JPH08319160A - Strontium-bismuth-tantalum-oxygen dielectric substance, thin film of dielectric substance, composition for forming thin film and production of the thin film - Google Patents
Strontium-bismuth-tantalum-oxygen dielectric substance, thin film of dielectric substance, composition for forming thin film and production of the thin filmInfo
- Publication number
- JPH08319160A JPH08319160A JP7122423A JP12242395A JPH08319160A JP H08319160 A JPH08319160 A JP H08319160A JP 7122423 A JP7122423 A JP 7122423A JP 12242395 A JP12242395 A JP 12242395A JP H08319160 A JPH08319160 A JP H08319160A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- composition
- dielectric substance
- forming
- film layer
- 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 abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000000126 substance Substances 0.000 title abstract 6
- 238000004519 manufacturing process Methods 0.000 title description 2
- XYPATZIUBZEANJ-UHFFFAOYSA-N [O].[Ta].[Sr].[Bi] Chemical compound [O].[Ta].[Sr].[Bi] XYPATZIUBZEANJ-UHFFFAOYSA-N 0.000 title 1
- 239000010408 film Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000009413 insulation Methods 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 description 13
- 238000001354 calcination Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000005755 formation reaction Methods 0.000 description 9
- 239000003989 dielectric material Substances 0.000 description 7
- 229910052797 bismuth Inorganic materials 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- 230000002411 adverse Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 4
- -1 strontium carboxylic acid salts Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 3
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229940117955 isoamyl acetate Drugs 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical class [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- BXCONTUBAJHQLF-UHFFFAOYSA-N strontium octan-1-olate Chemical class [Sr++].CCCCCCCC[O-].CCCCCCCC[O-] BXCONTUBAJHQLF-UHFFFAOYSA-N 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229940070710 valerate Drugs 0.000 description 2
- GEGLCBTXYBXOJA-UHFFFAOYSA-N 1-methoxyethanol Chemical compound COC(C)O GEGLCBTXYBXOJA-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- VYTORLUEUJJLTP-UHFFFAOYSA-I 2-ethylbutanoate tantalum(5+) Chemical compound C(C)C(C(=O)[O-])CC.[Ta+5].C(C)C(C(=O)[O-])CC.C(C)C(C(=O)[O-])CC.C(C)C(C(=O)[O-])CC.C(C)C(C(=O)[O-])CC VYTORLUEUJJLTP-UHFFFAOYSA-I 0.000 description 1
- IUGCUEGFROWYOX-UHFFFAOYSA-N 2-methoxyethanolate;tantalum(5+) Chemical compound [Ta+5].COCC[O-].COCC[O-].COCC[O-].COCC[O-].COCC[O-] IUGCUEGFROWYOX-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229910002835 Pt–Ir Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DPASUYABUPGRDP-UHFFFAOYSA-K [Bi+3].CCC(CC)C([O-])=O.CCC(CC)C([O-])=O.CCC(CC)C([O-])=O Chemical compound [Bi+3].CCC(CC)C([O-])=O.CCC(CC)C([O-])=O.CCC(CC)C([O-])=O DPASUYABUPGRDP-UHFFFAOYSA-K 0.000 description 1
- PLDOOTHQYVPQJW-UHFFFAOYSA-I [Ta+5].CCCCCC([O-])=O.CCCCCC([O-])=O.CCCCCC([O-])=O.CCCCCC([O-])=O.CCCCCC([O-])=O Chemical compound [Ta+5].CCCCCC([O-])=O.CCCCCC([O-])=O.CCCCCC([O-])=O.CCCCCC([O-])=O.CCCCCC([O-])=O PLDOOTHQYVPQJW-UHFFFAOYSA-I 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- PVZMSIQWTGPSHJ-UHFFFAOYSA-N butan-1-ol;tantalum Chemical compound [Ta].CCCCO.CCCCO.CCCCO.CCCCO.CCCCO PVZMSIQWTGPSHJ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- OLZYZWRTOLJEAJ-UHFFFAOYSA-M oxobismuthanyl pentanoate Chemical compound CCCCC(=O)O[Bi]=O OLZYZWRTOLJEAJ-UHFFFAOYSA-M 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LJTHRDIGXSIYMM-UHFFFAOYSA-N propan-1-olate tantalum(5+) Chemical compound [Ta+5].CCC[O-].CCC[O-].CCC[O-].CCC[O-].CCC[O-] LJTHRDIGXSIYMM-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- XKFQWWYUSWDWTF-UHFFFAOYSA-L strontium;2-ethylbutanoate Chemical class [Sr+2].CCC(CC)C([O-])=O.CCC(CC)C([O-])=O XKFQWWYUSWDWTF-UHFFFAOYSA-L 0.000 description 1
- YTBRWVXQNMQQTK-UHFFFAOYSA-N strontium;ethanolate Chemical compound CCO[Sr]OCC YTBRWVXQNMQQTK-UHFFFAOYSA-N 0.000 description 1
- APYGJERPTRNPHO-UHFFFAOYSA-L strontium;hexanoate Chemical class [Sr+2].CCCCCC([O-])=O.CCCCCC([O-])=O APYGJERPTRNPHO-UHFFFAOYSA-L 0.000 description 1
- FTTZMRHPHQKQQK-UHFFFAOYSA-N strontium;propan-1-olate Chemical compound [Sr+2].CCC[O-].CCC[O-] FTTZMRHPHQKQQK-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、半導体メモリや光スイ
ッチ等に用いられるＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体及び
その薄膜と、この薄膜形成用の組成物及び薄膜形成方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Sr-Bi-Ta-O-based dielectric material used for semiconductor memories, optical switches and the like, a thin film thereof, a composition for forming the thin film and a thin film forming method.
【０００２】[0002]
【従来の技術】従来、Ｓｒ，Ｂｉ，Ｔａを含む誘電体組
成としてはＳｒＢｉ2 Ｔａ2 Ｏ9 が知られている。この
材料は薄膜化した際に、ＰＺＴに見られるような分極反
転を繰り返すと分極が小さくなるという膜疲労が少ない
ことから、半導体メモリに組み込むことによって、その
ヒステリシス特性を利用した不揮発性メモリへ応用する
ことが考えられている。 2. Description of the Related Art Conventionally, SrBi 2 Ta 2 O 9 is known as a dielectric composition containing Sr, Bi and Ta. When this material is made into a thin film, there is little film fatigue that the polarization becomes small when repeating polarization inversion as seen in PZT. Therefore, by incorporating it in a semiconductor memory, it is applied to a non-volatile memory utilizing its hysteresis characteristics. It is thought to do.
【０００３】このＳｒＢｉ2 Ｔａ2 Ｏ9 の分極値は、バ
ルクの分極値でＰｒ＝５．８μＣ／ｃｍ2 である。将
来、強誘電体材料が高集積化された時に必要とされる残
留分極値は２５６Ｍｂで２Ｐｒ＝１５μＣ／ｃｍ2 以上
といわれており、従って、膜疲労がより一層低減された
薄膜を得るためにはこの材料の残留分極値の改善が望ま
れる。The polarization value of SrBi 2 Ta 2 O 9 is Pr = 5.8 μC / cm 2 in terms of bulk polarization value. In the future, when the ferroelectric material is highly integrated, the remanent polarization value required at 256 Mb is said to be 2 Pr = 15 μC / cm 2 or more. Therefore, in order to obtain a thin film with further reduced film fatigue. It is desired to improve the remanent polarization value of this material.
【０００４】このＳｒＢｉ2 Ｔａ2 Ｏ9 薄膜の形成方法
として、ＰＣＴ公開公報ＷＯ９４／１０７０２には、組
成比をＳｒ：Ｂｉ：Ｔａ＝１：２．４：２として前駆体
溶液を調製した後、成膜、乾燥、仮焼を繰り返して結晶
化を行うことが記載されている。ここで２０％のＢｉ過
剰分は結晶化熱処理時に拡散或いは蒸発するＢｉ分を補
うためである。使用する基板（例えば、Ｐｔ／Ｔｉ／Ｓ
ｉＯ2 ／Ｓｉ基板など）は、成膜前に成膜終了プロセス
までにかける最高温度かそれ以上で一度焼成を行ってい
る。また、上記特性を満たす電気特性を得るための仮焼
温度は７００℃位である。As a method for forming this SrBi 2 Ta 2 O 9 thin film, PCT publication WO 94/10702 discloses a precursor solution having a composition ratio of Sr: Bi: Ta = 1: 2.4: 2, It is described that crystallization is performed by repeating film formation, drying and calcination. The 20% Bi excess is to supplement the Bi content that diffuses or evaporates during the crystallization heat treatment. The substrate used (eg Pt / Ti / S
iO 2 / Si substrate, etc.), is performed once fired at a maximum temperature or above to be applied to up to completion of the film formation process before the formation. Further, the calcination temperature for obtaining the electrical characteristics satisfying the above characteristics is about 700 ° C.
【０００５】なお、従来、ＳｒＢｉ2 Ｔａ2 Ｏ9 のバル
クの報告例はあるが、（Ｓｒx Ｂｉ1-x ）Ｂｉ2 Ｔａ2
Ｏy （０＜ｘ＜１）の組成の報告例はない。Although there have been reports of SrBi 2 Ta 2 O 9 in bulk, (Sr x Bi 1-x ) Bi 2 Ta 2 has been reported.
There is no report of the composition of O y (0 <x <1).
【０００６】[0006]
【発明が解決しようとする課題】ＷＯ９４／１０７０２
にあっては、成膜前の基板熱処理の温度と、成膜乾燥後
の仮焼温度が高く（即ち、良好な電気特性を得るには、
いずれも７００〜８００℃程度）、このため、基板への
熱的ダメージは相当に大きい。例えば、Ｐｔ／Ｔｉ／Ｓ
ｉＯ2 、又はＰｔ／Ｔａ／ＳｉＯ2 基板を８００℃で焼
成した場合には、表面の金属光沢が失われ、ＴａやＴｉ
が析出すると共に、酸化により表面が荒れる現象が発生
する。Problems to be Solved by the Invention WO94 / 10702
Then, the temperature of the substrate heat treatment before film formation and the calcination temperature after film formation drying are high (that is, in order to obtain good electrical characteristics,
In each case, the temperature is about 700 to 800 ° C.), so that the thermal damage to the substrate is considerably large. For example, Pt / Ti / S
When an io 2 or Pt / Ta / SiO 2 substrate is baked at 800 ° C, the metallic luster of the surface is lost and Ta or Ti
And the surface is roughened by oxidation.
【０００７】本発明は、上記従来の問題点を解決し、残
留分極値が大きく、膜疲労のないＳｒ−Ｂｉ−Ｔａ−Ｏ
系誘電体及び誘電体薄膜を提供することを目的とする。
また、本発明は、成膜前の高温プロセスを必要とせずに
良好な電気特性を有する強誘電体薄膜を形成することが
できる薄膜形成用組成物及び形成方法を提供することを
目的とする。The present invention solves the above-mentioned conventional problems, has a large remanent polarization value, and is free from film fatigue Sr-Bi-Ta-O.
An object is to provide a system dielectric and a dielectric thin film.
It is another object of the present invention to provide a thin film forming composition and a forming method capable of forming a ferroelectric thin film having good electric characteristics without requiring a high temperature process before film formation.
【０００８】[0008]
【課題を解決するための手段】本発明のＳｒ−Ｂｉ−Ｔ
ａ−Ｏ系誘電体は、Ｓｒ−Ｂｉ−Ｔａの複合酸化物より
なり、組成が（Ｓｒx Ｂｉ1-x ）Ｂｉ2 Ｔａ2 Ｏy で表
され、０＜ｘ＜１，ｙはそれぞれの金属に付随する酸素
原子の合計で表されるものである。The Sr-Bi-T of the present invention
a-O based dielectric is made of a composite oxide of Sr-Bi-Ta, the composition is represented by (Sr x Bi 1-x) Bi 2 Ta 2 O y, 0 <x <1, y is respectively It is represented by the total number of oxygen atoms associated with the metal.
【０００９】本発明のＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体薄
膜は、この誘電体の薄膜よりなるものである。The Sr-Bi-Ta-O-based dielectric thin film of the present invention comprises this dielectric thin film.
【００１０】本発明のＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体薄
膜形成用組成物は、溶液中の金属組成比（モル比）がＳ
ｒ：Ｂｉ：Ｔａ＝Ｘ：Ｙ：Ｚで表され、０．０５≦Ｘ／
Ｚ≦０．５，０．７≦Ｙ／Ｚ≦２となるように有機溶媒
中に金属化合物を混合してなるものである。The composition of the present invention for forming a Sr-Bi-Ta-O-based dielectric thin film has a metal composition ratio (molar ratio) in the solution of S.
r: Bi: Ta = X: Y: Z, and 0.05 ≦ X /
A metal compound is mixed in an organic solvent so that Z ≦ 0.5 and 0.7 ≦ Y / Z ≦ 2.
【００１１】本発明のＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体薄
膜の形成方法は、この組成物を基板上に塗布し、乾燥及
び仮焼成を目的の膜厚になるまで複数回繰り返した後、
焼成して結晶化させるものである。The method of forming the Sr-Bi-Ta-O-based dielectric thin film of the present invention comprises applying this composition onto a substrate, repeating drying and pre-baking a plurality of times until a target film thickness is obtained,
It is crystallized by firing.
【００１２】以下に本発明を詳細に説明する。The present invention will be described in detail below.
【００１３】本発明のＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体に
おいて、（Ｓｒx Ｂｉ1-x ）Ｂｉ2Ｔａ2 Ｏy における
ｘが０であっても１であっても良好な誘電特性が得られ
ない。組成（Ｓｒx Ｂｉ1-x ）Ｂｉ2 Ｔａ2 Ｏy におけ
るｘは特に０．５≦ｘ＜１、とりわけ０．５≦ｘ＜０．
９であり、ｙはそれぞれの金属に付随する酸素原子の合
計で表されることが好適である。[0013] In Sr-Bi-Ta-O based dielectric of the present invention, the (Sr x Bi 1-x) Bi 2 Ta 2 O y be a 1 even x is 0 in good dielectric properties I can't get it. In the composition (Sr x Bi 1-x ) Bi 2 Ta 2 O y , x is particularly 0.5 ≦ x <1, particularly 0.5 ≦ x <0.
It is 9 and y is preferably represented by the total number of oxygen atoms associated with each metal.
【００１４】本発明のＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体薄
膜は、このようなＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体を好ま
しくは１０ｎｍ〜１μｍ、より好ましくは８０〜８００
ｎｍの膜厚の薄膜としたものである。この膜厚が１０ｎ
ｍ未満では薄すぎるため絶縁性を得にくく、１μｍを超
えると粒成長が激しく表面が粗れるため、１０ｎｍ〜１
μｍの範囲とするのが好ましい。The Sr-Bi-Ta-O-based dielectric thin film of the present invention preferably comprises such an Sr-Bi-Ta-O-based dielectric material in a thickness of 10 nm to 1 μm, more preferably 80 to 800 μm.
The thin film has a thickness of nm. This film thickness is 10n
If it is less than m, it is difficult to obtain insulation because it is too thin, and if it exceeds 1 μm, grain growth is severe and the surface is roughened.
It is preferably in the range of μm.
【００１５】また、本発明のＳｒ−Ｂｉ−Ｔａ−Ｏ系誘
電体薄膜形成用組成物は、このようなＳｒ−Ｂｉ−Ｔａ
−Ｏ系誘電体薄膜を形成するためのものであって、溶液
中の金属組成比（モル比）がＳｒ：Ｂｉ：Ｔａ＝Ｘ：
Ｙ：Ｚで表され、０．０５≦Ｘ／Ｚ≦０．５、０．７≦
Ｙ／Ｚ≦２、好ましくは０．３≦Ｘ／Ｚ≦０．４、０．
８≦Ｙ／Ｚ≦１．５となるように有機溶媒中に金属の有
機化合物又は無機化合物を混合してなり、このような金
属組成比とすることにより、高温プロセスを必要とする
ことなく、従って、基板への熱的悪影響を防止して、上
記高特性誘電体薄膜を形成して良好な電気特性を得るこ
とができる。The composition for forming a Sr-Bi-Ta-O-based dielectric thin film of the present invention is such an Sr-Bi-Ta.
This is for forming an —O-based dielectric thin film, and the metal composition ratio (molar ratio) in the solution is Sr: Bi: Ta = X:
Y: represented by Z, 0.05 ≦ X / Z ≦ 0.5, 0.7 ≦
Y / Z ≦ 2, preferably 0.3 ≦ X / Z ≦ 0.4, 0.
The organic compound or the inorganic compound of the metal is mixed in the organic solvent so that 8 ≦ Y / Z ≦ 1.5. By setting such a metal composition ratio, a high temperature process is not required, Therefore, it is possible to prevent thermal adverse effects on the substrate, form the high-performance dielectric thin film, and obtain good electrical properties.
【００１６】なお、このＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体
薄膜形成用組成物に用いられる有機溶媒としては、酢酸
エチル、酢酸プロピル、酢酸ブチル、酢酸イソアミル等
の酢酸エステル類、エタノール、プロパノール、ブタノ
ール、２−メトキシエタノール等のアルコール類が挙げ
られる。また、Ｓｒ化合物としては、オクチル酸ストロ
ンチウム、ｎ−ヘキサン酸ストロンチウム、２−エチル
酪酸ストロンチウム、ｉ−吉草酸ストロンチウム等のス
トロンチウムのカルボン酸塩や、ストロンチウムエトキ
シド、ストロンチウムプロポキシド、ストロンチウム２
−メトキシエトキシド等のストロンチウムアルコキシド
類等が、Ｂｉ化合物としては、オクチル酸ビスマス、ｎ
−ヘキサン酸ビスマス、２−エチル酪酸ビスマス、ｉ−
吉草酸ビスマス等のビスマスのカルボン酸塩等の有機Ｂ
ｉ化合物、硝酸ビスマス等の無機Ｂｉ化合物が、また、
Ｔａ化合物としては、タンタルエトキシド、タンタルプ
ロポキシド、タンタルブトキシド、タンタル２−メトキ
シエトキシド等のタンタルのアルコキシドやオクチル酸
タンタル、ｎ−ヘキサン酸タンタル、２−エチル酪酸タ
ンタル、ｉ−吉草酸タンタル等のタンタルのカルボン酸
塩等が挙げられる。The organic solvent used in the composition for forming the Sr-Bi-Ta-O type dielectric thin film includes acetic acid esters such as ethyl acetate, propyl acetate, butyl acetate and isoamyl acetate, ethanol, propanol, Examples include alcohols such as butanol and 2-methoxyethanol. Further, as the Sr compound, strontium carboxylic acid salts of strontium octylate, strontium n-hexanoate, strontium 2-ethylbutyrate, strontium i-valerate, etc., strontium ethoxide, strontium propoxide, strontium 2
-Strontium alkoxides such as methoxyethoxide are bismuth octylate, n
-Bismuth hexanoate, bismuth 2-ethylbutyrate, i-
Organic B such as bismuth carboxylate such as bismuth valerate
Inorganic Bi compounds such as i compounds and bismuth nitrate,
Examples of the Ta compound include tantalum alkoxides such as tantalum ethoxide, tantalum propoxide, tantalum butoxide, and tantalum 2-methoxyethoxide, tantalum octylate, tantalum n-hexanoate, tantalum 2-ethylbutyrate, and tantalum i-valerate. And tantalum carboxylic acid salts thereof.
【００１７】これらの金属化合物は、組成物中の酸化物
換算の合計濃度が５〜１５重量％となるように、前記有
機溶媒に混合される。These metal compounds are mixed with the organic solvent so that the total concentration of oxides in the composition is 5 to 15% by weight.
【００１８】本発明のＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体薄
膜の形成方法は、このようなＳｒ−Ｂｉ−Ｔａ−Ｏ系誘
電体薄膜形成用組成物を、基板上に塗布し、乾燥及び仮
焼成を目的の膜厚になるまで複数回繰り返した後、焼成
して結晶化させるものである。The method of forming a Sr-Bi-Ta-O-based dielectric thin film of the present invention comprises applying such a composition for forming a Sr-Bi-Ta-O-based dielectric thin film onto a substrate, followed by drying and drying. The calcination is repeated several times until the target film thickness is obtained, and then the calcination is performed to crystallize.
【００１９】ここで、基板としては、Ｐｔ／Ｔｉ／Ｓｉ
Ｏ2 ／Ｓｉ基板、Ｐｔ／Ｔａ／ＳｉＯ2 ／Ｓｉ基板，Ｐ
ｔ／ＳｉＯ2 ／Ｓｉ基板、Ｉｒ／ＩｒＯ2 ／Ｓｉ基板、
Ｐｔ／ＴｉＮ／ＳｉＯ2 ／Ｓｉ基板、Ｐｔ／Ｉｒ／Ｓｉ
Ｏ2 ／Ｓｉ基板、（Ｐｔ−Ｉｒ合金）／ＩｒＯ2 ／Ｓｉ
基板、Ｐｔ／Ｉｒ／ＩｒＯ2 ／Ｓｉ基板等を用いること
ができる。Here, the substrate is Pt / Ti / Si
O 2 / Si substrate, Pt / Ta / SiO 2 / Si substrate, P
t / SiO 2 / Si substrate, Ir / IrO 2 / Si substrate,
Pt / TiN / SiO 2 / Si substrate, Pt / Ir / Si
O 2 / Si substrate, (Pt-Ir alloy) / IrO 2 / Si
A substrate, a Pt / Ir / IrO 2 / Si substrate, or the like can be used.
【００２０】本発明の方法によれば、これらの基板は熱
処理を行うことなく、成膜に供することができる。According to the method of the present invention, these substrates can be subjected to film formation without heat treatment.
【００２１】基板への薄膜形成用組成物の塗布方法とし
てはスピンコート法、ディップコート法、噴霧法等を採
用することができ、所定の膜厚の誘電体薄膜が得られる
ように、繰り返し塗布、乾燥及び仮焼成を行う。本発明
においては、この仮焼成は、２００〜６００℃、特に２
００〜４００℃の低温で１〜３０分程度行えば良い。As a method for applying the thin film forming composition to the substrate, a spin coating method, a dip coating method, a spraying method or the like can be adopted, and the composition is repeatedly applied so that a dielectric thin film having a predetermined thickness can be obtained. , Drying and calcination are performed. In the present invention, this calcination is performed at 200 to 600 ° C., especially 2
It may be performed at a low temperature of 00 to 400 ° C. for about 1 to 30 minutes.
【００２２】誘電体薄膜形成用組成物を、基板上に、所
望の膜厚に塗布、乾燥及び仮焼成した後は、本焼成を行
って結晶化させる。本発明においては、この本焼成は、
酸化雰囲気中にて、６００〜９００℃、特に６００〜８
００℃で２０分〜２時間行う。これにより、残留分極値
が大きく、膜疲労の少ない、高誘電特性のＳｒ−Ｂｉ−
Ｔａ−Ｏ系誘電体薄膜を、高温プロセスを必要とするこ
となく、容易に形成することができる。After the composition for forming a dielectric thin film is applied on a substrate to a desired film thickness, dried and calcined, main calcination is performed to crystallize. In the present invention, this main firing is
600 to 900 ° C., especially 600 to 8 in an oxidizing atmosphere
It is carried out at 00 ° C for 20 minutes to 2 hours. As a result, the remanent polarization value is large, the film fatigue is small, and Sr-Bi- having a high dielectric property is used.
The Ta-O-based dielectric thin film can be easily formed without requiring a high temperature process.
【００２３】[0023]
【作用】本発明のＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体は、従
来提供されているＳｒＢｉ2 Ｔａ2 Ｏ9 の強誘電性を向
上させるために、組成中のＳｒの一部をＢｉで置換した
ものであり、本発明の誘電体組成とすることにより、残
留分極が大きく、膜疲労の少ない強誘電性Ｓｒ−Ｂｉ−
Ｔａ−Ｏ系誘電体が提供される。The Sr-Bi-Ta-O-based dielectric material of the present invention replaces a part of Sr in the composition with Bi in order to improve the ferroelectricity of SrBi 2 Ta 2 O 9 provided conventionally. By using the dielectric composition of the present invention, the ferroelectric Sr-Bi- which has a large remanent polarization and a small film fatigue.
A Ta-O based dielectric is provided.
【００２４】また、本発明のＳｒ−Ｂｉ−Ｔａ−Ｏ系誘
電体薄膜形成用組成物及び薄膜形成方法によれば、成膜
前の基板熱処理を行うことなく、また、低い成膜時仮焼
成温度にて、従って、基板に熱的悪影響を及ぼすことな
く、高特性誘電体薄膜を形成することができる。According to the composition for forming a Sr-Bi-Ta-O-based dielectric thin film and the thin film forming method of the present invention, the substrate heat treatment before film formation is not performed, and a low calcination during film formation is performed. It is possible to form high performance dielectric thin films at temperature and therefore without adversely affecting the substrate.
【００２５】[0025]
【実施例】以下に実施例及び比較例を挙げて本発明をよ
り具体的に説明する。EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples below.
【００２６】なお、以下の実施例及び比較例において、
薄膜形成用組成物の有機溶媒としては、酢酸イソアミル
を用い、Ｔａ化合物としてはタンタルエトキシドを、Ｂ
ｉ化合物としてはオクチル酸ビスマスを、また、Ｓｒ化
合物としてはオクチル酸ストロンチウムをそれぞれ用
い、各化合物は、組成物中の酸化物換算の合計濃度が１
０重量％となるように所定の組成比で混合した。In the following examples and comparative examples,
Isoamyl acetate was used as the organic solvent for the thin film-forming composition, and tantalum ethoxide was used as the Ta compound.
Bismuth octylate was used as the i compound, and strontium octylate was used as the Sr compound, and each compound had a total concentration in terms of oxides of 1 in the composition.
Mixing was carried out at a predetermined composition ratio so that the content became 0% by weight.
【００２７】実施例１〜５，比較例１，２ Ｔａ化合物，Ｂｉ化合物及びＳｒ化合物を表１に示す金
属組成となるように混合して薄膜形成用組成物を調製
し、この組成物をＰｔ／Ｔａ／ＳｉＯ2 ／Ｓｉ基板上に
表１に示す回数スピンコート法による塗布、乾燥及び仮
焼を繰り返し行った。仮焼条件は表１に示す通りであ
る。Examples 1 to 5, Comparative Examples 1 and 2 Ta compounds, Bi compounds and Sr compounds were mixed so as to have the metal compositions shown in Table 1 to prepare thin film forming compositions, and the compositions were used for Pt. On the / Ta / SiO 2 / Si substrate, coating, drying and calcination by the spin coating method shown in Table 1 were repeated. The calcination conditions are as shown in Table 1.
【００２８】その後、酸素雰囲気中にて表１に示す条件
で焼成して結晶化を行って、表１に示す膜厚及び組成の
誘電体薄膜を得た。Then, it was fired in an oxygen atmosphere under the conditions shown in Table 1 for crystallization to obtain a dielectric thin film having the film thickness and composition shown in Table 1.
【００２９】この薄膜上に、真空蒸着法により上部電極
として金を蒸着し、その後、８００℃で１０分間アニー
ル処理を行って試料とした。Gold was vapor-deposited as an upper electrode on the thin film by a vacuum vapor deposition method, and then annealed at 800 ° C. for 10 minutes to obtain a sample.
【００３０】各試料の残留分極及び膜疲労特性（１０10
回反転後の残留分極の初期値に対する割合（％））を調
べ、結果を表１に示した。Residual polarization and film fatigue characteristics of each sample (10 10
The ratio (%) of the remanent polarization after the reversal to the initial value was examined, and the results are shown in Table 1.
【００３１】表１より、本発明の誘電体薄膜は、残留分
極が大きく、膜疲労が少ないことが明らかである。From Table 1, it is clear that the dielectric thin film of the present invention has large remanent polarization and little film fatigue.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【発明の効果】以上詳述した通り、本発明のＳｒ−Ｂｉ
−Ｔａ−Ｏ系誘電体及びＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体
薄膜によれば、強誘電性で残留分極が大きく、膜疲労の
少ないＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体及びＳｒ−Ｂｉ−
Ｔａ−Ｏ系誘電体薄膜が提供される。As described in detail above, the Sr-Bi of the present invention is
According to the -Ta-O-based dielectric material and the Sr-Bi-Ta-O-based dielectric thin film, the Sr-Bi-Ta-O-based dielectric material and the Sr-Bi-based dielectric material having ferroelectricity, large remanent polarization and little film fatigue are used. −
A Ta-O based dielectric thin film is provided.
【００３４】また、本発明の薄膜形成用組成物及び薄膜
形成方法によれば、高温プロセスを必要とすることな
く、従って、基板に熱的な悪影響を及ぼすことなく、こ
のような高特性Ｓｒ−Ｂｉ−Ｔａ−Ｏ系誘電体及びＳｒ
−Ｂｉ−Ｔａ−Ｏ系誘電体薄膜を形成することができ
る。Further, according to the thin film forming composition and the thin film forming method of the present invention, such a high-performance Sr-type film can be obtained without requiring a high temperature process and therefore without adversely affecting the substrate thermally. Bi-Ta-O system dielectric and Sr
A -Bi-Ta-O-based dielectric thin film can be formed.
【００３５】本発明に係る誘電体材料を半導体メモリ等
に使用した場合には、膜疲労のない優れたデバイスを作
製することが可能である。When the dielectric material according to the present invention is used for a semiconductor memory or the like, it is possible to manufacture an excellent device without film fatigue.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成８年５月３０日[Submission date] May 30, 1996
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項３[Name of item to be corrected] Claim 3
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】本発明のＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体薄
膜形成用組成物は、溶液中の金属組成比（モル比）がＳ
ｒ：Ｂｉ：Ｔａ＝Ｘ：Ｙ：Ｚで表され、０．０５≦Ｘ／
Ｚ＜０．５，０．７≦Ｙ／Ｚ≦２となるように有機溶媒
中に金属化合物を混合してなるものである。The composition of the present invention for forming a Sr-Bi-Ta-O-based dielectric thin film has a metal composition ratio (molar ratio) in the solution of S.
r: Bi: Ta = X: Y: Z, and 0.05 ≦ X /
A metal compound is mixed in an organic solvent so that Z < 0.5 and 0.7 ≦ Y / Z ≦ 2.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Name of item to be corrected] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１５】また、本発明のＳｒ−Ｂｉ−Ｔａ−Ｏ系誘
電体薄膜形成用組成物は、このようなＳｒ−Ｂｉ−Ｔａ
−Ｏ系誘電体薄膜を形成するためのものであって、溶液
中の金属組成比（モル比）がＳｒ：Ｂｉ：Ｔａ＝Ｘ：
Ｙ：Ｚで表され、０．０５≦Ｘ／Ｚ＜０．５、０．７≦
Ｙ／Ｚ≦２、好ましくは０．３≦Ｘ／Ｚ≦０．４、０．
８≦Ｙ／Ｚ≦１．５となるように有機溶媒中に金属の有
機化合物又は無機化合物を混合してなり、このような金
属組成比とすることにより、高温プロセスを必要とする
ことなく、従って、基板への熱的悪影響を防止して、上
記高特性誘電体薄膜を形成して良好な電気特性を得るこ
とができる。The composition for forming a Sr-Bi-Ta-O-based dielectric thin film of the present invention is such an Sr-Bi-Ta.
This is for forming an —O-based dielectric thin film, and the metal composition ratio (molar ratio) in the solution is Sr: Bi: Ta = X:
Y: represented by Z, 0.05 ≦ X / Z < 0.5, 0.7 ≦
Y / Z ≦ 2, preferably 0.3 ≦ X / Z ≦ 0.4, 0.
The organic compound or the inorganic compound of the metal is mixed in the organic solvent so that 8 ≦ Y / Z ≦ 1.5. By setting such a metal composition ratio, a high temperature process is not required, Therefore, it is possible to prevent thermal adverse effects on the substrate, form the high-performance dielectric thin film, and obtain good electrical properties.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３２[Name of item to be corrected] 0032
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３２】[0032]
【表１】 [Table 1]
Claims (4)
り、組成が（Ｓｒx Ｂｉ1-x ）Ｂｉ2 Ｔａ2 Ｏy で表さ
れ、０＜ｘ＜１，ｙはそれぞれの金属に付随する酸素原
子の合計で表されるＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体。1. A composite oxide of Sr-Bi-Ta, the composition of which is represented by (Sr x Bi 1-x ) Bi 2 Ta 2 O y , where 0 <x <1, y is associated with each metal. Sr-Bi-Ta-O-based dielectric represented by the total of oxygen atoms.
なり、組成が（Ｓｒx Ｂｉ1-x ）Ｂｉ2 Ｔａ2 Ｏy で表
され、０＜ｘ＜１，ｙはそれぞれの金属に付随する酸素
原子の合計で表されるＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電体薄
膜。2. A composite oxide thin film of Sr-Bi-Ta, the composition of which is represented by (Sr x Bi 1-x ) Bi 2 Ta 2 O y , where 0 <x <1 and y are the respective metals. A Sr-Bi-Ta-O-based dielectric thin film represented by the total of attached oxygen atoms.
Ｂｉ：Ｔａ＝Ｘ：Ｙ：Ｚで表され、０．０５≦Ｘ／Ｚ≦
０．５，０．７≦Ｙ／Ｚ≦２となるように有機溶媒中に
金属化合物を混合してなるＳｒ−Ｂｉ−Ｔａ−Ｏ系誘電
体薄膜形成用組成物。3. The metal composition ratio (molar ratio) in the solution is Sr:
Bi: Ta = X: Y: Z, and 0.05 ≦ X / Z ≦
A composition for forming a Sr-Bi-Ta-O-based dielectric thin film, which is obtained by mixing a metal compound in an organic solvent so that 0.5 and 0.7 ≦ Y / Z ≦ 2.
燥及び仮焼成を目的の膜厚になるまで複数回繰り返した
後、焼成して結晶化させることを特徴とするＳｒ−Ｂｉ
−Ｔａ−Ｏ系誘電体薄膜の形成方法。4. The Sr-Bi composition comprising applying the composition of claim 3 onto a substrate, repeating drying and pre-baking a plurality of times until a target film thickness is obtained, and then baking and crystallizing.
-Method for forming Ta-O based dielectric thin film.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07122423A JP3120696B2 (en) | 1995-05-22 | 1995-05-22 | Sr-Bi-Ta-O based dielectric, dielectric thin film, thin film forming composition and thin film forming method |
| KR1019960017151A KR100381498B1 (en) | 1995-05-22 | 1996-05-21 | Bismuth-based total oil thin film, method for forming the same, and composition for the thin film type |
| US08/651,593 US5807495A (en) | 1995-05-22 | 1996-05-22 | Bi-based dielectric thin films, and compositions and method for forming them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07122423A JP3120696B2 (en) | 1995-05-22 | 1995-05-22 | Sr-Bi-Ta-O based dielectric, dielectric thin film, thin film forming composition and thin film forming method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08319160A true JPH08319160A (en) | 1996-12-03 |
| JP3120696B2 JP3120696B2 (en) | 2000-12-25 |
Family
ID=14835471
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07122423A Expired - Lifetime JP3120696B2 (en) | 1995-05-22 | 1995-05-22 | Sr-Bi-Ta-O based dielectric, dielectric thin film, thin film forming composition and thin film forming method |
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| Country | Link |
|---|---|
| JP (1) | JP3120696B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR980012088A (en) * | 1996-07-24 | 1998-04-30 | 이데이 노부유끼 | Layered crystal structure oxide and method for producing the same |
| EP0954030A1 (en) * | 1998-04-30 | 1999-11-03 | Siemens Aktiengesellschaft | Process of manufacturing a capacitor for a semiconductor memory |
-
1995
- 1995-05-22 JP JP07122423A patent/JP3120696B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR980012088A (en) * | 1996-07-24 | 1998-04-30 | 이데이 노부유끼 | Layered crystal structure oxide and method for producing the same |
| EP0954030A1 (en) * | 1998-04-30 | 1999-11-03 | Siemens Aktiengesellschaft | Process of manufacturing a capacitor for a semiconductor memory |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3120696B2 (en) | 2000-12-25 |
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