JPS63166198A - Method of forming ferrodielectric thin film - Google Patents
Method of forming ferrodielectric thin filmInfo
- Publication number
- JPS63166198A JPS63166198A JP61315038A JP31503886A JPS63166198A JP S63166198 A JPS63166198 A JP S63166198A JP 61315038 A JP61315038 A JP 61315038A JP 31503886 A JP31503886 A JP 31503886A JP S63166198 A JPS63166198 A JP S63166198A
- Authority
- JP
- Japan
- Prior art keywords
- target
- thin film
- substrate
- sputtering
- ferroelectric thin
- 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.)
- Granted
Links
- 239000010409 thin film Substances 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 19
- 239000000758 substrate Substances 0.000 claims description 39
- 239000010408 film Substances 0.000 claims description 29
- 238000004544 sputter deposition Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims 1
- 239000010936 titanium Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 11
- 238000009434 installation Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 239000000470 constituent Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000005401 electroluminescence Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 229910003781 PbTiO3 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 101100481408 Danio rerio tie2 gene Proteins 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 101100481410 Mus musculus Tek gene Proteins 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- PDGYMUBNWUUWEI-UHFFFAOYSA-N strontium zirconium Chemical compound [Sr].[Zr] PDGYMUBNWUUWEI-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 that is Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔概要〕
ＡＢＯｓ（ＡおよびＢは単一の元素、或いは複数の元素
を示す記号）で表示されるペロブスカイト型構造の強誘
電薄膜を形成する方法であって、スパッタ装置の容器内
に該強誘電薄膜の各構成元素、或いは該各構成元素の酸
化物よりなるターゲットを酸素元素を除いて薄膜の構成
元素に該当する数量だけ配置し、各ターゲット上に基板
を順次移動させながらスパッタ用ガスを用いてターゲッ
トの成分を、組成比が０．５ ＜Ａ／Ｂ ＜２．０とな
るように、かつ基板が各ターゲット上を（格子定数／膜
の成長速度≧基板がターゲットを通過する周期）となる
条件で通過するようにしてスパッタすることで、低温で
成膜できるようにし、基板が軟化しない状態で’ｔ４８
Ｍ電膜が得られるようにする。[Detailed Description of the Invention] [Summary] A method for forming a ferroelectric thin film with a perovskite structure represented by ABOs (A and B are symbols indicating a single element or a plurality of elements), the method comprising: a sputtering device; In a container, targets made of each constituent element of the ferroelectric thin film or an oxide of each constituent element are placed in the number corresponding to the constituent elements of the thin film, excluding oxygen element, and the substrates are sequentially moved onto each target. The components of the target are mixed using a sputtering gas while the substrate is on each target so that the composition ratio is 0.5 < A/B < 2.0, and the substrate is Sputtering is performed under conditions such that the target passes through the target at a period of
Make sure that an M electric film is obtained.
本発明はペロブスカイト型構造の強誘電薄膜の形成方法
に係り、特にスパッタ法を用いて低基板温度で、かつ組
成制御が容易な強誘電薄膜の形成方法に関する。The present invention relates to a method for forming a ferroelectric thin film having a perovskite structure, and more particularly to a method for forming a ferroelectric thin film using a sputtering method at a low substrate temperature and whose composition can be easily controlled.
最近のオプトエレクトロニクスの分野では、透明な強誘
電薄膜の出現が要望されている。Recently, in the field of optoelectronics, there has been a demand for transparent ferroelectric thin films.
例えばエレクトロルミネッセンス（ＥＬ）を利用した薄
膜構造の表示デバイスでは、駆動電圧の低減のために高
誘電率透明絶縁膜の開発が待たれているし、光通信用光
導波路や圧電素子の設計に於いてもそのような薄膜が要
望されている。For example, in display devices with a thin film structure using electroluminescence (EL), the development of high dielectric constant transparent insulating films is awaited to reduce the driving voltage, and the design of optical waveguides for optical communication and piezoelectric elements is required. However, there is a demand for such thin films.
従来、このような強誘電薄膜の形成方法としては本出願
人が既に特開昭５６−４５８２７号公報、および特開昭
５６−１３８８１３号公報に於いて提案している。Conventionally, the present applicant has already proposed a method for forming such a ferroelectric thin film in Japanese Patent Application Laid-Open No. 56-45827 and Japanese Patent Application Laid-Open No. 56-138813.
この方法は第６図に示すように、加熱源１を備えた基板
ホルダ２に設置されたガラス基板３と、これに対向する
ように、形成すべきチタン酸鉛（ＰｂＴｉ（ｈ）の原料
である酸化鉛（ＰｂＯ）の粉末と酸化チタン（ＴｉＯ□
）の粉末を化学Ｍ論的組成比となるように秤量した粉末
４を充填した容器５を設置し、この容器５を石英板６を
介して水冷されたカソード７上に設置している。そして
これらを図示しないスパッタ容器内に設置している。As shown in FIG. 6, this method involves a glass substrate 3 placed on a substrate holder 2 equipped with a heating source 1, and a raw material for lead titanate (PbTi(h)) to be formed facing the glass substrate 3. A certain lead oxide (PbO) powder and titanium oxide (TiO□
) A container 5 filled with powder 4 weighed so as to have a chemical composition ratio is installed, and this container 5 is placed on a water-cooled cathode 7 via a quartz plate 6. These are placed in a sputtering container (not shown).
しかしてそのプロセスは、スパッタ容器内を排気した後
、アルゴン（Ａｒ）ガスと酸素（０□）ガスの混合ガス
より成るスパッタガスを該容器内に専大し、基板ホルダ
２をアノードとし、前記したカソード７との間に高周波
電圧を印加して基板３上にＰｂＴｉ０：＋のスパッタ膜
を形成していた。In this process, after the inside of the sputtering container is evacuated, a sputtering gas consisting of a mixed gas of argon (Ar) gas and oxygen (0□) gas is exclusively poured into the container, and the substrate holder 2 is used as an anode. A high frequency voltage was applied between the cathode 7 and the substrate 3 to form a sputtered film of PbTi0:+.
ところが、このような従来の方法では、第７図に示すよ
うに、基板温度が５００℃以上の高温でないと強誘電性
を示すペロブスカイト型の結晶構造が現れず、基板温度
が５００℃以下の低温であると、常誘電性を示すパイロ
クロア型の結晶構造しか現れず、強誘電薄膜が形成でき
ない問題がある。However, in such conventional methods, as shown in Figure 7, a perovskite crystal structure exhibiting ferroelectricity does not appear unless the substrate temperature is at a high temperature of 500°C or higher; In this case, only a pyrochlore type crystal structure exhibiting paraelectricity appears, and there is a problem that a ferroelectric thin film cannot be formed.
然し、ＥＬ素子の基板として通常用いられているガラス
基板の温度を、５００℃以上に保とうとすると、そのガ
ラス基板が軟化し、そのためこの５００℃の高温まで耐
えられる特殊なガラス基板を必要とし、ＥＬ素子の製造
に困難をきたしていた。However, if you try to keep the temperature of the glass substrate normally used as a substrate for EL elements above 500°C, the glass substrate will soften, so a special glass substrate that can withstand this high temperature of 500°C is required. This has caused difficulties in manufacturing EL elements.
そこで、基板温度を低下させて強誘電薄膜の形成を試み
、以下のような結論を得た。即ち本発明者等は低基板温
度で従来の方法を用いてスパッタ法で形成した強誘電薄
膜を調査した処、形成されたＰｂＴｉＯ３膜に於けるＰ
ｂ／Ｔｉの原子比は１である化学量論的な組成比より大
きく逸脱していることを確かめた。Therefore, we attempted to form a ferroelectric thin film by lowering the substrate temperature, and came to the following conclusions. That is, the present inventors investigated ferroelectric thin films formed by sputtering using conventional methods at low substrate temperatures, and found that P in the formed PbTiO3 film
It was confirmed that the atomic ratio b/Ti greatly deviated from the stoichiometric composition ratio of 1.
従って低基板温度でスパッタ法により強誘電薄膜を形成
する際、その強誘電薄膜がペロブスカイト型構造を呈す
るようにするためには、Ｐｂ／Ｔｉの原子比が、化学量
論的組成比１となるように、制御できるような方法が必
要となる。Therefore, when forming a ferroelectric thin film by sputtering at a low substrate temperature, in order for the ferroelectric thin film to exhibit a perovskite structure, the atomic ratio of Pb/Ti must be set to a stoichiometric composition ratio of 1. Therefore, a method that can be controlled is needed.
本発明の強誘電薄膜の形成方法は、第１図の原理図に示
すように、ＡおよびＢを単一元素、或いは複数の元素を
示す記号とし、組成がＡＢＯ３で表されるペロブスカイ
ト型強誘電薄膜を基板上にスパッタ法で形成する場合に
於いて、
スパッタ用ガスが満たされた容器内に前記ＡおよびＢを
構成する元素、或いはＡおよびＢを構成する元素と酸素
を含んだ化合物で構成された二つのターゲラ） （１１
Ａ、１１Ｂ）を別個に配置し、これ等ターゲット上に前
記基板（１２）を所定の繰り返し周期で交互に移動させ
、成膜組成が、０．５ ＜Ａ／Ｂ ＜２．０の範囲の原
子比となるようにスパッタリングを行う。As shown in the principle diagram of FIG. 1, the method for forming a ferroelectric thin film of the present invention is a perovskite-type ferroelectric film whose composition is represented by ABO3, where A and B are symbols representing a single element or a plurality of elements. When forming a thin film on a substrate by sputtering, a container containing a sputtering gas containing the elements constituting A and B, or a compound containing the elements constituting A and B and oxygen is placed in a container filled with sputtering gas. (11)
A and 11B) were placed separately, and the substrate (12) was moved alternately over these targets at a predetermined repetition period, so that the film composition was in the range of 0.5 < A/B < 2.0. Sputtering is performed to achieve the same atomic ratio.
本発明の方法は、形成すべき強誘電薄膜の構成元素、或
いは該構成元素のターゲットをそれぞれ別個に容器内に
設け、この各ターゲット上を基板を順次移動させ、この
各々のターゲットに印加する電力を、構成元素比が１対
Ｉの化学量論比を満足するように印加し、かつこの基板
の移動速度を（格子定数／膜成長速度上基板がターゲッ
トを通過する周期）とすることで、基板を４００℃以下
の低温に保った場合においても、ペロブスカイト型の結
晶構造の強誘電薄膜が容易に得られるようにする。In the method of the present invention, constituent elements of a ferroelectric thin film to be formed or targets for the constituent elements are separately provided in a container, a substrate is sequentially moved over each target, and electric power is applied to each target. By applying so that the constituent element ratio satisfies the stoichiometric ratio of 1 to I, and the moving speed of the substrate is (lattice constant/period of the substrate passing the target on the film growth rate), To easily obtain a ferroelectric thin film having a perovskite crystal structure even when a substrate is kept at a low temperature of 400° C. or lower.
以下、図面を用いながら本発明の一実施例につき詳細に
説明する。Hereinafter, one embodiment of the present invention will be described in detail with reference to the drawings.
第２図に示すように、スパッタ容器１３内に円板状のｐ
ｂｏ ターゲット１１八と、ＴｉＯ□ターゲットＩＩＢ
とを、それぞれカソードとなるターゲット設置台１４Ａ
および１４Ｂ上に設置する。As shown in FIG. 2, a disk-shaped p
bo Target 118 and TiO□Target IIB
and the target installation stand 14A, each serving as a cathode.
and installed on 14B.
一方、このターゲットＩＩＡ、ＩＩＢに対向するように
、ガラス基板１２を、加熱ヒータ１５を有する基板設置
台１６に設置する。On the other hand, the glass substrate 12 is placed on a substrate installation stand 16 having a heater 15 so as to face the targets IIA and IIB.
これ等のターゲットＩＩＡ、 ＩＩＢを載置したターゲ
ット設置台１４Ａと１４Ｂは同一円周上に別個に設置さ
れ、これらの上を基板１２を！！置した基板設置台１６
がモータ等の移動装置（図示せず）を用いて回転移動す
るようにしても良いし、また直線上にこれらのターゲッ
ト設置台１４八と１４Ｂを別個に設置し、その上を基板
１２がモータ等を用いて往復移動するようにしても良い
。The target installation tables 14A and 14B on which these targets IIA and IIB are placed are separately installed on the same circumference, and the substrate 12 is placed on top of these tables 14A and 14B. ! Board installation stand 16
may be rotated using a moving device (not shown) such as a motor, or the target installation stands 148 and 14B may be installed separately on a straight line, and the board 12 may be moved by the motor. It may also be possible to move back and forth using, for example.
このような装置構成に於いて、排気バルブ１７を開放に
して排気管１８に連なる真空ポンプ（図示せず）を用い
て、スパッタ容器１３内を１０− ’ ｔｏｒｒの真空
度に成るまで迄排気した後、バルブ１７を閉じてガス導
入管Ｉ９より、酸素ガスを２０容量％含んだＡｒガスを
、スパッタガスとして容器１３内の圧力が１Ｏ−２ｔｏ
ｒｒの圧力となるように導入する。In such an apparatus configuration, the exhaust valve 17 was opened and a vacuum pump (not shown) connected to the exhaust pipe 18 was used to evacuate the inside of the sputtering container 13 to a degree of vacuum of 10-' torr. After that, the valve 17 is closed and Ar gas containing 20% by volume of oxygen gas is introduced from the gas inlet pipe I9 as a sputtering gas until the pressure inside the container 13 reaches 1O-2 to
Introduce the water to a pressure of rr.
この状態で周波数を１３．５６ＭＨｚとし、ｐｂｏター
ゲットＩＩＡに印加される電力を３０Ｗとし、Ｔｉ０ｚ
ターゲツト１１Ｂに印加される電力を３００ Ｗとし、
基板設置台１６とターゲット設置台１４Δ、１４Ｂ間に
高周波電圧を印加する。In this state, the frequency is set to 13.56 MHz, the power applied to the pbo target IIA is set to 30 W, and the Ti0z
The power applied to the target 11B is 300 W,
A high frequency voltage is applied between the substrate installation stand 16 and the target installation stands 14Δ, 14B.
そしてヒータ１５を用いてガラス基板１２を２００°Ｃ
の温度に加熱する。Then, using the heater 15, the glass substrate 12 is heated to 200°C.
Heat to temperature.
この条件で、形成されるＰｂＴｉＯ３のスパッタ膜の成
膜速度は０，１６人／ｓｅｃ、この被膜の格子定数は４
人程度であるので、４１０．１６＝２５ｓｅｃ以下の周
期で基板１２が、各ターゲ７ ）１１Ａ、ＩＩＢを通過
するようにすると、Ｖ厚が格子定数の厚さに到達する以
前に、基板１２が各ターゲツト１１Ａ、１１Ｂ上を通過
することになるので、ｐｂとＴｉの原子比Ｐｂ／Ｔｉが
１の強誘電性を示すペロブスカイト型結晶構造のＰｂＴ
ｉ０＋のスパッタ膜が得られる。Under these conditions, the deposition rate of the sputtered PbTiO3 film is 0.16 persons/sec, and the lattice constant of this film is 4.
If the substrate 12 is made to pass through each target 7) 11A and IIB at a period of 410.16 = 25 seconds or less, the substrate 12 will Since it passes over each target 11A and 11B, PbT with a perovskite crystal structure exhibiting ferroelectricity with an atomic ratio of Pb and Ti of 1, Pb/Ti,
A sputtered film of i0+ is obtained.
ここで第３図にＰｂＯターゲッｌ−１１Ａに印加される
電ツノと、ＴｉＯ□ターゲットＩＩＢに印加される電力
と、スパッタによって形成されるＰｂＴｉＯ３の強誘電
薄膜膜のｐｂとＴｉの原子比Ｐｂ／Ｔ ｉ との関係を
示す。Here, FIG. 3 shows the electric power applied to the PbO target I-11A, the electric power applied to the TiO□ target IIB, and the atomic ratio of pb and Ti of the ferroelectric thin film of PbTiO3 formed by sputtering, Pb/ The relationship with T i is shown.
図の横軸はＰｂＯターゲット１１八に印加される電力を
示し、図の縦軸はＴｉｅ２ターゲッ）ＩＩＢに印加され
る電力を示し、図の曲線２１は形成されるＰｂＴｉ０＋
の強誘電薄膜のｐｂとＴｔの原子比、即ちＰｂ／Ｔｉ
＝１となる曲線を示す。The horizontal axis of the figure shows the power applied to the PbO target 118, the vertical axis of the figure shows the power applied to the Tie2 target (IIB), and the curve 21 of the figure shows the PbTi0+ formed
The atomic ratio of pb and Tt of the ferroelectric thin film, that is, Pb/Ti
A curve with =1 is shown.
図示するように曲線２１の上側の領域はｐｂとＴｉの原
子比がＰｂ／Ｔｉ ＜ １となり、曲線２１の下側の領
域はｐｂとＴｉの原子比がＰｂ／Ｔｉ ＜ ｌ となる
。As shown, in the region above the curve 21, the atomic ratio of pb and Ti is Pb/Ti<1, and in the region below the curve 21, the atomic ratio of pb and Ti is Pb/Ti<l.
従ってＰｂＯターゲッ目ＩＡに印加される電力と、Ｔｉ
０ｚターゲツ）１１Ｂに印加される電力を適宜選んで、
ｐｂとＴｉの原子比Ｐｂ／Ｔｉ ＝１となるようにする
と良い。Therefore, the power applied to the PbO target IA and the Ti
0z target) Select the power applied to 11B appropriately,
It is preferable that the atomic ratio of pb and Ti is Pb/Ti=1.
ここで第４図にＰｂＯターゲットＩＩＡに印加される電
力と、ＴｉＯ□ターゲットＩＩＢに印加される電力を適
宜’＞’Ａ ン”ｉ！？、Ｐｂ、ｌ！：Ｔｉミノ子比（
７）Ｐｂ／Ｔｉを変化させた時に形成されるスパッタ膜
の膜質を調べた結果を示す。Here, the power applied to the PbO target IIA and the power applied to the TiO□ target IIB are shown in FIG. 4 as appropriate.
7) The results of examining the film quality of sputtered films formed when Pb/Ti was varied are shown.
図の横軸はｐｂとＴｉの原子比Ｐｂ／Ｔｉを示し、図の
縦軸は形成されたスパッタ膜をＸ線回折装置で検査して
、ペロブスカイト型構造を示すピーク波形の面積とパイ
クロア型構造を示すピーク波形の面積との比をとった値
を示し、この値が大きい程、そのスパッタ膜にペロブス
カイト型構造の結晶が多く含有されて、強誘電特性が大
の被膜が得られたことになる。The horizontal axis of the figure shows the atomic ratio Pb/Ti of pb and Ti, and the vertical axis of the figure shows the area of the peak waveform showing the perovskite structure when the formed sputtered film was inspected with an X-ray diffraction device, and the pyrochlore structure. The value is the ratio of the area of the peak waveform showing Become.
図の曲線３１に示すようにｐｂとＴｉの原子比Ｐｂ／Ｔ
ｉ力０．５〜２．０の範囲で、ペロブスカイト型構造の
強誘電膜が得られやすいことが判明した。As shown in curve 31 in the figure, the atomic ratio of pb and Ti is Pb/T
It has been found that a ferroelectric film having a perovskite structure can be easily obtained when the i-force is in the range of 0.5 to 2.0.
また第５図に基板を加熱しない状態で、上記したような
条件でスパッタした場合に形成されたスパッタ膜のＸ線
回折の状態を示す。Further, FIG. 5 shows the state of X-ray diffraction of a sputtered film formed when sputtering was performed under the above-mentioned conditions without heating the substrate.
図の横軸はＸ線の回折角度を示し、縦軸はスパッタ膜に
Ｘ線が照射されて回折されたＸ線の強度をＸ線検知器で
検知した値を示す。The horizontal axis of the figure shows the diffraction angle of X-rays, and the vertical axis shows the intensity of the diffracted X-rays detected by the X-ray detector when the sputtered film is irradiated with the X-rays.
図の曲線４１に示すように、４１Ａ、４１Ｂ、４１Ｃ，
４１０の各々の箇所に於いて、ペロブスカイト構造のＰ
ｂＴｉ０１の（１００）面、（１０１）面、（１１０）
面、（１１１）面に対応するＸ線の回折ピークが現れて
おり、ペロブスカイト型の結晶構造を有するＰｂＴｉ０
：＋の強誘電膜が形成されていることが実験的に確かめ
られた。As shown in the curve 41 in the figure, 41A, 41B, 41C,
At each location of 410, P of the perovskite structure
(100) plane, (101) plane, (110) of bTi01
X-ray diffraction peaks corresponding to the (111) plane appear, and PbTi0 has a perovskite crystal structure.
: It was experimentally confirmed that a positive ferroelectric film was formed.
尚、本実施例ではＰｂＴｉＯｘのスパッタ膜の形成方法
に例を用いて説明したが、本発明はＡおよびＢを単一の
元素、或いは複数の元素を組み合わせた記号としＡＢＯ
３の形で表されるチタン酸バリウム（ＢａＴｉＯｚ）、
チタン酸ストロンチウム（ＳｒＴｉ（ｈ）、ジルコニウ
ムチタン酸ストロンチウム（Ｓｒ（Ｚｒｏ、 ｚＴｉｏ
、 ｓ）０＋、ＰＬＺＴ （（Ｐｂ ・しａ ）（Ｚ
ｒ −Ｔｉ）（ｈ ）等のペロブスカイト構造の強誘
電薄膜の形成にも適用できる。In this example, the method for forming a sputtered film of PbTiOx was explained using an example, but in the present invention, A and B are symbols for a single element or a combination of multiple elements, and ABO
Barium titanate (BaTiOz) expressed in the form 3,
Strontium titanate (SrTi(h), zirconium strontium titanate (Sr(Zro, zTio)
, s) 0+, PLZT ((Pb ・shia ) (Z
It can also be applied to the formation of ferroelectric thin films with a perovskite structure such as r -Ti) (h).
また本実施例のように各ターゲットに印加する電力を制
御する代わりに、各ターゲット上にスリットを設けた遮
蔽板を設置し、このスリットの開口部の面積を調整する
ことで、各ターゲットより基板上にスパッタされるター
ゲットの成分を調整し、これによって形成されるスパッ
タ膜の構成原子比を制御する方法を採っても良い。Furthermore, instead of controlling the power applied to each target as in this embodiment, by installing a shielding plate with slits on each target and adjusting the area of the opening of the slit, it is possible to A method may also be adopted in which the components of the target sputtered thereon are adjusted, thereby controlling the constituent atomic ratio of the sputtered film formed.
以上述べたように、本発明の方法によれば、形成される
スパッタ膜の組成の制御が容易となり、基板が低温の状
態でスパッタ膜を形成しても、ペロブスカイト型構造の
強誘電薄膜が容易に形成でき、本発明の方法で形成した
強誘電薄膜を用いてＥＬ素子を形成すれば、低駆動電圧
の高性能のＥＬ素子が得られる効果がある。As described above, according to the method of the present invention, it is easy to control the composition of the sputtered film to be formed, and even when the sputtered film is formed when the substrate is at a low temperature, it is easy to form a ferroelectric thin film with a perovskite structure. If an EL element is formed using a ferroelectric thin film formed by the method of the present invention, a high-performance EL element with a low driving voltage can be obtained.
第１図は本発明の方法を示す原理図、
第２図は本発明の一実施例を示す模式図、第３図は本発
明に於ける各ターゲットの印加電力と形成されるスパッ
タ膜の構成原子の原子比との関係図、
第４図は本発明に於けるスパッタ膜の構成原子の原子比
と膜質との関係図、
第５図は本発明の方法で形成したスパッタ膜のＸ線回折
図、
第６図は従来の方法を示す模式図、
第７図は従来の方法で形成したスパッタ膜の結晶構造と
基板温度の関係図である。
図に於いて、
１１Ａ はｐｂｏ ターゲット、ＩＩＢ はＴｉ０ｉタ
ーゲツト、１２は基板、１３は容器、１４Ａ、 １４Ｂ
はターゲット設置台、１５はヒータ、１６は基板設置台
、１７は排気バルブ、１８は排気管、１９はガス導入管
、２１はターゲットの印加電力と形成される強誘電薄膜
の原子比との関係曲線、３１は強誘電薄膜の原子比と膜
質との関係曲線、４１．４１Ａ、４１Ｂ、４１Ｃ，４１
Ｄは強誘電薄膜のＸ線回折ピークを示す。
′ｓ １ 図
、ｔａｉとり−・′＃メイ七イケリめ番り蓼式ワ凸第２
図
第３図
や
→方ｉ犯尤Fig. 1 is a principle diagram showing the method of the present invention, Fig. 2 is a schematic diagram showing an embodiment of the present invention, and Fig. 3 is a diagram showing the applied power to each target and the structure of the sputtered film formed in the present invention. Figure 4 is a diagram showing the relationship between the atomic ratio of atoms and film quality in the sputtered film according to the present invention. Figure 5 is an X-ray diffraction diagram of the sputtered film formed by the method of the present invention. 6 is a schematic diagram showing the conventional method, and FIG. 7 is a diagram showing the relationship between the crystal structure of a sputtered film formed by the conventional method and the substrate temperature. In the figure, 11A is a pbo target, IIB is a Ti0i target, 12 is a substrate, 13 is a container, 14A, 14B
15 is a target installation stand, 15 is a heater, 16 is a substrate installation stand, 17 is an exhaust valve, 18 is an exhaust pipe, 19 is a gas introduction pipe, and 21 is the relationship between the applied power to the target and the atomic ratio of the ferroelectric thin film to be formed. Curve 31 is a relationship curve between atomic ratio and film quality of ferroelectric thin film, 41.41A, 41B, 41C, 41
D shows the X-ray diffraction peak of the ferroelectric thin film. 's 1 Figure, tai-・'# Mei 7 Ikeri Mebanori Tateshiki Wa Convex 2nd
Figure 3 and → direction i criminal law
Claims (3)
記号とし、組成がＡＢＯ＿３で表されるペロブスカイト
型強誘電薄膜を基板（１２）上にスパツタ法で形成する
場合に於いて、 スパツタ用ガスが満たされた容器内に前記ＡおよびＢを
構成する元素、或いはＡおよびＢを構成する元素と酸素
を含んだ化合物で構成された二つのターゲツト（１１Ａ
，１１Ｂ）を別個に配置し、これ等ターゲツト上に前記
基板（１２）を所定の繰り返し周期で交互に移動させ、
成膜組成が、０．５＜Ａ／Ｂ＜２．０の範囲の原子比と
なるようにスパツタリングを行うことを特徴とする強誘
電薄膜の形成方法。(1) When forming a perovskite-type ferroelectric thin film with the composition ABO_3 on the substrate (12) by sputtering, where A and B are symbols indicating a single element or multiple elements, sputtering Two targets (11A
, 11B) are placed separately, and the substrates (12) are alternately moved over these targets at a predetermined repetition period,
A method for forming a ferroelectric thin film, comprising performing sputtering so that the film composition has an atomic ratio in the range of 0.5<A/B<2.0.
１Ｂ）を（格子定数／膜の成長速度≧基板がターゲツト
を通過する周期）となる条件で移動させることを特徴と
する特許請求の範囲第１項に記載の強誘電薄膜の形成方
法。(2) The substrate (12) is connected to each target (11A, 1
1B) is moved under the condition that (lattice constant/film growth rate≧period in which the substrate passes the target).
ることを特徴とする特許請求の範囲第１項および第２項
のいずれかに記載の強誘電薄膜の形成方法。(3) The method for forming a ferroelectric thin film according to any one of claims 1 and 2, wherein the atmosphere in the sputtering container is an oxidizing atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61315038A JPH0670920B2 (en) | 1986-12-26 | 1986-12-26 | Method for forming ferroelectric thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61315038A JPH0670920B2 (en) | 1986-12-26 | 1986-12-26 | Method for forming ferroelectric thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63166198A true JPS63166198A (en) | 1988-07-09 |
| JPH0670920B2 JPH0670920B2 (en) | 1994-09-07 |
Family
ID=18060674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61315038A Expired - Lifetime JPH0670920B2 (en) | 1986-12-26 | 1986-12-26 | Method for forming ferroelectric thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0670920B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0294507A (en) * | 1988-09-30 | 1990-04-05 | Toshiba Corp | Ferroelectric thin-film and manufacture thereof |
| JPH04147964A (en) * | 1990-10-11 | 1992-05-21 | Sharp Corp | Production of thin film of ferroelectric substance |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62272402A (en) * | 1986-05-20 | 1987-11-26 | 松下電器産業株式会社 | Manufacture of thin film |
-
1986
- 1986-12-26 JP JP61315038A patent/JPH0670920B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62272402A (en) * | 1986-05-20 | 1987-11-26 | 松下電器産業株式会社 | Manufacture of thin film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0294507A (en) * | 1988-09-30 | 1990-04-05 | Toshiba Corp | Ferroelectric thin-film and manufacture thereof |
| JPH04147964A (en) * | 1990-10-11 | 1992-05-21 | Sharp Corp | Production of thin film of ferroelectric substance |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0670920B2 (en) | 1994-09-07 |
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