JPH08335676A - Manufacture of crystalline thin film of composite oxide - Google Patents
Manufacture of crystalline thin film of composite oxideInfo
- Publication number
- JPH08335676A JPH08335676A JP14275795A JP14275795A JPH08335676A JP H08335676 A JPH08335676 A JP H08335676A JP 14275795 A JP14275795 A JP 14275795A JP 14275795 A JP14275795 A JP 14275795A JP H08335676 A JPH08335676 A JP H08335676A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- crystalline thin
- lower electrode
- complex oxide
- iridium
- 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.)
- Withdrawn
Links
- 239000010409 thin film Substances 0.000 title claims description 72
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000002131 composite material Substances 0.000 title claims description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 230000006911 nucleation Effects 0.000 claims description 11
- 238000010899 nucleation Methods 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910000575 Ir alloy Inorganic materials 0.000 claims description 4
- 229910001260 Pt alloy Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims 1
- 239000010936 titanium Substances 0.000 abstract description 12
- 229910052719 titanium Inorganic materials 0.000 abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 8
- 238000003980 solgel method Methods 0.000 abstract description 3
- 238000004544 sputter deposition Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 38
- 229910000457 iridium oxide Inorganic materials 0.000 description 12
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910020684 PbZr Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- -1 and for example Chemical compound 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910002113 barium titanate 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
- 230000004888 barrier function Effects 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Semiconductor Integrated Circuits (AREA)
- Formation Of Insulating Films (AREA)
- Semiconductor Memories (AREA)
- Non-Volatile Memory (AREA)
- Inorganic Insulating Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は複合酸化物の結晶性薄
膜に関するものであり、特にその表面モフォロジの改善
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline thin film of complex oxide, and more particularly to improvement of its surface morphology.
【０００２】[0002]
【従来の技術】一般に、強誘電体層を含む半導体素子の
電極として白金が用いられている。これは、第１に導電
率が高い、第２に前記強誘電体層形成工程における高温
に耐え得る、第３に強誘電体膜の配向性が担保できるか
らである。2. Description of the Related Art Generally, platinum is used as an electrode of a semiconductor device including a ferroelectric layer. This is because firstly, the conductivity is high, secondly, it can withstand the high temperature in the step of forming the ferroelectric layer, and thirdly, the orientation of the ferroelectric film can be secured.
【０００３】配向性の担保について簡単に説明する。白
金はアモルファス膜の上に形成された場合にも、配向膜
となる性質を有している。したがって、アモルファス膜
である酸化シリコン膜４の上に下部電極を形成し、さら
にその上にＰＺＴ膜８に形成しても、この下部電極を白
金で構成すれば、ＰＺＴ膜８は配向するため、強誘電性
が損なわれることがない。Securing the orientation will be briefly described. Platinum has the property of forming an alignment film even when formed on an amorphous film. Therefore, even if the lower electrode is formed on the amorphous silicon oxide film 4 and the PZT film 8 is further formed thereon, the PZT film 8 is oriented if the lower electrode is made of platinum. Ferroelectricity is not impaired.
【０００４】ただ、白金をポリシリコン層の上に形成す
ると、シリサイド化するという問題があった。この問題
を解決する為、発明者は、白金以外の電極材料として、
イリジウム（Ｉｒ）を用いると、前記シリサイド化の問
題を解決できることを見い出した。However, when platinum is formed on the polysilicon layer, there is a problem that it is silicidized. In order to solve this problem, the inventor, as an electrode material other than platinum,
It has been found that the problem of silicidation can be solved by using iridium (Ir).
【０００５】図４に、白金とイリジウムの物性を比較し
て掲げる。この表からも明らかなように、イリジウムの
抵抗率は、白金と比較して小さく電極材料として問題は
ない。FIG. 4 compares the physical properties of platinum and iridium. As is clear from this table, the resistivity of iridium is smaller than that of platinum and there is no problem as an electrode material.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、数々の
実験を繰返した結果、イリジウムを下部電極として用い
た場合には、白金と比較して、上に形成される強誘電体
膜の緻密性が低いことが判明した。すなわち、均一な強
誘電体膜が形成されない。したがって、かかる強誘電体
膜を分割して素子を形成した時に、素子同志の特性にば
らつきが生ずるおそれがあった。かかる問題は、微細化
が進むほど重要な問題となる。However, as a result of repeating a number of experiments, when iridium is used as the lower electrode, the denseness of the ferroelectric film formed above is lower than that of platinum. It has been found. That is, a uniform ferroelectric film is not formed. Therefore, when elements are formed by dividing the ferroelectric film, the characteristics of the elements may vary. This problem becomes more important as miniaturization progresses.
【０００７】この発明は、上記の問題点を解決して、緻
密性の高い複合酸化物の結晶性薄膜を提供することを目
的とする。It is an object of the present invention to solve the above problems and provide a highly dense crystalline oxide thin film of complex oxide.
【０００８】[0008]
【課題を解決するための手段】請求項１の複合酸化物の
結晶性薄膜の製造方法においては、イリジウムを含む下
部電極の上に、複合酸化物の結晶性薄膜を生成する方法
であって、前記下部電極の一部に、前記結晶性薄膜の成
分元素の核、または、この成分元素の酸化物の核を形成
する核形成ステップ、前記核を形成した後、前記複合酸
化物の結晶性薄膜を形成する結晶性薄膜形成ステップ、
を備えたことを特徴とする。A method for producing a crystalline thin film of a complex oxide according to claim 1 is a method of forming a crystalline thin film of a complex oxide on a lower electrode containing iridium. A nucleation step of forming a nucleus of a component element of the crystalline thin film or a nucleus of an oxide of the component element in a part of the lower electrode, and after forming the nucleus, a crystalline thin film of the complex oxide. Forming a crystalline thin film,
It is characterized by having.
【０００９】請求項２の複合酸化物の結晶性薄膜の製造
方法においては、前記下部電極はイリジウムで構成され
ていることを特徴とする。In the method for producing a crystalline thin film of a complex oxide according to a second aspect, the lower electrode is composed of iridium.
【００１０】請求項３の複合酸化物の結晶性薄膜の製造
方法においては、前記下部電極は、イリジウムと白金の
合金で構成されていることを特徴とする。According to a third aspect of the present invention, there is provided a method for producing a crystalline thin film of a complex oxide, wherein the lower electrode is composed of an alloy of iridium and platinum.
【００１１】請求項４の複合酸化物の結晶性薄膜の製造
方法においては、前記下部電極は、イリジウム層および
このイリジウム層の上に形成された白金層を有すること
を特徴とする。In the method for producing a crystalline thin film of a complex oxide according to claim 4, the lower electrode has an iridium layer and a platinum layer formed on the iridium layer.
【００１２】請求項５の複合酸化物の結晶性薄膜の製造
方法においては、前記核形成ステップで形成される核の
成分元素は、前記結晶性薄膜を構成する元素のうち、そ
の酸化物が前記複合酸化物より結晶化温度の低い元素で
あることを特徴とする。In the method for producing a crystalline thin film of a complex oxide according to claim 5, the constituent element of the nucleus formed in the nucleation step is one of the elements constituting the crystalline thin film whose oxide is the It is characterized in that it is an element having a lower crystallization temperature than the complex oxide.
【００１３】請求項６の複合酸化物の結晶性薄膜の製造
方法においては、前記核形成ステップで形成される核
は、厚みが１ｎｍ〜１０ｎｍであることを特徴とする。In the method for producing a crystalline thin film of a complex oxide according to claim 6, the nuclei formed in the nucleation step have a thickness of 1 nm to 10 nm.
【００１４】請求項７の複合酸化物の結晶性薄膜の製造
方法においては、下部電極の上に、複合酸化物の結晶性
薄膜を生成する方法であって、前記下部電極の一部に、
前記結晶性薄膜の成分元素の核、または、この成分元素
の酸化物の核を形成する核形成ステップ、前記核を形成
した後、前記複合酸化物の結晶性薄膜を形成する結晶性
薄膜形成ステップ、を備えたことを特徴とする。A method for producing a crystalline thin film of a complex oxide according to claim 7 is a method of forming a crystalline thin film of a complex oxide on a lower electrode, wherein a part of the lower electrode comprises:
Nucleation step of forming a nucleus of a component element of the crystalline thin film, or a nucleus of an oxide of the component element, and a crystalline thin film forming step of forming a crystalline thin film of the complex oxide after forming the nucleus. , Is provided.
【００１５】[0015]
【作用および発明の効果】請求項１の複合酸化物の結晶
性薄膜の製造方法においては、前記核形成ステップに
て、前記下部電極の一部に、前記結晶性薄膜の成分元素
の核、または、この成分元素の酸化物の核を形成してい
る。前記結晶性薄膜形成ステップにて、この核が中心と
なって前記複合酸化物の結晶性薄膜が形成される。これ
により、緻密性の高い複合酸化物の結晶性薄膜を提供す
ることができる。In the method for producing a crystalline thin film of a complex oxide according to claim 1, in the nucleation step, a nucleus of a constituent element of the crystalline thin film, or a part of the lower electrode, or , Form the nuclei of oxides of this component element. In the crystalline thin film forming step, the crystalline thin film of the complex oxide is formed with the nuclei as the center. This makes it possible to provide a crystalline thin film of a complex oxide having a high density.
【００１６】請求項２の複合酸化物の結晶性薄膜の製造
方法においては、前記下部電極はイリジウムで構成され
ている。したがって、前記結晶性薄膜形成ステップに
て、前記下部電極の表面に酸化イリジウムが形成されて
も、この核が中心となって前記複合酸化物の結晶性薄膜
が形成される。これにより、緻密性の高い複合酸化物の
結晶性薄膜を提供することができる。In the method for producing a crystalline thin film of a complex oxide according to claim 2, the lower electrode is made of iridium. Therefore, even if iridium oxide is formed on the surface of the lower electrode in the crystalline thin film forming step, the crystalline thin film of the complex oxide is formed around the nuclei. This makes it possible to provide a crystalline thin film of a complex oxide having a high density.
【００１７】請求項３の複合酸化物の結晶性薄膜の製造
方法においては、前記下部電極は、イリジウムと白金の
合金である。したがって、前記結晶性薄膜形成ステップ
にて、前記下部電極の表面に酸化イリジウムが形成され
ても、この核が中心となって前記複合酸化物の結晶性薄
膜が形成される。これにより、緻密性の高い複合酸化物
の結晶性薄膜を提供することができる。In the method for producing a crystalline thin film of complex oxide according to claim 3, the lower electrode is an alloy of iridium and platinum. Therefore, even if iridium oxide is formed on the surface of the lower electrode in the crystalline thin film forming step, the crystalline thin film of the complex oxide is formed around the nuclei. This makes it possible to provide a crystalline thin film of a complex oxide having a high density.
【００１８】請求項４の複合酸化物の結晶性薄膜の製造
方法においては、前記下部電極は、イリジウム層および
このイリジウム層の上に形成された白金層を有する。し
たがって、前記結晶性薄膜形成ステップにて、前記下部
電極の表面に酸化イリジウムが形成されても、この核が
中心となって前記複合酸化物の結晶性薄膜が形成され
る。これにより、緻密性の高い複合酸化物の結晶性薄膜
を提供することができる。In the method for producing a crystalline thin film of a complex oxide according to claim 4, the lower electrode has an iridium layer and a platinum layer formed on the iridium layer. Therefore, even if iridium oxide is formed on the surface of the lower electrode in the crystalline thin film forming step, the crystalline thin film of the complex oxide is formed around the nuclei. This makes it possible to provide a crystalline thin film of a complex oxide having a high density.
【００１９】請求項５の複合酸化物の結晶性薄膜の製造
方法においては、前記核形成ステップで形成される核の
成分元素は、前記結晶性薄膜を構成する元素のうち、そ
の酸化物が前記複合酸化物より結晶化温度の低い元素で
ある。したがって、前記結晶性薄膜形成ステップの早い
段階にて、前記核を中心として、複合酸化物の結晶性薄
膜が形成される。これにより、より緻密性の高い複合酸
化物の結晶性薄膜を提供することができる。In the method for producing a crystalline thin film of a complex oxide according to claim 5, the constituent element of the nuclei formed in the nucleation step is the oxide of the elements constituting the crystalline thin film, It is an element whose crystallization temperature is lower than that of the composite oxide. Therefore, in the early stage of the crystalline thin film forming step, the crystalline thin film of the complex oxide is formed around the nucleus. This makes it possible to provide a more dense crystalline oxide thin film of the composite oxide.
【００２０】請求項６の複合酸化物の結晶性薄膜の製造
方法においては、前記核形成ステップで形成される核
は、厚みが１ｎｍ〜１０ｎｍである。したがって、前記
結晶性薄膜の電気特性に悪影響を及ぼすことがなく、か
つ緻密性の高い複合酸化物の結晶性薄膜を提供すること
ができる。In the method for producing a crystalline thin film of complex oxide according to claim 6, the nuclei formed in the nucleation step have a thickness of 1 nm to 10 nm. Therefore, it is possible to provide a highly dense crystalline oxide thin film of composite oxide without adversely affecting the electrical characteristics of the crystalline oxide thin film.
【００２１】請求項７の複合酸化物の結晶性薄膜の製造
方法においては、前記核形成ステップにて、前記下部電
極の一部に、前記結晶性薄膜の成分元素の核、または、
この成分元素の酸化物の核を形成している。前記結晶性
薄膜形成ステップにて、この核が中心となって前記複合
酸化物の結晶性薄膜が形成される。これにより、イリジ
ウムを含む下部電極の上に緻密性の高い複合酸化物の結
晶性薄膜を提供することができる。In the method for producing a crystalline thin film of a complex oxide according to claim 7, in the nucleation step, a nucleus of a constituent element of the crystalline thin film is formed in a part of the lower electrode, or
It forms the nucleus of the oxide of this component element. In the crystalline thin film forming step, the crystalline thin film of the complex oxide is formed with the nuclei as the center. This makes it possible to provide a highly dense composite oxide crystalline thin film on the lower electrode containing iridium.
【００２２】[0022]
【実施例】図１に、この発明の一実施例による強誘電体
層を含む半導体装置の製造工程を示す。ここでは、強誘
電体層を含む半導体装置として、強誘電体キャパシタを
製造した場合を例として説明する。FIG. 1 shows a process of manufacturing a semiconductor device including a ferroelectric layer according to an embodiment of the present invention. Here, a case where a ferroelectric capacitor is manufactured as a semiconductor device including a ferroelectric layer will be described as an example.
【００２３】まず、図１Ａに示すように、シリコン基板
２の表面を熱酸化し、酸化シリコン層４を形成する。こ
こでは、酸化シリコン層４の厚さを６００ｎｍとした。
つぎに、図１Ｂに示すように、イリジウムをターゲット
として用いて、スパッタリングによりイリジウムを、酸
化シリコン層４の上に形成し、これを下部電極１２とす
る。ここでは、下部電極１２を２００ｎｍの厚さに形成
した。First, as shown in FIG. 1A, the surface of the silicon substrate 2 is thermally oxidized to form a silicon oxide layer 4. Here, the thickness of the silicon oxide layer 4 is 600 nm.
Next, as shown in FIG. 1B, using iridium as a target, iridium is formed on the silicon oxide layer 4 by sputtering, and this is used as the lower electrode 12. Here, the lower electrode 12 is formed to a thickness of 200 nm.
【００２４】つぎに、図１Ｃに示すように、下部電極１
２の上に、チタン（Ｔｉ）の核１４を複数形成した。本
実施例においては、ＲＦマグネトロンスパッタ法によ
り、基板加熱なし、アルゴン圧力［１１ｍＴｏｒｒ］、
高周波パワー［３００Ｗ／４インチφ］、時間［２０
秒］の条件で生成した。これにより、厚みｔ＝２ｎｍの
核１４が形成された（図１Ｃ参照）。Next, as shown in FIG. 1C, the lower electrode 1
A plurality of titanium (Ti) nuclei 14 were formed on No. 2. In this embodiment, the substrate is not heated by the RF magnetron sputtering method, the argon pressure is [11 mTorr],
High frequency power [300W / 4 inch φ], time [20
Seconds]. As a result, a nucleus 14 having a thickness t = 2 nm was formed (see FIG. 1C).
【００２５】つぎに、Ｓｏｌ−Ｇｅｌ（ゾルゲル）法に
よって、この下部電極１２および核１４を覆うように、
強誘電体膜であるＰＺＴ膜８を形成する（図４Ｃ）。出
発原料として、Pb(CH3COO)2・3H2O,Zr(tーOC4H9)4、Ti(i-O
C3H7)4の混合溶液を用いた。この混合溶液を塗布し、ス
ピンコートした後、１５０℃で乾燥させ、ドライエア雰
囲気において４００℃で３０秒の仮焼成を行った。これ
を５回繰り返した後、酸素雰囲気中で、７００℃以上の
熱処理を施した。これにより、ＰＺＴ膜８は焼結して結
晶化し成膜する。このようにして、ＰＺＴ膜８の膜厚を
２５０ｎｍに形成した。なお、ここでは、PbZrxTi1-xO3
において、ｘを０．５２とした。Next, the lower electrode 12 and the nucleus 14 are covered by a Sol-Gel (sol-gel) method,
A PZT film 8 which is a ferroelectric film is formed (FIG. 4C). As a starting material, Pb (CH 3 COO) 2 3H 2 O, Zr (t-OC 4 H 9 ) 4 , Ti (iO
A mixed solution of C 3 H 7 ) 4 was used. This mixed solution was applied, spin-coated, dried at 150 ° C., and pre-baked at 400 ° C. for 30 seconds in a dry air atmosphere. After repeating this 5 times, it heat-processed at 700 degreeC or more in oxygen atmosphere. As a result, the PZT film 8 is sintered and crystallized to form a film. Thus, the PZT film 8 was formed to a thickness of 250 nm. In addition, here, PbZr x Ti 1-x O 3
In, x was set to 0.52.
【００２６】なお、下部電極とＰＺＴ膜８との界面に
は、ＰＺＴ膜８の焼成ステップにて、酸化イリジウムが
形成される。Iridium oxide is formed on the interface between the lower electrode and the PZT film 8 in the firing step of the PZT film 8.
【００２７】このＰＺＴ膜８の上に、スパッタリングに
よりイリジウムを形成し、上部電極１５とする（図
２）。ここでは、上部電極１５を２００ｎｍの厚さに形
成した。このようにして、強誘電体キャパシタが得られ
る。Iridium is formed on the PZT film 8 by sputtering to form the upper electrode 15 (FIG. 2). Here, the upper electrode 15 is formed to a thickness of 200 nm. In this way, a ferroelectric capacitor is obtained.
【００２８】このように、ＰＺＴ膜８を形成する前に、
下部電極１２の上にチタンの核１４を形成している。チ
タンは、ＰＺＴ膜８を構成する元素（Pb、Zr、Ti)のう
ち、結晶化温度が一番低い。したがって、ＰＺＴ膜形成
ステップの早い段階にて、このチタンの核１４を中心と
して、ＰＺＴ膜が形成される。これによりＰＺＴ膜の緻
密性が向上する。As described above, before the PZT film 8 is formed,
A titanium nucleus 14 is formed on the lower electrode 12. Titanium has the lowest crystallization temperature among the elements (Pb, Zr, Ti) forming the PZT film 8. Therefore, in the early stage of the PZT film forming step, the PZT film is formed around the titanium nucleus 14. This improves the denseness of the PZT film.
【００２９】なお、チタンではなく、ＰＺＴ膜８を構成
する他の元素を核として用いてもよい。さらに、ＰＺＴ
膜８を構成する元素そのものではなく、その酸化物（Pb
0,ZrO2、PbTiO3）を核として用いてもよい。Incidentally, instead of titanium, other elements forming the PZT film 8 may be used as nuclei. Furthermore, PZT
The oxide itself (Pb
0, ZrO 2 , PbTiO 3 ) may be used as a nucleus.
【００３０】緻密性の向上について、核１４を形成しな
い場合の、ＰＺＴ膜８の表面モフォロジ（組織）の模式
図を、図３に示す。このように、核１４を形成しない場
合、ＰＺＴ膜８の表面モフォロジの緻密性が低い。この
理由は明らかではないが、前記混合溶液中に存在する元
素のうち、結晶温度の低いチタンが不規則的に核となっ
て、結晶化が進行する為ではないかと発明者は考えた。
これに対して、核１４を形成した場合、各々の核１４を
中心として、ＰＺＴ膜の結晶化が進むので、より、緻密
性の高いＰＺＴ膜８が得られる。FIG. 3 shows a schematic diagram of the surface morphology (structure) of the PZT film 8 in the case where the nucleus 14 is not formed for improving the compactness. As described above, when the nuclei 14 are not formed, the surface morphology of the PZT film 8 has low density. The reason for this is not clear, but the inventor considered that titanium having a low crystal temperature among the elements present in the mixed solution irregularly serves as nuclei to promote crystallization.
On the other hand, when the nuclei 14 are formed, the crystallization of the PZT film proceeds around each of the nuclei 14, so that the PZT film 8 having a higher density can be obtained.
【００３１】なお、本実施例においては、核１４の厚み
ｔ＝２ｎｍとした。これはつぎの様な理由による。各々
の核１４を中心として、ＰＺＴ膜が形成される為に、核
１４の密度が高いほど緻密なＰＺＴ膜が形成されると考
えられる。一方、核の密度が高すぎると、ＰＺＴ膜生成
後の界面にチタンオキサイドが残存し、ＰＺＴ膜の電気
特性が悪くなるおそれがある。このような理由により、
発明者は、核１４の厚みｔは、密度が高すぎることのな
い１〜１０ｎｍが望ましく、さらに望ましくは、１〜３
ｎｍで、最も望ましいのが、２ｎｍであると考えた。In this example, the thickness t of the nucleus 14 was t = 2 nm. This is due to the following reasons. Since the PZT film is formed around each nucleus 14, it is considered that a denser PZT film is formed as the nucleus 14 has a higher density. On the other hand, if the density of the nuclei is too high, titanium oxide may remain at the interface after the PZT film is formed, and the electrical characteristics of the PZT film may deteriorate. For this reason,
The inventor preferably has a thickness t of the core 14 of 1 to 10 nm so that the density is not too high, and more preferably 1 to 10 nm.
In terms of nm, the most desirable is 2 nm.
【００３２】なお、本実施例においては、ＲＦマグネト
ロンスパッタ法により、核１４を形成したが、どのよう
な方法でもよく、例えば、ＣＶＤ法、ゾルゲル法、蒸着
法等を用いてもよい。なお、ゾルゲル法の場合は、濃度
を低く調整することにより、所望の厚みの核を形成する
ことができる。Although the nuclei 14 are formed by the RF magnetron sputtering method in this embodiment, any method may be used, for example, the CVD method, the sol-gel method, the vapor deposition method or the like may be used. In the case of the sol-gel method, the nuclei having a desired thickness can be formed by adjusting the concentration to be low.
【００３３】なお、下部電極１２はイリジウムに限定さ
れず、イリジウムを含む物質であればどのようなもので
もよく、イリジウム単体であってもよい。また、白金と
イリジウムとの合金で形成してもよい。さらに、下部電
極１２を複数層で構成し、そのいずれかにイリジウム層
または酸化イリジウム層を設けるようにしてもよい。例
えば、下部層をイリジウム層、上部層を白金層としてよ
い。さらに、その中間に、他の金属層を含むようにして
もよい。The lower electrode 12 is not limited to iridium, and any substance containing iridium may be used, or iridium alone may be used. Alternatively, it may be formed of an alloy of platinum and iridium. Further, the lower electrode 12 may be composed of a plurality of layers, and an iridium layer or an iridium oxide layer may be provided on any of them. For example, the lower layer may be an iridium layer and the upper layer may be a platinum layer. Further, another metal layer may be included in the middle thereof.
【００３４】本実施例においては、ＰＺＴ膜８の焼成ス
テップにて、酸化イリジウム層が形成されている。しか
しながら、酸化イリジウム層を有するように下部電極を
形成してもよい。すなわち、下部電極に酸化イリジウム
を含むことによりバリア効果が働くので、酸化イリジウ
ム層については、後工程で生成されたか、当初から生成
されたかにかかわりなく、ＰＺＴ膜８からの酸素の抜け
出しを防止することができる。In this embodiment, an iridium oxide layer is formed in the firing step of the PZT film 8. However, the lower electrode may be formed to have an iridium oxide layer. That is, since the lower electrode contains iridium oxide, a barrier effect is exerted. Therefore, the iridium oxide layer prevents oxygen from escaping from the PZT film 8 regardless of whether the iridium oxide layer is formed in a later process or originally. be able to.
【００３５】なお、ＰＺＴ膜８を常温にて生成すること
も考えられる。この場合、イリジウムが酸化されない場
合もある。この様な場合、下部電極には酸化イリジウム
層は形成されない。It is also possible to form the PZT film 8 at room temperature. In this case, iridium may not be oxidized. In such a case, the iridium oxide layer is not formed on the lower electrode.
【００３６】なお、一般に、イリジウムと酸化シリコン
との密着性はあまりよくない。このため、部分的に合金
層がはがれ、強誘電特性を劣化させるおそれがある。こ
のように、イリジウムを用いる場合は、下部電極１２と
酸化シリコン層４との間に、両者の接合性を改善する接
合層を設ける様にすればよい。接合層としては、どのよ
うなものでもあってもよく、チタン層、白金層（例え
ば、５ｎｍ）を用いればよい。Generally, the adhesion between iridium and silicon oxide is not so good. Therefore, the alloy layer may be partly peeled off, and the ferroelectric characteristics may be deteriorated. As described above, when iridium is used, a bonding layer that improves the bonding property between the lower electrode 12 and the silicon oxide layer 4 may be provided between the lower electrode 12 and the silicon oxide layer 4. The bonding layer may be of any type, and a titanium layer or a platinum layer (for example, 5 nm) may be used.
【００３７】なお、本実施例においては、複合酸化物の
結晶性薄膜として、強誘電体であるＰＺＴを用いたが、
他の強誘電体、例えば、ＰｂＴｉＯ3、チタン酸バリウ
ム、チタン酸ビスマス、ＰＬＺＴ等の強誘電性を示す物
質を用いてもよい。Although PZT, which is a ferroelectric substance, is used as the crystalline thin film of the composite oxide in this embodiment,
Other ferroelectric substances such as PbTiO 3 , barium titanate, bismuth titanate and PLZT may be used.
【００３８】また、上記実施例においては、複合酸化物
の結晶性薄膜に強誘電体膜を採用した場合について、説
明した。しかし、これに限定されず、複合酸化物の結晶
性薄膜であればどのようなものにも適用でき、例えば、
ペロブスカイト構造を有する高誘電体薄膜（ＳｒＴｉＯ
3、（Ｓｒ，Ｂａ）ＴｉＯ3等）を採用してもよい。高誘
電薄膜に用いた場合も、緻密性が向上することにより、
比誘電率が高くなる。Further, in the above embodiment, the case where the ferroelectric film is used as the crystalline thin film of the composite oxide has been described. However, the present invention is not limited to this, and can be applied to any crystalline thin film of a composite oxide, for example,
High dielectric thin film (SrTiO 3) having a perovskite structure
3 , (Sr, Ba) TiO 3, etc.) may be adopted. Even when used for high-dielectric thin film, it improves the compactness,
High relative permittivity.
【００３９】上記実施例においては、イリジウム層の上
に強誘電体膜を形成する場合について説明したが、イリ
ジウムに限定されず、例えば、ルテニウム（Ｒｕ），レ
ニウム（Ｒｅ），パラジウム（Ｐｄ），オスミウム（Ｏ
ｓ）等の他の貴金属を用いてもよい。また、これらの酸
化物を採用してもよい。In the above embodiment, the case where the ferroelectric film is formed on the iridium layer has been described, but the invention is not limited to iridium, and for example, ruthenium (Ru), rhenium (Re), palladium (Pd), Osmium (O
Other noble metals such as s) may be used. Moreover, you may employ | adopt these oxides.
【００４０】さらに、本発明は、下部電極を白金で形成
した場合にも、同様に、緻密な膜を形成することができ
る。Further, according to the present invention, a dense film can be similarly formed even when the lower electrode is formed of platinum.
【００４１】なお、上記実施例では、強誘電体層を含む
半導体装置として強誘電体キャパシタを例として説明し
たが、導電体層の上に強誘電体層が形成されている半導
体装置であれば、強誘電体メモリ等、どのようなもので
あってもよい。In the above embodiments, the ferroelectric capacitor has been described as an example of the semiconductor device including the ferroelectric layer, but any semiconductor device in which the ferroelectric layer is formed on the conductor layer may be used. , A ferroelectric memory, or the like.
【図１】この発明の一実施例による強誘電体キャパシタ
の製造工程を示す図である。FIG. 1 is a diagram showing a manufacturing process of a ferroelectric capacitor according to an embodiment of the present invention.
【図２】強誘電体キャパシタの要部断面図である。FIG. 2 is a sectional view of an essential part of a ferroelectric capacitor.
【図３】核１４を形成しない場合の、表面モフォロジを
示す図である。FIG. 3 is a diagram showing a surface morphology in the case where a nucleus 14 is not formed.
【図４】白金とイリジウムの物性比較を示す図である。FIG. 4 is a diagram showing a comparison of physical properties of platinum and iridium.
２・・・シリコン基板 ４・・・酸化シリコン層 ８・・・ＰＺＴ膜 １２・・・下部電極 １５・・・上部電極 2 ... Silicon substrate 4 ... Silicon oxide layer 8 ... PZT film 12 ... Lower electrode 15 ... Upper electrode
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｌ 21/316 Ｈ０１Ｌ 27/10 ４５１ 27/04 27/04 Ｃ 21/822 29/78 ３７１ 27/10 ４５１ 41/22 Ａ 21/8247 29/788 29/792 41/24 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication location H01L 21/316 H01L 27/10 451 27/04 27/04 C 21/822 29/78 371 27 / 10 451 41/22 A 21/8247 29/788 29/792 41/24
Claims (7)
化物の結晶性薄膜を生成する方法であって、 前記下部電極の一部に、前記結晶性薄膜の成分元素の
核、または、この成分元素の酸化物の核を形成する核形
成ステップ、 前記核を形成した後、前記複合酸化物の結晶性薄膜を形
成する結晶性薄膜形成ステップ、 を備えたことを特徴とする複合酸化物の結晶性薄膜の製
造方法。1. A method for forming a crystalline thin film of a complex oxide on a lower electrode containing iridium, wherein a part of the lower electrode has a nucleus of a component element of the crystalline thin film, or A nucleation step of forming a nucleus of an oxide of a component element; a crystalline thin film forming step of forming a crystalline thin film of the complex oxide after forming the nucleus; Manufacturing method of crystalline thin film.
方法において、 前記下部電極はイリジウムで構成されていること、 を特徴とする複合酸化物の結晶性薄膜の製造方法。2. The method for producing a crystalline thin film of a complex oxide according to claim 1, wherein the lower electrode is made of iridium.
方法において、 前記下部電極は、イリジウムと白金の合金で構成されて
いること、 を特徴とする複合酸化物の結晶性薄膜の製造方法。3. The method for producing a crystalline thin film of a complex oxide according to claim 1, wherein the lower electrode is composed of an alloy of iridium and platinum. Production method.
方法において、 前記下部電極は、イリジウム層およびこのイリジウム層
の上に形成された白金層を有すること、 を特徴とする複合酸化物の結晶性薄膜の製造方法。4. The method for producing a crystalline thin film of a complex oxide according to claim 1, wherein the lower electrode has an iridium layer and a platinum layer formed on the iridium layer. Method for producing crystalline thin film of material.
物の結晶性薄膜の製造方法において、 前記核形成ステップで形成される核の成分元素は、前記
結晶性薄膜を構成する元素のうち、その酸化物が前記複
合酸化物より結晶化温度の低い元素であること、 を特徴とする複合酸化物の結晶性薄膜の製造方法。5. The method for producing a crystalline thin film of a complex oxide according to claim 1, wherein the element element of the nucleus formed in the nucleation step is an element constituting the crystalline thin film. Among them, the oxide is an element having a crystallization temperature lower than that of the complex oxide, and a method for producing a crystalline thin film of the complex oxide.
物の結晶性薄膜の製造方法において、 前記核形成ステップで形成される核は、厚みが１ｎｍ〜
１０ｎｍであること、 を特徴とする複合酸化物の結晶性薄膜の製造方法。6. The method for producing a crystalline thin film of a complex oxide according to claim 1, wherein the nuclei formed in the nucleation step have a thickness of 1 nm to
10 nm, The manufacturing method of the crystalline thin film of the complex oxide characterized by the above-mentioned.
を生成する方法であって、 前記下部電極の一部に、前記結晶性薄膜の成分元素の
核、または、この成分元素の酸化物の核を形成する核形
成ステップ、 前記核を形成した後、前記複合酸化物の結晶性薄膜を形
成する結晶性薄膜形成ステップ、 を備えたことを特徴とする複合酸化物の結晶性薄膜の製
造方法。7. A method of forming a crystalline thin film of a composite oxide on a lower electrode, wherein the part of the lower electrode comprises a core of a constituent element of the crystalline thin film or a core of the constituent element. A step of forming a nucleus of an oxide, a step of forming a crystalline thin film of the complex oxide after forming the nucleus, and a step of forming a crystalline thin film of the complex oxide. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14275795A JPH08335676A (en) | 1995-06-09 | 1995-06-09 | Manufacture of crystalline thin film of composite oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14275795A JPH08335676A (en) | 1995-06-09 | 1995-06-09 | Manufacture of crystalline thin film of composite oxide |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004335812A Division JP4245552B2 (en) | 2004-11-19 | 2004-11-19 | Method for producing crystalline thin film of composite oxide |
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| Publication Number | Publication Date |
|---|---|
| JPH08335676A true JPH08335676A (en) | 1996-12-17 |
Family
ID=15322873
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|---|---|---|---|
| JP14275795A Withdrawn JPH08335676A (en) | 1995-06-09 | 1995-06-09 | Manufacture of crystalline thin film of composite oxide |
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| Country | Link |
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| JP (1) | JPH08335676A (en) |
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