４０〜４００ｍＪ／ｃｍ２であることが好ましく、パルス周波数（１秒間に照射するパルスの数）は１〜１００Ｈｚ程度とすることが好ましい。なお、１パルスの照射時間は、例えば、１０〜１００ｎｓとすることができる。また、金属酸化物膜の各場所に対して照射する総パルス数は例えば、５〜５００００とすることができる。 Subsequently, the metal oxide film 20 is maintained at about 25 to 600 ° C., preferably about 25 to 500 ° C., and the metal oxide film 20 is irradiated with ultraviolet rays in this state. The wavelength of the ultraviolet light is, for example, 100 to 500 nm, preferably 100 to 400 nm. The ultraviolet light is preferably laser light such as ArF (193 nm), XeCl (308 nm), KrF (248 nm). Of the laser beams, pulsed laser beams are preferable. The energy per pulse is preferably 40 to 400 mJ / cm 2 , and the pulse frequency (number of pulses irradiated per second) is preferably about 1 to 100 Hz. In addition, the irradiation time of 1 pulse can be 10-100 ns, for example. Moreover, the total number of pulses irradiated with respect to each place of a metal oxide film can be 5-50000, for example.

具体的には、例えば、図２のような装置を用いることができる。加熱ステージ１１０上に基材１０を載せて基材１０上の金属酸化物膜２０を２５〜５００℃に維持し、この金属酸化物膜２０に対してレーザ光源２００からレーザ光を照射すればよい。   Specifically, for example, an apparatus as shown in FIG. 2 can be used. The base material 10 is placed on the heating stage 110 and the metal oxide film 20 on the base material 10 is maintained at 25 to 500 ° C., and laser light is irradiated from the laser light source 200 to the metal oxide film 20. .

なお、パルス光でなく連続光でも実施は可能であり、また、レーザ光でなくても水銀ランプ等の紫外線ランプの光を照射しても実施は可能である。また、図２以外の装置によって金属酸化物膜２０を加熱しても良いのは言うまでもない。   It should be noted that the present invention can be carried out using continuous light instead of pulsed light, and can also be carried out by irradiating light from an ultraviolet lamp such as a mercury lamp without using laser light. Needless to say, the metal oxide film 20 may be heated by an apparatus other than FIG.

そして、上述の温度条件下で、金属酸化物に対して紫外線を照射すると、金属酸化物膜２０の結晶配向度が顕著に向上する。   When the metal oxide is irradiated with ultraviolet rays under the above temperature conditions, the degree of crystal orientation of the metal oxide film 20 is significantly improved.

特に、金属膜１４の表面が（１１１）結晶面であり、この金属膜１４の（１１１）結晶面上に金属酸化物膜２０が直接形成されており、さらに、金属酸化物膜２０がＢａ及びＴｉを含む金属酸化物から形成された膜である場合には、上述の温度条件下での紫外線照射により、金属酸化物の（１００）結晶面を膜面と平行に特に優先配向させることができて特に好ましい。具体的には、金属酸化物膜２０のＸ線回折チャートにおける（１００）結晶面の回折線のピーク強度をＩ（１００）とし、（１１０）結晶面の回折線のピーク強度をＩ（１１０）としたとき、結晶配向度Ｆ、すなわち、ピーク強度比Ｆ＝（Ｉ（１００）／Ｉ（１１０））を２以上とすることが容易である。このような構造の金属膜１４及び金属酸化物膜２０を有する積層体５０は従来得られなかったものである。ここで、Ｘ線回折チャートにおける（１００）結晶面の回折線は擬立方晶として指数付けしたものであってよい。擬立方晶とは、例えば、（１００）結晶面と（００１）結晶面との格子定数の差が小さくなり、Ｘ線回折による解析では分離困難であることを意味する。金属膜１４の膜厚は、０．０１〜５００μｍ程度であることが好ましい。   In particular, the surface of the metal film 14 is a (111) crystal plane, the metal oxide film 20 is directly formed on the (111) crystal plane of the metal film 14, and the metal oxide film 20 further includes Ba and In the case of a film formed from a metal oxide containing Ti, the (100) crystal plane of the metal oxide can be particularly preferentially oriented parallel to the film plane by ultraviolet irradiation under the temperature conditions described above. It is particularly preferable. Specifically, the peak intensity of the diffraction line on the (100) crystal plane in the X-ray diffraction chart of the metal oxide film 20 is I (100), and the peak intensity of the diffraction line on the (110) crystal plane is I (110). In this case, it is easy to set the crystal orientation degree F, that is, the peak intensity ratio F = (I (100) / I (110)) to 2 or more. The laminate 50 having the metal film 14 and the metal oxide film 20 having such a structure has not been obtained conventionally. Here, the diffraction line of the (100) crystal plane in the X-ray diffraction chart may be indexed as a pseudo-cubic crystal. Pseudocubic means, for example, that the difference in lattice constant between the (100) crystal plane and the (001) crystal plane is small, and it is difficult to separate by analysis by X-ray diffraction. The film thickness of the metal film 14 is preferably about 0.01 to 500 μm.

また、上述のような金属酸化物膜の形成工程と、この金属酸化物膜を所定の温度に維持しつつ紫外線を照射する金属酸化物処理工程と、を含む一連の工程を複数回繰り返すことにより、図３に示すように結晶配向度の優れた金属酸化物膜２０を多数積層して比較的厚みのある金属酸化物膜２０Ａを形成してもよい。   In addition, by repeating a series of processes including the above-described metal oxide film forming process and the metal oxide treatment process of irradiating ultraviolet rays while maintaining the metal oxide film at a predetermined temperature, a plurality of times. As shown in FIG. 3, a relatively thick metal oxide film 20A may be formed by laminating a large number of metal oxide films 20 having excellent crystal orientation.

続いて、この様にして得られた金属酸化物膜を用いた電子デバイスの例として、誘電体膜として金属酸化物膜２０を含む薄膜コンデンサ素子１について、図４を参照して詳細に説明する。   Subsequently, as an example of an electronic device using the metal oxide film thus obtained, a thin film capacitor element 1 including a metal oxide film 20 as a dielectric film will be described in detail with reference to FIG. .

この薄膜コンデンサ素子１は、Ｓｉ等の基板１１上に、バッファ（密着）層として、ＳｉＯ２等の金属酸化物膜１２及びＴｉＯ２等の金属酸化物膜１３を形成し、Ａｕ、Ｐｔ、Ａｇ、Ｉｒ、Ｒｕ、Ｃｏ、Ｎｉ、Ｆｅ、Ｃｕ、Ａｌ等の金属膜（電極膜）１４を形成し、金属酸化物層２０又は２０Ａを形成し、さらに、金属酸化物膜２０又は２０Ａ上にさらに電極としての金属膜１４を形成したものである。 In this thin film capacitor element 1, a metal oxide film 12 such as SiO 2 and a metal oxide film 13 such as TiO 2 are formed as a buffer (adhesion) layer on a substrate 11 such as Si, and Au, Pt, Ag , Ir, Ru, Co, Ni, Fe, Cu, Al, or the like is formed, a metal oxide layer 20 or 20A is formed, and further on the metal oxide film 20 or 20A A metal film 14 is formed as an electrode.

基板１１の厚みは例えば０．１〜５ｍｍ、バッファ層の厚みは例えば５〜２０００ｎｍ、金属膜１４の厚みは例えば０．０１〜５００μｍ、金属酸化物膜２０又は２０Ａの厚みは例えば１００〜１０００ｎｍとすることができる。   The thickness of the substrate 11 is, for example, 0.1 to 5 mm, the thickness of the buffer layer is, for example, 5 to 2000 nm, the thickness of the metal film 14 is, for example, 0.01 to 500 μm, and the thickness of the metal oxide film 20 or 20A is, for example, 100 to 1000 nm. can do.

このような薄膜コンデンサ素子１においては、金属酸化物膜２０の結晶配向度が高いので、金属酸化物膜２０の膜厚が薄くても好適な性能を発揮し得る。なお、このような金属酸化物膜２０を一対の金属膜１４で挟んだ構造の積層体を有する電子デバイスは、薄膜コンデンサに限られず、ＦｅＲＡＭ、チューナブルフィルタ等のデバイスにも使用可能である。   In such a thin film capacitor element 1, since the crystal orientation degree of the metal oxide film 20 is high, suitable performance can be exhibited even if the metal oxide film 20 is thin. Note that an electronic device having a stacked structure in which such a metal oxide film 20 is sandwiched between a pair of metal films 14 is not limited to a thin film capacitor, and can be used for devices such as FeRAMs and tunable filters.

次に、具体的な実施例を示し更に詳細に本願発明について説明する。なお、本願発明は以下の実施例に限定されるものではない。   Next, the present invention will be described in more detail by showing specific examples. The present invention is not limited to the following examples.

（実施例１）
まず基材を用意した。まず、表面に熱酸化膜が５００ｎｍ形成された多結晶のＳｉ基板上にスパッタ法によりＴｉＯ２膜を２０ｎｍ形成し、さらに、ＴｉＯ２膜上にスパッタ法によりＰｔ膜を２００ｎｍ形成した。Ｐｔ膜の表面は（１１１）結晶面に配向していた。 (Example 1)
First, a substrate was prepared. First, a 20 nm TiO 2 film was formed by sputtering on a polycrystalline Si substrate having a thermal oxide film of 500 nm formed on the surface, and a 200 nm Pt film was further formed by sputtering on the TiO 2 film. The surface of the Pt film was oriented in the (111) crystal plane.

続いて、７ｗｔ％のチタン酸バリウム膜形成用のチタン、及び、バリウムを含む金属化合物原料液を、スピンコータ（３０００ｒｐｍ、１５ｓｅｃ）でＰｔ膜上に塗布し、ホットプレート上で１５０℃１０分間乾燥させ、その後、ホットプレートで４００℃１０分間仮焼きを行ってＰｔ膜上にほぼ非晶質のチタン酸バリウム膜（膜厚約１１０ｎｍ）を金属酸化物膜として形成した。   Subsequently, a titanium compound for forming a 7 wt% barium titanate film and a metal compound raw material liquid containing barium were applied onto the Pt film with a spin coater (3000 rpm, 15 sec), and dried on a hot plate at 150 ° C. for 10 minutes. Thereafter, calcination was performed at 400 ° C. for 10 minutes on a hot plate to form a substantially amorphous barium titanate film (thickness: about 110 nm) as a metal oxide film on the Pt film.

続いて、ホットプレート上で金属酸化物膜を４００℃に維持しながら、ＫｒＦパルスレーザ源から、１パルスあたりの照射エネルギーが７０ｍＪ／ｃｍ２、合計パルス数が１０００、パルス周波数（１秒間に照射されるパルスの数）が１０Ｈｚとなるように紫外線パルスレーザを各場所に照射し、その後金属酸化物膜を常温に戻した。 Subsequently, while maintaining the metal oxide film at 400 ° C. on the hot plate, the irradiation energy per pulse is 70 mJ / cm 2 , the total number of pulses is 1000, and the pulse frequency (irradiated for 1 second) from the KrF pulse laser source. Each position was irradiated with an ultraviolet pulse laser so that the number of applied pulses was 10 Hz, and then the metal oxide film was returned to room temperature.

（実施例２〜５）
実施例２〜５では、合計パルス数をそれぞれ２０００，３０００，４０００，６０００とする以外は実施例１と同様とした。 (Examples 2 to 5)
Examples 2 to 5 were the same as Example 1 except that the total number of pulses was 2000, 3000, 4000, and 6000, respectively.

（実施例６〜７）
実施例６〜７では、金属酸化物膜として、チタン酸バリウム膜に代えて、（Ｂａ，Ｓｒ）ＴｉＯ３膜（膜厚約１２０ｎｍ）を形成し、金属酸化物膜のレーザ照射時の温度を３００℃とし、紫外線パルスレーザのパルス周波数を３０Ｈｚとし、１パルスのエネルギーを実施例６では８０ｍＪ／ｃｍ２とし実施例７では９０ｍＪ／ｃｍ２とする以外はそれぞれ実施例１と同様とした。なお、金属酸化物膜におけるＢａとＳｒとの元素モル比は７：３である。 (Examples 6 to 7)
In Examples 6 to 7, instead of the barium titanate film, a (Ba, Sr) TiO 3 film (film thickness of about 120 nm) is formed as the metal oxide film, and the temperature of the metal oxide film during laser irradiation is set. and 300 ° C., the pulse frequency of the pulsed ultraviolet laser as a 30 Hz, except that the energy of one pulse as in example 80 mJ / cm 2 in 6 and 90 mJ / cm 2 in example 7 was the same as each example 1. The element molar ratio of Ba and Sr in the metal oxide film is 7: 3.

（実施例８）
実施例８では、金属酸化物膜の形成及び当該金属酸化物に対する所定温度条件下での紫外線照射処理を含む工程を合計２回繰り返す以外は実施例１と同様にした。 (Example 8)
Example 8 was the same as Example 1 except that the process including the formation of the metal oxide film and the ultraviolet irradiation treatment under a predetermined temperature condition for the metal oxide was repeated a total of two times.

（比較例１）
紫外線照射をせずに、仮焼き後にさらに、８００℃で金属酸化物膜の焼成を行った以外は実施例１と同様にして金属酸化物膜を得た。 (Comparative Example 1)
A metal oxide film was obtained in the same manner as in Example 1 except that the metal oxide film was further baked at 800 ° C. after calcination without ultraviolet irradiation.

図６に実施例１〜５における金属酸化物膜のＸ線回折チャートを、図７に実施例６〜７における金属酸化物膜のＸ線回折チャートを、図８に実施例８における金属酸化物膜のＸ線回折チャートを、図９に比較例３における金属酸化物膜のＸ線回折チャートを図示する。   6 shows an X-ray diffraction chart of the metal oxide film in Examples 1 to 5, FIG. 7 shows an X-ray diffraction chart of the metal oxide film in Examples 6 to 7, and FIG. 8 shows a metal oxide film in Example 8. The X-ray diffraction chart of the film is shown in FIG. 9, and the X-ray diffraction chart of the metal oxide film in Comparative Example 3 is shown in FIG.

実施例１〜８においては、金属酸化物膜がＸ線回折チャートにおいて（１００）の十分な結晶配向を有することがわかった。一方、比較例１においては、（１００）の結晶配向はほとんど認められなかった。   In Examples 1 to 8, it was found that the metal oxide film had a sufficient crystal orientation of (100) in the X-ray diffraction chart. On the other hand, in Comparative Example 1, almost no (100) crystal orientation was observed.

図１は、本発明の実施形態に係る金属酸化物膜の製造方法を説明するための概略断面図である。FIG. 1 is a schematic cross-sectional view for explaining a method for producing a metal oxide film according to an embodiment of the present invention. 図２は、本発明の実施形態に係る金属酸化物膜の製造方法を説明するための図１に続く概略断面図である。FIG. 2 is a schematic cross-sectional view subsequent to FIG. 1 for explaining the metal oxide film manufacturing method according to the embodiment of the present invention. 図３は、本発明の実施形態に係る金属酸化物膜の製造方法を説明するための概略断面図である。FIG. 3 is a schematic cross-sectional view for explaining a method for producing a metal oxide film according to an embodiment of the present invention. 図４は、本発明の実施形態に係る電子デバイスを説明するための概略断面図である。FIG. 4 is a schematic cross-sectional view for explaining an electronic device according to an embodiment of the present invention. 図５は、実施例１〜８及び比較例１の金属酸化物膜の製造方法及びその結果を示す表である。FIG. 5 is a table showing methods for producing metal oxide films of Examples 1 to 8 and Comparative Example 1 and results thereof. 図６は、実施例１〜５における金属酸化物膜のＸ線回折チャートである。FIG. 6 is an X-ray diffraction chart of the metal oxide films in Examples 1 to 5. 図７は、実施例６〜７における金属酸化物膜のＸ線回折チャートである。FIG. 7 is an X-ray diffraction chart of the metal oxide films in Examples 6-7. 図８は、実施例８における金属酸化物膜のＸ線回折チャートである。FIG. 8 is an X-ray diffraction chart of the metal oxide film in Example 8. 図９は、比較例１における金属酸化物膜のＸ線回折チャートである。FIG. 9 is an X-ray diffraction chart of the metal oxide film in Comparative Example 1.

符号の説明Explanation of symbols

１…薄膜コンデンサ素子（電子デバイス）、１０…基材、２０…金属酸化物膜、１４…金属膜、５０…積層体。   DESCRIPTION OF SYMBOLS 1 ... Thin film capacitor element (electronic device), 10 ... Base material, 20 ... Metal oxide film, 14 ... Metal film, 50 ... Laminated body.

Claims (10)

基材上に、（１１１）結晶面を有する金属膜を形成する工程と、
前記金属膜の（１１１）結晶面上に金属酸化物膜を直接形成する工程と、
前記金属酸化物膜の温度を２５〜６００℃に維持し、前記金属酸化物膜に対して紫外線を照射する工程と、を備える金属酸化物膜の製造方法。 Forming a metal film having a (111) crystal plane on a substrate;
Forming a metal oxide film directly on the (111) crystal plane of the metal film;
Maintaining the temperature of the metal oxide film at 25 to 600 ° C., and irradiating the metal oxide film with ultraviolet rays. 前記金属酸化物膜はＢａ及びＴｉを含む金属酸化物である請求項１に記載の金属酸化物膜の製造方法。   The method of manufacturing a metal oxide film according to claim 1, wherein the metal oxide film is a metal oxide containing Ba and Ti. 前記紫外線の波長は、１００〜５００ｎｍである請求項１又は２記載の金属酸化物膜の製造方法。   The method for producing a metal oxide film according to claim 1 or 2, wherein the wavelength of the ultraviolet light is 100 to 500 nm. 前記紫外線はレーザ光である請求項１〜３のいずれかに記載の金属酸化物膜の製造方法。   The method for producing a metal oxide film according to claim 1, wherein the ultraviolet light is laser light. 前記レーザ光はパルスレーザ光である請求項４に記載の金属酸化物膜の製造方法。   The method for producing a metal oxide film according to claim 4, wherein the laser beam is a pulsed laser beam. 前記パルスレーザ光のエネルギーは、１パルスあたり４０〜４００ｍＪ／ｃｍ２である請求項５に記載の金属酸化物膜の製造方法。 The method for producing a metal oxide film according to claim 5, wherein the energy of the pulse laser beam is 40 to 400 mJ / cm 2 per pulse. 前記パルスレーザ光のパルス周波数は１〜１０００Ｈｚである請求項５又は６に記載の金属酸化物膜の製造方法。   The method of manufacturing a metal oxide film according to claim 5 or 6, wherein a pulse frequency of the pulse laser beam is 1-1000 Hz. （１１１）結晶面を有する金属膜と、
前記金属膜の（１１１）結晶面上に直接設けられた金属酸化物膜と、を備え、
前記金属酸化物膜のＸ線回折チャートにおける（１００）結晶面の回折線のピーク強度をＩ（１００）とし、（１１０）結晶面の回折線のピーク強度をＩ（１１０）としたとき、ピーク強度比（Ｉ（１００）／Ｉ（１１０））が２以上である積層体。 A metal film having a (111) crystal plane;
A metal oxide film provided directly on the (111) crystal plane of the metal film,
The peak intensity of the diffraction line on the (100) crystal plane in the X-ray diffraction chart of the metal oxide film is I (100), and the peak intensity of the diffraction line on the (110) crystal plane is I (110). A laminate having an intensity ratio (I (100) / I (110)) of 2 or more. 前記金属酸化物はＢａ及びＴｉを含む金属酸化物である請求項８に記載の積層体。   The laminate according to claim 8, wherein the metal oxide is a metal oxide containing Ba and Ti. 請求項８又は９の積層体を有する電子デバイス。   An electronic device having the laminate according to claim 8.
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