JP2000256862A - Production of composite oxidized film - Google Patents
Production of composite oxidized filmInfo
- Publication number
- JP2000256862A JP2000256862A JP11063295A JP6329599A JP2000256862A JP 2000256862 A JP2000256862 A JP 2000256862A JP 11063295 A JP11063295 A JP 11063295A JP 6329599 A JP6329599 A JP 6329599A JP 2000256862 A JP2000256862 A JP 2000256862A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- film
- light
- composite oxide
- excimer laser
- 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
- 239000002131 composite material Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000010409 thin film Substances 0.000 claims abstract description 56
- 238000000576 coating method Methods 0.000 claims abstract description 51
- 239000011248 coating agent Substances 0.000 claims abstract description 50
- 239000010408 film Substances 0.000 claims abstract description 41
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 28
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 25
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 229910052788 barium Inorganic materials 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 230000001678 irradiating effect Effects 0.000 claims abstract description 8
- 150000003138 primary alcohols Chemical class 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 150000004703 alkoxides Chemical class 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 11
- 150000007942 carboxylates Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910018663 Mn O Inorganic materials 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 22
- 238000010438 heat treatment Methods 0.000 abstract description 14
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 40
- 239000011572 manganese Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 3
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 3
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- OHULXNKDWPTSBI-UHFFFAOYSA-N strontium;propan-2-olate Chemical compound [Sr+2].CC(C)[O-].CC(C)[O-] OHULXNKDWPTSBI-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- -1 alkali metal alkoxide Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- BHVPEUGTPDJECS-UHFFFAOYSA-L manganese(2+);diformate Chemical compound [Mn+2].[O-]C=O.[O-]C=O BHVPEUGTPDJECS-UHFFFAOYSA-L 0.000 description 1
- ZGIHUCQOMWIMKH-UHFFFAOYSA-L manganese(2+);propanoate Chemical compound [Mn+2].CCC([O-])=O.CCC([O-])=O ZGIHUCQOMWIMKH-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YTBRWVXQNMQQTK-UHFFFAOYSA-N strontium;ethanolate Chemical compound CCO[Sr]OCC YTBRWVXQNMQQTK-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Chemically Coating (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、複数種類の元素
の複合酸化物、特に、Ｌａの酸化物とＣａ、Ｓｒもしく
はＢａの酸化物とＭｎの酸化物とから構成される複合酸
化物の薄膜を製造する複合酸化物膜の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite oxide of a plurality of elements, and more particularly to a thin film of a composite oxide composed of an oxide of La and an oxide of Ca, Sr or Ba and an oxide of Mn. And a method for producing a composite oxide film.
【０００２】[0002]
【従来の技術】希土類元素の酸化物、アルカリ土類金属
の酸化物、および、遷移金属のうち特定の元素の酸化物
から構成される複合酸化物には、導電性や磁気抵抗特性
などの各種の機能性を有する多くの物質が存在する。そ
の代表的な例の１つとして、（Ｌａ１−ｘＭｘ）ＭｎＯ
３−δ（Ｍ：Ｃａ，Ｓｒ，Ｂａ、０．０９≦ｘ≦０．５
０）の組成式で表されるペロブスカイト型構造を有する
複合酸化物があり、それが持つ導電性および磁気抵抗特
性を利用して、固体電解質燃料電池の電極や冷陰極管等
の電子放出用電極の材料、磁気センサや磁気抵抗ヘッド
の磁性薄膜の材料などへの応用が試みられている。この
複合酸化物のバルク体や薄膜は、従来、各種の方法によ
り製造されている。2. Description of the Related Art Oxides of rare earth elements, oxides of alkaline earth metals, and composite oxides composed of oxides of specific elements among transition metals include various oxides such as conductivity and magnetoresistance. There are many substances having the functionality of One of the representative examples is (La 1-x M x ) MnO.
3-δ (M: Ca, Sr, Ba, 0.09 ≦ x ≦ 0.5
There is a composite oxide having a perovskite structure represented by the composition formula of 0), and by utilizing the conductivity and magnetoresistance characteristics of the composite oxide, an electron emission electrode such as an electrode of a solid electrolyte fuel cell or a cold cathode tube. Of materials for magnetic sensors, magnetic thin films of magnetic sensors and magnetoresistive heads, and the like. Conventionally, bulk bodies and thin films of this composite oxide have been produced by various methods.
【０００３】例えば、バルク体の製造方法として、特開
平７−１９６３６７号公報、特開平７−２１５７６４号
公報等には、（Ｌａ１−ｘＳｒｘ）ＭｎＯ３（０．０５
≦ｘ≦０．５）を主成分とするセラミックス粉末を成形
し焼成して、固相法により導電性セラミック焼結体を製
造する方法が開示されている。特開平８−１３３８９５
号公報には、Ｌａ、ＳｒおよびＭｎを、特開平９−２６
３４９５号公報には、Ｎｄ、ＳｒおよびＭｎとＬａまた
はＰｒとを、それぞれ、酸化物または加熱により酸化物
に変換可能な化合物の形で所定の原子比となる割合で混
合し、この混合物を焼結した後、得られた焼結体を溶融
状態からフローティングゾーン法で結晶成長させること
により、一般式（Ｌａ１−ｘＳｒｘ）ＭｎＯ３（ｘ＝
０．１６８〜０．１７８）および一般式（Ｎｄ１−ｘＭ
ｘ）１−ｙＳｒｙＭｎＯ３（Ｍ：Ｌａ，Ｐｒ、０．２５
≦ｘ≦０．６、０．４≦ｙ≦０．６）でそれぞれ表され
る組成のペロブスカイト型構造をもつ無粒界型マンガン
酸化物結晶体を得る方法が開示されている。また、特開
平８−２２２１２７号公報には、Ｌａ、ＳｒおよびＭｎ
の各硝酸塩の水溶液に焼結用（Ｌａ１−ｘＳｒｘ）Ｍｎ
Ｏ３ 粉末を混ぜた原料混合物を作成し、この原料混合
物を予備加熱した後、原料混合物を粉砕、混合し、その
後加圧成形して未焼結電極を形成し、その未焼結電極を
さらに焼結させることにより、酸化物電極焼結体を製造
する方法が開示されている。[0003] For example, as a manufacturing method for bulk body, JP-A-7-196367 and JP-A Hei 7-215764 discloses such, (La 1-x Sr x ) MnO 3 (0.05
A method is disclosed in which a ceramic powder mainly composed of (≦ x ≦ 0.5) is molded and fired to produce a conductive ceramic sintered body by a solid phase method. JP-A-8-133895
Japanese Patent Laid-Open No. 9-26 describes La, Sr and Mn.
Japanese Patent No. 3495 discloses that Nd, Sr and Mn and La or Pr are mixed at a predetermined atomic ratio in the form of an oxide or a compound which can be converted to an oxide by heating, and the mixture is calcined. After sintering, the obtained sintered body is crystal-grown from a molten state by a floating zone method to obtain a general formula (La 1-x Sr x ) MnO 3 (x =
0.168 to 0.178) and the general formula (Nd 1-x M
x) 1-y Sr y MnO 3 (M: La, Pr, 0.25
≤ x ≤ 0.6 and 0.4 ≤ y ≤ 0.6) are disclosed, which provide a method for obtaining a grain-free manganese oxide crystal having a perovskite structure having a composition represented by each of the following formulas. Japanese Patent Application Laid-Open No. 8-222127 discloses La, Sr and Mn.
Sintering the aqueous solutions of nitrates of (La 1-x Sr x) Mn
A raw material mixture in which O 3 powder is mixed is prepared, and after preheating the raw material mixture, the raw material mixture is pulverized and mixed, and then pressure-formed to form a green electrode. A method for producing a sintered oxide electrode by sintering is disclosed.
【０００４】また、薄膜の製造方法として、特開平７−
１９３２９８号公報等には、スパッタ法やアブレージョ
ン法により組成がＸＭｎＯｙ（Ｘ：Ｌａ，Ｃａ，Ｓｒ，
Ｂａ、２≦ｙ≦３．５）である膜を基板上に形成する方
法が開示されている。特開平８−２９３４２６号公報に
は、金属原料として、Ｌａ、ＣａおよびＳｒの各アルコ
キシドとＭｎのカルボン酸塩、もしくは、Ｌａ、Ｃａお
よびＳｒの各カルボン酸塩とＭｎのアルコキシド、また
は、Ｌａ、ＣａおよびＳｒの各アセチルアセトン塩とＭ
ｎのアルコキシドもしくはカルボン酸塩とを使用し、有
機溶媒中で金属（Ｌａ，Ｃａ，Ｓｒ，Ｍｎ）−酸素結合
を有する前駆体溶液を調製して、その前駆体溶液を基板
上に塗布した後、６００℃〜９００℃の温度で熱処理を
行うことにより、プロブスカイト型構造を有する（Ｌａ
１−ｘ−ｙＣａｘＳｒｙ）ＭｎＯ ３＋δ（０≦ｘ≦０．
４、０≦ｙ≦０．４）の酸化物薄膜を製造する方法が開
示されている。また、特開平９−５９０２２号公報に
は、金属Ａ（Ａ：Ｌａ，Ｐｒ，Ｃａ，Ｓｒ）のアルコキ
シドとＭｎのアルコキシドもしくはアセチルアセトン塩
との有機溶媒溶液、または、その溶液に所定の割合の水
を添加して部分加水分解した溶液を基板に塗布した後、
乾燥させ、８００℃程度の温度で焼成することにより、
一般式ＡＭｎＯ３で示されるＭｎ系ペロブスカイト型酸
化物の薄膜を製造する方法が開示されている。As a method for producing a thin film, Japanese Patent Laid-Open No.
No. 193298 discloses a sputtering method and an abrasion method.
XMnOy (X: La, Ca, Sr,
Ba, a film that satisfies 2 ≦ y ≦ 3.5) on a substrate
A law is disclosed. Japanese Patent Application Laid-Open No. 8-293426
Are the respective metals of La, Ca and Sr as metal raw materials.
Carboxylates of oxide and Mn, or La, Ca and
And each carboxylate of Sr and an alkoxide of Mn,
Represents the acetylacetone salts of La, Ca and Sr and M
n alkoxide or carboxylate
(La, Ca, Sr, Mn) -oxygen bond in organic solvent
A precursor solution having the formula:
After applying on top, heat treatment at a temperature of 600 to 900 ° C
By doing so, it has a proovskite structure (La
1-xyCaxSry) MnO 3 + δ(0 ≦ x ≦ 0.
4,0 ≦ y ≦ 0.4)
It is shown. Also, Japanese Patent Application Laid-Open No. 9-59022 discloses
Is the alkoxide of metal A (A: La, Pr, Ca, Sr)
Alkoxide or acetylacetone salt of Sid and Mn
With an organic solvent solution, or a predetermined proportion of water in the solution
After applying the partially hydrolyzed solution to the substrate,
By drying and firing at a temperature of about 800 ° C,
General formula AMnO3Mn-based perovskite acid represented by
A method for producing a thin film of a nitride is disclosed.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、特開平
７−１９６３６７号公報、特開平７−２１５７６４号公
報等に開示された固相法では、セラミックス粉末を成形
した後に１，３００℃〜１，６００℃といった高温での
加熱処理が必要である。また、特開平８−１３３８９５
号、特開平９−２６３４９５号公報等に開示されたフロ
ーティングゾーン法でも、固相法で焼結体を作成した後
に、焼結体を単結晶化する必要がある。特開平８−２２
２１２７号公報に開示された方法でも、未焼結体を焼結
させるのに、８００℃程度の温度での加熱処理が必要で
ある。However, according to the solid-phase method disclosed in Japanese Patent Application Laid-Open Nos. 7-196367 and 7-215764, after the ceramic powder is formed, the temperature is raised from 1,300 ° C. to 1,600 ° C. Heat treatment at a high temperature such as ° C is required. Also, JP-A-8-133895
Also, in the floating zone method disclosed in Japanese Patent Application Laid-Open No. 9-263495, it is necessary to produce a sintered body by a solid-phase method and then to monocrystallize the sintered body. JP-A-8-22
Even in the method disclosed in Japanese Patent No. 2127, a heat treatment at a temperature of about 800 ° C. is required to sinter the green body.
【０００６】特開平７−１９３２９８号公報等に開示さ
れているように、スパッタ法やアブレージョン法により
基板上に複合酸化物の薄膜を形成する方法では、焼結体
であるターゲットが必要であり、そのターゲットを得る
過程において、上記と同様の問題点がある。また、これ
らの方法では、真空プロセスで処理が行われるため、大
掛かりな装置が必要になる、といった問題点もある。As disclosed in Japanese Patent Application Laid-Open No. 7-193298, a method of forming a thin film of a composite oxide on a substrate by a sputtering method or an abrasion method requires a target that is a sintered body. In the process of obtaining the target, there are similar problems as described above. In addition, in these methods, since processing is performed in a vacuum process, there is a problem that a large-scale apparatus is required.
【０００７】また、特開平８−２９３４２６号公報、特
開平９−５９０２２号等に開示されたアルコキシド法で
も、前駆体溶液を基板上に塗布して成膜した後に、６０
０℃〜９００℃の温度で熱処理を行う必要がある。In the alkoxide method disclosed in Japanese Patent Application Laid-Open Nos. 8-293426 and 9-59022, a precursor solution is coated on a substrate to form a film.
It is necessary to perform the heat treatment at a temperature of 0 ° C to 900 ° C.
【０００８】上記したように、従来のいずれの方法で
も、高温での加熱処理が必要であり、このため、従来の
方法によっては、プラスチックスなどのような耐熱性の
低い基体上に、（Ｌａ１−ｘＭｘ）ＭｎＯ３−δ（Ｍ：
Ｃａ，Ｓｒ，Ｂａ、０．０９≦ｘ≦０．５０）の組成式
で表されるペロブスカイト型構造を有する複合酸化物の
薄膜を形成することができなかった。[0008] As described above, any of the conventional methods requires heat treatment at a high temperature. For this reason, depending on the conventional method, (La) may be formed on a substrate having low heat resistance such as plastics. 1-x M x) MnO 3 -δ (M:
(Ca, Sr, Ba, 0.09 ≦ x ≦ 0.50) A thin film of a composite oxide having a perovskite structure represented by a composition formula of 0.09 ≦ x ≦ 0.50 could not be formed.
【０００９】この発明は、以上のような事情に鑑みてな
されたものであり、高温での加熱処理を行わなくても複
合酸化物の薄膜を得ることができる複合酸化物膜の製造
方法を提供することを目的とする。The present invention has been made in view of the above circumstances, and provides a method of manufacturing a composite oxide film that can obtain a composite oxide thin film without performing heat treatment at a high temperature. The purpose is to do.
【００１０】[0010]
【課題を解決するための手段】請求項１に係る発明は、
Ｌａ、ＭｎおよびＣａ、ＳｒもしくはＢａの各酸化物の
原料成分を含む前駆体塗布液を被塗布物の表面に塗布し
て成膜した後、被塗布物表面に形成された薄膜を結晶化
させて、組成式（Ｌａ１−ｘＭｘ）ＭｎＯ３− δ（Ｍ：
Ｃａ，Ｓｒ，Ｂａ、０．０９≦ｘ≦０．５０）で表され
るペロブスカイト型構造を有する複合酸化物の薄膜を形
成する複合酸化物膜の製造方法において、前記前駆体塗
布液を被塗布物の表面に塗布して成膜した後、被塗布物
表面に形成された薄膜に対し波長が３６０ｎｍ以下であ
る光を照射して薄膜を結晶化させることを特徴とする。The invention according to claim 1 is
After applying a precursor coating solution containing the raw material components of La, Mn and Ca, Sr or Ba oxide to the surface of the object to be coated to form a film, the thin film formed on the surface of the object is crystallized. The composition formula (La 1-x M x ) MnO 3- δ (M:
(Ca, Sr, Ba, 0.09 ≦ x ≦ 0.50) In the method for producing a composite oxide film having a perovskite structure represented by the following formula, the precursor coating solution is applied. The method is characterized in that a thin film formed on a surface of an object is irradiated with light having a wavelength of 360 nm or less, and then the thin film is crystallized after being applied to the surface of the object to form a film.
【００１１】請求項２に係る発明は、請求項１記載の製
造方法において、被塗布物の表面に形成された薄膜に対
して光を照射する光源として、ＡｒＦエキシマレーザ、
ＫｒＦエキシマレーザ、ＸｅＣｌエキシマレーザ、Ｘｅ
Ｆエキシマレーザ、ＹＡＧレーザの３倍波光またはＹＡ
Ｇレーザの４倍波光を用いることを特徴とする。According to a second aspect of the present invention, in the manufacturing method of the first aspect, an ArF excimer laser is used as a light source for irradiating light to a thin film formed on the surface of the object.
KrF excimer laser, XeCl excimer laser, Xe
F excimer laser, third harmonic of YAG laser or YA
It is characterized by using fourth harmonic light of a G laser.
【００１２】請求項３に係る発明は、請求項１または請
求項２記載の製造方法において、Ｌａのアルカノールア
ミン配位化合物と、Ｍｎのカルボン酸塩と、Ｍの金属ま
たはアルコキシドとを、炭素数が１〜４である一級アル
コール中で混合させ反応させて、被塗布物の表面に塗布
される前駆体塗布液を調製することを特徴とする。According to a third aspect of the present invention, in the method according to the first or second aspect, the alkanolamine coordination compound of La, the carboxylate of Mn, and the metal or alkoxide of M are used. Are mixed and reacted in a primary alcohol having 1 to 4 to prepare a precursor coating solution to be coated on the surface of the object to be coated.
【００１３】請求項１に係る発明の製造方法によると、
Ｌａ、ＭｎおよびＣａ、ＳｒもしくはＢａの各酸化物の
原料成分を含む前駆体塗布液を被塗布物の表面に塗布し
て成膜した後、被塗布物上の薄膜に対し波長が３６０ｎ
ｍ以下である光を照射することにより、光を薄膜が吸収
してそのエネルギーで複合酸化物が結晶化される。した
がって、複合酸化物の結晶化のために高温での加熱処理
を行う必要が無いので、プラスチックスのような耐熱性
の低い基体上に、組成式（Ｌａ１−ｘＭｘ）ＭｎＯ
３−δ（Ｍ：Ｃａ，Ｓｒ，Ｂａ、０．０９≦ｘ≦０．５
０）で表されるペロブスカイト型構造を有する複合酸化
物の薄膜を形成することも可能になる。According to the manufacturing method of the first aspect,
A precursor coating solution containing the raw material components of La, Mn, and each oxide of Ca, Sr or Ba is applied to the surface of the object to form a film, and the wavelength of the thin film on the object is 360 n.
By irradiating light of m or less, the light is absorbed by the thin film, and the composite oxide is crystallized by the energy. Therefore, since it is not necessary to perform heat treatment at a high temperature for crystallization of the composite oxide, the composition formula (La 1−x M x ) MnO 2 is formed on a substrate having low heat resistance such as plastics.
3-δ (M: Ca, Sr, Ba, 0.09 ≦ x ≦ 0.5
It is also possible to form a composite oxide thin film having a perovskite structure represented by 0).
【００１４】請求項３に係る発明の製造方法によると、
Ｌａ、ＭｎおよびＣａ、ＳｒもしくはＢａの各酸化物の
原料成分の濃度が高く安定性に優れ純度の高い前駆体塗
布液が調製され、その前駆体塗布液を使用して複合酸化
物の薄膜が形成される。According to the manufacturing method of the third aspect of the present invention,
A precursor coating solution having a high concentration of the raw material components of La, Mn and Ca, Sr or Ba oxides with high stability and high purity is prepared, and a thin film of the composite oxide is prepared using the precursor coating solution. It is formed.
【００１５】ここで、上述した特開平９−５９０２２号
等に開示されたアルコキシド法では、出発原料としてア
ルコキシドを用いているが、ＭｎやＬａのアルコキシド
は、溶解度が非常に低く、このため、高濃度でかつ安定
性に優れた前駆体塗布液を得ることは非常に難しい。ま
た、ＭｎやＬａのアルコキシドは、アルカリ金属アルコ
キシドとＭｎやＬａの金属塩とのアルコキシ交換反応に
より合成されているので、アルカリ金属の混入を抑える
ことが非常に難しい。このため、高純度のＭｎやＬａの
アルコキシドを合成することは非常に難しく、通常は数
％程度の割合でＮａ等のアルカリ金属が出発原料中に共
存することになる。この結果、目的とする組成の高純度
の複合酸化物膜を得ることができない、といった問題点
がある。In the alkoxide method disclosed in JP-A-9-59022 and the like, alkoxide is used as a starting material. However, alkoxides of Mn and La have very low solubility, and It is very difficult to obtain a precursor coating solution having a high concentration and excellent stability. Further, since the alkoxide of Mn or La is synthesized by an alkoxy exchange reaction between an alkali metal alkoxide and a metal salt of Mn or La, it is very difficult to suppress the incorporation of the alkali metal. For this reason, it is very difficult to synthesize high-purity Mn or La alkoxides, and alkali metals such as Na usually coexist in the starting material at a rate of about several percent. As a result, there is a problem that a high-purity composite oxide film having a desired composition cannot be obtained.
【００１６】これに対し、請求項３に係る発明の製造方
法では、上記したように、各元素の酸化物の原料成分の
濃度が高く安定性に優れ純度の高い前駆体塗布液を使用
して複合酸化物の薄膜が形成されるので、高純度で優れ
た膜質の複合酸化物の薄膜が得られる。On the other hand, in the production method according to the third aspect of the present invention, as described above, the precursor coating solution having a high concentration of the raw material components of the oxides of the respective elements, a high stability and a high purity is used. Since the composite oxide thin film is formed, a composite oxide thin film having high purity and excellent film quality can be obtained.
【００１７】[0017]
【発明の実施の形態】以下、この発明の好適な実施形態
について説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below.
【００１８】この発明において目的とする複合酸化物の
薄膜は、Ｌａの酸化物とＣａ、ＳｒまたはＢａの酸化物
とＭｎの酸化物との複合酸化物の薄膜、すなわち、組成
式（Ｌａ１−ｘＭｘ）ＭｎＯ３−δ（Ｍ：Ｃａ，Ｓｒ，
Ｂａ、０．０９≦ｘ≦０．５０）で表されるペロブスカ
イト型構造を有する複合酸化物の薄膜である。目的の複
合酸化物の薄膜は、Ｌａ、ＭｎおよびＣａ、Ｓｒもしく
はＢａの各酸化物の原料成分を含む前駆体塗布液を調製
し、その前駆体塗布液を基板の表面に塗布して成膜した
後、基板表面に形成された薄膜に対し波長が３６０ｎｍ
以下である光を照射して薄膜を結晶化させることにより
形成される。The thin film of the composite oxide intended in the present invention is a thin film of a composite oxide of an oxide of La and an oxide of Ca, Sr or Ba and an oxide of Mn, that is, the composition formula (La 1− x M x) MnO 3-δ (M: Ca, Sr,
Ba, 0.09 ≦ x ≦ 0.50) is a thin film of a composite oxide having a perovskite structure. A thin film of the target composite oxide is formed by preparing a precursor coating solution containing raw material components of La, Mn and Ca, Sr or Ba oxides, and applying the precursor coating solution to the surface of the substrate. After that, a wavelength of 360 nm is applied to the thin film formed on the substrate surface.
It is formed by irradiating the following light to crystallize the thin film.
【００１９】Ｌａの酸化物の原料としては、Ｌａのアル
カノールアミン配位化合物が使用され、Ｌａのアルカノ
ールアミン配位化合物は、Ｌａ塩とアルカノールアミン
との反応により得られる。Ｌａ塩としては、塩化物、硝
酸塩等の無機塩や酢酸塩、蟻酸塩等のカルボン酸塩など
が使用される。アルカノールアミンとしては、モノエタ
ノールアミン、ジエタノールアミン、トリエタノールア
ミンなどが使用される。Ｌａのアルカノールアミン配位
化合物を得るためのＬａ塩とアルカノールアミンとの比
率は、１：０．５〜１：３であることが好ましい。As a raw material of the La oxide, a La alkanolamine coordination compound is used, and the La alkanolamine coordination compound is obtained by reacting a La salt with an alkanolamine. As the La salt, an inorganic salt such as chloride or nitrate, or a carboxylate such as acetate or formate is used. As the alkanolamine, monoethanolamine, diethanolamine, triethanolamine and the like are used. The ratio of the La salt to the alkanolamine for obtaining the La alkanolamine coordination compound is preferably from 1: 0.5 to 1: 3.
【００２０】Ｍｎの酸化物の原料としては、Ｍｎのカル
ボン酸塩、例えば蟻酸マンガン、酢酸マンガン、プロピ
オン酸マンガンなどが使用され、特に好ましくは酢酸マ
ンガンが用いられる。また、カルボン酸塩の水和物とし
て用いることも可能である。As a raw material of the Mn oxide, a carboxylate of Mn, for example, manganese formate, manganese acetate, manganese propionate or the like is used, and manganese acetate is particularly preferable. Further, it can be used as a hydrate of a carboxylate.
【００２１】Ｃａ、ＳｒまたはＢａの酸化物の原料とし
ては、金属またはアルコキシドが使用される。すなわ
ち、アルコールを溶剤として用いる場合は、Ｃａ、Ｓｒ
またはＢａを金属として添加し、反応によりアルコキシ
ドとすることが可能であり、出発原料としてアルコキシ
ドを用いるようにしてもよい。残留有機物を低減するた
めには、使用するアルコールあるいはアルコキシドは、
炭素数が１〜４であることが好ましい。Metals or alkoxides are used as raw materials for Ca, Sr or Ba oxides. That is, when alcohol is used as a solvent, Ca, Sr
Alternatively, Ba can be added as a metal to form an alkoxide by a reaction, and the alkoxide may be used as a starting material. To reduce residual organics, the alcohol or alkoxide used should be
It is preferable that the carbon number is 1 to 4.
【００２２】溶剤としては、上記した各原料成分が混合
された後に可溶になるものであれば、特に種類は限定さ
れないが、一級アルコールを用いることが好ましく、特
に、メタノール、エタノールまたはプロパノールを用い
ることが好ましい。The solvent is not particularly limited as long as it becomes soluble after the above-mentioned raw materials are mixed, but a primary alcohol is preferably used, and particularly, methanol, ethanol or propanol is used. Is preferred.
【００２３】上記した各原料成分の組合せおよび溶剤と
の組合せが、原料成分の溶解度、安定性および純度を満
足させるような複合酸化物膜形成用塗布液を得るために
重要である。なお、Ｌａの酸化物の原料としてＬａのア
ルカノールアミン配位化合物を用いる代わりに、Ｌａ塩
を含む反応溶液中にアルカノールアミンを添加して、塗
布液を調製するようにしてもよい。その際のアルカノー
ルアミンの添加量は、アルカノールアミン配位化合物を
合成するためのＬａ塩とアルカノールアミンとの上記比
率と同様となるようにする。The combination of each of the above-mentioned raw material components and the combination with a solvent are important for obtaining a coating solution for forming a composite oxide film which satisfies the solubility, stability and purity of the raw material components. Instead of using the La alkanolamine coordination compound as a raw material of the La oxide, an alkanolamine may be added to a reaction solution containing a La salt to prepare a coating solution. The amount of the alkanolamine to be added at this time is set to be the same as the above-mentioned ratio between the La salt and the alkanolamine for synthesizing the alkanolamine coordination compound.
【００２４】塗布液は、上記した各原料成分を有機溶剤
中に添加し、混合溶液を室温であるいは加熱しながら撹
拌することにより得られる。そして、上記したような出
発原料の組合せであれば、反応により均質な塗布液が得
られる。The coating liquid can be obtained by adding the above-mentioned raw materials to an organic solvent and stirring the mixed solution at room temperature or while heating. And if it is a combination of the starting materials as described above, a homogeneous coating solution can be obtained by the reaction.
【００２５】得られた塗布液は、通常の方法により基板
の表面に塗布して基板上に成膜することができる。この
場合、塗布液は安定性に優れているため、スピンコー
ト、ディップコート、スプレーコート、フローコート、
バーコートなどの各種のコーティング方法により成膜が
可能である。The obtained coating solution can be applied on the surface of the substrate by a usual method to form a film on the substrate. In this case, since the coating solution has excellent stability, spin coating, dip coating, spray coating, flow coating,
Film formation is possible by various coating methods such as bar coating.
【００２６】基板上に薄膜が形成されると、その薄膜に
対して波長が３６０ｎｍ以下である光を照射する。光源
としては、波長が３６０ｎｍ以下である光を照射可能で
あれば、その種類を問わないが、例えば、ＡｒＦエキシ
マレーザ、ＫｒＦエキシマレーザ、ＸｅＣｌエキシマレ
ーザ、ＸｅＦエキシマレーザ、ＹＡＧレーザの３倍波光
またはＹＡＧレーザの４倍波光などが使用される。ま
た、これらの光源のうち２つもしくはそれ以上のものを
組み合わせて使用することも可能である。この薄膜に対
する光照射の際に、目的に応じて、基板を加熱したり、
基板を減圧下に置いたり、雰囲気（酸化雰囲気または非
酸化雰囲気）を制御したりすることも可能である。ま
た、薄膜に対する光の照射を２段階で行うようにしても
よい。例えば、低圧水銀ランプ等を使用して、薄膜に対
し光の照射を行った後、ＫｒＦエキシマレーザ光等を薄
膜に対してさらに照射するようにしてもよい。薄膜に対
して光が照射されることにより、薄膜が結晶化され、基
板の表面に目的の複合酸化物の薄膜、すなわち組成式
（Ｌａ１−ｘＭｘ）ＭｎＯ３−δ（Ｍ：Ｃａ，Ｓｒ，Ｂ
ａ、０．０９≦ｘ≦０．５０）で表されるペロブスカイ
ト型構造を有する複合酸化物の薄膜となる。When a thin film is formed on a substrate, the thin film is irradiated with light having a wavelength of 360 nm or less. Any type of light source can be used as long as it can emit light having a wavelength of 360 nm or less. For example, an ArF excimer laser, a KrF excimer laser, a XeCl excimer laser, a XeF excimer laser, a third harmonic of a YAG laser, or For example, fourth harmonic light of a YAG laser is used. It is also possible to use two or more of these light sources in combination. When irradiating this thin film with light, depending on the purpose, the substrate may be heated,
It is also possible to place the substrate under reduced pressure or to control the atmosphere (oxidizing atmosphere or non-oxidizing atmosphere). The irradiation of light to the thin film may be performed in two stages. For example, after the thin film is irradiated with light using a low-pressure mercury lamp or the like, the thin film may be further irradiated with KrF excimer laser light or the like. By irradiating the thin film with light, the thin film is crystallized, and the target composite oxide thin film, that is, the composition formula (La 1-x M x ) MnO 3-δ (M: Ca, Sr, B
a, 0.09 ≦ x ≦ 0.50) as a thin film of a composite oxide having a perovskite structure.
【００２７】[0027]
【実施例】次に、この発明のより具体的に実施例につい
て、比較例を示しながら説明する。EXAMPLES Next, more specific examples of the present invention will be described with reference to comparative examples.
【００２８】（塗布液の調製） 〔実施例１〕メタノール中に酢酸ランタンとＬａの３モ
ル倍のモノエタノールアミンとを添加した後、溶液を１
０時間還流させ、Ｌａのエタノールアミン配位化合物を
合成した。得られた溶液に、（Ｌａ０．７３Ｓｒ
０．２７）ＭｎＯ３の組成となるようにジイソプロポキ
シストロンチウムを添加し、さらに酢酸マンガン４水和
物を添加して、溶液を室温で撹拌した。これにより、均
質な褐色の塗布液（塗布液１）が得られた。塗布液の濃
度は、最終的な酸化物濃度で４重量％となるように調整
した。(Preparation of Coating Solution) [Example 1] After adding lanthanum acetate and 3 times by mole of monoethanolamine to La in methanol, 1 part of the solution was added.
The mixture was refluxed for 0 hour to synthesize an ethanolamine coordination compound of La. (La 0.73 Sr) was added to the obtained solution.
0.27 ) Diisopropoxystrontium was added to give a composition of MnO 3 , manganese acetate tetrahydrate was further added, and the solution was stirred at room temperature. As a result, a homogeneous brown coating liquid (coating liquid 1) was obtained. The concentration of the coating solution was adjusted so that the final oxide concentration was 4% by weight.
【００２９】〔実施例２〕ジエトキシストロンチウムの
エタノール溶液中に、（Ｌａ０．７３Ｓｒ０．２ ７）Ｍ
ｎＯ３の組成となるようにトリイソプロポキシランタン
とジエトキシマンガンとを添加した後、エタノールと等
量のエトキシエタノールを加えて、溶液を加熱しながら
撹拌した。これにより、酸化物濃度で１重量％の塗布液
（塗布液２）が得られた。The ethanol solution of Example 2 diethoxy strontium, (La 0.73 Sr 0.2 7) M
After addition of the tri-iso-propoxy lanthanum diethoxy manganese so as to have the composition of nO 3, the addition of ethanol and an equal volume of ethoxyethanol and the solution was stirred while heating. As a result, a coating solution (coating solution 2) having an oxide concentration of 1% by weight was obtained.
【００３０】(塗布膜の作成および結晶化処理) 〔実施例３〜９〕上記した実施例１、２で得られた塗布
液１、２を使用し、スピンコーターを使用して、単結晶
ＳｒＴｉＯ３基板上に塗布液を塗布し２，０００ｒｐｍ
の回転数で３０秒間処理して成膜した。基板上に形成さ
れた塗布膜を１２０℃の温度で３０分間乾燥させた後、
塗布膜に対して紫外光を照射した。(Formation of Coating Film and Crystallization Treatment) [Examples 3 to 9] Using the coating solutions 1 and 2 obtained in the above Examples 1 and 2, a single crystal SrTiO was formed using a spin coater. 3 Apply the coating solution on the substrate and apply 2,000 rpm
The film was formed by processing at a rotation speed of 30 seconds. After drying the coating film formed on the substrate at a temperature of 120 ° C. for 30 minutes,
The coating film was irradiated with ultraviolet light.
【００３１】得られた薄膜について、回折法により結晶
相の同定を行い、また段差計により膜厚を測定した。光
の照射条件と得られた薄膜の評価結果とを表１にまとめ
て示す。The crystal phase of the obtained thin film was identified by a diffraction method, and the film thickness was measured by a step meter. Table 1 summarizes the light irradiation conditions and the evaluation results of the obtained thin films.
【００３２】[0032]
【表１】 [Table 1]
【００３３】また、実施例４により得られた（Ｌａ
０．７３Ｓｒ０．２７）ＭｎＯ３の組成を有する薄膜の
Ｘ線回折パターンを図１に示す。図１から分かるよう
に、薄膜には明確なペロブスカイト型構造の生成が認め
られた。Further, (La obtained in Example 4)
FIG. 1 shows an X-ray diffraction pattern of a thin film having a composition of 0.73 Sr 0.27 ) MnO 3 . As can be seen from FIG. 1, formation of a clear perovskite structure was observed in the thin film.
【００３４】〔比較例〕上記実施例３で作成された塗布
膜を４００℃の温度で３０分間仮焼した。この操作を２
回繰り返した後、大気中で８００℃の温度で２時間焼成
した。これにより、（Ｌａ０．７３Ｓｒ０．２７）Ｍｎ
Ｏ３の単相膜が得られた。Comparative Example The coating film formed in Example 3 was calcined at a temperature of 400 ° C. for 30 minutes. This operation 2
After repeating the process twice, firing was performed in the air at a temperature of 800 ° C. for 2 hours. Thereby, (La 0.73 Sr 0.27 ) Mn
A single phase film of O 3 was obtained.
【００３５】〔実施例１０〕上記実施例３で作成された
塗布膜に対して低圧水銀ランプ（波長：２５４ｎｍ）の
光を１時間照射した後、ＫｒＦエキシマレーザ光を薄膜
に対してさらに照射した。Example 10 The coating film formed in Example 3 was irradiated with light from a low-pressure mercury lamp (wavelength: 254 nm) for 1 hour, and then the thin film was further irradiated with KrF excimer laser light. .
【００３６】〔実施例１１〕メタノール中に酢酸ランタ
ンとＬａの３モル倍のモノエタノールアミンとを添加し
た後、溶液を１０時間還流させ、Ｌａのエタノールアミ
ン配位化合物を合成した。得られた溶液に、（Ｌａ
０．５５Ｓｒ０．４５）ＭｎＯ３の組成となるようにジ
イソプロポキシストロンチウムを添加し、さらに酢酸マ
ンガン４水和物を添加して、溶液を室温で撹拌した。こ
れにより、均質な褐色の塗布液が得られた。塗布液の濃
度は、最終的な酸化物濃度で４重量％となるように調整
した。Example 11 After adding lanthanum acetate and monoethanolamine three times as much as La in methanol, the solution was refluxed for 10 hours to synthesize a La ethanolamine coordination compound. (La)
0.55 Sr 0.45 ) MnO 3 was added to give diisopropoxystrontium, and manganese acetate tetrahydrate was added, and the solution was stirred at room temperature. As a result, a homogeneous brown coating liquid was obtained. The concentration of the coating solution was adjusted so that the final oxide concentration was 4% by weight.
【００３７】スピンコーターを使用して、単結晶ＳｒＴ
ｉＯ３基板上に塗布液を塗布し２，０００ｒｐｍの回転
数で３０秒間処理して成膜した。基板上に形成された塗
布膜を１２０℃の温度で３０分間乾燥させた後、塗布膜
に対して低圧水銀ランプ（波長：２５４ｎｍ）の光を１
時間照射した後、ＫｒＦエキシマレーザ光を塗布膜に対
してさらに照射した。得られた薄膜は、Ｘ線回折法によ
る結晶相の同定の結果、ペロブスカイト単相膜であるこ
とが確認された。Using a spin coater, single crystal SrT
A coating solution was applied on an iO 3 substrate and processed at a rotation speed of 2,000 rpm for 30 seconds to form a film. After drying the coating film formed on the substrate at a temperature of 120 ° C. for 30 minutes, light of a low-pressure mercury lamp (wavelength: 254 nm) is applied to the coating film for 1 minute.
After irradiation for an hour, the coating film was further irradiated with a KrF excimer laser beam. As a result of identification of the crystal phase by the X-ray diffraction method, the obtained thin film was confirmed to be a perovskite single-phase film.
【００３８】〔実施例１２〕メタノール中に酢酸ランタ
ンとＬａの３モル倍のモノエタノールアミンとを添加し
た後、溶液を１０時間還流させ、Ｌａのエタノールアミ
ン配位化合物を合成した。得られた溶液に、（Ｌａ
０．９０Ｓｒ０．１０）ＭｎＯ３の組成となるようにジ
イソプロポキシストロンチウムを添加し、さらに酢酸マ
ンガン４水和物を添加して、溶液を室温で撹拌した。こ
れにより、均質な褐色の塗布液が得られた。塗布液の濃
度は、最終的な酸化物濃度で４重量％となるように調整
した。Example 12 After adding lanthanum acetate and monoethanolamine 3 times the molar amount of La in methanol, the solution was refluxed for 10 hours to synthesize a La ethanolamine coordination compound. (La)
0.90 Sr 0.10 ) MnO 3 , diisopropoxystrontium was added so as to have a composition, and manganese acetate tetrahydrate was further added, and the solution was stirred at room temperature. As a result, a homogeneous brown coating liquid was obtained. The concentration of the coating solution was adjusted so that the final oxide concentration was 4% by weight.
【００３９】スピンコーターを使用して、単結晶ＳｒＴ
ｉＯ３基板上に塗布液を塗布し２，０００ｒｐｍの回転
数で３０秒間処理して成膜した。基板上に形成された塗
布膜を１２０℃の温度で３０分間乾燥させた後、塗布膜
に対して低圧水銀ランプ（波長：２５４ｎｍ）の光を１
時間照射した後、ＫｒＦエキシマレーザ光を塗布膜に対
してさらに照射した。得られた薄膜は、Ｘ線回折法によ
る結晶相の同定の結果、ペロブスカイト単相膜であるこ
とが確認された。Using a spin coater, single crystal SrT
A coating solution was applied on an iO 3 substrate and processed at a rotation speed of 2,000 rpm for 30 seconds to form a film. After drying the coating film formed on the substrate at a temperature of 120 ° C. for 30 minutes, light of a low-pressure mercury lamp (wavelength: 254 nm) is applied to the coating film for 1 minute.
After irradiation for an hour, the coating film was further irradiated with a KrF excimer laser beam. As a result of identification of the crystal phase by the X-ray diffraction method, the obtained thin film was confirmed to be a perovskite single-phase film.
【００４０】また、上記実施例４、１１、１２で示した
各組成におけるＭをＳｒからＣａまたはＢａに置換した
組成の複合酸化物の薄膜についても、上記した実施例と
同様にペロブスカイト相の結晶化が認められた。In the same manner as in the above-described embodiment, the thin film of the composite oxide having the composition in which M in each of the embodiments 4, 11, and 12 was replaced with Sr or Ca or Ba was also used. Conversion was observed.
【００４１】以上の結果から分かるように、この発明の
実施例によれば、目的とする（Ｌａ １−ｘＭｘ）ＭｎＯ
３−δ（Ｍ：Ｃａ，Ｓｒ，Ｂａ、０．０９≦ｘ≦０．５
０）の組成の複合酸化物の薄膜を、加熱処理を行わなく
ても製造することが可能となる。As can be seen from the above results, the present invention
According to the embodiment, the target (La 1-xMx) MnO
3-δ(M: Ca, Sr, Ba, 0.09 ≦ x ≦ 0.5
The thin film of the composite oxide having the composition of 0) was prepared without performing the heat treatment.
Can be manufactured.
【００４２】[0042]
【発明の効果】請求項１に係る発明の製造方法による
と、組成式（Ｌａ１−ｘＭｘ）ＭｎＯ３ −δ（Ｍ：Ｃ
ａ，Ｓｒ，Ｂａ、０．０９≦ｘ≦０．５０）で表される
ペロブスカイト型構造を有する複合酸化物の薄膜を、高
温での加熱処理を行わなくても得ることができる。した
がって、プラスチックス等の耐熱性に劣る基板上にも、
上記組成の複合酸化物の薄膜を形成することが可能とな
る。According to the manufacturing method of invention according to claim 1, according to the present invention, the composition formula (La 1-x M x) MnO 3 -δ (M: C
(a, Sr, Ba, 0.09 ≦ x ≦ 0.50) The thin film of the composite oxide having a perovskite structure can be obtained without performing heat treatment at a high temperature. Therefore, even on substrates with poor heat resistance, such as plastics,
A thin film of the composite oxide having the above composition can be formed.
【００４３】請求項２に係る発明の製造方法では、高温
での加熱処理を行わなくても、光のエネルギーによって
複合酸化物の薄膜を結晶化することができる。In the manufacturing method according to the second aspect of the present invention, the thin film of the composite oxide can be crystallized by the energy of light without performing the heat treatment at a high temperature.
【００４４】請求項３に係る発明の製造方法によると、
上記組成を有する高純度で優れた膜質の複合酸化物の薄
膜を得ることができる。According to the manufacturing method of the third aspect of the present invention,
A thin film of a high-purity and excellent-quality composite oxide having the above composition can be obtained.
【図１】この発明の実施例４で得られた薄膜のＸ線回折
パターンを示す図である。FIG. 1 is a view showing an X-ray diffraction pattern of a thin film obtained in Example 4 of the present invention.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D075 BB48Z DB31 DC21 EB01 EC01 EC10 4G042 DA02 DB15 DC03 DD02 DE07 DE09 DE14 4G048 AA05 AB01 AC04 AD02 AE05 AE08 4G075 AA24 AA30 BB02 CA02 CA32 CA33 CA36 CA51 4K022 AA13 BA11 BA15 BA27 BA28 BA33 DA08 DB01 DB04 DB07 DB08 ──────────────────────────────────────────────────続 き Continued on front page F-term (reference) 4D075 BB48Z DB31 DC21 EB01 EC01 EC10 4G042 DA02 DB15 DC03 DD02 DE07 DE09 DE14 4G048 AA05 AB01 AC04 AD02 AE05 AE08 4G075 AA24 AA30 BB02 CA02 CA32 CA33 CA36 CA51 4K022 BA27 BA27 BA27 DA08 DB01 DB04 DB07 DB08
Claims (3)
ａの各酸化物の原料成分を含む前駆体塗布液を被塗布物
の表面に塗布して成膜した後、被塗布物表面に形成され
た薄膜を結晶化させて、組成式（Ｌａ１−ｘＭｘ）Ｍｎ
Ｏ３−δ（Ｍ：Ｃａ，Ｓｒ，Ｂａ、０．０９≦ｘ≦０．
５０）で表されるペロブスカイト型構造を有する複合酸
化物の薄膜を形成する複合酸化物膜の製造方法におい
て、 前記前駆体塗布液を被塗布物の表面に塗布して成膜した
後、被塗布物表面に形成された薄膜に対し波長が３６０
ｎｍ以下である光を照射して薄膜を結晶化させることを
特徴とする複合酸化物膜の製造方法。1. La, Mn and Ca, Sr or B
After a precursor coating solution containing the raw material components of each oxide a is applied to the surface of the object to form a film, the thin film formed on the surface of the object is crystallized, and the composition formula (La 1− x M x) Mn
O 3-δ (M: Ca, Sr, Ba, 0.09 ≦ x ≦ 0.
50) In a method for producing a composite oxide film having a perovskite structure represented by the formula (50), a precursor coating solution is applied to the surface of an object to form a film. The wavelength is 360 for the thin film formed on the object surface.
A method for producing a composite oxide film, characterized in that a thin film is crystallized by irradiating light having a wavelength of at most nm.
て光を照射する光源が、ＡｒＦエキシマレーザ、ＫｒＦ
エキシマレーザ、ＸｅＣｌエキシマレーザ、ＸｅＦエキ
シマレーザ、ＹＡＧレーザの３倍波光またはＹＡＧレー
ザの４倍波光である請求項１記載の複合酸化物膜の製造
方法。2. A light source for irradiating light to a thin film formed on the surface of an object to be coated is an ArF excimer laser or KrF.
The method for producing a composite oxide film according to claim 1, wherein the method is a third harmonic light of an excimer laser, a XeCl excimer laser, a XeF excimer laser, a YAG laser, or a fourth harmonic of a YAG laser.
液が、 Ｌａのアルカノールアミン配位化合物と、Ｍｎのカルボ
ン酸塩と、Ｍの金属またはアルコキシドとを、炭素数が
１〜４である一級アルコール中で混合させ反応させて調
製される請求項１または請求項２記載の複合酸化物膜の
製造方法。3. A precursor coating liquid applied to the surface of an object to be coated, comprising: an alkanolamine coordination compound of La, a carboxylate of Mn, and a metal or alkoxide of M, having 1 to 4 carbon atoms. The method for producing a composite oxide film according to claim 1, wherein the composite oxide film is prepared by mixing and reacting in a primary alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11063295A JP2000256862A (en) | 1999-03-10 | 1999-03-10 | Production of composite oxidized film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11063295A JP2000256862A (en) | 1999-03-10 | 1999-03-10 | Production of composite oxidized film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000256862A true JP2000256862A (en) | 2000-09-19 |
Family
ID=13225197
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11063295A Pending JP2000256862A (en) | 1999-03-10 | 1999-03-10 | Production of composite oxidized film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000256862A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002310813A (en) * | 2001-04-10 | 2002-10-23 | Toyota Central Res & Dev Lab Inc | Load sensor element |
| JP2006096577A (en) * | 2004-09-28 | 2006-04-13 | Tokyo Institute Of Technology | Metal oxide film, metal oxide film production method and molded product |
| JP2008037726A (en) * | 2006-08-10 | 2008-02-21 | National Institute Of Advanced Industrial & Technology | Method for producing superconducting oxide material |
| CN100374615C (en) * | 2006-01-18 | 2008-03-12 | 北京工业大学 | Preparation method of lanthanum calcium manganese oxide film |
| JP2008156188A (en) * | 2006-12-26 | 2008-07-10 | National Institute Of Advanced Industrial & Technology | Method for producing A-site layered ordered perovskite Mn oxide thin film |
| JP2009132932A (en) * | 2008-12-24 | 2009-06-18 | National Institute Of Advanced Industrial & Technology | Phosphor with crystallized metal oxide thin film |
| KR100910145B1 (en) * | 2006-08-11 | 2009-07-30 | 도꾸리쯔교세이호진 상교기쥬쯔 소고겡뀨죠 | Producing method and use of crystallized metallic oxide thin film |
| DE112008000019T5 (en) | 2007-02-08 | 2010-03-11 | National Institute Of Advanced Industrial Science And Technology | Method for producing superconductive oxide material |
| CN101775271B (en) * | 2009-12-29 | 2012-06-06 | 同济大学 | Material with substantial reversible change emissivity induced by temperature under normal temperature |
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1999
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002310813A (en) * | 2001-04-10 | 2002-10-23 | Toyota Central Res & Dev Lab Inc | Load sensor element |
| JP2006096577A (en) * | 2004-09-28 | 2006-04-13 | Tokyo Institute Of Technology | Metal oxide film, metal oxide film production method and molded product |
| CN100374615C (en) * | 2006-01-18 | 2008-03-12 | 北京工业大学 | Preparation method of lanthanum calcium manganese oxide film |
| DE112007000115B4 (en) | 2006-08-10 | 2011-01-05 | National Institute Of Advanced Industrial Science And Technology | Method for producing oxide superconducting material |
| JP2008037726A (en) * | 2006-08-10 | 2008-02-21 | National Institute Of Advanced Industrial & Technology | Method for producing superconducting oxide material |
| US9096440B2 (en) | 2006-08-10 | 2015-08-04 | National Institute Of Advanced Industrial Science And Technology | Method of producing superconductive oxide material |
| KR100910145B1 (en) * | 2006-08-11 | 2009-07-30 | 도꾸리쯔교세이호진 상교기쥬쯔 소고겡뀨죠 | Producing method and use of crystallized metallic oxide thin film |
| US7771531B2 (en) | 2006-08-11 | 2010-08-10 | National Institute Of Advanced Industrial Science And Technology | Manufacturing method and usage of crystallized metal oxide thin film |
| JP2008156188A (en) * | 2006-12-26 | 2008-07-10 | National Institute Of Advanced Industrial & Technology | Method for producing A-site layered ordered perovskite Mn oxide thin film |
| DE112008000019T5 (en) | 2007-02-08 | 2010-03-11 | National Institute Of Advanced Industrial Science And Technology | Method for producing superconductive oxide material |
| US8716189B2 (en) | 2007-02-08 | 2014-05-06 | National Institute Of Advanced Industrial Science And Technology | Method of producing superconductive oxide material |
| JP2009132932A (en) * | 2008-12-24 | 2009-06-18 | National Institute Of Advanced Industrial & Technology | Phosphor with crystallized metal oxide thin film |
| CN101775271B (en) * | 2009-12-29 | 2012-06-06 | 同济大学 | Material with substantial reversible change emissivity induced by temperature under normal temperature |
| US9187842B2 (en) | 2010-04-13 | 2015-11-17 | National Institute Of Advanced Industrial Science And Technology | Oriented perovskite oxide thin film |
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