JP3186381B2 - Method for producing oriented conductive thin film - Google Patents
Method for producing oriented conductive thin filmInfo
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- JP3186381B2 JP3186381B2 JP29762093A JP29762093A JP3186381B2 JP 3186381 B2 JP3186381 B2 JP 3186381B2 JP 29762093 A JP29762093 A JP 29762093A JP 29762093 A JP29762093 A JP 29762093A JP 3186381 B2 JP3186381 B2 JP 3186381B2
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- JP
- Japan
- Prior art keywords
- thin film
- conductive thin
- oriented
- single crystal
- producing
- 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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Description
【０００１】[0001]
【産業上の利用分野】本発明は、不揮発性メモリーやキ
ャパシター等の電子素子、更には光変調素子などに用い
る電極または抵抗体に適した配向性導電性薄膜の作製方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an oriented conductive thin film suitable for an electrode or a resistor used for an electronic device such as a nonvolatile memory or a capacitor, and also for a light modulation device.
【０００２】[0002]
【従来の技術】従来、各種の電子部品に用いられる薄膜
電極および発熱抵抗体は、電子ビーム蒸着法やスパッタ
リング法等の気相法によって形成されてきた。一方、有
機金属法（ＭＯＤ）またはペースト法によって、電極お
よび発熱抵抗体として導電性の主に厚膜が形成されてい
る。しかし、前者は設備コスト、薄膜の組成制御、大面
積化等、後者は膜質および薄膜化等に問題があった。こ
のうち、設備コスト、薄膜の組成制御、大面積化等に優
れた後者のペースト法では、Ｐｄ，Ａｇ，Ｐｄ−Ａｇ，
Ｐｔ等の貴金属粉末を導電材として、これにバインダ
ー、溶剤、ガラス・フリット等を混合したものを基板に
塗布し、焼き付けることによって、Ｐｄ，Ａｇ，Ｐｄ−
Ａｇ，Ｐｔ等の貴金属厚膜が作製されている。しかし、
これらの貴金属膜は酸化に強い反面、コストが著しく高
い。このため、特開昭６１−２２５７１１においては、
ＢａＰｂＯ3 等の導電性酸化物をペースト法によって形
成することが述べられているが、薄膜を必要とする電子
素子にはペースト法は前記のように不適である。また、
強誘電体薄膜を用いた不揮発性メモリーにおいては、Ｐ
ｔ等の金属電極を用いるとスイッチングに伴い強誘電体
の疲労がみられるが、近年、酸化物電極が強誘電体薄膜
のスイッチング疲労を抑制することが公知となった。例
えばＪ．Ｌｅｅ等，Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，
６３，２７（１９９３）では、ＹＢａ2 Ｃｕ3 Ｏx のＰ
ｂ（Ｚｒ0.52Ｔｉ0.48）Ｏ3 のスイッチング疲労への効
果が報告されている。しかし、超伝導体であるＹＢａ2
Ｃｕ3 Ｏx 薄膜の作製は、酸素濃度のコントロール等の
面において容易ではない。2. Description of the Related Art Heretofore, thin-film electrodes and heating resistors used for various electronic parts have been formed by a vapor phase method such as an electron beam evaporation method or a sputtering method. On the other hand, a conductive mainly thick film is formed as an electrode and a heating resistor by an organic metal method (MOD) or a paste method. However, the former equipment cost, composition control of the thin film, large area, etc., the latter has a problem in quality and thinning the like. Among these, Pd, Ag, Pd-Ag, Pd, Ag, Pd-Ag,
A mixture of a noble metal powder such as Pt as a conductive material, a binder, a solvent, a glass frit, or the like, is applied to a substrate and baked, whereby Pd, Ag, Pd-
Noble metal thick films of Ag, Pt, etc. have been produced. But,
While these noble metal films are resistant to oxidation, their cost is extremely high. For this reason, in Japanese Patent Application Laid-Open No. 61-225711,
Although it is described that a conductive oxide such as BaPbO 3 is formed by a paste method, the paste method is not suitable for an electronic element requiring a thin film as described above. Also,
In a nonvolatile memory using a ferroelectric thin film, P
When a metal electrode such as t is used, fatigue of the ferroelectric is observed with switching. In recent years, it has been known that an oxide electrode suppresses switching fatigue of a ferroelectric thin film. For example, Lee et al., Appl. Phys. Lett. ,
63 , 27 (1993), P of YBa 2 Cu 3 O x
The effect of b (Zr 0.52 Ti 0.48 ) O 3 on switching fatigue has been reported. However, the superconductor YBa 2
Fabrication of a Cu 3 O x thin film is not easy in terms of controlling the oxygen concentration.
【０００３】一方、本発明者は、既にＫ．Ｎａｓｈｉｍ
ｏｔｏ等，Ｍａｔｅｒ．Ｌｅｔｔ．，１０（７，８），
３４８（１９９１）に報告したように、有機金属化合物
であるＬｉＯＣ2 Ｈ5 およびＮｂ（ＯＣ2 Ｈ5 ）5 を加
水分解を予め行わないで用いると、サファイア（Ａｌ2
Ｏ3 ）単結晶基板上に単結晶の強誘電体薄膜であるＬｉ
ＮｂＯ3 がエピタキシャル成長することを発見した。具
体的には、エタノールを溶媒とするＬｉ［Ｎｂ（ＯＣ2
Ｈ5 ）6 ］前駆体溶液に水を加えていくと、ＬｉＮｂＯ
3 薄膜は配向性膜から焼成後に多結晶膜へと変化してい
くが、水分量をゼロとして前駆体を焼成すると、ＬｉＮ
ｂＯ3 薄膜はわずか４００℃の温度でエピタキシャル成
長をした。しかし、同様の方法にてエピタキシャルまた
は配向性の導電性酸化物が今までに作製されたことはな
かった。また、本発明者は、化学的に極めて安定なＭｇ
Ｏをバッファ層として半導体基板上へエピタキシャル成
長させ、更にその上にエピタキシャルまたは配向性の強
誘電体薄膜が形成された構造を得ることができることを
既に発明したが、エピタキシャルまたは配向性の導電性
酸化物をその上に作製するに至っていなかった。On the other hand, the present inventor has already described K. Nashim
oto et al., Mater. Lett. , 10 (7,8),
348 (1991), when the organometallic compounds LiOC 2 H 5 and Nb (OC 2 H 5 ) 5 are used without prior hydrolysis, sapphire (Al 2
O 3 ) Single crystal ferroelectric thin film Li on a single crystal substrate
It has been discovered that NbO 3 grows epitaxially. Specifically, Li [Nb (OC 2
H 5 ) 6 ] As water is added to the precursor solution, LiNbO
(3) The thin film changes from an oriented film to a polycrystalline film after firing, but when the precursor is fired with the water content being zero, LiN
The bO 3 thin film grew epitaxially at a temperature of only 400 ° C. However, epitaxial or oriented conductive oxides have not been produced by a similar method.
It was . Further, the present inventor has found that chemically extremely stable Mg
It has already been invented that a structure in which O is epitaxially grown on a semiconductor substrate as a buffer layer and an epitaxial or oriented ferroelectric thin film is further formed thereon can be obtained. Was not produced on it.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、有機
金属化合物を用いて、良質なエピタキシャルまたは配向
性の酸化物薄膜電極や酸化物薄膜抵抗体用の配向性導電
性薄膜の作製方法を提供し、これにより、強誘電体や半
導体等の薄膜成長用の導電性基板を安価に作製しようと
するものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a high quality epitaxial or oriented oxide thin film electrode or an oriented conductive thin film for an oxide thin film resistor using an organometallic compound. An object of the present invention is to provide an inexpensive conductive substrate for growing a thin film such as a ferroelectric or a semiconductor.
【０００５】[0005]
【課題を解決するための手段】本発明者は、従来から配
向性導電性薄膜について研究を重ねてきたところ、有機
金属化合物を原料として、エピタキシャルまたは配向性
の導電性薄膜を形成することによって、形成された導電
性酸化物が多くの強誘電体の格子定数および結晶構造に
近い格子定数および結晶構造を有するという知見を得
て、本発明を完成するに至ったものである。すなわち、
本発明の配向性導電性薄膜の作製方法は、加水分解され
ていない状態の有機金属化合物を成分とする有機金属化
合物前駆体溶液を窒素雰囲気中で単結晶基板上に塗布し
て薄膜を形成し、次いで、熱分解に続いてアニールする
ことにより、エピタキシャルまたは配向性のＡＢＯ3 型
の酸化物導電性薄膜を形成することを特徴とする。Means for Solving the Problems The inventor of the present invention has been conducting research on oriented conductive thin films, and found that by forming an epitaxial or oriented conductive thin film using an organometallic compound as a raw material, The inventors have found that the formed conductive oxide has lattice constants and crystal structures close to those of many ferroelectrics, and have completed the present invention. That is,
The method for producing an oriented conductive thin film of the present invention comprises forming a thin film by applying an organometallic compound precursor solution containing an unhydrolyzed organometallic compound as a component on a single crystal substrate in a nitrogen atmosphere. Then, annealing is performed after thermal decomposition to form an epitaxial or oriented ABO 3 type oxide conductive thin film.
【０００６】以下、本発明について詳細に説明する。本
発明の配向性導電性薄膜の作製方法おいては、原料とし
て、金属アルコキシド類または有機酸金属塩類より選ば
れる有機金属化合物が使用される。アルコキシドおよび
有機酸塩における金属としては、後述するＡＢＯ3 型複
合酸化物に含まれる金属が用いられる。これらの原料
は、アルコール類、ジケトン類、ケト酸類、アルキルエ
ステル類、オキシ酸類、オキシケトン類および酢酸等の
脂肪酸類などより選ばれる溶媒と所定の組成で反応させ
た後、あるいは溶媒中に溶解した後、基板へ塗布する。
溶媒との反応生成物または有機金属化合物を溶媒中に溶
解した溶液は、ＭｇＯ，ＭｇＡｌ2 Ｏ4 ，ＳｒＴｉ
Ｏ3 ，ＢａＺｒＯ3 ，ＬａＡｌＯ3 ，ＺｎＯ，Ａｌ2 Ｏ
3 ，Ｓｉ，ＧａＡｓ等の単結晶基板上、またはエピタキ
シャルまたは配向性のＭｇＯ，ＭｇＡｌ2 Ｏ4 等の単層
バッファ層もしくはＰｂ（Ｚｒ0.53Ｔｉ0.47）Ｏ3 （Ｐ
ＺＴ）／ＭｇＯ等の二層以上のバッファ層を表面に持つ
単結晶基板上に、スピンコート法、ディッピング法、ス
プレー法、スクリーン印刷法、インクジェット法等より
選ばれる方法により塗布される。上記有機金属化合物
は、加水分解した後に塗布することも可能であるが、エ
ピタキシャルまたは高配向性の強誘電体薄膜を得るため
には、加水分解をしないものが使用される。Hereinafter, the present invention will be described in detail. In the method for producing an oriented conductive thin film of the present invention, an organic metal compound selected from metal alkoxides or organic acid metal salts is used as a raw material. As the metal in the alkoxide and the organic acid salt, a metal contained in an ABO 3 type composite oxide described later is used. These raw materials were reacted with a solvent selected from alcohols, diketones, keto acids, alkyl esters, oxy acids, oxy ketones and fatty acids such as acetic acid, etc. with a predetermined composition, or dissolved in the solvent. Then, it is applied to the substrate.
The solution obtained by dissolving the reaction product with the solvent or the organometallic compound in the solvent is MgO, MgAl 2 O 4 , SrTi
O 3 , BaZrO 3 , LaAlO 3 , ZnO, Al 2 O
3 , a single-layer buffer layer such as MgO, MgAl 2 O 4 or a single-layer buffer layer of Pb (Zr 0.53 Ti 0.47 ) O 3 (P
A single crystal substrate having two or more buffer layers such as ZT) / MgO on the surface is applied by a method selected from a spin coating method, a dipping method, a spray method, a screen printing method, an ink jet method and the like. The above-mentioned organometallic compound can be applied after being hydrolyzed. However, in order to obtain an epitaxial or highly oriented ferroelectric thin film, one that does not hydrolyze is used .
【０００７】その後、前処理として酸素を含む雰囲気中
望ましくは酸素気流中で、０．１〜５００℃／秒の昇温
速度、望ましくは短時間に熱処理を行うために１〜５０
０℃／秒の急速昇温により基板を加熱し、１００〜５０
０℃の結晶化の起こらない温度範囲で塗布層を熱分解す
る。塗布と熱分解は一回以上の所定回数繰り返す。そし
て更に、酸素を含む雰囲気中もしくは酸素を含まない雰
囲気中、または酸素を含む雰囲気中に続いて酸素を含ま
ない雰囲気中で、０．１〜５００℃／秒の昇温速度、望
ましくは短時間に熱処理を行うために１〜５００℃／秒
の急速昇温により基板を加熱し、３００〜１２００℃の
温度範囲でアニールすることによって、エピタキシャル
または配向性の導電性薄膜を得ることができる。これら
の雰囲気としては乾燥した雰囲気が使用される。Then, as a pretreatment, a heat treatment is performed in an atmosphere containing oxygen, preferably in an oxygen stream, at a rate of 0.1 to 500 ° C./sec.
The substrate is heated by a rapid temperature rise of 0 ° C./sec.
The coating layer is thermally decomposed in a temperature range of 0 ° C. where crystallization does not occur. The application and thermal decomposition are repeated one or more predetermined times. Further, in an oxygen-containing atmosphere, an oxygen-free atmosphere, or an oxygen-containing atmosphere followed by an oxygen-free atmosphere, the temperature is increased at a rate of 0.1 to 500 ° C./sec, desirably for a short time. The substrate is heated by a rapid temperature rise of 1 to 500 ° C./sec to perform a heat treatment, and annealed in a temperature range of 300 to 1200 ° C., whereby an epitaxial or oriented conductive thin film can be obtained. A dry atmosphere is used as these atmospheres.
【０００８】以上の方法によって、基板上にＡＢＯ3 型
の酸化物導電性薄膜が形成される。ＡＢＯ3 型の酸化物
しては、特にＢａＰｂＯ3 または（Ｂａ1-2x/mＣ2x/m）
（Ｐｂ1-4y/nＤ4y/n）Ｏ3 で表される複合酸化物が好ま
しく使用される。ここで、Ｃは周期律表Ｉａ族，IIａ族
およびIII ａ族より選ばれる少なくとも一種の原子を表
し、Ｄは周期律表IIｂ族，IVａ族，IVｂ族，Ｖａ族，Ｖ
ｂ族およびVIII族より選ばれる少なくとも一種の原子を
表す。これらの原子のうち、ＣはＬｉ，Ｎａ，Ｋ，Ｓ
ｒ，Ｙ，Ｌａ，Ｃｅ，Ｇｄの少なくとも一つが望まし
く、ＤはＳｉ，Ｔｉ，Ｖ，Ｆｅ，Ｃｏ，Ｚｎ，Ｚｒ，Ｎ
ｂ，Ｓｎ，Ｓｂ，Ｔａ，Ｂｉの少なくとも一つが望まし
い。ｘおよびｙは、０＜ｘ，ｙ≦１であり、ｍはＣの原
子価を意味し、ｎはＤの原子価を意味する。また、本発
明における配向性導電性薄膜の上には、更にエピタキシ
ャルまたは配向性のＡＢＯ3 型強誘電体薄膜を気相成長
法またはゾルゲル法等により形成して、配向性強誘電体
薄膜を作製することができる。By the above method, an ABO 3 type oxide conductive thin film is formed on the substrate. As the ABO 3 type oxide, in particular, BaPbO 3 or (Ba 1-2x / m C 2x / m )
A composite oxide represented by (Pb 1-4y / n D 4y / n ) O 3 is preferably used. Here, C represents at least one atom selected from the group Ia, IIa and IIIa of the periodic table, and D represents the group IIb, IVa, IVb, Va, V
It represents at least one atom selected from group b and group VIII. Of these atoms, C is Li, Na, K, S
At least one of r, Y, La, Ce and Gd is desirable, and D is Si, Ti, V, Fe, Co, Zn, Zr, N
At least one of b, Sn, Sb, Ta, and Bi is desirable. x and y are 0 <x, y ≦ 1, m means the valence of C, and n means the valence of D. Further, on the oriented conductive thin film of the present invention, an epitaxial or oriented ABO 3 type ferroelectric thin film is further formed by a vapor phase growth method or a sol-gel method to produce an oriented ferroelectric thin film. can do.
【０００９】[0009]
【実施例】以下に、実施例によって本発明をより具体的
に説明するが、本発明はこれらの実施例に限定されるも
のではない。 実施例１ 等モル量のＢａ（ＯＣ2 Ｈ5 ）2 およびＰｂ（ＯＣ3 Ｈ
7 ）2 をモレキュラー・シーブで脱水した２−メトキシ
エタノールに溶解し、０．６Ｍ溶液を得た。この溶液を
攪拌しつつ２時間蒸留し、更に２２時間還流してダブル
・アルコキシドＢａＰｂ（ＯＣ2 Ｈ4 ＯＣＨ3 ）4 を得
た。このアルコール置換反応は 1ＨＮＭＲスペクトルに
よって確認した。このＢａＰｂＯ3 前駆構造を有するア
ルコキシドの形成は、Ｂａ／Ｐｂ＝１／１組成の制御と
分子レベルの均一性のために重要である。その後、得ら
れた前駆体溶液を０．２μｍのフィルターに通して、Ｍ
ｇＯ（１００）単結晶基板へ２０００ｒｐｍでスピンコ
ーティングを行った。以上の操作はすべて窒素雰囲気中
で行った。スピンコーティングの前に、ＭｇＯ基板は溶
剤洗浄、塩酸によるエッチング、脱イオン水によるリン
スを行い、最後に窒素気流中でエタノールのスピンコー
ティングによって乾燥した。スピンコーティングされた
基板は、室温にて脱イオン水中でバブリングした酸素雰
囲気中で１０℃／秒の速度で急速昇温して３００℃に２
分間保持した後、４５０〜６５０℃に３０分間保持し、
最後に電気炉の電源を切り冷却した。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 Equimolar amounts of Ba (OC 2 H 5 ) 2 and Pb (OC 3 H
7 ) 2 was dissolved in 2-methoxyethanol dehydrated with molecular sieve to obtain a 0.6M solution. The solution was distilled for 2 hours with stirring and refluxed for 22 hours to obtain double alkoxide BaPb (OC 2 H 4 OCH 3 ) 4 . This alcohol substitution reaction was confirmed by the 1 H NMR spectrum. The formation of the alkoxide having the BaPbO 3 precursor structure is important for controlling the composition of Ba / Pb = 1/1 and for homogeneity at the molecular level. Thereafter, the obtained precursor solution was passed through a 0.2 μm filter to remove M
Spin coating was performed on the gO (100) single crystal substrate at 2000 rpm. All of the above operations were performed in a nitrogen atmosphere. Prior to spin coating, the MgO substrate was washed with a solvent, etched with hydrochloric acid, rinsed with deionized water, and finally dried by spin coating with ethanol in a nitrogen stream. The spin-coated substrate was rapidly heated to 300 ° C. at a rate of 10 ° C./sec in an oxygen atmosphere bubbled in deionized water at room temperature.
After holding for 450 minutes at 450-650 ° C. for 30 minutes,
Finally, the electric furnace was turned off and cooled.
【００１０】塗布した基板を３００℃で熱分解を行った
後、更に酸素気流中で４５０℃以上で加熱を行うと、１
０℃／秒という高速で昇温したにもかかわらず、得られ
た膜厚０．１μｍのＢａＰｂＯ3 薄膜は（１１０）配向
に結晶化したＸ線回折パターンを示した。さらに比較の
ために、１０℃／秒で急速昇温して３００℃で熱分解を
行うことなく、６５０℃で結晶化したＢａＰｂＯ3 薄膜
の表面をＳＥＭ（走査型電子顕微鏡）によって観察した
ところ、薄膜に割れと気泡がみられ、極めて品質が悪か
った。一方、３００℃での熱分解を行った場合には良好
なＢａＰｂＯ3薄膜が得られた。このように急速昇温の
際には、結晶化の前に熱分解を行うことが有効であっ
た。得られたＢａＰｂＯ3 薄膜の抵抗を四端子法によっ
て測定したところ、４５０℃アニール薄膜は９×１０-4
Ω・ｃｍ、５５０℃アニール薄膜は３×１０-4Ω・ｃ
ｍ、６５０℃アニール薄膜は２×１０-4Ω・ｃｍの低い
抵抗値を示した。ＢａＰｂＯ3 はバンド・ギャップが狭
いため金属的電気伝導を示すが、可視光に対してはこの
ため透明ではない。しかし、本実施例におけるＢａＰｂ
Ｏ3 薄膜は、アニール温度、膜厚あるいは組成（例えば
次の実施例２）によっては、可視光に対してある程度の
透明性が観察された。After the applied substrate is thermally decomposed at 300 ° C. and further heated at 450 ° C. or higher in an oxygen stream,
Despite heating at a high temperature of 0 ° C./sec, the obtained BaPbO 3 thin film having a thickness of 0.1 μm showed an X-ray diffraction pattern crystallized in (110) orientation. For further comparison, the surface of the BaPbO 3 thin film crystallized at 650 ° C. was observed by SEM (scanning electron microscope) without being thermally decomposed at 300 ° C. by rapidly increasing the temperature at 10 ° C./sec. Cracks and bubbles were observed in the thin film, and the quality was extremely poor. On the other hand, when thermal decomposition was performed at 300 ° C., a good BaPbO 3 thin film was obtained. Thus, during rapid temperature rise, it was effective to carry out thermal decomposition before crystallization. When the resistance of the obtained BaPbO 3 thin film was measured by a four-terminal method, the thin film annealed at 450 ° C. was 9 × 10 −4.
Ω · cm, 550 ° C annealed thin film is 3 × 10 -4 Ω · c
The m, 650 ° C. annealed thin film exhibited a low resistance value of 2 × 10 −4 Ω · cm. BaPbO 3 exhibits metallic electrical conduction due to its narrow band gap, but is not transparent to visible light. However, in this embodiment, BaPb
The O 3 thin film was observed to have a certain degree of transparency to visible light depending on the annealing temperature, film thickness, or composition (for example, the following Example 2).
【００１１】次に、モル比でＰｂ：Ｚｒ：Ｔｉ＝１．０
０：０．５３：０．４７のＰｂ（ＣＨ3 ＣＯＯ）2 、Ｚ
ｒ（Ｏ -i-Ｃ3 Ｈ7 ）4 およびＴｉ（Ｏ -i-Ｃ3 Ｈ7 ）
4 を２−メトキシエタノールに溶解し、６時間蒸留した
後、１８時間還流し、最終的に、Ｐｂ濃度で０．５Ｍの
Ｐｂ（Ｚｒ0.53Ｔｉ0.47）Ｏ3 （ＰＺＴ）の前駆体溶液
を得た。この前駆体溶液を上記のＢａＰｂＯ3 （１１
０）／ＭｇＯ（１００）基板上に２０００ｒｐｍでスピ
ンコーティングを行った。以上の操作はすべて窒素雰囲
気中で行った。スピンコーティングされた基板は、１０
℃／秒で昇温し、酸素雰囲気中３５０℃で熱分解を行っ
た後、基板を６５０℃で３０分間加熱することによりＰ
ＺＴ薄膜が結晶化し、（１１０）に配向したＰＺＴ薄膜
が得られた。更に、このＰＺＴ薄膜上にＢａＰｂＯ3 薄
膜を上記と同じ方法によって再度形成した。得られた配
向性導電性薄膜は、図１に示すように、酸化物基板１ａ
上に導電体層２、強誘電体層３および導電体層２が形成
された層構造からなる。このようにして作製したＢａＰ
ｂＯ3 ／ＰＺＴ／ＢａＰｂＯ3 ／ＭｇＯ素子を用いて、
ＢａＰｂＯ3 を上下部電極として電圧を印加することに
より、ＰＺＴの分極特性を試験したところ、金属電極と
比較して良好なスイッチング特性と疲労特性を示した。Next, the molar ratio of Pb: Zr: Ti = 1.0
0: 0.53: 0.47 Pb (CH 3 COO) 2 , Z
r (O -i-C 3 H 7) 4 and Ti (O -i-C 3 H 7)
4 was dissolved in 2-methoxyethanol and distilled for 6 hours, and then refluxed for 18 hours. Finally, a precursor solution of Pb (Zr 0.53 Ti 0.47 ) O 3 (PZT) having a Pb concentration of 0.5M was obtained. Was. This precursor solution was mixed with the above BaPbO 3 (11
0) / MgO (100) substrate was spin-coated at 2000 rpm. All of the above operations were performed in a nitrogen atmosphere. Spin-coated substrates are 10
The temperature was raised at a rate of 350 ° C./sec, and pyrolysis was carried out at 350 ° C. in an oxygen atmosphere.
The ZT thin film crystallized, and a (110) -oriented PZT thin film was obtained. Further, a BaPbO 3 thin film was formed again on the PZT thin film by the same method as described above. The obtained oriented conductive thin film is, as shown in FIG.
It has a layer structure in which the conductor layer 2, the ferroelectric layer 3, and the conductor layer 2 are formed thereon. BaP prepared in this manner
Using a bO 3 / PZT / BaPbO 3 / MgO element,
The polarization characteristics of PZT were tested by applying a voltage using BaPbO 3 as the upper and lower electrodes. As a result, better switching characteristics and better fatigue characteristics were exhibited as compared with the metal electrodes.
【００１２】実施例２ 原料として、モル比でＢａ：Ｓｒ：Ｐｂ＝０．７：０．
３：１．０のＢａ（ＯＣ2 Ｈ5 ）2 、Ｓｒ（ＯＣ
2 Ｈ5 ）2 およびＰｂ（ＯＣ3 Ｈ7 ）2 を脱水した２−
メトキシエタノールに溶解し、Ｐｂ濃度で０．６Ｍの溶
液を得た。この溶液を攪拌しつつ２時間蒸留し、更に２
２時間還流して複合アルコキシドを得た。この前駆体溶
液を０．２μｍのフィルターに通して、（Ｂａ0.7 Ｓｒ
0.3 ）Ｐｂ（ＯＣ2 Ｈ4 ＯＣＨ3 ）4 溶液をＳｒＴｉＯ
3 （１００）単結晶基板へ２０００ｒｐｍでスピンコー
ティングを行った。以上の操作はすべて窒素雰囲気中で
行い、スピンコーティングの前に、基板は実施例１と同
様に溶剤洗浄、エッチング、リンス、乾燥を行った。ス
ピンコーティングされた基板は、乾燥した酸素雰囲気中
１０℃／秒で昇温して３００℃に保持した後、６５０℃
に保持し、最後に電気炉の電源を切り冷却した。これに
より、（１００）に配向した（Ｂａ0.7 Ｓｒ0.3 ）Ｐｂ
Ｏ3 薄膜が得られた。この薄膜は２×１０-4Ω・ｃｍの
低い抵抗値を示した。Example 2 As a raw material, a molar ratio of Ba: Sr: Pb = 0.7: 0.
3: 1.0 Ba (OC 2 H 5 ) 2 , Sr (OC
2 H 5) 2 and Pb (OC 3 H 7) 2 were dehydrated 2-
It was dissolved in methoxyethanol to obtain a solution having a Pb concentration of 0.6 M. This solution was distilled for 2 hours with stirring, and further 2 hours.
The mixture was refluxed for 2 hours to obtain a composite alkoxide. The precursor solution was passed through a 0.2 μm filter to obtain (Ba 0.7 Sr
0.3 ) Pb (OC 2 H 4 OCH 3 ) 4 solution was converted to SrTiO
3 Spin coating was performed on a (100) single crystal substrate at 2000 rpm. All the above operations were performed in a nitrogen atmosphere, and the substrate was subjected to solvent washing, etching, rinsing, and drying in the same manner as in Example 1 before spin coating. The spin-coated substrate is heated at a rate of 10 ° C./sec in a dry oxygen atmosphere and maintained at 300 ° C., and then at 650 ° C.
And finally the electric furnace was turned off to cool. Thereby, (Ba 0.7 Sr 0.3 ) Pb oriented to (100)
An O 3 thin film was obtained. This thin film showed a low resistance value of 2 × 10 −4 Ω · cm.
【００１３】実施例３ 実施例１と同様にして、ＰＺＴの前駆体溶液をＳｒＴｉ
Ｏ3 （１００）単結晶基板上に２０００ｒｐｍでスピン
コーティングした。この基板を１０℃／秒で昇温し、酸
素雰囲気中で３５０℃で塗布膜を熱分解した後、６５０
℃において加熱することにより、（００１）の方位にエ
ピタキシャルなＰＺＴ薄膜を得た。このＰＺＴ薄膜をエ
ピタキシャル・バッファ層として、ＢａＰｂＯ3 薄膜を
実施例１と同様にして形成すると、ＢａＰｂＯ3 は（１
００）の方位にエピタキシャルに結晶化した。更に、こ
の上に、実施例１と同様の方法によりＰＺＴ薄膜を形成
することによって、ＰＺＴ（００１）／ＢａＰｂＯ
3 （１００）／ＰＺＴ（００１）／ＳｒＴｉＯ3 （１０
０）の多層エピタキシャル構造を得た。Example 3 In the same manner as in Example 1, the precursor solution of PZT was
Spin coating was performed on an O 3 (100) single crystal substrate at 2000 rpm. This substrate was heated at a rate of 10 ° C./sec, and thermally decomposed the coating film at 350 ° C. in an oxygen atmosphere.
By heating at ° C, a PZT thin film epitaxially oriented in the (001) direction was obtained. When this PZT thin film is used as an epitaxial buffer layer and a BaPbO 3 thin film is formed in the same manner as in Example 1, BaPbO 3 becomes (1
Crystallized epitaxially in the orientation of (00). Further, a PZT thin film is formed thereon in the same manner as in Example 1 to obtain PZT (001) / BaPbO.
3 (100) / PZT (001) / SrTiO 3 (10
0) A multilayer epitaxial structure was obtained.
【００１４】実施例４ ターゲット表面をＵＶレーザー・パルスにより瞬間的に
加熱して蒸着するエキシマ・レーザー・デポジション法
によって、ＧａＡｓ（１００）単結晶基板上にエピタキ
シャル・バッファ層を形成した。すなわち、レーザー
は、波長３０８ｎｍのＸｅＣｌエキシマ・レーザーを用
い、パルス周期４Ｈｚ、パルス長１７ｎｓ、エネルギー
１３０ｍＪ（ターゲット表面でのエネルギー密度１．３
Ｊ／ｃｍ2）の条件とした。ターゲットは金属Ｍｇを用
い、ＭｇＯを反応成長させた。ＧａＡｓ単結晶基板は溶
剤洗浄後、硫酸系の溶液でエッチングを行った。更に、
この基板を脱イオン水とエタノールでリンスし、最後に
窒素気流中でエタノールによるスピン乾燥を行った。ス
ピン乾燥後に、基板を直ちにデポジション・チャンバー
に導入し、一定温度に加熱して５００オンク゛ストロ-ムのエピ
タキシャルＭｇＯ（１００）バッファ層の成膜を行っ
た。次に、実施例１と同様にして、前駆体溶液よりＰＺ
Ｔ、ＢａＰｂＯ3 、更に（Ｐｂ0.72Ｌａ0.28）ＴｉＯ3
（ＰＬＴ）を形成することにより、ＰＬＴ（００１）／
ＢａＰｂＯ3 （１００）／ＰＺＴ（００１）／ＭｇＯ
（１００）／ＧａＡｓ（１００）の多層エピタキシャル
構造を得た。得られた配向性導電性薄膜の多層構造を図
２に示す。この層構造は、表面に第一バッファ層４ａお
よび第二バッファ層４ｂを有する半導体基板１ｂ上に、
導電体層２および強誘電体層３が形成されている。Example 4 An epitaxial buffer layer was formed on a GaAs (100) single crystal substrate by an excimer laser deposition method in which the target surface was instantaneously heated and deposited by a UV laser pulse. That is, a XeCl excimer laser having a wavelength of 308 nm is used as the laser, and the pulse period is 4 Hz, the pulse length is 17 ns, and the energy is 130 mJ (the energy density at the target surface is 1.3
J / cm 2 ). MgO was used as a target, and MgO was reacted and grown. The GaAs single crystal substrate was etched with a sulfuric acid-based solution after washing with a solvent. Furthermore,
This substrate was rinsed with deionized water and ethanol, and finally spin-dried with ethanol in a nitrogen stream. After the spin drying, the substrate was immediately introduced into a deposition chamber and heated to a constant temperature to form a 500 Å epitaxial MgO (100) buffer layer. Next, PZ was prepared from the precursor solution in the same manner as in Example 1.
T, BaPbO 3 , and (Pb 0.72 La 0.28 ) TiO 3
By forming (PLT), PLT (001) /
BaPbO 3 (100) / PZT (001) / MgO
A multilayer epitaxial structure of (100) / GaAs (100) was obtained. FIG. 2 shows a multilayer structure of the obtained oriented conductive thin film. This layer structure is formed on a semiconductor substrate 1b having a first buffer layer 4a and a second buffer layer 4b on the surface.
The conductor layer 2 and the ferroelectric layer 3 are formed.
【００１５】[0015]
【発明の効果】本発明の配向性導電性薄膜の作製方法に
よれば、精密な化学組成制御、分子レベルの均一性、プ
ロセスの低温化、大面積化、低設備コスト等の面で有利
である有機金属化合物溶液を用いて、コスト、耐酸化性
に優れたエピタキシャルまたは配向性の導電性酸化物薄
膜を短時間に得ることが可能となる。このため、不揮発
性メモリーや光変調素子の電極としての導電性酸化物薄
膜の作製が可能となる。さらに、本発明における導電性
酸化物は、多くの強誘電体の格子定数および結晶構造に
近い格子定数および結晶構造を有するために、この導電
性酸化物薄膜上にエピタキシャルまたは配向性の強誘電
体薄膜等を堆積することが可能となり、高性能な素子の
作製が可能となる。According to the method for producing an oriented conductive thin film of the present invention, it is advantageous in terms of precise chemical composition control, uniformity at a molecular level, low temperature of the process, large area, low equipment cost, and the like. By using a certain organometallic compound solution, an epitaxial or oriented conductive oxide thin film excellent in cost and oxidation resistance can be obtained in a short time. Therefore, a conductive oxide thin film as an electrode of a nonvolatile memory or a light modulation element can be manufactured. Further, since the conductive oxide in the present invention has a lattice constant and a crystal structure close to those of many ferroelectrics, an epitaxial or oriented ferroelectric substance is formed on the conductive oxide thin film. A thin film or the like can be deposited, and a high-performance device can be manufactured.
【図１】 ＭｇＯ（１００）基板上に配向性ＢａＰｂＯ
3 （１１０）／ＰＺＴ（１１０）／ＢａＰｂＯ3 （１１
０）を形成した実施例１の配向性導電性薄膜を示す。FIG. 1. Oriented BaPbO on MgO (100) substrate
3 (110) / PZT (110) / BaPbO 3 (11
1 shows an oriented conductive thin film of Example 1 in which No. 0) was formed.
【図２】 ＧａＡｓ（１００）基板上にＭｇＯ（１０
０）／ＰＺＴ（００１）／ＢａＰｂＯ3 （１００）／Ｐ
ＬＴ（００１）を形成した実施例４の多層エピタキシャ
ル構造の配向性導電性薄膜を示す。FIG. 2 shows an example in which MgO (10) is formed on a GaAs (100) substrate.
0) / PZT (001) / BaPbO 3 (100) / P
7 shows an oriented conductive thin film having a multilayer epitaxial structure of Example 4 in which LT (001) was formed.
１ａ…酸化物基板、１ｂ…半導体基板、２…導電体層、
３…強誘電体層、４ａ…第一バッファ層、４ｂ…第二バ
ッファ層。1a: oxide substrate, 1b: semiconductor substrate, 2: conductor layer,
3 ... ferroelectric layer, 4a ... first buffer layer, 4b ... second buffer layer.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−234809（ＪＰ，Ａ) Ｔ．Ａｚｕｍａ ｅｔ．ａｉ．，”Ｐ ｒｅｐａｒａｔｉｏｎ ａｎｄ ｂａｓ ｉｃ ｐｒｏｐｅｒｔｉｅｓ ｏｆ Ｂ ａＴｉＯ３−ＢａＰｂＯ３ ｍｕｌｔｉ ｌａｙｅｒ ｔｈｉｎ ｆｉｌｍｓ ｂ ｙ ｍｅｔａｌ−ａｌｋｏｘｉｄｅｓ ｍｅｔｈｏｄ”，Ｊｐｎ．Ｊ．Ａｐｐ ｌ．Ｐｈｙｓ．Ｐａｒｔ １，Ｖｏｌ. 32，Ｎｏ．９Ｂ，Ｓｅｐ．1993，ｐｐ. 4089−4091 (58)調査した分野(Int.Cl.7，ＤＢ名) C30B 1/00 - 35/00 H01B 3/00 H01L 21/314 H01L 21/822 H01L 27/04 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ) ＷＰＩ（ＤＩＡＬＯＧ)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-234809 (JP, A) Azuma et. ai. , "Preparation and basic properties of BaTiO3-BaPbO3 multi layer thin films by metal-alkoxides method", Jpn. J. Appl. Phys. Part 1, Vol. 32, No. 9B, Sep. 1993, pp. 4089-4091 (58) Fields investigated (Int. Cl. 7 , DB name) C30B 1/00-35/00 H01B 3/00 H01L 21/314 H01L 21/822 H01L 27/04 CA (STN ) REGISTRY (STN) WPI (DIALOG)
Claims (7)
合物を成分とする有機金属化合物前駆体溶液を窒素雰囲
気中で単結晶基板上に塗布して薄膜を形成し、次いで、
熱分解に続いてアニールすることにより、エピタキシャ
ルまたは配向性のＡＢＯ3 型の酸化物導電性薄膜を形成
することを特徴とする配向性導電性薄膜の作製方法。An organometallic compound precursor solution containing an unhydrolyzed organometallic compound as a component is coated on a single crystal substrate in a nitrogen atmosphere to form a thin film. ,
A method for producing an oriented conductive thin film, comprising forming an epitaxial or oriented ABO 3 type oxide conductive thin film by annealing after thermal decomposition.
秒で行なうことを特徴とする請求項１記載の配向性導電
性薄膜の作製方法。 2. The method according to claim 1, wherein the annealing is performed at a temperature rise of 1 to 500 ° C. /
2. The oriented conductive material according to claim 1, wherein the process is performed in seconds.
Method for producing conductive thin film.
コキシド類および有機酸金属塩類より選ばれる有機金属
化合物の混合物またはそれらの反応生成物である請求項
１記載の配向性導電性薄膜の作製方法。3. The method for producing an oriented conductive thin film according to claim 1, wherein the organometallic compound precursor is a mixture of organometallic compounds selected from metal alkoxides and organic acid metal salts or a reaction product thereof. .
キシエタノールと混合または反応して形成されたもので
あることを特徴とする請求項３記載の配向性導電性薄膜
の作製方法。Wherein the organometallic compound precursor, a method for manufacturing a orientation conductive thin film according to claim 3, characterized in that formed by mixing or reacting with 2-methoxyethanol.
導体単結晶より選ばれる請求項１記載の配向性導電性薄
膜の作製方法。5. The method according to claim 1, wherein the single crystal substrate is selected from an oxide single crystal and a semiconductor single crystal.
配向性のバッファ層を表面に持つ請求項１記載の配向性
導電性薄膜の作製方法。6. The method for producing an oriented conductive thin film according to claim 1, wherein the single crystal substrate has an epitaxial or oriented buffer layer on the surface.
ある請求項１記載の配向性導電性薄膜の作製方法。7. The method for producing an oriented conductive thin film according to claim 1, wherein said oxide conductive thin film is BaPbO 3 .
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| JP29762093A JP3186381B2 (en) | 1993-11-04 | 1993-11-04 | Method for producing oriented conductive thin film |
| US08/439,371 US5650362A (en) | 1993-11-04 | 1995-05-11 | Oriented conductive film and process for preparing the same |
| US08/620,752 US5656382A (en) | 1993-11-04 | 1996-03-18 | Oriented conductive film and process for preparing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29762093A JP3186381B2 (en) | 1993-11-04 | 1993-11-04 | Method for producing oriented conductive thin film |
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|---|---|
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| JP5899615B2 (en) * | 2010-03-18 | 2016-04-06 | 株式会社リコー | Insulating film manufacturing method and semiconductor device manufacturing method |
| JP2011012349A (en) * | 2010-10-01 | 2011-01-20 | Hochiki Corp | Thin film deposition apparatus and thin film deposition method using the same |
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1993
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Non-Patent Citations (1)
| Title |
|---|
| Ｔ．Ａｚｕｍａ ｅｔ．ａｉ．，"Ｐｒｅｐａｒａｔｉｏｎ ａｎｄ ｂａｓｉｃ ｐｒｏｐｅｒｔｉｅｓ ｏｆ ＢａＴｉＯ３−ＢａＰｂＯ３ ｍｕｌｔｉｌａｙｅｒ ｔｈｉｎ ｆｉｌｍｓ ｂｙ ｍｅｔａｌ−ａｌｋｏｘｉｄｅｓ ｍｅｔｈｏｄ"，Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ．Ｐａｒｔ １，Ｖｏｌ．３２，Ｎｏ．９Ｂ，Ｓｅｐ．１９９３，ｐｐ．４０８９−４０９１ |
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