JPH05234800A - Magnetic semiconductor oxide thin film and manufacture thereof - Google Patents
Magnetic semiconductor oxide thin film and manufacture thereofInfo
- Publication number
- JPH05234800A JPH05234800A JP7243292A JP7243292A JPH05234800A JP H05234800 A JPH05234800 A JP H05234800A JP 7243292 A JP7243292 A JP 7243292A JP 7243292 A JP7243292 A JP 7243292A JP H05234800 A JPH05234800 A JP H05234800A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- semiconductor oxide
- magnetic semiconductor
- magnetic
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高い磁気転移温度と抵
抗との半導体的性質を有した磁性半導体酸化薄膜および
その形成方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic semiconductor oxide thin film having semiconductor properties of high magnetic transition temperature and resistance and a method for forming the same.
【０００２】[0002]
【従来の技術】磁性半導体酸化物はフェリ磁性やフェロ
磁性などの強い磁性と半導体の性質とを合わせ持つ物質
であり、大きな磁気抵抗を有するなどの実用上興味深い
組成物である。かかる磁性半導体酸化物として従来は、
ＥｕＯが知られており、このＥｕＯの実用化に多くに研
究がなされていた。2. Description of the Related Art A magnetic semiconductor oxide is a substance having both strong magnetism such as ferrimagnetism and ferromagnetism and semiconductor properties, and is a practically interesting composition having a large magnetic resistance. Conventionally, as such a magnetic semiconductor oxide,
EuO is known, and much research has been done to put it into practical use.
【０００３】[0003]
【発明が解決しようとする課題】しかしながらＥｕＯは
磁気転移温度（Ｔｃ）がチッ素の液化温度付近と極めて
低いため、このＥｕＯを薄膜化しても極低温でしか使用
できず、実用性に乏しいものとなっていた。However, since the magnetic transition temperature (Tc) of EuO is extremely low near the liquefaction temperature of nitrogen, even if EuO is made into a thin film, it can be used only at an extremely low temperature and is not practical. It was.
【０００４】本発明は上記事情を考慮してなされたもの
であり、磁気転移温度が高く実用性を有した磁性半導体
酸化薄膜およびその形成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 an object thereof is to provide a magnetic semiconductor oxide thin film having a high magnetic transition temperature and practicality, and a method for forming the same.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
の本発明の磁性半導体酸化薄膜は、ＲＺＭｎＯ3 （Ｒは
３価の希土類元素、Ｚは２価のＳｒ、ＣａまたはＰｂの
中から選ばれる元素）の組成を有していることを特徴と
する。The magnetic semiconductor oxide thin film of the present invention for achieving the above object is formed of RZMnO 3 (R is a trivalent rare earth element, Z is a divalent Sr, Ca or Pb). It is characterized by having the composition
【０００６】この磁性半導体酸化薄膜を形成する本発明
の形成方法は、Ｒ（ＮＯ3 ）3 ・６Ｈ2 Ｏ（Ｒは希土類
元素）と、Ｚ（ＮＯ3 ）2 （Ｚは２価のＳｒ，Ｃａ、Ｐ
ｂの中から選ばれる元素）と、Ｍｎ（ＮＯ3 ）3 ・６Ｈ
2 Ｏとを有機溶媒に溶解した後、加熱して薄膜とするこ
とを特徴とする。ここで有機溶媒としてはエタノールな
どのアルコール類あるいは１−メチル−２−ピロリドン
などのケトン類を選択使用することができる。The method of forming the magnetic semiconductor oxide thin film according to the present invention comprises R (NO 3 ) 3 .6H 2 O (R is a rare earth element) and Z (NO 3 ) 2 (Z is divalent Sr, Ca, P
b the element) selected from among, Mn (NO 3) 3 · 6H
It is characterized in that after 2 O is dissolved in an organic solvent, it is heated to form a thin film. Here, alcohols such as ethanol or ketones such as 1-methyl-2-pyrrolidone can be selectively used as the organic solvent.
【０００７】[0007]
【実施例】Ｌａ（ＮＯ3 ）3 ・６Ｈ2 Ｏと、Ｓｒ（ＮＯ
3 ）2 と、Ｍｎ（ＮＯ3 ）3 ・６Ｈ2 Ｏとを重量比１：
１：１の割合でエタノールに溶解して０．２ｍｏｌ／ｌ
濃度の溶液とした。この溶液を５ｃｍ×５ｃｍの石英ガ
ラスからなる基板上に１ｃｃ塗布した。基板への塗布は
スプレー、ハケ塗り、あるいは基板を回転させながら溶
液を滴下して拡散させるスピンコートのいずれであって
も良い。EXAMPLES La (NO 3 ) 3 .6H 2 O and Sr (NO
3 ) 2 and Mn (NO 3 ) 3 .6H 2 O in a weight ratio of 1:
0.2 mol / l dissolved in ethanol at a ratio of 1: 1
A solution having a concentration was prepared. 1 cc of this solution was applied onto a 5 cm × 5 cm substrate made of quartz glass. The application to the substrate may be either spraying, brush coating, or spin coating in which the solution is dropped while the substrate is rotated to diffuse the solution.
【０００８】次に、この基板を真空室内で真空乾燥す
る。図２はこの乾燥に用いられる乾燥装置であり、真空
室１内にホルダ２が配設されている。ホルダ２は基板３
をチャッキング、吸着などにより支持するものである。
また、真空室１はバルブ４を介してロータリーポンプ５
に連結され、ロータリーポンプ５の作動により、真空室
１が所定の減圧状態に維持される。溶液が塗布された基
板３はホルダ２によって保持され、真空室１内を減圧す
ることにより基板３上の溶液が真空乾燥される。かかる
真空乾燥は数Ｔｏｒｒ〜１０-2Ｔｏｒｒ程度の真空度で
約２時間で終了する。Next, this substrate is vacuum dried in a vacuum chamber. FIG. 2 shows a drying device used for this drying, in which a holder 2 is arranged in a vacuum chamber 1. Holder 2 is substrate 3
Is supported by chucking, adsorption or the like.
Further, the vacuum chamber 1 is provided with a rotary pump 5 via a valve 4.
The vacuum chamber 1 is maintained in a predetermined depressurized state by the operation of the rotary pump 5. The substrate 3 coated with the solution is held by the holder 2, and the solution on the substrate 3 is vacuum dried by reducing the pressure in the vacuum chamber 1. The vacuum drying is completed in about 2 hours at a degree of vacuum of several Torr to 10 -2 Torr.
【０００９】このような一連の操作により基板３上には
膜厚１０００Å未満の薄膜が形成される。従って、さら
に膜厚を増大させる必要があるときは、上記操作を繰り
返すことにより調整することができる。By such a series of operations, a thin film having a film thickness of less than 1000Å is formed on the substrate 3. Therefore, when the film thickness needs to be further increased, it can be adjusted by repeating the above operation.
【００１０】上記乾燥後においては、基板を電気炉内に
投入して、加熱することにより熱分解反応を行う。この
場合、７５０℃前後で約２時間放置することにより熱分
解が終了する。かかる加熱によって、Ｌａ0.5 Ｓｒ0.5
ＭｎＯ3 の組成を有した磁性半導体酸化薄膜を基板上に
形成することができる。この薄膜はフェロブスカイト型
マンガン酸化物となっており、磁気転移温度が３５５°
Ｋと高く、磁性半導体酸化物として実用上有効な薄膜で
ある。After the drying, the substrate is put into an electric furnace and heated to cause a thermal decomposition reaction. In this case, thermal decomposition is completed by leaving it at about 750 ° C. for about 2 hours. By such heating, La 0.5 Sr 0.5
A magnetic semiconductor oxide thin film having a composition of MnO 3 can be formed on the substrate. This thin film is a ferroskite-type manganese oxide and has a magnetic transition temperature of 355 °.
It has a high K and is a thin film which is practically effective as a magnetic semiconductor oxide.
【００１１】図１はかかる磁性半導体酸化薄膜のＸ線回
折図を示し、横軸に２θ（ｄｅｇ）を、縦軸に反射Ｘ線
の強度をプロットしてある。同図に示すように、全ての
ピークが薄膜の各組成に対応し、不純物のない良好な磁
性半導体酸化薄膜であることが判る。なお、上記実施例
では真空室内で有機溶媒を蒸発させながら、常圧下で基
板をある程度、加熱して蒸発させても良い。FIG. 1 shows an X-ray diffraction diagram of such a magnetic semiconductor oxide thin film, in which the horizontal axis plots 2θ (deg) and the vertical axis plots the intensity of reflected X-rays. As shown in the figure, it can be seen that all peaks correspond to the respective compositions of the thin film, and that it is a good magnetic semiconductor oxide thin film with no impurities. In the above embodiment, the substrate may be heated to some extent under normal pressure to evaporate the organic solvent while evaporating the organic solvent in the vacuum chamber.
【００１２】上記実施例ではＲ1-x ＺX ＭｎＯ3 であら
わされる薄膜に於いて、３価の希土類としてＬａ（ラン
タン）を用い、ＺとしてＳｒ（ストロンチウム）、ｘの
値を０．５としたが、これらは種々変更することができ
る。In the above embodiment, in the thin film represented by R 1-x Z x MnO 3 , La (lanthanum) is used as the trivalent rare earth, Sr (strontium) is used as Z, and the value of x is 0.5. However, these can be variously changed.
【００１３】図３のプロットＡＯ、Ａ１、Ａ２は夫々Ｌ
ａ1-X ＳｒX ＭｎＯ3 において、Ｘをそれぞれ０．３、
０．４、０．５とした時のＸ線回析によって同定した格
子定数である。同図からも判るように、希土類をＳｒで
置換することによって、即ちＳｒが増加することによっ
て格子定数は減少する。このことは、希土類としてＮｄ
（ネオジム）を用いた際にも見られた。即ち、図３のプ
ロットＢＯ，Ｂ１，Ｂ２は夫々Ｎｄ1-x Ｓｒx ＭｎＯ3
において、Ｘをそれぞれ０．２，０．３，０．４とした
時の格子定数であり、希土類をＳｒで置換することによ
って、即ちＳｒが増加することによって格子定数が減少
している。このことは、希土類が３価であり、Ｓｒが２
価であるから４価のＭｎの増加が原因と考えられる。Plots AO, A1 and A2 in FIG. 3 are L, respectively.
a 1-X Sr X MnO 3 , X is 0.3,
It is a lattice constant identified by X-ray diffraction when 0.4 and 0.5 are set. As can be seen from the figure, the lattice constant is decreased by replacing the rare earth element with Sr, that is, by increasing Sr. This means that Nd as a rare earth
It was also seen when using (neodymium). That is, plots BO, B1 and B2 in FIG. 3 are Nd 1-x Sr x MnO 3 respectively.
In, the lattice constants are obtained when X is 0.2, 0.3, and 0.4, respectively, and the lattice constant is reduced by substituting the rare earth with Sr, that is, by increasing Sr. This means that rare earths are trivalent and Sr is 2
Since it is valence, it is considered that the increase in tetravalent Mn is the cause.
【００１４】また、上記Ｌａ1-X ＳｒX ＭｎＯ3 で表さ
れる薄膜に於いて、Ｘ＝０．４の時の磁気転移温度は３
６０°Ｋ、Ｘ＝０．３の時の磁気転移温度は３４５°Ｋ
であり、また、Ｎｄ1-x Ｓｒx ＭｎＯ3 に於いて、Ｘを
それぞれ０．２，０．３，０．４とした時の磁気転移温
度は、夫々１７５°Ｋ，２００°Ｋ，２３５°Ｋであっ
た。なお、図３におけるプロットＣＯ、Ｃ１は３価の希
土類ＲとしてサマリウムＳｍを用いた例である。In the thin film represented by La 1-X Sr X MnO 3 , the magnetic transition temperature at X = 0.4 is 3
Magnetic transition temperature at 60 ° K and X = 0.3 is 345 ° K
Further, in Nd 1-x Sr x MnO 3 , the magnetic transition temperatures when X is 0.2, 0.3 and 0.4 are 175 ° K, 200 ° K and 235, respectively. It was ° K. Plots CO and C1 in FIG. 3 are examples in which samarium Sm is used as the trivalent rare earth R.
【００１５】[0015]
【発明の効果】以上説明したように本発明は、磁気転移
温度の高い磁性半導体酸化薄膜であるため、実用性の高
いものとすることができる。また、本発明の方法は、こ
の磁性半導体酸化薄膜を簡単に、しかも高純度で形成す
ることができる。As described above, since the present invention is a magnetic semiconductor oxide thin film having a high magnetic transition temperature, it can be made highly practical. Further, the method of the present invention can easily form this magnetic semiconductor oxide thin film with high purity.
【図１】本発明の実施例のＸ線回折図である。FIG. 1 is an X-ray diffraction diagram of an example of the present invention.
【図２】乾燥装置の一例の断面図である。FIG. 2 is a cross-sectional view of an example of a drying device.
【図３】本発明による薄膜の格子定数を示す図である。FIG. 3 is a diagram showing a lattice constant of a thin film according to the present invention.
Claims (2)
Ｚは２価のＳｒ、ＣａまたはＰｂの中から選ばれる元
素）の組成を有していることを特徴とする磁性半導体酸
化薄膜。1. RZMnO 3 (R is a trivalent rare earth element,
Z is an element selected from divalent Sr, Ca or Pb), which is a magnetic semiconductor oxide thin film.
元素）と、Ｚ（ＮＯ3 ）2 （Ｚは２価のＳｒ，Ｃａ、Ｐ
ｂの中から選ばれる元素）と、Ｍｎ（ＮＯ3）3 ・６Ｈ
2 Ｏとを有機溶媒に溶解した後、加熱して薄膜とするこ
とを特徴とする磁性半導体酸化薄膜の形成方法。2. R (NO 3 ) 3 .6H 2 O (R is a rare earth element) and Z (NO 3 ) 2 (Z is divalent Sr, Ca, P).
b the element) selected from among, Mn (NO 3) 3 · 6H
A method for forming a magnetic semiconductor oxide thin film, which comprises dissolving 2 O and an organic solvent and then heating the mixture to form a thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7243292A JPH05234800A (en) | 1992-02-21 | 1992-02-21 | Magnetic semiconductor oxide thin film and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7243292A JPH05234800A (en) | 1992-02-21 | 1992-02-21 | Magnetic semiconductor oxide thin film and manufacture thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10954893A Division JP3293231B2 (en) | 1993-05-11 | 1993-05-11 | Method of forming perovskite-type composite oxide thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05234800A true JPH05234800A (en) | 1993-09-10 |
Family
ID=13489136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7243292A Pending JPH05234800A (en) | 1992-02-21 | 1992-02-21 | Magnetic semiconductor oxide thin film and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05234800A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432474B1 (en) * | 1998-06-29 | 2002-08-13 | Sharp Kabushiki Kaisha | Thin film of perovskite type manganese oxide process for producing the same thin film and an infrared sensing element using the same thin film |
| CN1324720C (en) * | 2001-09-20 | 2007-07-04 | 北京有色金属研究总院 | Perovskite rare earth manganese oxide giant magnetic resistance material, preparing process and its use |
-
1992
- 1992-02-21 JP JP7243292A patent/JPH05234800A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432474B1 (en) * | 1998-06-29 | 2002-08-13 | Sharp Kabushiki Kaisha | Thin film of perovskite type manganese oxide process for producing the same thin film and an infrared sensing element using the same thin film |
| CN1324720C (en) * | 2001-09-20 | 2007-07-04 | 北京有色金属研究总院 | Perovskite rare earth manganese oxide giant magnetic resistance material, preparing process and its use |
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