JP2547204B2 - Method for forming bismuth titanate thin film - Google Patents
Method for forming bismuth titanate thin filmInfo
- Publication number
- JP2547204B2 JP2547204B2 JP62002539A JP253987A JP2547204B2 JP 2547204 B2 JP2547204 B2 JP 2547204B2 JP 62002539 A JP62002539 A JP 62002539A JP 253987 A JP253987 A JP 253987A JP 2547204 B2 JP2547204 B2 JP 2547204B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- material containing
- raw material
- atoms
- 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.)
- Expired - Fee Related
Links
Landscapes
- Physical Vapour Deposition (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、電界効果トランジスタ（FET）、光スイッ
チ、メモリー等の用途に用いられるチタン酸ビスマス
（以下、Bi4Ti3O12と表す。）薄膜の形成方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention refers to bismuth titanate (hereinafter referred to as Bi 4 Ti 3 O 12 ) used for applications such as field effect transistors (FETs), optical switches, and memories. ) It relates to a method for forming a thin film.
（従来の技術） Bi4Ti3O12の薄膜はFET、光スイッチ、メモリー等の用
途に用いられる可能性を持っている。この物質の単結晶
は空間群がB2cb（ａ＝5.448、ｂ＝32.83、ｅ＝5.411,z
＝４）に属する層状化合物であり、ｂ軸は第１図に示す
ように、層に対して垂直である。この物質は675℃にキ
ューリー点を持ち、この温度以下で強誘電性を示し、双
極子ベクトルは、ａ−ｂ面上に存在する。この双極子の
向きが電界の印加によって変る特性を利用して上記の光
スイッチ等に使用されている。この時のスイッチング動
作には３〜4kV/cmのしきい電圧が存在するため、メモリ
ーデバイスとしても適材である。(Prior Art) The thin film of Bi 4 Ti 3 O 12 has a possibility of being used for FETs, optical switches, memories and the like. The single crystal of this material has a space group of B2cb (a = 5.448, b = 32.83, e = 5.411, z
= 4), the b-axis is perpendicular to the layer as shown in FIG. This substance has a Curie point at 675 ° C., exhibits ferroelectricity below this temperature, and a dipole vector exists on the ab plane. This dipole is used in the above-mentioned optical switch or the like by utilizing the characteristic that the direction of the dipole changes by the application of an electric field. Since the switching operation at this time has a threshold voltage of 3 to 4 kV / cm, it is suitable as a memory device.
しかし、前述のように、しきい電圧が大きいため、あ
る程度の厚さの単結晶ではスイッチングのための動作電
圧が高すぎるという問題があった。このためBi4Ti3O12
薄膜を形成し、動作電圧を下げることが提案されている
（例えば、特開昭61−6123号、特開昭61−6124号）。こ
の提案は、Bi4Ti3O12膜をスパッタリング法で形成しよ
うとするものであり、プレナーマグネトロンスパッタ法
でターゲットとしてBi4Ti3O12を60〜80ωｔ％、Bi12TiO
20を40〜20ωｔ％の割合で含む焼結体を用いている。However, as described above, since the threshold voltage is large, there is a problem that the operating voltage for switching is too high with a single crystal having a certain thickness. For this reason Bi 4 Ti 3 O 12
It has been proposed to form a thin film and reduce the operating voltage (for example, Japanese Patent Laid-Open Nos. 61-6123 and 61-6124). This proposal is intended to form a Bi 4 Ti 3 O 12 film by a sputtering method, 60～80Omegati% a Bi 4 Ti 3 O 12 as a target in planar magnetron sputtering, Bi 12 TiO
A sintered body containing 20 in a ratio of 40 to 20 ωt% is used.
（発明が解決しようとする問題点） しかし、Biの蒸気圧とTiの蒸気圧とは異なるため、一
定組成比を持つ均質物質を得ることはかなりむずかしか
った。(Problems to be Solved by the Invention) However, since the vapor pressure of Bi and the vapor pressure of Ti are different, it is quite difficult to obtain a homogeneous substance having a constant composition ratio.
また、基板温度も約600℃以下では、Bi2O3、TiO2、Ti
2O3等の混合物薄膜になり目的のBi4Ti3O12が得られない
という問題があった。Also, when the substrate temperature is less than about 600 ° C, Bi 2 O 3 , TiO 2 , Ti
There has been a problem that the desired thin film of Bi 4 Ti 3 O 12 cannot be obtained because it becomes a mixture thin film of 2 O 3 or the like.
このため、従来の蒸着法では、基板温度を600〜750℃
と非常に高くするか、室温でまず蒸着し、その後600〜7
00℃で熱処理をしてBi4Ti3O12薄膜を形成させていた。Therefore, the conventional vapor deposition method requires a substrate temperature of 600 to 750 ° C.
Very high or vapor deposition first at room temperature, then 600 ~ 7
It was heat treated at 00 ° C. to form a Bi 4 Ti 3 O 12 thin film.
又、きれいな結晶軸配向性を持つ薄膜（例えばｂ軸配
向膜）を得ることは一般的に困難であり、基板物質によ
りその面上に堆積される結晶の方向性に影響があり、従
って基板物質としてごく限られた基板物質しか使用する
ことが出来ない。Also, it is generally difficult to obtain a thin film having a good crystal axis orientation (for example, a b-axis orientation film), and the orientation of crystals deposited on the surface is influenced by the substrate material, and thus the substrate material As a result, only a very limited substrate material can be used.
本発明は以上のような問題点、即ちBi成分とTi成分
の組成比の制御が不安定であること、基板温度が高い
こと、限られた基板物質しか使用できないこと、とい
う問題点を解決しようとするものである。The present invention solves the above problems, that is, the control of the composition ratio of the Bi component and the Ti component is unstable, the substrate temperature is high, and only a limited substrate material can be used. It is what
（問題点を解決する為の手段） 上記問題点は、少なくともチタン原子を含む原料物質
と、少なくともビスマス原子を含む原料物質のそれぞれ
から蒸発せしめられた蒸発物質を所望の位置に配せられ
た基板上に蒸着するチタン酸ビスマス薄膜の形成方法に
おいて、前記蒸発物質のいずれか一方をイオンビーム蒸
着法によって蒸着させ、前記基板上にBi4Ti3O12からな
る薄膜を形成することを特徴とするチタン酸ビスマス薄
膜の形成方法によって解決される。(Means for Solving Problems) The above-mentioned problems are caused by a substrate on which vaporized substances evaporated from the raw material containing at least titanium atoms and the raw material containing at least bismuth atoms are arranged at desired positions. In the method of forming a bismuth titanate thin film to be vapor-deposited on, one of the vaporized substances is vapor-deposited by an ion beam vapor deposition method to form a thin film of Bi 4 Ti 3 O 12 on the substrate. This is solved by a method of forming a bismuth titanate thin film.
本発明によって、任意の基板、例えば、各種ガラス
板、各種セラミック板、酸化物単結晶板、金属板又は合
金板の表面に、Bi4Ti3O12の多結晶膜、アモルファス
膜、あるいは一軸配向膜を自由に形成し、必要な結晶性
を有するBi4Ti3O12薄膜を得ることができる。According to the present invention, any substrate, for example, various glass plate, various ceramic plate, oxide single crystal plate, metal plate or alloy plate surface, Bi 4 Ti 3 O 12 polycrystalline film, amorphous film, or uniaxial orientation The film can be formed freely and a Bi 4 Ti 3 O 12 thin film having the required crystallinity can be obtained.
以下、本発明を図面を用いて詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to the drawings.
第２図に本発明に用いた蒸着装置の概略図を示す。第
２図において、１は基板、２は形成したBi4Ti3O12薄
膜、３、４は原料物質を入れたルツボであり、図示して
いない装置で温度制御が可能である。又、５はルツボか
ら出た蒸発物質である蒸気をイオン化するためのイオン
化ユニット、６はイオン化された蒸気を加速するための
加速電極、７、８はルツボ３、４から蒸発した蒸気及び
そのイオンビームである。更に、９はイオン化された蒸
気を加速するための加速電源で、この図では基板をアー
ス電位として10kV程度までの任意の加速が可能である。
10は真空容器である。なお、基板１の温度、イオン化ユ
ニット５におけるイオン化電流、真空容器10の真空度は
夫々、図示していない装置により制御できるようになっ
ている。FIG. 2 shows a schematic diagram of the vapor deposition apparatus used in the present invention. In FIG. 2, 1 is a substrate, 2 is a formed Bi 4 Ti 3 O 12 thin film, and 3 and 4 are crucibles containing raw materials, and the temperature can be controlled by an apparatus (not shown). Further, 5 is an ionization unit for ionizing vapor, which is a vaporized substance emitted from the crucible, 6 is an accelerating electrode for accelerating the ionized vapor, 7 and 8 are vapors vaporized from the crucibles 3 and 4 and their ions. The beam. Further, 9 is an accelerating power source for accelerating the ionized vapor, and in this figure, arbitrary acceleration up to about 10 kV is possible with the substrate at the ground potential.
10 is a vacuum container. The temperature of the substrate 1, the ionization current in the ionization unit 5, and the vacuum degree of the vacuum container 10 can be controlled by a device (not shown).
このような装置により、以下のようにしてBi4Ti3O12
薄膜を形成することができる。まず、真空容器10の真空
度を10-6Torr程度より高真空にし、基板１の温度を所定
の温度に設定する。ルツボ３、４に原料物質、例えば、
Bi、Bi2O3等の酸化ビスマスの中のいずれか一つとTi、T
iO2、Ti2O3等の酸化チタンの中のいずれか一つを入れ、
蒸気圧が10-4Torr程度以上になるように加熱する。この
とき基板１の周辺に設置した膜厚モニター（例えば、水
晶振動子、図示していない。）で、Bi、Ti成分の組成比
を測定し、所望の比率になるようにルツボの温度を調整
する。次に、イオン化ユニット、加速電源を用いてルツ
ボ４から蒸発した蒸発物質をイオンビーム化し、Bi4Ti3
O12薄膜を基板上に形成する。蒸着中、真空容器10に設
けた導入口よりO2ガスを９〜12ml/secの割合で導入す
る。一般的には、Bi成分のみをイオン化した場合、同じ
結晶性の薄膜を得るためには、より結晶性の良いBi4Ti3
O12薄膜が得られ、基板温度も低くすることができる。
これに対して、Ti成分のみをイオンビーム化した場合、
同じ結晶性の薄膜を得るためには、基板温度を上昇させ
る必要があり、また、Bi4Ti3O12の形成速度が低下する
傾向がある。第１表にBi、Tiのどちらの成分をイオン化
するか、その場合のイオン化電流、加速電圧、基板温度
の組み合せの一例を示した。Bi原子を含む原料物質とし
てBi2O3、Ti原子を含む原料物質としてTiを用い、基板
に石英ガラスを用いた場合の結果を以下に示す。第１表
において、No.1、２、６はルツボ３にBi2O3を入れ、No.
3、４、５はルツボ３にTiを入れた場合である。With such a device, Bi 4 Ti 3 O 12
A thin film can be formed. First, the vacuum degree of the vacuum container 10 is set to a vacuum higher than about 10 −6 Torr, and the temperature of the substrate 1 is set to a predetermined temperature. Source material, for example, in crucibles 3 and 4
Any one of Bi, Bi 2 O 3 etc. Bismuth oxide and Ti, T
Put any one of titanium oxide such as iO 2 and Ti 2 O 3 ,
Heat to a vapor pressure of 10 -4 Torr or higher. At this time, the composition ratio of the Bi and Ti components is measured with a film thickness monitor (for example, a crystal oscillator, not shown) installed around the substrate 1, and the temperature of the crucible is adjusted to a desired ratio. To do. Then, ion beam the evaporation material evaporated from the crucible 4 with ionizing unit, an acceleration power supply, Bi 4 Ti 3
An O 12 thin film is formed on the substrate. During vapor deposition, O 2 gas is introduced at a rate of 9 to 12 ml / sec from the inlet provided in the vacuum container 10. In general, when only the Bi component is ionized, in order to obtain a thin film with the same crystallinity, Bi 4 Ti 3 with better crystallinity is used.
An O 12 thin film can be obtained, and the substrate temperature can be lowered.
On the other hand, when only the Ti component is converted to an ion beam,
In order to obtain a thin film having the same crystallinity, it is necessary to raise the substrate temperature, and the Bi 4 Ti 3 O 12 formation rate tends to decrease. Table 1 shows an example of a combination of ionizing current, accelerating voltage and substrate temperature in which component of Bi or Ti is ionized. The results obtained when Bi 2 O 3 was used as the raw material containing Bi atoms, Ti was used as the raw material containing Ti atoms, and quartz glass was used as the substrate are shown below. In Table 1, Nos. 1, 2 and 6 were No. 1 and No. 2 with Bi 2 O 3 in crucible 3.
3, 4 and 5 are the cases where Ti was put in the crucible 3.
第１表中のNo.1の条件では、得られたBi4Ti3O12薄膜
のＸ線回折パターンは、第３図のようになり、図中Ａの
部分に（171）回折線がわずかに認められるがほとんど
が基板のハローパターンである。しかし、No.2の条件、
つまり基板温度を高くすると第４図のようなＸ線回折パ
ターンとなる。また、No.6の条件でも、得られたBi4Ti3
O12薄膜はNo.2と同等のＸ線回折パターンとなりTi成分
をより多くイオン化し、より強く加速することにより同
じ結晶質の薄膜を得るために必要とされる基板温度を低
下させることができる。また、第１表No.3の蒸着条件で
は第４図のＸ線回折パターンを示すBi4Ti3O12薄膜が得
られた。さらにNo.4の条件では第５図に示すようなｂ軸
配向したBi4Ti3O12薄膜ができていることを示すＸ線回
折パターンが得られ、イオン化電流、加速電圧をより大
きな値にしたNo.5の条件では、より結晶性が良くなった
ｂ軸配向膜が形成される（第６図参照）。このように蒸
着条件を変えることで形成されるBi4Ti3O12薄膜の結晶
状態を自由に変化させることができる。Under the condition of No. 1 in Table 1, the X-ray diffraction pattern of the obtained Bi 4 Ti 3 O 12 thin film is as shown in FIG. 3, and there is a slight (171) diffraction line in the portion A in the figure. However, most of them are halo patterns of the substrate. However, No.2 condition,
That is, when the substrate temperature is increased, the X-ray diffraction pattern shown in FIG. 4 is obtained. Moreover, even under the condition of No. 6, the obtained Bi 4 Ti 3
The O 12 thin film has the same X-ray diffraction pattern as No. 2 and can ionize more Ti components and accelerate more strongly to lower the substrate temperature required to obtain the same crystalline thin film. . Further, under the vapor deposition conditions shown in Table 1, No. 3, a Bi 4 Ti 3 O 12 thin film having the X-ray diffraction pattern shown in FIG. 4 was obtained. Further, under the condition of No. 4, an X-ray diffraction pattern showing that a b-axis oriented Bi 4 Ti 3 O 12 thin film as shown in Fig. 5 was formed, and the ionization current and accelerating voltage were increased to larger values. Under the condition No. 5 described above, a b-axis oriented film having better crystallinity is formed (see FIG. 6). In this way, the crystal state of the Bi 4 Ti 3 O 12 thin film formed can be freely changed by changing the vapor deposition conditions.
さらに、第２図におけるルツボ３、４において、例え
ば、ルツボの出口にノズルを設置するなどルツボ形状を
変化させることにより、基板温度をより低くすることも
可能である。Further, in the crucibles 3 and 4 in FIG. 2, the substrate temperature can be further lowered by changing the crucible shape such as installing a nozzle at the crucible outlet.
（実施例） 以下、本発明の実施例を説明する。(Example) Hereinafter, the Example of this invention is described.
［実施例１］ 第２図に示した装置を用いて、以下のようにBi4Ti3O
12薄膜を作製した。Example 1 Using the apparatus shown in FIG. 2, Bi 4 Ti 3 O was prepared as follows.
12 thin films were prepared.
まず、Bi原子を含む原料物質としてBi2O3を、Ti原子
を含む原料物質としてTiをそれぞれルツボ３、４に入れ
る（純度はいずれも99.9％以上）。基板としてコーニン
グ7059ガラス、石英ガラスを用い、その温度を200℃に
設定した。真空容器10の真空度を２×10-6Torr程度と
し、真空容器10内へ、ガスの導入口より９〜10ml/secの
割合で酸素ガスを導入した。Ti成分を第１表No.1と同様
にイオン化、加速した。一方、Bi原子を含む原料物質か
ら発生した蒸発物質は抵抗加熱法で蒸着した。ルツボ
３、４の温度を調整し、基板付近のBi、Ti成分の合計で
２〜３Å/secの速度で蒸着した。得られたBi4Ti3O12薄
膜の厚さは約2000Åであり、第３図と同等のＸ線回折パ
ターンを示すアモルファス状の薄膜が得られた。First, Bi 2 O 3 as a raw material containing Bi atoms and Ti as a raw material containing Ti atoms are put in crucibles 3 and 4 (purity is 99.9% or more in all). Corning 7059 glass and quartz glass were used as the substrate, and the temperature was set to 200 ° C. The vacuum degree of the vacuum container 10 was set to about 2 × 10 −6 Torr, and oxygen gas was introduced into the vacuum container 10 through the gas inlet at a rate of 9 to 10 ml / sec. The Ti component was ionized and accelerated in the same manner as No. 1 in Table 1. On the other hand, the evaporation material generated from the raw material containing Bi atoms was deposited by the resistance heating method. The temperature of the crucibles 3 and 4 was adjusted, and vapor deposition was performed at a rate of 2 to 3 Å / sec in total of Bi and Ti components near the substrate. The thickness of the obtained Bi 4 Ti 3 O 12 thin film was about 2000Å, and an amorphous thin film showing an X-ray diffraction pattern equivalent to that of FIG. 3 was obtained.
［実施例２］ Bi原子を含む原料物質としてBi2O3、Ti原子を含む原
料物質としてTiを用い、基板としてコーニング7059ガラ
ス、石英ガラス及び（100）面のSiウエハを用いた。第
１表のNo.2の条件で基板温度、Ti原子を含む原料物質か
ら発生した蒸発物質成分のイオン化加速電圧を設定し、
実施例１と同様に蒸着した。なお、Bi原子を含む原料物
質から発生した蒸発物質は電子ビーム加熱法で蒸着し
た。基板がコーニング7059ガラス及び石英ガラスの場
合、Ｘ線回折パターンは、第４図と同等であった。ま
た、基板が（100）面Siウエハの場合、第５図のような
Ｘ線回折パターンであり、ｂ軸配向したBi4Ti3O12薄膜
が得られた。膜厚は1500Åであった。Example 2 Bi 2 O 3 was used as a raw material containing Bi atoms, Ti was used as a raw material containing Ti atoms, and Corning 7059 glass, quartz glass, and a (100) plane Si wafer were used as substrates. Set the substrate temperature and the ionization acceleration voltage of the vaporized material components generated from the raw material containing Ti atoms under the conditions of No. 2 in Table 1,
Vapor deposition was performed in the same manner as in Example 1. Note that the evaporation material generated from the raw material containing Bi atoms was deposited by an electron beam heating method. When the substrates were Corning 7059 glass and quartz glass, the X-ray diffraction pattern was the same as in FIG. When the substrate was a (100) plane Si wafer, the X-ray diffraction pattern as shown in FIG. 5 was obtained, and a Bi 4 Ti 3 O 12 thin film oriented in the b axis was obtained. The film thickness was 1500Å.
［実施例３］ Bi原子を含む原料物質としてBiを、Ti原子を含む原料
物質としてTiO2あるいはTi2O3のいずれか一方を用い、
基板としては石英ガラス、前記ガラス上に金、白金、
銅、パラジウム電極をとりつけたもの、並びに（100）
面のSiウエハを用いた。第１表No.3の条件で酸素ガスを
10〜12ml/secの割合で導入し、実施例１と同様に蒸着し
た。なお、Ti原子を含む原料物質から発生した蒸発物質
は抵抗加熱法で蒸着した。膜厚は2000Åであった。（10
0）面のSiウエハの場合には、第５図に示すＸ線回折パ
ターンを示すｂ軸配向膜が得られた。他の基板では第４
図のような、多結晶のBi4Ti3O12であることを示すＸ線
回折パターンが得られた。Example 3 Bi was used as a raw material containing Bi atoms, and either TiO 2 or Ti 2 O 3 was used as a raw material containing Ti atoms.
Quartz glass as the substrate, gold, platinum on the glass,
Copper and palladium electrodes attached, as well as (100)
A surface Si wafer was used. Oxygen gas under the conditions of No. 3 in Table 1
It was introduced at a rate of 10 to 12 ml / sec and deposited in the same manner as in Example 1. The evaporation material generated from the raw material containing Ti atoms was deposited by the resistance heating method. The film thickness was 2000Å. (Ten
In the case of the (0) plane Si wafer, a b-axis alignment film having an X-ray diffraction pattern shown in FIG. 5 was obtained. No. 4 on other substrates
As shown in the figure, an X-ray diffraction pattern indicating that the crystal was polycrystalline Bi 4 Ti 3 O 12 was obtained.
［実施例４］ Bi原子を含む原料物質としてBi2O3を、Ti原子を含む
原料物質としてTiO2、Ti2O3のいずれか一方を、基板と
して石英ガラス、白金、銅、ニッケル、MgO単結晶、PLZ
Tセラミックス、（100）面のSiウエハを用いた。第１表
のNo.4の蒸着条件で膜厚1000Å程度に蒸着した。なお、
Ti原子を含む原料物質から発生した蒸発物質は電子ビー
ム加熱法で蒸着した。得られたBi4Ti3O12薄膜のＸ線回
折パターンは、（100）面のSiウエハでは第６図、その
他の基板では第５図と同等であった。また、金属基板上
のBi4Ti3O12薄膜にAl電極を取り付け、誘電率を測定す
ると130〜140の値が得られ、バルクと同等の値であっ
た。[Example 4] Bi 2 O 3 as a raw material containing Bi atoms, one of TiO 2 and Ti 2 O 3 as a raw material containing Ti atoms, and quartz glass, platinum, copper, nickel, MgO as a substrate. Single crystal, PLZ
A T-ceramic, (100) plane Si wafer was used. Under the vapor deposition conditions of No. 4 in Table 1, vapor deposition was performed to a film thickness of about 1000Å. In addition,
The evaporation material generated from the raw material containing Ti atoms was deposited by the electron beam heating method. The X-ray diffraction pattern of the obtained Bi 4 Ti 3 O 12 thin film was equivalent to that of FIG. 6 for the (100) plane Si wafer and FIG. 5 for the other substrates. Further, when an Al electrode was attached to the Bi 4 Ti 3 O 12 thin film on the metal substrate and the dielectric constant was measured, a value of 130 to 140 was obtained, which was equivalent to that of the bulk.
［実施例５］ Bi原子を含む原料物質としてBiあるいはBi2O3、Ti原
子を含む原料物質としてTi、TiO2、Ti2O3のいずれか一
種を用い、基板としては実施例４と同様の材料を用い
た。第１表No.5の条件で、膜厚500〜3000ÅのBi4Ti3O12
薄膜を実施例１と同様にして作製した。なお、Ti原子を
含む原料物質から発生した蒸発物質は抵抗加熱法で蒸着
した。得られた薄膜は、いずれも第６図と同等のＸ線回
折パターンを示し、石英ガラスのような非品質物質を基
板にしてもｂ軸配向性の良い薄膜が得られた。さらに、
電気特性も単結晶と同等で良好な特性が得られた。[Example 5] Bi or Bi 2 O 3 was used as the source material containing Bi atoms, and any one of Ti, TiO 2 , and Ti 2 O 3 was used as the source material containing Ti atoms, and the substrate was the same as in Example 4. Was used. Bi 4 Ti 3 O 12 with a film thickness of 500 to 3000Å under No. 5 in Table 1
A thin film was prepared in the same manner as in Example 1. The evaporation material generated from the raw material containing Ti atoms was deposited by the resistance heating method. The obtained thin films all showed an X-ray diffraction pattern equivalent to that shown in FIG. 6, and even if a non-quality substance such as quartz glass was used as the substrate, a thin film having a good b-axis orientation was obtained. further,
The electrical characteristics were similar to those of single crystals, and good characteristics were obtained.
［実施例６］ Bi原子を含む原料物質としてBi2O3、Ti原子を含む原
料物質としてTiを用い、石英ガラス、（100）面のSiウ
エハを基板に用いた。第１表No.6の条件で、実施例１と
同様に1500Å厚のBi4Ti3O12薄膜を作製した。なお、Bi
原子を含む原料物質から発生した蒸発物質は抵抗加熱法
で蒸着した。石英ガラス基板では第４図のＸ線回折パタ
ーン、（100）面のSiウエハでは第５図のＸ線回折パタ
ーンと同等のＸ線回折パターンを示すBi4Ti3O12薄膜が
られた。Example 6 Bi 2 O 3 was used as a raw material containing Bi atoms, Ti was used as a raw material containing Ti atoms, and quartz glass and a (100) plane Si wafer were used as substrates. Under the conditions shown in Table 1, No. 6, a 1500 Å-thick Bi 4 Ti 3 O 12 thin film was prepared in the same manner as in Example 1. Note that Bi
The evaporation material generated from the source material containing atoms was deposited by the resistance heating method. On the quartz glass substrate, a Bi 4 Ti 3 O 12 thin film having an X-ray diffraction pattern similar to the X-ray diffraction pattern of FIG. 5 was formed on the X-ray diffraction pattern of FIG. 4 and on the (100) plane Si wafer.
［実施例７］ 第２図におけるルツボ４の出口に内径2mmφ高さ2mmの
ノズルを取り付けたルツボを使用し、この中にBi原子を
含む原料物質としてBiを入れた。イオン化電流を50.0m
A、加速電圧を1.5kVとした。Ti原子を含む原料物質とし
てはTiを用い、酸素ガスを10〜12ml/secの割合で導入し
た。基板温度を150℃に設定して実施例３と同様に蒸着
した。基板温度が実施例３に対して100℃程低いが得ら
れたBi4Ti3O12薄膜は、実施例３と同様のＸ線回折パタ
ーンを示した。[Example 7] A crucible having a nozzle with an inner diameter of 2 mm and a height of 2 mm attached to the outlet of the crucible 4 in Fig. 2 was used, and Bi was put therein as a raw material containing Bi atoms. Ionizing current 50.0m
A, acceleration voltage was set to 1.5 kV. Ti was used as a raw material containing Ti atoms, and oxygen gas was introduced at a rate of 10 to 12 ml / sec. The substrate temperature was set to 150 ° C. and vapor deposition was performed as in Example 3. The obtained Bi 4 Ti 3 O 12 thin film having a substrate temperature lower than that of Example 3 by about 100 ° C. showed an X-ray diffraction pattern similar to that of Example 3.
［実施例８］ 第２図におけるルツボ３の出口に内径2mmφ高さ2mmの
ノズルを取り付けた以外実施例７と同一条件でBi4Ti3O
12薄膜を作製した。（100）面Siウエハ上のBi4Ti3O12薄
膜は第６図のＸ線回折パターンと同等のパターンを与え
た。[Embodiment 8] Bi 4 Ti 3 O under the same conditions as in Embodiment 7 except that a nozzle having an inner diameter of 2 mm and a height of 2 mm was attached to the outlet of the crucible 3 in FIG.
12 thin films were prepared. The Bi 4 Ti 3 O 12 thin film on the (100) plane Si wafer gave a pattern equivalent to the X-ray diffraction pattern of FIG.
前記実施例ではイオン化電流、加速電圧は、第１表の
条件のものに限定した。Bi4Ti3O12薄膜の場合、イオン
化電流が300mA、加速電圧が7kV以上になると、基板上の
Bi4Ti3O12薄膜がスパッタリングされるためか膜厚の制
御がむずかしくなる。しかし、前記の値以下であれば蒸
着条件を選択することにより、得られた薄膜の配向性を
制御できる。In the above embodiment, the ionization current and the accelerating voltage are limited to those shown in Table 1. In the case of Bi 4 Ti 3 O 12 thin film, when the ionization current is 300mA and the acceleration voltage is 7kV or more,
It is difficult to control the film thickness because the Bi 4 Ti 3 O 12 thin film is sputtered. However, if the value is less than the above value, the orientation of the obtained thin film can be controlled by selecting the vapor deposition conditions.
また、前記実施例では、導入した酸素は中性の酸素で
あるが、これをイオン化することにより、基板温度をよ
り低くすることが出来、より絶縁耐圧の高い薄膜を得る
ことが出来る。Further, in the above-mentioned embodiment, the introduced oxygen is neutral oxygen, but by ionizing this, the substrate temperature can be lowered and a thin film having a higher withstand voltage can be obtained.
さらに、ルツボに取り付けたノズルの形状を変えるこ
とにより、より緻密で、より膜表面が平坦なBi4Ti3O12
薄膜の作製が可能である。Furthermore, by changing the shape of the nozzle attached to the crucible, Bi 4 Ti 3 O 12 with a more precise and flat film surface can be obtained.
A thin film can be produced.
（発明の効果） 以上に説明したように本発明によれば、Ti成分とBi成
分のいずれか一方をイオンビーム蒸着法によって蒸着さ
せるので、アモルファス、単結晶、ｂ軸配向等のBi4Ti3
O12薄膜を、所望の基板上に500℃以下の低温で形成でき
る効果がある。According to the present invention as described above (Effect of the Invention), since one of Ti component and Bi component is deposited by ion beam deposition, amorphous, single crystal, Bi 4 Ti 3 such as b-axis-oriented
There is an effect that an O 12 thin film can be formed on a desired substrate at a low temperature of 500 ° C. or lower.
BiとTiの組成比は理論値Bi:Ti＝4:3（原子比）に対し
て５％以内で制御可能である。The composition ratio of Bi and Ti can be controlled within 5% with respect to the theoretical value Bi: Ti = 4: 3 (atomic ratio).
第１図はBi4Ti3O12の結晶構造図、第２図は本発明の実
施に用いる装置の概略図、第３図乃至第６図はBi4Ti3O
12薄膜のＸ線回折パターンの図である。 １……基板、２……Bi4Ti3O12薄膜 ３、４……ルツボ、５、６……イオン化ユニット ６……加速電極、７……蒸発物質の蒸気 ８……イオンビーム、９……加速電源 10……真空容器FIG. 1 is a crystal structure diagram of Bi 4 Ti 3 O 12 , FIG. 2 is a schematic diagram of an apparatus used for carrying out the present invention, and FIGS. 3 to 6 are Bi 4 Ti 3 O 12.
It is a figure of the X-ray-diffraction pattern of 12 thin films. 1 ... Substrate, 2 ... Bi 4 Ti 3 O 12 thin film 3, 4 ... Crucible, 5, 6 ... Ionization unit 6 ... Accelerating electrode, 7 ... Vapor of vaporized material 8 ... Ion beam, 9 ... Acceleration power supply 10 ... Vacuum container
───────────────────────────────────────────────────── フロントページの続き (72)発明者 新部 正人 東京都大田区下丸子３丁目30番２号 キ ヤノン株式会社内 (72)発明者 元井 泰子 東京都大田区下丸子３丁目30番２号 キ ヤノン株式会社内 (72)発明者 塚本 健夫 東京都大田区下丸子３丁目30番２号 キ ヤノン株式会社内 (56)参考文献 特開 昭61−6123（ＪＰ，Ａ) 特開 昭61−6124（ＪＰ，Ａ) 特公 昭55−11245（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masato Nibe 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yasuko Motoi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Takeo Tsukamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP 61-6123 (JP, A) JP 61-6124 (JP, A) JP-B-55-11245 (JP, B2)
Claims (5)
少なくともビスマス原子を含む原料物質のそれぞれから
蒸発せしめられた蒸発物質を所望の位置に配せられた基
板上に蒸着するチタン酸ビスマス薄膜の形成方法におい
て、前記蒸発物質のいずれか一方をイオンビーム蒸着法
によって蒸着させ、前記基板上にBi4Ti3O12からなる薄
膜を形成することを特徴とするチタン酸ビスマス薄膜の
形成方法。1. A raw material containing at least titanium atoms,
In a method for forming a bismuth titanate thin film, wherein vaporized substances vaporized from respective source substances containing at least bismuth atoms are vapor-deposited on a substrate placed at a desired position, one of the vaporized substances is ion beam evaporated. A method of forming a bismuth titanate thin film, which comprises depositing a thin film of Bi 4 Ti 3 O 12 on the substrate by a vapor deposition method.
はTi2O3である特許請求の範囲第１項記載のチタン酸ビ
スマス薄膜の形成方法。2. The method for forming a bismuth titanate thin film according to claim 1, wherein the raw material containing titanium atoms is Ti, TiO 2 or Ti 2 O 3 .
2O3である特許請求の範囲第１項記載のチタン酸ビスマ
ス薄膜の形成方法。3. The raw material containing a bismuth atom is Bi or Bi.
The method for forming a bismuth titanate thin film according to claim 1, which is 2 O 3 .
セラミック板、酸化物単結晶板、酸化物単結晶板、金属
板又は合金板を用いる特許請求の範囲第１項記載のチタ
ン酸ビスマス薄膜の形成方法。4. The bismuth titanate according to claim 1, wherein the glass substrate, silicon plate, ceramic plate, oxide single crystal plate, oxide single crystal plate, metal plate or alloy plate is used as the substrate. Method of forming thin film.
第１項記載のチタン酸ビスマス薄膜の形成方法。5. The method for forming a bismuth titanate thin film according to claim 1, wherein the substrate is kept at 500 ° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62002539A JP2547204B2 (en) | 1987-01-08 | 1987-01-08 | Method for forming bismuth titanate thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62002539A JP2547204B2 (en) | 1987-01-08 | 1987-01-08 | Method for forming bismuth titanate thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63171870A JPS63171870A (en) | 1988-07-15 |
| JP2547204B2 true JP2547204B2 (en) | 1996-10-23 |
Family
ID=11532182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62002539A Expired - Fee Related JP2547204B2 (en) | 1987-01-08 | 1987-01-08 | Method for forming bismuth titanate thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2547204B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0774341B2 (en) * | 1990-09-25 | 1995-08-09 | 北陸電気工業株式会社 | Method for producing bismuth layered structure compound thin film |
| JP4612340B2 (en) | 2003-05-21 | 2011-01-12 | 独立行政法人科学技術振興機構 | Method for producing multi-element oxide single crystal containing bismuth as a constituent element |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5946368B2 (en) * | 1978-07-11 | 1984-11-12 | 日本電信電話株式会社 | Manufacturing method of multi-bit spatial optical phase modulation plate |
| JPS6037526A (en) * | 1983-08-10 | 1985-02-26 | Mitsubishi Electric Corp | Method for driving liquid crystal display element |
| JPS6199669A (en) * | 1984-10-18 | 1986-05-17 | Matsushita Electric Ind Co Ltd | Method and device for vapor deposition |
| JPS61193406A (en) * | 1985-02-22 | 1986-08-27 | Saitama Univ | Amorphous ferromagnetic oxide thin film and manufacture thereof |
-
1987
- 1987-01-08 JP JP62002539A patent/JP2547204B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63171870A (en) | 1988-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4397511B2 (en) | Low resistance ITO thin film and manufacturing method thereof | |
| JP2547204B2 (en) | Method for forming bismuth titanate thin film | |
| JP2547203B2 (en) | Method for forming bismuth titanate thin film | |
| Shigesato et al. | ITO thin-film transparent conductors: Microstructure and processing | |
| EP0631332B1 (en) | Method of manufacturing Y-Ba-Cu-O superconducting thin film | |
| JP5035857B2 (en) | Low resistance ITO thin film and manufacturing method thereof | |
| JPH09208394A (en) | Production of ferroelectric thin film and ferroelectric thin film capacitor | |
| JPS5850419B2 (en) | Method for manufacturing piezoelectric thin film | |
| JPH02258700A (en) | Ferroelectric thin film and production thereof | |
| JPH0329216A (en) | Formation of transparent conductive film | |
| JP3095232B2 (en) | Method for producing transparent conductive film | |
| JPH0639707B2 (en) | Thin film forming equipment | |
| JP2000273617A (en) | Production of transparent electrically conductive film | |
| JPH09170993A (en) | Manufacture of tin oxide film and gas detecting sensor usingthin film thereof | |
| Bunton et al. | The preparation and electrical properties of thin chalcogenide semiconductor films | |
| JP3831433B2 (en) | Transparent conductive film and method for producing the same | |
| JP2971541B2 (en) | Thin film forming equipment | |
| JP2777599B2 (en) | Manufacturing method of single crystal thin film | |
| Kumar et al. | Annealing-induced structural changes in tellurium dioxide thin films | |
| JPH078760B2 (en) | Method for manufacturing superconducting ceramic thin film | |
| Kaneko et al. | Low‐temperature deposition of ferroelectric Bi4Ti3O12 films by the reactive ionized cluster beam method | |
| Maiwa et al. | Preparation of Pb5Ge3O11 thin films by multiple cathode sputtering | |
| KR19990048866A (en) | Fabrication of SNO2 Thin Films for Gas Sensors from SN Taeget using Dual-ion Beam Sputtering | |
| JPH06450Y2 (en) | Coil movable ion plating device | |
| JP2736062B2 (en) | Method for producing oxide superconductor thin film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |