JP2916514B2 - Manufacturing method of oxide thin film - Google Patents
Manufacturing method of oxide thin filmInfo
- Publication number
- JP2916514B2 JP2916514B2 JP2441590A JP2441590A JP2916514B2 JP 2916514 B2 JP2916514 B2 JP 2916514B2 JP 2441590 A JP2441590 A JP 2441590A JP 2441590 A JP2441590 A JP 2441590A JP 2916514 B2 JP2916514 B2 JP 2916514B2
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- Japan
- Prior art keywords
- thin film
- oxide thin
- oxygen
- substrate
- evaporation
- 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.)
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- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、超伝導素子、光学素子、圧電素子、表面弾
性素子などに使用される各種酸化物薄膜の製造方法に関
するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing various oxide thin films used for superconducting elements, optical elements, piezoelectric elements, surface elastic elements, and the like.
［従来の技術］ 従来、酸化物薄膜を作製する方法として最もよく用い
られている方法は、スパッタ法である。しかし、周知の
ように、スパッタ法においては、酸素量の制御が充分で
なく、またターゲット組成比の経時変化等により金属組
成比の制御も充分でないという欠点があった。この欠点
のため、特に酸化物単結晶薄膜を作製する場合のように
精密な組成制御を必要とする時には、スパッタ法によっ
て充分な膜質を得ることは困難であった。[Prior Art] Conventionally, the most frequently used method for producing an oxide thin film is a sputtering method. However, as is well known, the sputtering method has a defect that the control of the amount of oxygen is not sufficient and the control of the metal composition ratio is not sufficient due to a change with time of the target composition ratio. Due to this drawback, it has been difficult to obtain a sufficient film quality by the sputtering method particularly when precise composition control is required as in the case of producing an oxide single crystal thin film.
このようなスパッタ法の欠点を克服して、精密に組成
制御された緻密な酸化物薄膜を得るために、酸化ビーム
照射蒸着法（従来例1;特願昭63-42211）が発明された。
この方法に用いられる装置を第１図に示した。図中、符
号１は基板ホルダを示すものであり、２は基板を、３は
電子ビーム蒸着源を、４はＫ−セルを、５は排気口を、
６はファラデーカップを、７を膜厚モニタを、８はイオ
ン源を、９はガス導入口を、10はマイクロ波源を、11を
プラズマ室を、12は中和用フィラメントを、13は基板ヒ
ータを、14は成膜室を、それぞれ示すものである。In order to overcome such disadvantages of the sputtering method and obtain a dense oxide thin film whose composition is precisely controlled, an oxidation beam irradiation evaporation method (conventional example 1; Japanese Patent Application No. 63-42211) was invented.
The apparatus used in this method is shown in FIG. In the figure, reference numeral 1 denotes a substrate holder, 2 denotes a substrate, 3 denotes an electron beam evaporation source, 4 denotes a K-cell, 5 denotes an exhaust port,
6 is a Faraday cup, 7 is a film thickness monitor, 8 is an ion source, 9 is a gas inlet, 10 is a microwave source, 11 is a plasma chamber, 12 is a neutralizing filament, and 13 is a substrate heater. Denotes a film forming chamber.
この装置を用いて行う従来の酸素ビーム照射蒸着法
は、蒸発レートを精密に制御した蒸着法に酸素ビーム照
射を組み合せた方法であり、酸素を含めた薄膜組成の制
御性がよく緻密な膜が制作できるという特徴がある。具
体的な方法としては、第１図の電子ビーム蒸発源３また
はＫ−セル蒸発源4a、4bにより蒸発させた各薄膜構成原
料を基板２に全て同時に堆積させ、プラズマ室14より発
生され、引き出された酸素イオンビームを10ないし500e
Vのエネルギーで薄膜堆積と同時に基板２に照射し、真
空中で酸化物薄膜を製造する。この方法の特徴を発揮す
るには、酸素の照射量制御の他に、薄膜組成を精密に制
御することが重要であり、そのためにはできるだけ安定
な蒸発源によりその蒸発レートを制御する必要がある。
上記Ｋ−セル蒸発源は、電子ビーム蒸発源に比べて、一
般に蒸発レートの安定度は高い。しかし、安定な蒸発レ
ートの制御は難しい。活性な金属は、大気中または成膜
室中に残留する酸素や水蒸気と反応して酸化物や水酸化
物を形成する。その結果、蒸発レートが時間的に不安定
になってしまう。また、Ｋ−セルでは1500℃を越える蒸
発温度を持つ元素の蒸着は困難であり、なおかつ1500℃
以下でも1300℃以上の高温になるほど不純物汚染やＫ−
セル構成材料寿命の極端な低下などの問題がある。The conventional oxygen beam irradiation vapor deposition method using this device is a method in which oxygen beam irradiation is combined with a vapor deposition method that precisely controls the evaporation rate, and a dense film with good controllability of the thin film composition including oxygen is obtained. There is a feature that it can be produced. As a specific method, all the thin film constituent materials evaporated by the electron beam evaporation source 3 or the K-cell evaporation sources 4a and 4b shown in FIG. 1 are all simultaneously deposited on the substrate 2, and are generated and extracted from the plasma chamber 14. 10 to 500e
The substrate 2 is irradiated simultaneously with the deposition of the thin film with the energy of V to produce an oxide thin film in a vacuum. In order to demonstrate the features of this method, it is important to precisely control the composition of the thin film, in addition to controlling the dose of oxygen, and for that purpose, it is necessary to control the evaporation rate with an evaporation source that is as stable as possible. .
The K-cell evaporation source generally has higher evaporation rate stability than the electron beam evaporation source. However, stable control of the evaporation rate is difficult. The active metal reacts with oxygen or water vapor remaining in the atmosphere or in a deposition chamber to form an oxide or a hydroxide. As a result, the evaporation rate becomes temporally unstable. Further, in the K-cell, it is difficult to deposit an element having an evaporation temperature exceeding 1500 ° C.
Even below, impurity contamination and K-
There are problems such as an extremely shortened life of the cell constituent material.
一方、この活性な金属による蒸発の不安定さを克服す
るために、酸素ビーム照射を用いない一般的な蒸着法に
おいて、BaF2などの金属の沸化物を蒸発源として用いる
酸化物薄膜の制作方法が公表されている（従来例2;Mank
iewich et a,Appl.Phys.Lett.51（1987）1753. およ
び、従来例3;Mankiewich et al,Mat.Res.Symp.Proc.99
（1988）119.）。前記従来例２においては、金属Baに代
えてBaF2を用いることにより蒸発が安定におこなられ、
薄膜組成の制御性が向上したことが記載されている。し
かしながら、従来例３に記載されているとおり、一般的
な蒸着法によっては蒸着中にBaF2は解離しないため、Ba
F2を解離させて不必要なF2を薄膜中から取り除くために
水蒸気を含んだ雰囲気中で蒸着後に熱処理する必要があ
った。On the other hand, in order to overcome the instability of evaporation caused by this active metal, a method of producing an oxide thin film using a boride of a metal such as BaF 2 as an evaporation source in a general evaporation method without oxygen beam irradiation. Has been published (Conventional Example 2; Mank
iewich et a, Appl. Phys. Lett. 51 (1987) 1753. and Conventional Example 3; Mankiewich et al, Mat. Res. Symp. Proc. 99
(1988) 119.). In the conventional example 2, evaporation is stably performed by using BaF2 instead of metal Ba,
It describes that the controllability of the composition of the thin film was improved. However, as described in Conventional Example 3, BaF 2 does not dissociate during vapor deposition by a general vapor deposition method.
Unnecessary F 2 by dissociating the F 2 was necessary to heat treatment after the deposition in an atmosphere containing steam in order to remove the thin film.
［発明が解決しようとする課題］ 本発明は、化学的に活性で蒸発が不安定な金属や、蒸
着に高温（1300℃以上）を必要とする金属を構成元素と
して含む酸化物薄膜を、金属組成および酸素組成を精密
に制御するとともに成膜後の熱処理などのプロセスをも
必要とせずに、製造することのできる方法を提供するこ
とを目的とする。[Problems to be Solved by the Invention] The present invention relates to a method for forming an oxide thin film containing, as a constituent element, a metal that is chemically active and is unstable in evaporation, or a metal that requires a high temperature (1300 ° C. or higher) for vapor deposition. It is an object of the present invention to provide a method capable of precisely controlling the composition and the oxygen composition and manufacturing without requiring a process such as heat treatment after film formation.
［課題を解決するための手段］ 前記のような課題を達成するために、本発明は、高真
空中において、酸化物薄膜構成原料を蒸発させて基板に
堆積させると同時に、一定エネルギーの酸素イオンを前
記基板に照射し、前記基板上に酸化物薄膜を形成する酸
化物薄膜の製造方法において、前記酸化物薄膜構成原料
として金属沸化物または金属窒化物を用いることを特徴
とする。[Means for Solving the Problems] In order to achieve the above-mentioned problems, the present invention provides a method of evaporating an oxide thin film forming material and depositing the same on a substrate in a high vacuum, Is irradiated on the substrate to form an oxide thin film on the substrate, wherein a metal boride or a metal nitride is used as a material for forming the oxide thin film.
本発明において、前記真空度は１×10-3Torrより高真
空であることが好ましい。また、前記一定エネルギーの
酸素イオンは、10〜500eVに加速されたビーム状の酸素
プラズマであるか、酸素プラズマより引き出され10〜50
0eVに加速されたビーム状の酸素イオンであることが望
ましい。さらに、前記ビーム状の酸素イオンが中性化さ
れたものであることもある。In the present invention, the degree of vacuum is preferably higher than 1 × 10 −3 Torr. Further, the oxygen ions having a constant energy are beam-shaped oxygen plasma accelerated to 10 to 500 eV, or are extracted from the oxygen plasma by 10 to 50 eV.
Desirably, it is a beam-like oxygen ion accelerated to 0 eV. Further, the beam-like oxygen ions may be neutralized.
［作用］ 本発明によれば、充分安定に蒸発が可能な金属元素は
単体金属のままで、また化学的に活性であったり蒸発温
度が高かったりするために安定に蒸着が困難な金属元素
は、金属沸化物または金属窒化物の形態で、それぞれ酸
化物薄膜構成元素を充填された蒸発源より蒸発させた制
御性のよい分子線蒸着により、基板上に薄膜を堆積させ
ることによって、金属組成が精密に制御された酸化物薄
膜を得ることができる。[Action] According to the present invention, a metal element that can be sufficiently stably evaporated remains a simple metal, and a metal element that is chemically active or has a high evaporation temperature and is difficult to stably deposit is a metal element. By depositing a thin film on a substrate in a form of metal boride or metal nitride by molecular beam evaporation with good controllability, which is evaporated from an evaporation source filled with the constituent elements of the oxide thin film, the metal composition is increased. A precisely controlled oxide thin film can be obtained.
また、本発明によれば、上記薄膜堆積と同時に10〜50
0eVのエネルギーの酸素プラズマビームまたは酸素イオ
ンビームを基板上の堆積膜に照射することにより、真空
中でも充分な酸化が起こって酸素の組成も精密に制御さ
れるとともに、上記金属沸化物または金属窒化物などの
蒸発化合物が上記酸素ビーム照射の効果により薄膜堆積
中に基板上で解離し、かつ沸素などの化合物中の不必要
な元素は堆積薄膜中より蒸発除去することができるた
め、薄膜堆積後に熱処理などのプロセスを必要とするこ
とがなく、結晶欠陥のない酸化物薄膜が製造できる。According to the present invention, 10 to 50 simultaneously with the deposition of the thin film.
By irradiating the deposited film on the substrate with an oxygen plasma beam or an oxygen ion beam having an energy of 0 eV, sufficient oxidation occurs even in a vacuum and the composition of oxygen is precisely controlled. The vaporized compound such as dissociates on the substrate during the deposition of the thin film due to the effect of the above-mentioned oxygen beam irradiation, and unnecessary elements in the compound such as boron can be removed by evaporation from the deposited thin film. An oxide thin film having no crystal defects can be manufactured without requiring a process such as heat treatment.
［実施例］ 以下、本発明の実施例を図面を参照して説明するが、
その前に本発明の原理的構成を説明する。EXAMPLES Hereinafter, examples of the present invention will be described with reference to the drawings.
Before that, the basic configuration of the present invention will be described.
本発明方法に使用する酸化物薄膜製造装置としては、
第１図に示した前記従来の装置を使用することができ
る。本発明方法によれば、この第１の装置を以下のよう
に動作させる。まず、成膜室14をクライオポンプなどに
よって１×10-5Torrよりも高真空にする。その後、イオ
ン源８のガス導入口９より酸素ガスを導入し、プラズマ
室11内にプラズマを生成するために必要なガス圧（１×
10-3から１×10-5Torrまでの真空度）、例えば、１×10
-4Torrになるまで酸素ガスを導入する。そして、酸素以
外の元素の蒸着を行う分子線蒸着において、前記真空度
（例えば、１×10-4Torr）中で、Ｋ−セル蒸発源4a、4b
または電子ビーム蒸発源３から基板２に蒸着を行う。こ
のとき分子線強度を水晶振動子またはイオンゲージなど
のモニタ７によって監視し、これを蒸発源にフィードバ
ックすることのよって各蒸発源への入力パワーを制御す
ることができる。As an oxide thin film manufacturing apparatus used in the method of the present invention,
The conventional device shown in FIG. 1 can be used. According to the method of the present invention, this first device is operated as follows. First, the film forming chamber 14 is evacuated to a higher pressure than 1 × 10 −5 Torr by a cryopump or the like. Thereafter, an oxygen gas is introduced from the gas inlet 9 of the ion source 8 and a gas pressure (1 ×
Vacuum degree from 10 -3 to 1 × 10 -5 Torr), for example, 1 × 10
Introduce oxygen gas to -4 Torr. Then, in the molecular beam deposition for depositing elements other than oxygen, the K-cell evaporation sources 4a and 4b are kept at the above-mentioned degree of vacuum (for example, 1 × 10 −4 Torr).
Alternatively, evaporation is performed on the substrate 2 from the electron beam evaporation source 3. At this time, the molecular beam intensity is monitored by a monitor 7 such as a quartz oscillator or an ion gauge, and the input power to each evaporation source can be controlled by feeding it back to the evaporation source.
ここで、前記のＫ−セル蒸発源4a、4bまたは電子ビー
ム蒸発源３に、単体金属（例えば、Ba）を充填する代り
に化合物（例えば、BaF2などの沸化物またはBaN6などの
窒化物）を充填し、単体金属と同様に蒸発させることに
より、単体金属に比べて安定な蒸発レートを得ることが
できる。従って、その金属の薄膜中の組成をより精密に
制御できる。同様に、例えば、金属Ｙの代りにYF3など
の化合物を用いる場合は、蒸発温度をかなり（例えば、
300℃以上）下げることができるので、蒸発源から発生
する不純物の低減効果や、Ｋ−セル構成材料の疲労によ
る蒸発レートの不安定化の低減効果が得られる。Here, it said K- cell evaporation source 4a, 4b, or electron-beam evaporation source 3, elemental metals (e.g., Ba) compound instead of filling (e.g., boiling products or BaN 6 nitride such as such as BaF 2 ) And vaporized in the same manner as the simple metal, it is possible to obtain a stable evaporation rate as compared with the simple metal. Therefore, the composition of the metal in the thin film can be controlled more precisely. Similarly, for example, if a compound such as YF 3 is used instead of metal Y, the evaporation temperature may be significantly (eg,
(300 ° C. or higher), so that the effect of reducing impurities generated from the evaporation source and the effect of reducing the instability of the evaporation rate due to fatigue of the K-cell constituent material can be obtained.
また、プラズマ室11で発生し、10ないし500eVのエネ
ルギーで引き出された酸素イオンビームまたは酸素プラ
ズマビームは、前記薄膜堆積中の基板２に照射される。
このとき、酸素イオンビームはファラデーカップ６によ
って監視され、マイクロ波源にフィードバックされてイ
オン電流値が制御される。この時、照射される酸素イオ
ンビームまたは酸素プラズマビーム中の酸素イオンの電
流値は、10ないし2000μA/cm2で可変である。An oxygen ion beam or an oxygen plasma beam generated in the plasma chamber 11 and extracted at an energy of 10 to 500 eV is applied to the substrate 2 during the deposition of the thin film.
At this time, the oxygen ion beam is monitored by the Faraday cup 6 and fed back to the microwave source to control the ion current value. At this time, the current value of oxygen ions in the irradiated oxygen ion beam or oxygen plasma beam is variable from 10 to 2000 μA / cm 2 .
前記酸素イオンビームまたは酸素プラズマビームのエ
ネルギーは、薄膜をスパッタせず、薄膜に結晶欠陥を作
らずに、薄膜結晶の生成に必要なエネルギーを供給し、
しかもBaF2などの化合物の解離に充分なエネルギーを持
つように設定されている。The energy of the oxygen ion beam or the oxygen plasma beam does not sputter the thin film, and does not create a crystal defect in the thin film, and supplies the energy required for generating the thin film crystal.
Moreover, it is set to have sufficient energy for dissociation of compounds such as BaF 2 .
このような蒸着法により、従来のスパッタ法に比較し
て、酸素を含めた組成を安定に制御することができる。
その結果、精密に組成制御された酸化物薄膜を得ること
ができる。また、化合物蒸発源を用いて組成制御を精密
に行った従来の蒸着法に比べても、成膜後のアニール工
程が不必要となるため、工程数を減らせるとともに、成
膜後に同一成膜室中で別の薄膜を連続成膜するなどのデ
バイス応用のためのプロセスも新たに実施可能となる利
点もある。By such an evaporation method, the composition including oxygen can be controlled more stably than in the conventional sputtering method.
As a result, an oxide thin film whose composition is precisely controlled can be obtained. Also, compared with the conventional vapor deposition method in which the composition is precisely controlled using a compound evaporation source, an annealing step after film formation is not necessary, so that the number of steps can be reduced and the same film formation after film formation can be achieved. There is also an advantage that a process for device application such as continuous formation of another thin film in a chamber can be newly performed.
（実施例１） Ba2YCu3O7-y膜の製造 第１図の成膜室14の真空度を１×10-6Torrまで排気
し、その後、ガス導入口９より酸素ガスを導入し、イオ
ン源８および成膜室14の真空度を１×10-4Torrとした。
この時、プラズマ室11で生成された酸素イオンを50eVの
エネルギーで引出し、基板近くのイオン電流モニタのフ
ァラデーカップ６で250μA/cm2のイオン電流となるよう
にイオン源へのマイクロ波入射パワーを設定した。(Example 1) Production of Ba 2 YCu 3 O 7-y film The degree of vacuum in the film forming chamber 14 in FIG. 1 was evacuated to 1 × 10 −6 Torr, and then oxygen gas was introduced from the gas inlet 9. The degree of vacuum in the ion source 8 and the film forming chamber 14 was 1 × 10 −4 Torr.
At this time, oxygen ions generated in the plasma chamber 11 are extracted with an energy of 50 eV, and the microwave incident power to the ion source is adjusted by the Faraday cup 6 of the ion current monitor near the substrate so that the ion current becomes 250 μA / cm 2. Set.
基板としてはSrTiO3（100）面および（110）面を用い
た。ここで、予め３本用意しておいたＫ−セル４に、そ
れぞれBaF2、YF3、Cuを充填して蒸発され、基板２上に
堆積した膜の組成がBa:Y:Cu＝2:1:3となるように、かつ
基板２上の蒸着レートが0.8A/sとなるように、各Ｋ−セ
ルの温度を制御し、同時に酸素イオンビームを50eV、25
0μA/cm2の条件でSrTiO3（100）面および（110）面基板
上に照射することによって、化学量論比のBa2YCuO6.8の
多結晶または単結晶薄膜が得られた。特に基板温度を40
0℃から800℃の間の一定温度に保持することによりBa2Y
CuO6.8の単結晶膜が得られた。この時、SrTiO3（100）
面上にはBa2YCuO6.8の（001）面がエピタキシャル成長
し、SrTiO3（110）面上にはBa2YCuO6.8の（110）面がエ
ピタキシャル成長した。このBa2YCuO6.8の（001）面ま
たは（110）面単結晶膜の超伝導転移温度Tc（電気抵抗
がゼロとなる点）は88k以上と高く、臨界電流密度Jcも
温度77Kで１×106A/cm2以上と高かった。ここで、BaF2
の蒸着レートの時間変動は、第２図（ａ）に示すよう
に、１時間で±２％以内と充分に小さく、精密な組成制
御が可能になることによって、高いTc値、高いJc値の薄
膜が得られた。これに対して、BaF2の代りにBa金属を用
いた場合のBaの蒸着レートの時間変動は、第２図（ｂ）
に示すように、１時間で±30％と大きく、薄膜組成制御
性を大きく低下させる。SrTiO 3 (100) and (110) planes were used as substrates. Here, three previously prepared K-cells 4 were filled with BaF 2 , YF 3 , and Cu, respectively, evaporated, and the composition of the film deposited on the substrate 2 was Ba: Y: Cu = 2: The temperature of each K-cell was controlled so as to be 1: 3 and the deposition rate on the substrate 2 was 0.8 A / s, and at the same time, the oxygen ion beam was irradiated at 50 eV and 25 eV.
By irradiating the SrTiO 3 (100) and (110) plane substrates under the condition of 0 μA / cm 2 , a polycrystalline or single crystal thin film of Ba 2 YCuO 6.8 having a stoichiometric ratio was obtained. Especially when the substrate temperature is 40
By maintaining a constant temperature between 0 ° C and 800 ° C, Ba 2 Y
A single crystal film of CuO 6.8 was obtained. At this time, SrTiO 3 (100)
The (001) plane of Ba 2 YCuO 6.8 was epitaxially grown on the plane, and the (110) plane of Ba 2 YCuO 6.8 was epitaxially grown on the SrTiO 3 (110) plane. The superconducting transition temperature Tc (point at which the electric resistance becomes zero) of the (001) plane or (110) plane single crystal film of Ba 2 YCuO 6.8 is as high as 88 k or more, and the critical current density Jc is 1 × 10 at 77 K. It was as high as 6 A / cm 2 or more. Where BaF 2
As shown in FIG. 2 (a), the time variation of the deposition rate is sufficiently small within ± 2% in one hour, and by enabling precise composition control, a high Tc value and a high Jc value can be obtained. A thin film was obtained. On the other hand, when Ba metal is used in place of BaF 2 , the time variation of the deposition rate of Ba is shown in FIG.
As shown in (1), it is as large as ± 30% in one hour, which greatly reduces the controllability of the composition of the thin film.
また、YF3の蒸発温度は1100℃と金属Ｙの1430℃に比
べて大きく低下した。これによってＫ−セル構成材料の
寿命が３倍以上になるとともに、蒸着レートの時間変動
も金属Ｙの±10％（１時間）に対しYF3の±２％と小さ
くなり、組成制御性向上に寄与した。The evaporation temperature of YF 3 was 1100 ° C., which was much lower than that of metal Y at 1430 ° C. As a result, the life of the K-cell constituent material is more than tripled, and the time variation of the deposition rate is reduced to ± 2% of YF 3 with respect to ± 10% (1 hour) of metal Y, thereby improving composition controllability. Contributed.
また、蒸着後、アニールをしないで、このように高い
Tc値、Jc値を示すことにより、BaF2、YF3が蒸着中に解
離し、かつ不要なＦ原子は堆積薄膜中より除去されてい
ることがわかった。この解離効果が酸素イオンビーム照
射によって起こっていることを示す実験結果が第３図で
ある。第３図では照射イオン電流を最適値より減少させ
ればさせるほど、製造された薄膜中のBaF2の結晶の量が
増えたいくことがわかった。YF3についても同様の効果
が得られている。Also, after the deposition, do not anneal,
By indicating the Tc value and the Jc value, it was found that BaF 2 and YF 3 were dissociated during vapor deposition, and unnecessary F atoms were removed from the deposited thin film. FIG. 3 shows an experimental result showing that this dissociation effect is caused by oxygen ion beam irradiation. In FIG. 3, it was found that the amount of BaF 2 crystals in the manufactured thin film increased as the irradiation ion current was reduced below the optimum value. Similar effect is obtained for YF 3.
以上の結果より、本発明に係る酸化物薄膜の製造方法
によれば、BaやＹを含む酸化物薄膜でも、酸素を含めた
組成が再現性よく充分制御されることがわかった。From the above results, it was found that according to the method for manufacturing an oxide thin film according to the present invention, even in an oxide thin film containing Ba or Y, the composition including oxygen was sufficiently controlled with good reproducibility.
なお、この実施例１において、BaF2（沸化物）の代り
にBaN6（窒化物）を用いたところ、上記と同様に好結果
が得られている。In Example 1, when BaN 6 (nitride) was used instead of BaF 2 (boride), good results were obtained in the same manner as described above.
（実施例２） LiNbO3薄膜の製造 サファイヤＣ面上にLiNbO3を成長させた。実施例１と
同様の方法で50eV、100μA/cm2の条件の酸素イオンビー
ムを得た後、中和フィラメントに通電加熱し、酸素イオ
ンビームに熱電子シャワーを当てることにより中性の酸
素ビームを得た。また、Ｋ−セル４よりLiFを蒸発させ
るととに電子ビーム蒸着源３よりNbを蒸発させて、酸素
ビームと同時にサファイヤＣ面基板上に照射することに
よりLiNbO3単結晶を得た。酸素イオンビームを中性化す
ることにより絶縁体のLiNbO3膜でもチャージアップする
ことなく、精密な組成制御が可能であった。波長633nm
の光に対する得られた膜の屈折率no（通常光）は2.31
で、ne（異常光）は2.17であり、バルクに近い密度のLi
NbO3膜が得られていることを示している。Example 2 Production of LiNbO 3 Thin Film LiNbO 3 was grown on a sapphire C surface. After obtaining an oxygen ion beam under the conditions of 50 eV and 100 μA / cm 2 in the same manner as in Example 1, the neutralizing filament is heated by electricity, and a neutral oxygen beam is applied by applying a thermoelectron shower to the oxygen ion beam. Obtained. In addition, LiF was evaporated from the K-cell 4 and Nb was evaporated from the electron beam evaporation source 3, and simultaneously irradiated with an oxygen beam onto a sapphire C-plane substrate to obtain a LiNbO 3 single crystal. By neutralizing the oxygen ion beam, precise composition control was possible without charging up the insulator LiNbO 3 film. Wavelength 633nm
Refractive index n o of the film obtained in respect to light (ordinary light) is 2.31
In, n e (extraordinary light) is 2.17, Li the density close to the bulk
This indicates that an NbO 3 film has been obtained.
また、前記中性酸素ビーム照射の代りに酸素イオンと
電子を含んだ酸素プラズマ照射を行ってもチャージアッ
プのない精密な組成制御が可能であり、前記と同様のLi
NbO3膜が得られた。In addition, even if oxygen plasma irradiation containing oxygen ions and electrons is performed instead of the neutral oxygen beam irradiation, precise composition control without charge-up is possible.
An NbO 3 film was obtained.
ここで、LiFの代りに金属Liを用いると、蒸発レート
の変動は±40％（１時間）と非常に大きく、また。Ｋ−
セル中のLiと水分との反応によるLi蒸発温度の不安定
化、成膜室14内壁のLiによる汚染による真空度変動の増
大などにより製造した薄膜特性の再現性低下が起こっ
た。LiFを用いた場合は、このような問題は起こらなか
った。Here, when metal Li is used instead of LiF, the fluctuation of the evaporation rate is as large as ± 40% (1 hour), and also. K-
The reproducibility of the characteristics of the manufactured thin film deteriorated due to the instability of the Li evaporation temperature due to the reaction between Li and moisture in the cell and the increase in the degree of vacuum fluctuation due to the contamination of the inner wall of the film forming chamber 14 by Li. When LiF was used, such a problem did not occur.
［発明の効果］ 以上説明したように、本発明に係る酸化物薄膜の製造
方法によれば、活性な金属や、蒸発に高温を必要とする
金属を含んでいても、バルクに近い密度を有する酸化物
単結晶薄膜が、酸素を含めて充分に組成制御され、再現
性よく安定に形成することができる。従って、高い超伝
導転移温度を持つ酸化物超伝導薄膜が、薄膜形成後の熱
処理なしで安定して製造することができる、などプロセ
スの簡素化、再現性向上および膜特性向上により、酸化
物薄膜の各種応用範囲が広がるという利点が得られる。[Effects of the Invention] As described above, according to the method for manufacturing an oxide thin film according to the present invention, even if it includes an active metal or a metal that requires a high temperature for evaporation, it has a density close to that of a bulk. The composition of the oxide single crystal thin film is sufficiently controlled including oxygen, and the oxide single crystal thin film can be stably formed with good reproducibility. Therefore, the oxide superconducting thin film having a high superconducting transition temperature can be stably manufactured without heat treatment after the thin film is formed. Has the advantage of widening the range of applications.
第１図は本発明方法に用いて好適な酸化物薄膜の製造装
置の一例を示す断面構成図、 第２図（ａ）は第１図の装置を用いて測定されたBaF2の
蒸着レートの時間変化を示すグラフ、 第２図（ｂ）は同様に金属Baの蒸着レートの時間変化を
示すグラフ、 第３図は本発明の実施例２で製造された薄膜のＸ線回折
パターン中に見られるBaF2結晶による回折ピーク強度が
膜製造時に照射される酸素イオン電流密度によりどう変
るかを示したグラフである。 １……基板ホルダ、２……基板、３……電子ビーム蒸着
源、４……Ｋ−セル、５……排気口、６……ファラデー
カップ、７……膜厚モニタ、８……イオン源、９……ガ
ス導入口、10……マイクロ波源、11……プラズマ室、12
……中和用フィラメント、13……基板ヒータ、14……成
膜室。FIG. 1 is a cross-sectional view showing an example of an apparatus for producing an oxide thin film suitable for use in the method of the present invention, and FIG. 2 (a) is a graph showing BaF 2 deposition rates measured using the apparatus of FIG. FIG. 2 (b) is a graph showing the time variation of the deposition rate of metal Ba, and FIG. 3 (b) is a graph showing the time variation in the X-ray diffraction pattern of the thin film produced in Example 2 of the present invention. 7 is a graph showing how the diffraction peak intensity of the obtained BaF 2 crystal changes depending on the oxygen ion current density irradiated during film production. DESCRIPTION OF SYMBOLS 1 ... Substrate holder, 2 ... Substrate, 3 ... Electron beam evaporation source, 4 ... K-cell, 5 ... Exhaust port, 6 ... Faraday cup, 7 ... Film thickness monitor, 8 ... Ion source , 9 ... gas inlet, 10 ... microwave source, 11 ... plasma chamber, 12
... Neutralizing filament, 13 ... Substrate heater, 14 ... Film forming chamber.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C01B 13/14 C01G 1/00 ZAA ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. 6 , DB name) C01B 13/14 C01G 1/00 ZAA
Claims (6)
蒸発させて基板に堆積させると同時に、一定エネルギー
の酸素イオンを前記基板に照射し、前記基板上に酸化物
薄膜を形成する酸化物薄膜の製造方法において、 前記酸化物薄膜構成原料として金属弗化物を用いること
を特徴とする酸化物薄膜の製造方法。An oxide for forming an oxide thin film on said substrate by simultaneously irradiating said substrate with oxygen ions having a constant energy by evaporating a material constituting said oxide thin film and depositing said material on a substrate in a high vacuum. A method for producing an oxide thin film, wherein a metal fluoride is used as the constituent material of the oxide thin film.
蒸発させて基板に堆積させると同時に、一定エネルギー
の酸素イオンを前記基板に照射し、前記基板上に酸化物
薄膜を形成する酸化物薄膜の製造方法において、 前記酸化物薄膜構成原料として金属窒化物を用いること
を特徴とする酸化物薄膜の製造方法。2. An oxide for forming an oxide thin film on said substrate by simultaneously irradiating said substrate with oxygen ions having a constant energy by evaporating a raw material constituting the oxide thin film on a substrate in a high vacuum. A method for producing an oxide thin film, comprising using a metal nitride as a raw material for forming an oxide thin film.
ることを特徴とする請求の範囲第１項または第２項に記
載の酸化物薄膜の製造方法。3. The method for producing an oxide thin film according to claim 1, wherein the degree of vacuum is higher than 1 × 10 −3 Torr.
500eVに加速されたビーム状の酸素プラズマであること
を特徴とする請求の範囲第１項ないし第３項のいずれか
に記載の酸化物薄膜の製造方法。4. The method according to claim 1, wherein the oxygen ion having a constant energy is 10 to
4. The method for producing an oxide thin film according to claim 1, wherein the oxygen plasma is a beam-like oxygen plasma accelerated to 500 eV.
プラズマより引き出され10〜500eVに加速されたビーム
状の酸素イオンであることを特徴とする請求の範囲第１
項ないし第３項のいずれかに記載の酸化物薄膜の製造方
法。5. The method according to claim 1, wherein said oxygen ions having a constant energy are beam-shaped oxygen ions extracted from oxygen plasma and accelerated to 10 to 500 eV.
Item 4. The method for producing an oxide thin film according to any one of Items 3 to 3.
ものであることを特徴とする請求の範囲第５項に記載の
酸化物薄膜の製造方法。6. The method for producing an oxide thin film according to claim 5, wherein said beam-like oxygen ions are neutralized.
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|---|---|---|---|
| JP2441590A JP2916514B2 (en) | 1990-02-05 | 1990-02-05 | Manufacturing method of oxide thin film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2441590A JP2916514B2 (en) | 1990-02-05 | 1990-02-05 | Manufacturing method of oxide thin film |
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| Publication Number | Publication Date |
|---|---|
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| JP2916514B2 true JP2916514B2 (en) | 1999-07-05 |
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