JP2010206150A - Composition for ferroelectric thin film formation, method for ferroelectric thin film formation, and ferroelectric thin film formed by the method - Google Patents
Composition for ferroelectric thin film formation, method for ferroelectric thin film formation, and ferroelectric thin film formed by the method Download PDFInfo
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- JP2010206150A JP2010206150A JP2009102817A JP2009102817A JP2010206150A JP 2010206150 A JP2010206150 A JP 2010206150A JP 2009102817 A JP2009102817 A JP 2009102817A JP 2009102817 A JP2009102817 A JP 2009102817A JP 2010206150 A JP2010206150 A JP 2010206150A
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- thin film
- ferroelectric thin
- composition
- metal oxide
- forming
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、高容量密度の薄膜キャパシタ用途に適した強誘電体薄膜形成用組成物、強誘電体薄膜の形成方法並びに該方法により形成された強誘電体薄膜に関するものである。 The present invention relates to a composition for forming a ferroelectric thin film suitable for use in a thin film capacitor having a high capacity density, a method for forming a ferroelectric thin film, and a ferroelectric thin film formed by the method.
この種の強誘電体膜の製造方法として、各成分金属のアルコキシドや有機酸塩を極性溶媒に溶解してなる混合溶液を用い、金属基板に塗布、乾燥して、塗膜を形成し、結晶化温度以上の温度に加熱して焼成することにより、誘電体薄膜を成膜することが一般的に知られている(例えば、特許文献1,2参照。)。 As a method of manufacturing this type of ferroelectric film, a mixed solution in which each component metal alkoxide or organic acid salt is dissolved in a polar solvent is used. It is generally known to form a dielectric thin film by heating to a temperature equal to or higher than the crystallization temperature and firing (see, for example, Patent Documents 1 and 2).
しかしながら、薄膜にした場合、基板の拘束による大きな応力が作用しており、充分な比誘電率を得ることができないという問題がある(例えば、非特許文献1参照。)。 However, when a thin film is used, there is a problem that a large stress due to the restraint of the substrate acts and a sufficient relative dielectric constant cannot be obtained (see, for example, Non-Patent Document 1).
そのため、微量元素を添加して、比誘電率を改善する試みが行われてきた(例えば、非特許文献2参照。)。 For this reason, attempts have been made to improve the dielectric constant by adding trace elements (see, for example, Non-Patent Document 2).
また、薄膜化することで、理論上、静電容量は高くなるので、薄膜化して静電容量を改善する試みも行われてきた。 In addition, since the electrostatic capacity is theoretically increased by reducing the thickness, attempts have been made to improve the electrostatic capacity by reducing the thickness.
しかし、静電容量を高くするため、形成した強誘電体薄膜の膜厚を薄くしてしまうと、リーク電流密度が高くなり、絶縁破壊する可能性もあることから、キャパシタとしての性能を十分に発揮することができなかった。また、微量元素を添加して比誘電率を高くする試みも充分に行われているとはいえない。 However, if the thickness of the formed ferroelectric thin film is reduced in order to increase the capacitance, the leakage current density increases and dielectric breakdown may occur. I couldn't do it. Moreover, it cannot be said that attempts to increase the relative dielectric constant by adding trace elements have been sufficiently performed.
本発明の目的は、簡便な手法で、従来の強誘電体薄膜よりも大幅に比誘電率を向上し得る、高容量密度の薄膜キャパシタ用途に適した強誘電体薄膜形成用組成物、強誘電体薄膜の形成方法並びに該方法により形成された強誘電体薄膜を提供することにある。 An object of the present invention is to provide a ferroelectric thin film forming composition suitable for high-capacity density thin film capacitor applications, which can significantly improve the relative permittivity over a conventional ferroelectric thin film by a simple method, and a ferroelectric It is an object to provide a method for forming a thin body film and a ferroelectric thin film formed by the method.
本発明の第1の観点は、PLZT、PZT及びPTからなる群より選ばれた1種の強誘電体薄膜を形成するための強誘電体薄膜形成用組成物において、一般式:(PbxLay)(ZrzTi(1-z))O3(式中0.9<x<1.3、0≦y<0.1、0≦z<0.9)で示される複合金属酸化物Aに、Smを含む複合金属酸化物Bが混合した混合複合金属酸化物の形態をとる薄膜を形成するための液状組成物であり、複合金属酸化物Aを構成するための原料並びに複合金属酸化物Bを構成するための原料が上記一般式で示される金属原子比を与えるような割合で、かつ、BとAとのモル比B/Aが0.005≦B/A<0.03の範囲内になるように、有機溶媒中に溶解している有機金属化合物溶液からなることを特徴とする。 A first aspect of the present invention is a composition for forming a ferroelectric thin film for forming one kind of ferroelectric thin film selected from the group consisting of PLZT, PZT, and PT, and has a general formula: (Pb x La y) (Zr z Ti (1 -z)) O 3 (0.9 <x <1.3,0 ≦ y <0.1,0 ≦ z composite metal oxide represented by <0.9) wherein A liquid composition for forming a thin film in the form of a mixed composite metal oxide in which a composite metal oxide B containing Sm is mixed with A, and a raw material for forming the composite metal oxide A and a composite metal oxide The raw material for constructing the product B is in such a ratio that gives the metal atomic ratio represented by the above general formula, and the molar ratio B / A between B and A is 0.005 ≦ B / A <0.03 It consists of the organometallic compound solution which is melt | dissolving in the organic solvent so that it may become in the range.
本発明の第2の観点は、第1の観点に基づく発明であって、更に複合金属酸化物A及び複合金属酸化物Bを構成するための原料が、有機基がその酸素又は窒素原子を介して金属元素と結合している化合物である強誘電体薄膜形成用組成物であることを特徴とする。 A second aspect of the present invention is an invention based on the first aspect, wherein the raw material for constituting the composite metal oxide A and the composite metal oxide B is an organic group via its oxygen or nitrogen atom. And a ferroelectric thin film forming composition which is a compound bonded to a metal element.
本発明の第3の観点は、第2の観点に基づく発明であって、更に複合金属酸化物A及び複合金属酸化物Bを構成するための原料が、金属アルコキシド、金属ジオール錯体、金属トリオール錯体、金属カルボン酸塩、金属β−ジケトネート錯体、金属β−ジケトエステル錯体、金属β−イミノケト錯体、及び金属アミノ錯体からなる群より選ばれた1種又は2種以上である強誘電体薄膜形成用組成物であることを特徴とする。 The third aspect of the present invention is the invention based on the second aspect, and the raw materials for constituting the composite metal oxide A and the composite metal oxide B are metal alkoxide, metal diol complex, metal triol complex. For forming a ferroelectric thin film that is one or more selected from the group consisting of metal carboxylates, metal β-diketonate complexes, metal β-diketoester complexes, metal β-iminoketo complexes, and metal amino complexes It is a composition.
本発明の第4の観点は、第1ないし第3の観点に基づく発明であって、更にβ−ジケトン、β−ケトン酸、β−ケトエステル、オキシ酸、ジオール、トリオール、高級カルボン酸、アルカノールアミン及び多価アミンからなる群より選ばれた1種又は2種以上の安定化剤を、組成物中の金属合計量1モルに対して、0.2〜3モルの割合で更に含有する強誘電体薄膜形成用組成物であることを特徴とする。 A fourth aspect of the present invention is an invention based on the first to third aspects, further comprising a β-diketone, β-ketone acid, β-ketoester, oxyacid, diol, triol, higher carboxylic acid, alkanolamine And one or more stabilizers selected from the group consisting of polyamines and a ferroelectric further containing 0.2 to 3 moles per mole of the total amount of metals in the composition It is a composition for body thin film formation.
本発明の第5の観点は、第1ないし第4の観点に基づく強誘電体薄膜形成用組成物を耐熱性基板に塗布し、空気中、酸化雰囲気中又は含水蒸気雰囲気中で加熱する工程を1回又は所望の厚さの膜が得られるまで繰返し、少なくとも最終工程における加熱中或いは加熱後に該膜を結晶化温度以上で焼成することを特徴とする強誘電体薄膜の形成方法である。 According to a fifth aspect of the present invention, there is provided a step of applying a ferroelectric thin film forming composition based on the first to fourth aspects to a heat resistant substrate and heating in air, an oxidizing atmosphere, or a water-containing atmosphere. It is a method for forming a ferroelectric thin film characterized in that it is repeated once or until a film having a desired thickness is obtained, and the film is fired at a temperature equal to or higher than the crystallization temperature at least after heating in the final step.
本発明の第6の観点は、第5の観点に基づく方法により形成された強誘電体薄膜である。 A sixth aspect of the present invention is a ferroelectric thin film formed by a method based on the fifth aspect.
本発明の第7の観点は、第6の観点に基づく強誘電体薄膜を有する薄膜コンデンサ、キャパシタ、IPD(Integrated Passive Device)、DRAMメモリ用コンデンサ、積層コンデンサ、トランジスタのゲート絶縁体、不揮発性メモリ、焦電型赤外線検出素子、圧電素子、電気光学素子、アクチュエータ、共振子、超音波モータ、又はLCノイズフィルタ素子の複合電子部品である。 A seventh aspect of the present invention is a thin film capacitor having a ferroelectric thin film based on the sixth aspect, a capacitor, an IPD (Integrated Passive Device), a DRAM memory capacitor, a multilayer capacitor, a gate insulator of a transistor, and a nonvolatile memory , A pyroelectric infrared detecting element, a piezoelectric element, an electro-optical element, an actuator, a resonator, an ultrasonic motor, or an LC noise filter element.
本発明の第8の観点は、第7の観点に基づく100MHz以上の周波数帯域に対応した、強誘電体薄膜を有する薄膜コンデンサ、キャパシタ、IPD、DRAMメモリ用コンデンサ、積層コンデンサ、トランジスタのゲート絶縁体、不揮発性メモリ、焦電型赤外線検出素子、圧電素子、電気光学素子、アクチュエータ、共振子、超音波モータ、又はLCノイズフィルタ素子の複合電子部品である。 An eighth aspect of the present invention is a thin film capacitor having a ferroelectric thin film, a capacitor, an IPD, a DRAM memory capacitor, a multilayer capacitor, and a gate insulator of a transistor, corresponding to a frequency band of 100 MHz or more based on the seventh aspect. , A composite electronic component of a nonvolatile memory, a pyroelectric infrared detection element, a piezoelectric element, an electro-optical element, an actuator, a resonator, an ultrasonic motor, or an LC noise filter element.
本発明の強誘電体薄膜形成用組成物は、一般式:(PbxLay)(ZrzTi(1-z))O3(式中0.9<x<1.3、0≦y<0.1、0≦z<0.9)で示される複合金属酸化物Aに、Smを含む複合金属酸化物Bが混合した混合複合金属酸化物の形態をとるように、有機金属化合物溶液に複合金属酸化物Aを構成するための原料並びに複合金属酸化物Bを構成するための原料を所定の割合で、かつ、BとAとのモル比B/Aが0.005≦B/A<0.03の範囲内となるように、有機溶媒中に溶解させている。この組成物を用いて強誘電体薄膜を形成することにより、従来の強誘電体薄膜よりも大幅に比誘電率を向上した高容量密度の薄膜キャパシタ用途に適した強誘電体薄膜を簡便な手法で得ることができる、という利点がある。 The composition for forming a ferroelectric thin film of the present invention has a general formula: (Pb x La y ) (Zr z Ti (1-z) ) O 3 (where 0.9 <x <1.3, 0 ≦ y <0.1, 0 ≦ z <0.9) An organic metal compound solution so as to take the form of a mixed composite metal oxide in which a composite metal oxide B containing Sm is mixed with a composite metal oxide A represented by The raw material for constituting the composite metal oxide A and the raw material for constituting the composite metal oxide B at a predetermined ratio, and the molar ratio B / A between B and A is 0.005 ≦ B / A It is dissolved in an organic solvent so that it is within the range of <0.03. By forming a ferroelectric thin film using this composition, a simple method for producing a ferroelectric thin film suitable for high-capacity-density thin film capacitors, which has a relative dielectric constant significantly improved over conventional ferroelectric thin films There is an advantage that it can be obtained.
次に本発明を実施するための形態を説明する。 Next, the form for implementing this invention is demonstrated.
本発明の強誘電体薄膜形成用組成物は、PLZT、PZT及びPTからなる群より選ばれた1種の強誘電体薄膜を形成するための組成物である。この組成物を用いて形成される強誘電体薄膜は、一般式:(PbxLay)(ZrzTi(1-z))O3(式中0.9<x<1.3、0≦y<0.1、0≦z<0.9)で示される複合金属酸化物Aに、Smを含む複合金属酸化物Bが混合した混合複合金属酸化物の形態をとる。なお、上記式のy≠0かつz≠0の場合はPLZTであり、y=0かつz≠0の場合はPZTであり、y=0かつz=0の場合はPTである。この組成物は、複合金属酸化物Aを構成するための原料と、複合金属酸化物Bを構成するための原料が上記一般式で示される金属原子比を与えるような割合で、かつ、BとAとのモル比B/Aが0.005≦B/A<0.03の範囲内、このうち特に好ましくは0.005≦B/A≦0.02となるように、有機溶媒中に溶解している有機金属化合物溶液からなる。上記範囲内であれば、従来の強誘電体薄膜よりも大幅に比誘電率を向上することができる。なお、下限値未満であったり、上限値を越える場合、サマリウムを添加しない場合と大差ない結果となり、高容量密度の薄膜キャパシタ用途には適さない。 The composition for forming a ferroelectric thin film of the present invention is a composition for forming one kind of ferroelectric thin film selected from the group consisting of PLZT, PZT and PT. A ferroelectric thin film formed using this composition has a general formula: (Pb x La y ) (Zr z Ti (1-z) ) O 3 (where 0.9 <x <1.3, 0 ≦ y <0.1, 0 ≦ z <0.9) takes the form of mixed composite metal oxide in which composite metal oxide A containing Sm is mixed with composite metal oxide A. In the above equation, when y ≠ 0 and z ≠ 0, it is PLZT, when y = 0 and z ≠ 0, it is PZT, and when y = 0 and z = 0, it is PT. This composition has a ratio such that the raw material for constituting the composite metal oxide A and the raw material for constituting the composite metal oxide B give a metal atomic ratio represented by the above general formula, and B and It is dissolved in an organic solvent so that the molar ratio B / A with A is in the range of 0.005 ≦ B / A <0.03, and particularly preferably 0.005 ≦ B / A ≦ 0.02. It consists of an organometallic compound solution. If it is in the said range, a dielectric constant can be improved significantly rather than the conventional ferroelectric thin film. In addition, when it is less than the lower limit or exceeds the upper limit, the result is not much different from the case where samarium is not added, and it is not suitable for high capacity density thin film capacitor applications.
複合金属酸化物A用原料並びに複合金属酸化物B用原料は、Pb、La、Zr、Ti及びSmの各金属元素に、有機基がその酸素又は窒素原子を介して結合している化合物が好適である。例えば、金属アルコキシド、金属ジオール錯体、金属トリオール錯体、金属カルボン酸塩、金属β−ジケトネート錯体、金属β−ジケトエステル錯体、金属β−イミノケト錯体、及び金属アミノ錯体からなる群より選ばれた1種又は2種以上が例示される。特に好適な化合物は、金属アルコキシド、その部分加水分解物、有機酸塩である。このうち、Pb化合物、La化合物、Sm化合物としては、酢酸塩(酢酸鉛、酢酸ランタン)、2−エチルヘキサン酸塩(2−エチルヘキサン酸サマリウム)、2−エチル酪酸塩(2−エチル酪酸サマリウム)等の有機酸塩、鉛ジイソプロポキシド、サマリウムテトラn−ブトキシド、サマリウムエトキシドなどのアルコキシド、トリス(アセチルアセトネート)サマリウムなどの金属β−ジケトネート錯体が挙げられる。Ti化合物としては、チタニウムテトラエトキシド、チタニウムテトライソプロポキシド、チタニウムテトラブトキシド、チタニウムジメトキシジイソプロポキシドなどのアルコキシドが挙げられる。Zr化合物としては、上記Ti化合物と同様なアルコキシド類が好ましい。金属アルコキシドはそのまま使用しても良いが、分解を促進させるためにその部分加水分解物を使用しても良い。 The raw material for composite metal oxide A and the raw material for composite metal oxide B are preferably compounds in which an organic group is bonded to each metal element of Pb, La, Zr, Ti and Sm via the oxygen or nitrogen atom. It is. For example, one kind selected from the group consisting of metal alkoxide, metal diol complex, metal triol complex, metal carboxylate, metal β-diketonate complex, metal β-diketoester complex, metal β-iminoketo complex, and metal amino complex Or 2 or more types are illustrated. Particularly suitable compounds are metal alkoxides, partial hydrolysates thereof, and organic acid salts. Among these, Pb compounds, La compounds, and Sm compounds include acetate (lead acetate, lanthanum acetate), 2-ethylhexanoate (samarium 2-ethylhexanoate), 2-ethylbutyrate (samarium 2-ethylbutyrate). ) And other organic acid salts, lead diisopropoxide, samarium tetra n-butoxide, alkoxides such as samarium ethoxide, and metal β-diketonate complexes such as tris (acetylacetonate) samarium. Examples of the Ti compound include alkoxides such as titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, and titanium dimethoxydiisopropoxide. The Zr compound is preferably an alkoxide similar to the Ti compound. Although the metal alkoxide may be used as it is, a partially hydrolyzed product thereof may be used in order to promote decomposition.
本発明の強誘電体薄膜形成用組成物を調製するには、これらの原料を所望の強誘電体薄膜組成に相当する比率で適当な溶媒に溶解して、塗布に適した濃度に調製する。 In order to prepare the composition for forming a ferroelectric thin film of the present invention, these raw materials are dissolved in an appropriate solvent at a ratio corresponding to the desired ferroelectric thin film composition, and prepared to a concentration suitable for coating.
ここで用いる強誘電体薄膜形成用組成物の溶媒は、使用する原料に応じて適宜決定されるが、一般的には、カルボン酸、アルコール、エステル、ケトン類(例えば、アセトン、メチルエチルケトン)、エーテル類(例えば、ジメチルエーテル、ジエチルエーテル)、シクロアルカン類(例えば、シクロヘキサン、シクロヘキサノール)、芳香族系(例えば、ベンゼン、トルエン、キシレン)、その他テトラヒドロフランなど、或いはこれらの2種以上の混合溶媒を用いることができる。 The solvent for the composition for forming a ferroelectric thin film used here is appropriately determined according to the raw material to be used. Generally, carboxylic acid, alcohol, ester, ketones (for example, acetone, methyl ethyl ketone), ether (E.g., dimethyl ether, diethyl ether), cycloalkanes (e.g., cyclohexane, cyclohexanol), aromatics (e.g., benzene, toluene, xylene), other tetrahydrofuran, or a mixture of two or more of these be able to.
カルボン酸としては、具体的には、n−酪酸、α−メチル酪酸、i−吉草酸、2−エチル酪酸、2,2−ジメチル酪酸、3,3−ジメチル酪酸、2,3−ジメチル酪酸、3−メチルペンタン酸、4−メチルペンタン酸、2−エチルペンタン酸、3−エチルペンタン酸、2,2−ジメチルペンタン酸、3,3−ジメチルペンタン酸、2,3−ジメチルペンタン酸、2−エチルヘキサン酸、3−エチルヘキサン酸を用いるのが好ましい。 Specific examples of the carboxylic acid include n-butyric acid, α-methylbutyric acid, i-valeric acid, 2-ethylbutyric acid, 2,2-dimethylbutyric acid, 3,3-dimethylbutyric acid, 2,3-dimethylbutyric acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, 2,2-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 2,3-dimethylpentanoic acid, 2- It is preferable to use ethylhexanoic acid or 3-ethylhexanoic acid.
また、エステルとしては、酢酸エチル、酢酸プロピル、酢酸n−ブチル、酢酸sec−ブチル、酢酸tert−ブチル、酢酸イソブチル、酢酸n−アミル、酢酸sec−アミル、酢酸tert−アミル、酢酸イソアミルを用いるのが好ましく、アルコールとしては、1−プロパノール、2−プロパノール、1−ブタノール、2−ブタノール、イソ−ブチルアルコール、1−ペンタノール、2−ペンタノール、2−メチル−2−ペンタノール、2−メトキシエタノールを用いるのが好適である。 As the ester, ethyl acetate, propyl acetate, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, isobutyl acetate, n-amyl acetate, sec-amyl acetate, tert-amyl acetate, isoamyl acetate are used. As the alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butyl alcohol, 1-pentanol, 2-pentanol, 2-methyl-2-pentanol, 2-methoxy It is preferred to use ethanol.
なお、強誘電体薄膜形成用組成物の有機金属化合物溶液中の有機金属化合物の合計濃度は、金属酸化物換算量で0.1〜20重量%程度とすることが好ましい。 The total concentration of the organometallic compound in the organometallic compound solution of the ferroelectric thin film forming composition is preferably about 0.1 to 20% by weight in terms of metal oxide.
この有機金属化合物溶液中には、必要に応じて安定化剤として、β−ジケトン類(例えば、アセチルアセトン、ヘプタフルオロブタノイルピバロイルメタン、ジピバロイルメタン、トリフルオロアセチルアセトン、ベンゾイルアセトン等)、β−ケトン酸類(例えば、アセト酢酸、プロピオニル酢酸、ベンゾイル酢酸等)、β−ケトエステル類(例えば、上記ケトン酸のメチル、プロピル、ブチル等の低級アルキルエステル類)、オキシ酸類(例えば、乳酸、グリコール酸、α−オキシ酪酸、サリチル酸等)、上記オキシ酸の低級アルキルエステル類、オキシケトン類(例えば、ジアセトンアルコール、アセトイン等)、ジオール、トリオール、高級カルボン酸、アルカノールアミン類(例えば、ジエタノールアミン、トリエタノールアミン、モノエタノールアミン)、多価アミン等を、(安定化剤分子数)/(金属原子数)で0.2〜3程度添加しても良い。 In this organometallic compound solution, β-diketones (for example, acetylacetone, heptafluorobutanoylpivaloylmethane, dipivaloylmethane, trifluoroacetylacetone, benzoylacetone, etc.) are used as stabilizers as necessary. , Β-ketone acids (for example, acetoacetic acid, propionylacetic acid, benzoylacetic acid, etc.), β-ketoesters (for example, lower alkyl esters such as methyl, propyl, and butyl of the above ketone acids), oxyacids (for example, lactic acid, Glycolic acid, α-oxybutyric acid, salicylic acid, etc.), lower alkyl esters of the above oxyacids, oxyketones (eg, diacetone alcohol, acetoin, etc.), diols, triols, higher carboxylic acids, alkanolamines (eg, diethanolamine, Triethanolamine, Roh ethanolamine), a polyvalent amine or the like, may be added from 0.2 to 3 approximately at (stabilizer number of molecules) / (number of metal atoms).
本発明では、上記調製された有機金属化合物溶液を濾過処理等によって、パーティクルを除去して、粒径0.5μm以上(特に0.3μm以上とりわけ0.2μm以上)のパーティクルの個数が溶液1mL当り50個/mL以下とするのが好ましい。 In the present invention, particles are removed from the prepared organometallic compound solution by filtration or the like, and the number of particles having a particle size of 0.5 μm or more (especially 0.3 μm or more, especially 0.2 μm or more) per 1 mL of the solution. It is preferable to be 50 / mL or less.
なお、当該有機金属化合物溶液中のパーティクルの個数の測定には、光散乱式パーティクルカウンターを用いる。 A light scattering particle counter is used for measuring the number of particles in the organometallic compound solution.
有機金属化合物溶液中の粒径0.5μm以上のパーティクルの個数が50個/mLを越えると、長期保存安定性が劣るものとなる。この有機金属化合物溶液中の粒径0.5μm以上のパーティクルの個数は少ない程好ましく、特に30個/mL以下であることが好ましい。 If the number of particles having a particle size of 0.5 μm or more in the organometallic compound solution exceeds 50 particles / mL, the long-term storage stability becomes poor. The smaller the number of particles having a particle size of 0.5 μm or more in this organometallic compound solution, the more preferable, and particularly preferably 30 particles / mL or less.
上記パーティクル個数となるように、調製後の有機金属化合物溶液を処理する方法は特に限定されるものではないが、例えば、次のような方法が挙げられる。第1の方法としては、市販の0.2μm孔径のメンブランフィルターを使用し、シリンジで圧送する濾過法である。第2の方法としては、市販の0.05μm孔径のメンブランフィルターと加圧タンクを組み合せた加圧濾過法である。第3の方法としては、上記第2の方法で使用したフィルターと溶液循環槽を組み合せた循環濾過法である。 The method for treating the organometallic compound solution after preparation so as to achieve the number of particles is not particularly limited, and examples thereof include the following method. The first method is a filtration method in which a commercially available membrane filter having a pore size of 0.2 μm is used and pressure-fed with a syringe. The second method is a pressure filtration method in which a commercially available membrane filter having a pore size of 0.05 μm and a pressure tank are combined. The third method is a circulation filtration method in which the filter used in the second method and the solution circulation tank are combined.
いずれの方法においても、溶液圧送圧力によって、フィルターによるパーティクル捕捉率が異なる。圧力が低いほど捕捉率が高くなることは一般的に知られており、特に、第1の方法、第2の方法について、粒径0.5μm以上のパーティクルの個数を50個以下とする条件を実現するためには、溶液を低圧で非常にゆっくりとフィルターに通すのが好ましい。 In any method, the particle capture rate by the filter varies depending on the solution pressure. It is generally known that the lower the pressure, the higher the capture rate. In particular, in the first method and the second method, the number of particles having a particle size of 0.5 μm or more is set to 50 or less. In order to achieve, it is preferable to pass the solution through the filter very slowly at low pressure.
本発明の強誘電体薄膜形成用組成物を用いることで、PLZT、PZT及びPTからなる群より選ばれた1種の複合金属酸化物Aに、Smを含む複合金属酸化物Bが混合した混合複合金属酸化物の形態をとる強誘電体薄膜を簡便に形成することができる。 By using the composition for forming a ferroelectric thin film of the present invention, a mixed metal oxide B containing Sm is mixed with one kind of mixed metal oxide A selected from the group consisting of PLZT, PZT, and PT. A ferroelectric thin film in the form of a composite metal oxide can be easily formed.
本発明の強誘電体薄膜形成用組成物を用いて、強誘電体薄膜を形成するには、上記組成物をスピンコート、ディップコート、LSMCD(Liquid Source MistedChemical Deposition)法等の塗布法により耐熱性基板上に塗布し、乾燥(仮焼成)及び本焼成を行う。 In order to form a ferroelectric thin film by using the composition for forming a ferroelectric thin film of the present invention, the composition is heat-resistant by a coating method such as spin coating, dip coating, or LSMCD (Liquid Source Misted Chemical Deposition). It apply | coats on a board | substrate and performs drying (temporary baking) and main baking.
使用される耐熱性基板の具体例としては、基板表層部に、単結晶Si、多結晶Si,Pt,Pt(最上層)/Ti,Pt(最上層)/Ta,Ru,RuO2,Ru(最上層)/RuO2,RuO2(最上層)/Ru,Ir,IrO2,Ir(最上層)/IrO2,Pt(最上層)/Ir,Pt(最上層)/IrO2,SrRuO3又は(LaxSr(1-x))CoO3等のペロブスカイト型導電性酸化物等を用いた基板が挙げられるが、これらに限定されるものではない。 As a specific example of the heat-resistant substrate to be used, the surface layer portion of the substrate includes single crystal Si, polycrystal Si, Pt, Pt (top layer) / Ti, Pt (top layer) / Ta, Ru, RuO 2 , Ru ( Top layer) / RuO 2 , RuO 2 (top layer) / Ru, Ir, IrO 2 , Ir (top layer) / IrO 2 , Pt (top layer) / Ir, Pt (top layer) / IrO 2 , SrRuO 3 or (La x Sr (1-x )) is a substrate with CoO 3 perovskite-type conductive oxide such like, but not limited thereto.
なお、1回の塗布では、所望の膜厚が得られない場合には、塗布、乾燥の工程を複数回繰返し行った後、本焼成を行う。ここで、所望の膜厚とは、本焼成後に得られる強誘電体薄膜の厚さをいい、高容量密度の薄膜キャパシタ用途の場合、本焼成後の強誘電体薄膜の膜厚が50〜500nmの範囲である。 In addition, when a desired film thickness cannot be obtained by one application, the application and drying steps are repeated a plurality of times, followed by firing. Here, the desired film thickness refers to the thickness of the ferroelectric thin film obtained after the main firing, and in the case of a high capacity density thin film capacitor, the film thickness of the ferroelectric thin film after the main firing is 50 to 500 nm. Range.
また、仮焼成は、溶媒を除去するとともに有機金属化合物を熱分解又は加水分解して複合酸化物に転化させるために行うことから、空気中、酸化雰囲気中、又は含水蒸気雰囲気中で行う。空気中での加熱でも、加水分解に必要な水分は空気中の湿気により十分に確保される。この加熱は、溶媒の除去のための低温加熱と、有機金属化合物の分解のための高温加熱の2段階で実施しても良い。 In addition, the preliminary calcination is performed in order to remove the solvent and thermally decompose or hydrolyze the organometallic compound to convert it into a composite oxide. Therefore, the calcination is performed in air, in an oxidizing atmosphere, or in a steam-containing atmosphere. Even in heating in the air, the moisture required for hydrolysis is sufficiently secured by the humidity in the air. This heating may be performed in two stages: low temperature heating for removing the solvent and high temperature heating for decomposing the organometallic compound.
本焼成は、仮焼成で得られた薄膜を結晶化温度以上の温度で焼成して結晶化させるための工程であり、これにより強誘電体薄膜が得られる。この結晶化工程の焼成雰囲気はO2、N2、Ar、N2O又はH2等或いはこれらの混合ガス等が好適である。 The main firing is a step for firing and crystallizing the thin film obtained by the pre-firing at a temperature equal to or higher than the crystallization temperature, whereby a ferroelectric thin film is obtained. The firing atmosphere in this crystallization step is preferably O 2 , N 2 , Ar, N 2 O, H 2, or a mixed gas thereof.
仮焼成は、150〜550℃で5〜10分間程度行われ、本焼成は450〜800℃で1〜60分間程度行われる。本焼成は、急速加熱処理(RTA処理)で行っても良い。RTA処理で本焼成する場合、その昇温速度は10〜100℃/秒が好ましい。 The pre-baking is performed at 150 to 550 ° C. for about 5 to 10 minutes, and the main baking is performed at 450 to 800 ° C. for about 1 to 60 minutes. The main baking may be performed by rapid heating treatment (RTA treatment). When the main baking is performed by the RTA treatment, the heating rate is preferably 10 to 100 ° C./second.
このようにして形成された本発明の強誘電体薄膜は、従来の強誘電体薄膜よりも大幅に比誘電率を向上したものとなり、キャパシタとしての基本的特性に優れ、高容量密度の薄膜キャパシタ用途に好適である。また、本発明の強誘電体薄膜は、IPDとしての基本的特性にも優れる。 The ferroelectric thin film of the present invention formed in this manner has a relative dielectric constant significantly improved as compared with the conventional ferroelectric thin film, has excellent basic characteristics as a capacitor, and has a high capacitance density. Suitable for use. The ferroelectric thin film of the present invention is also excellent in basic characteristics as an IPD.
また、本発明の強誘電体薄膜は、薄膜コンデンサ、キャパシタ、IPD、DRAMメモリ用コンデンサ、積層コンデンサ、トランジスタのゲート絶縁体、不揮発性メモリ、焦電型赤外線検出素子、圧電素子、電気光学素子、アクチュエータ、共振子、超音波モータ、又はLCノイズフィルタ素子の複合電子部品における構成材料として使用することができる。このうち特に100MHz以上の周波数帯域に対応したものに使用することもできる。 The ferroelectric thin film of the present invention includes a thin film capacitor, a capacitor, an IPD, a DRAM memory capacitor, a multilayer capacitor, a transistor gate insulator, a nonvolatile memory, a pyroelectric infrared detection element, a piezoelectric element, an electro-optical element, It can be used as a constituent material in composite electronic parts of actuators, resonators, ultrasonic motors, or LC noise filter elements. Among these, it can also be used especially for the thing corresponding to the frequency band of 100 MHz or more.
次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.
<実施例1〜5>
先ず、反応容器にジルコニウムテトラn−ブトキシドと安定化剤としてアセチルアセトンを添加し、窒素雰囲気下、150℃の温度で還流した。これにチタンテトライソプロポキシドと安定化剤としてアセチルアセトンを添加し、窒素雰囲気下、150℃の温度で還流した。次いで、これに酢酸鉛3水和物と溶媒としてプロピレングリコールを添加し、窒素雰囲気下、150℃の温度で還流した。その後、150℃で減圧蒸留して副生成物を除去し、更にプロピレングリコールを添加し、濃度調整することで酸化物換算で30質量%濃度の金属化合物を含有する液を得た。更に、希釈アルコールを添加することで酸化物換算で各金属比がPb/Zr/Ti=110/52/48の10質量%濃度の金属化合物を含有するゾルゲル液を得た。
<Examples 1-5>
First, zirconium tetra-n-butoxide and acetylacetone as a stabilizer were added to a reaction vessel, and refluxed at a temperature of 150 ° C. in a nitrogen atmosphere. Titanium tetraisopropoxide and acetylacetone as a stabilizer were added thereto and refluxed at a temperature of 150 ° C. in a nitrogen atmosphere. Next, lead acetate trihydrate and propylene glycol as a solvent were added thereto and refluxed at a temperature of 150 ° C. in a nitrogen atmosphere. Thereafter, the by-product was removed by distillation under reduced pressure at 150 ° C., and further, propylene glycol was added and the concentration was adjusted to obtain a liquid containing a 30% by mass metal compound in terms of oxide. Furthermore, by adding diluted alcohol, a sol-gel solution containing a metal compound having a concentration of 10% by mass with a metal ratio of Pb / Zr / Ti = 110/52/48 in terms of oxide was obtained.
次に、ゾルゲル液を5等分し、これらのゾルゲル液に外割で0.5mol%の各種サマリウム化合物(2−エチルヘキサン酸サマリウム、2−エチル酪酸サマリウム、サマリウムトリエトキシド、サマリウムトリn−ブトキシド、トリス(アセチルアセトネート)サマリウム)をそれぞれ添加することにより、5種類の薄膜形成用溶液を得た。 Next, the sol-gel solution is divided into five equal parts, and 0.5 mol% of various samarium compounds (samarium 2-ethylhexanoate, samarium 2-ethylbutyrate, samarium triethoxide, samarium tri-n- By adding butoxide and tris (acetylacetonate) samarium), five types of thin film forming solutions were obtained.
これら5種類の薄膜形成用溶液を用いて、下記方法によりCSD法による薄膜の形成を行った。即ち、各々の溶液をスピンコート法により500rpmで3秒間、その後3000rpmで15秒間の条件でPt薄膜を表面にスパッタリング法にて形成した6インチシリコン基板(Pt/TiO2/SiO2/Si(100)基板)上に塗布した。続いて、ホットプレートを用い、350℃で5分間加熱して仮焼成を行った。この塗布、仮焼成の工程を6回繰返した後、100%酸素雰囲気中で700℃、1分間RTA(急速加熱処理装置)で焼成して膜厚270nmの強誘電体薄膜を形成した。 Using these five types of thin film forming solutions, thin films were formed by the CSD method by the following method. That is, a 6-inch silicon substrate (Pt / TiO 2 / SiO 2 / Si (100) on which a Pt thin film was formed on the surface by a spin coating method at 500 rpm for 3 seconds and then at 3000 rpm for 15 seconds. ) Substrate). Subsequently, using a hot plate, heating was performed at 350 ° C. for 5 minutes to perform temporary baking. This coating and pre-baking process was repeated 6 times, and then baked with an RTA (rapid heat treatment apparatus) at 700 ° C. for 1 minute in a 100% oxygen atmosphere to form a 270 nm thick ferroelectric thin film.
<実施例6〜10>
ゾルゲル液に外割で1.0mol%の各種サマリウム化合物を添加して薄膜形成用溶液とした以外は、実施例1〜5と同様にして基板上に強誘電体薄膜を形成した。
<Examples 6 to 10>
A ferroelectric thin film was formed on the substrate in the same manner as in Examples 1 to 5 except that 1.0 mol% of various samarium compounds were added to the sol-gel solution to obtain a thin film forming solution.
<実施例11〜15>
ゾルゲル液に外割で2.0mol%の各種サマリウム化合物を添加して薄膜形成用溶液とした以外は、実施例1〜5と同様にして基板上に強誘電体薄膜を形成した。
<Examples 11 to 15>
A ferroelectric thin film was formed on the substrate in the same manner as in Examples 1 to 5 except that 2.0 mol% of various samarium compounds were added to the sol-gel solution to obtain a thin film forming solution.
<比較例1>
ゾルゲル液にサマリウム化合物を添加せず、薄膜形成用溶液とした以外は、実施例1〜5と同様にして基板上に強誘電体薄膜を形成した。
<Comparative Example 1>
A ferroelectric thin film was formed on the substrate in the same manner as in Examples 1 to 5, except that the samarium compound was not added to the sol-gel solution and the solution was used for forming a thin film.
<比較例2〜6>
ゾルゲル液に外割で3.0mol%の各種サマリウム化合物を添加して薄膜形成用溶液とした以外は、実施例1〜5と同様にして基板上に強誘電体薄膜を形成した。
<Comparative Examples 2-6>
A ferroelectric thin film was formed on the substrate in the same manner as in Examples 1 to 5, except that 3.0 mol% of various samarium compounds were added to the sol-gel solution to obtain a thin film forming solution.
<実施例16〜20>
先ず、反応容器にジルコニウムテトラn−ブトキシドと安定化剤としてジエタノールアミンを添加し、窒素雰囲気下、150℃の温度で還流した。これにチタンテトライソプロポキシドと安定化剤としてジエタノールアミンを添加し、窒素雰囲気下、150℃の温度で還流した。次いで、これに酢酸鉛3水和物と溶媒としてプロピレングリコールを添加し、窒素雰囲気下、150℃の温度で還流した。その後、150℃で減圧蒸留して副生成物を除去し、更にプロピレングリコールを添加し、濃度調整することで酸化物換算で30質量%濃度の金属化合物を含有する液を得た。更に、希釈アルコールを添加することで酸化物換算で各金属比がPb/Zr/Ti=110/52/48の10質量%濃度の金属化合物を含有するゾルゲル液を得た。
<Examples 16 to 20>
First, zirconium tetra n-butoxide and diethanolamine as a stabilizer were added to a reaction vessel, and the mixture was refluxed at a temperature of 150 ° C. in a nitrogen atmosphere. Titanium tetraisopropoxide and diethanolamine as a stabilizer were added thereto, and the mixture was refluxed at a temperature of 150 ° C. in a nitrogen atmosphere. Next, lead acetate trihydrate and propylene glycol as a solvent were added thereto and refluxed at a temperature of 150 ° C. in a nitrogen atmosphere. Thereafter, the by-product was removed by distillation under reduced pressure at 150 ° C., and further, propylene glycol was added and the concentration was adjusted to obtain a liquid containing a 30% by mass metal compound in terms of oxide. Furthermore, by adding diluted alcohol, a sol-gel solution containing a metal compound having a concentration of 10% by mass with a metal ratio of Pb / Zr / Ti = 110/52/48 in terms of oxide was obtained.
次に、ゾルゲル液を5等分し、これらのゾルゲル液に外割で0.5mol%の各種サマリウム化合物(2−エチルヘキサン酸サマリウム、2−エチル酪酸サマリウム、サマリウムトリエトキシド、サマリウムトリn−ブトキシド、トリス(アセチルアセトネート)サマリウム)をそれぞれ添加することにより、5種類の薄膜形成用溶液を得た。 Next, the sol-gel solution is divided into five equal parts, and 0.5 mol% of various samarium compounds (samarium 2-ethylhexanoate, samarium 2-ethylbutyrate, samarium triethoxide, samarium tri-n- By adding butoxide and tris (acetylacetonate) samarium), five types of thin film forming solutions were obtained.
これら5種類の薄膜形成用溶液を用いて、下記方法によりCSD法による薄膜の形成を行った。即ち、各々の溶液をスピンコート法により500rpmで3秒間、その後3000rpmで15秒間の条件でPt薄膜を表面にスパッタリング法にて形成した6インチシリコン基板(Pt/TiO2/SiO2/Si(100)基板)上に塗布した。続いて、ホットプレートを用い、350℃で5分間加熱して仮焼成を行った。この塗布、仮焼成の工程を6回繰返した後、100%酸素雰囲気中で700℃、1分間RTA(急速加熱処理装置)で焼成して膜厚270nmの強誘電体薄膜を形成した。 Using these five types of thin film forming solutions, thin films were formed by the CSD method by the following method. That is, a 6-inch silicon substrate (Pt / TiO 2 / SiO 2 / Si (100) on which a Pt thin film was formed on the surface by a spin coating method at 500 rpm for 3 seconds and then at 3000 rpm for 15 seconds. ) Substrate). Subsequently, using a hot plate, heating was performed at 350 ° C. for 5 minutes to perform temporary baking. This coating and pre-baking process was repeated 6 times, and then baked with an RTA (rapid heat treatment apparatus) at 700 ° C. for 1 minute in a 100% oxygen atmosphere to form a 270 nm thick ferroelectric thin film.
<実施例21〜25>
ゾルゲル液に外割で1.0mol%の各種サマリウム化合物を添加して薄膜形成用溶液とした以外は、実施例16〜20と同様にして基板上に強誘電体薄膜を形成した。
<Examples 21 to 25>
A ferroelectric thin film was formed on the substrate in the same manner as in Examples 16 to 20, except that 1.0 mol% of various samarium compounds were added to the sol-gel solution to obtain a thin film forming solution.
<実施例26〜30>
ゾルゲル液に外割で2.0mol%の各種サマリウム化合物を添加して薄膜形成用溶液とした以外は、実施例16〜20と同様にして基板上に強誘電体薄膜を形成した。
<Examples 26 to 30>
A ferroelectric thin film was formed on the substrate in the same manner as in Examples 16 to 20 except that 2.0 mol% of various samarium compounds were added to the sol-gel solution to obtain a thin film forming solution.
<比較例7>
ゾルゲル液にサマリウム化合物を添加せず、薄膜形成用溶液とした以外は、実施例16〜20と同様にして基板上に強誘電体薄膜を形成した。
<Comparative Example 7>
A ferroelectric thin film was formed on the substrate in the same manner as in Examples 16 to 20 except that the samarium compound was not added to the sol-gel solution and a thin film forming solution was used.
<比較例8〜12>
ゾルゲル液に外割で3.0mol%の各種サマリウム化合物を添加して薄膜形成用溶液とした以外は、実施例16〜20と同様にして基板上に強誘電体薄膜を形成した。
<Comparative Examples 8-12>
A ferroelectric thin film was formed on the substrate in the same manner as in Examples 16 to 20 except that 3.0 mol% of various samarium compounds were added to the sol-gel solution to obtain a thin film forming solution.
<実施例31〜35>
先ず、反応容器にジルコニウムテトラn−ブトキシドと安定化剤としてアセチルアセトンを添加し、窒素雰囲気下、150℃の温度で還流した。これにチタンテトライソプロポキシドと安定化剤としてアセチルアセトンを添加し、窒素雰囲気下、150℃の温度で還流した。次いで、これに酢酸鉛3水和物と溶媒としてプロピレングリコールを添加し、窒素雰囲気下、150℃の温度で還流した。その後、150℃で減圧蒸留して副生成物を除去し、更にプロピレングリコールを添加し、濃度調整することで酸化物換算で30質量%濃度の金属化合物を含有する液を得た。更に、希釈アルコールを添加することで酸化物換算で各金属比がPb/Zr/Ti=110/52/48の10質量%濃度の金属化合物を含有するゾルゲル液を得た。
<Examples 31-35>
First, zirconium tetra-n-butoxide and acetylacetone as a stabilizer were added to a reaction vessel, and refluxed at a temperature of 150 ° C. in a nitrogen atmosphere. Titanium tetraisopropoxide and acetylacetone as a stabilizer were added thereto and refluxed at a temperature of 150 ° C. in a nitrogen atmosphere. Next, lead acetate trihydrate and propylene glycol as a solvent were added thereto and refluxed at a temperature of 150 ° C. in a nitrogen atmosphere. Thereafter, the by-product was removed by distillation under reduced pressure at 150 ° C., and further, propylene glycol was added and the concentration was adjusted to obtain a liquid containing a 30% by mass metal compound in terms of oxide. Furthermore, by adding diluted alcohol, a sol-gel solution containing a metal compound having a concentration of 10% by mass with a metal ratio of Pb / Zr / Ti = 110/52/48 in terms of oxide was obtained.
次に、ゾルゲル液を5等分し、これらのゾルゲル液に外割で0.5mol%の各種サマリウム化合物(2−エチルヘキサン酸サマリウム、2−エチル酪酸サマリウム、サマリウムトリエトキシド、サマリウムトリn−ブトキシド、トリス(アセチルアセトネート)サマリウム)をそれぞれ添加することにより、5種類の薄膜形成用溶液を得た。 Next, the sol-gel solution is divided into five equal parts, and 0.5 mol% of various samarium compounds (samarium 2-ethylhexanoate, samarium 2-ethylbutyrate, samarium triethoxide, samarium tri-n- By adding butoxide and tris (acetylacetonate) samarium), five types of thin film forming solutions were obtained.
これら5種類の薄膜形成用溶液を用いて、下記方法によりCSD法による薄膜の形成を行った。即ち、各々の溶液をスピンコート法により500rpmで3秒間、その後3000rpmで15秒間の条件でPt薄膜を表面にスパッタリング法にて形成した6インチシリコン基板(Pt/TiO2/SiO2/Si(100)基板)上に塗布した。続いて、ホットプレートを用い、350℃で5分間加熱して仮焼成を行った。この塗布、仮焼成の工程を6回繰返した後、乾燥空気雰囲気中で700℃、1分間RTA(急速加熱処理装置)で焼成して膜厚270nmの強誘電体薄膜を形成した。 Using these five types of thin film forming solutions, thin films were formed by the CSD method by the following method. That is, a 6-inch silicon substrate (Pt / TiO 2 / SiO 2 / Si (100) on which a Pt thin film was formed on the surface by a spin coating method at 500 rpm for 3 seconds and then at 3000 rpm for 15 seconds. ) Substrate). Subsequently, using a hot plate, heating was performed at 350 ° C. for 5 minutes to perform temporary baking. This coating and pre-baking process was repeated 6 times, and then a 270 nm thick ferroelectric thin film was formed by baking at 700 ° C. for 1 minute in a dry air atmosphere with an RTA (rapid heat treatment apparatus).
<実施例36〜40>
ゾルゲル液に外割で1.0mol%の各種サマリウム化合物を添加して薄膜形成用溶液とした以外は、実施例31〜35と同様にして基板上に強誘電体薄膜を形成した。
<Examples 36 to 40>
A ferroelectric thin film was formed on the substrate in the same manner as in Examples 31 to 35, except that 1.0 mol% of various samarium compounds were added to the sol-gel solution to obtain a thin film forming solution.
<実施例41〜45>
ゾルゲル液に外割で2.0mol%の各種サマリウム化合物を添加して薄膜形成用溶液とした以外は、実施例31〜35と同様にして基板上に強誘電体薄膜を形成した。
<Examples 41 to 45>
A ferroelectric thin film was formed on the substrate in the same manner as in Examples 31 to 35 except that 2.0 mol% of various samarium compounds were added to the sol-gel solution to obtain a thin film forming solution.
<比較例13>
ゾルゲル液にサマリウム化合物を添加せず、薄膜形成用溶液とした以外は、実施例31〜35と同様にして基板上に強誘電体薄膜を形成した。
<Comparative Example 13>
A ferroelectric thin film was formed on the substrate in the same manner as in Examples 31 to 35 except that a samarium compound was not added to the sol-gel solution and a thin film forming solution was used.
<比較例14〜18>
ゾルゲル液に外割で3.0mol%の各種サマリウム化合物を添加して薄膜形成用溶液とした以外は、実施例31〜35と同様にして基板上に強誘電体薄膜を形成した。
<Comparative Examples 14-18>
A ferroelectric thin film was formed on the substrate in the same manner as in Examples 31 to 35 except that 3.0 mol% of various samarium compounds were added to the sol-gel solution to obtain a thin film forming solution.
<比較評価>
実施例1〜45及び比較例1〜18で得られた強誘電体薄膜を形成した基板について、メタルマスクを用い、表面に約250μm□のPt上部電極をスパッタリング法にて作製し、強誘電体薄膜直下のPt下部電極間にてC−V特性(静電容量の電圧依存性)を周波数1kHzにて−5〜5Vの範囲で評価し、静電容量の最大値より比誘電率εrを算出した。なお、C−V特性の測定にはHP社製4284A precision LCR meterを用い、Bias step 0.1V、Frequency 1kHz、Oscillation level 30mV、Delay time 0.2sec、Temperature 23℃、Hygrometry 50±10%の条件で測定した。その結果を次の表1〜表3にそれぞれ示す。
<Comparison evaluation>
About the board | substrate with which the ferroelectric thin film obtained in Examples 1-45 and Comparative Examples 1-18 was formed, about 250 micrometers square Pt upper electrode was produced with the sputtering method on the surface, and ferroelectric substance CV characteristics (voltage dependence of capacitance) are evaluated in the range of -5 to 5 V at a frequency of 1 kHz between the Pt lower electrodes directly under the thin film, and the relative dielectric constant εr is calculated from the maximum capacitance. did. In addition, HP measurement 4284A precision LCR meter was used for the measurement of CV characteristics, Bias step 0.1V, Frequency 1kHz, Oscillation level 30mV, Delay time 0.2sec, Temperature 23 ° C, Hygrometer 10 condition condition. Measured with The results are shown in the following Tables 1 to 3, respectively.
しかしながら、Smを3%添加した比較例2〜6,8〜12,14〜18の強誘電体薄膜では、Smを含まない比較例1,7,13のPZT強誘電体薄膜よりも低い結果となってしまった。 However, in the ferroelectric thin films of Comparative Examples 2-6, 8-12, and 14-18 to which 3% of Sm was added, the results were lower than the PZT ferroelectric thin films of Comparative Examples 1, 7, and 13 that did not contain Sm. It is had.
また、Smの添加量を変化させた実施例1〜45及び比較例2〜6,8〜12,14〜18の強誘電体薄膜の結果から、2%添加した実施例11〜15,26〜30,41〜45の結果が特に高く、次に、1%添加した実施例6〜10,21〜25,36〜40の結果、0.5%添加した実施例1〜5,16〜20,31〜35の結果と続き、そして、3%添加した比較例2〜6,8〜12,14〜18の結果が低い結果であった。 Further, from the results of the ferroelectric thin films of Examples 1 to 45 and Comparative Examples 2 to 6, 8 to 12, and 14 to 18 in which the addition amount of Sm was changed, Examples 11 to 15 and 26 to which 2% was added were added. The results of 30,41 to 45 were particularly high, and then Examples 6 to 10, 1 to 25, and 36 to 40 added at 1%, Examples 1 to 5, 16 to 20 added at 0.5%, The results of Comparative Examples 2 to 6, 8 to 12, and 14 to 18 added with 3% were low, following the results of 31 to 35.
この結果から、静電容量及び比誘電率εrの向上に寄与し得る適切なSm添加量の範囲が存在することが確認された。 From this result, it was confirmed that there exists an appropriate range of Sm addition amount that can contribute to the improvement of the capacitance and the relative dielectric constant εr.
本発明の強誘電体薄膜形成用組成物、強誘電体薄膜の形成方法並びに該方法により形成された強誘電体薄膜は、キャパシタとしての基本的特性に優れ、高容量密度の薄膜キャパシタの用途に利用可能である。その他、IPDとしての基本的特性にも優れ、IPD、DRAMメモリ用コンデンサ、積層コンデンサ、トランジスタのゲート絶縁体、不揮発性メモリ、焦電型赤外線検出素子、圧電素子、電気光学素子、アクチュエータ、共振子、超音波モータ、又はLCノイズフィルタ素子等の複合電子部品に利用が可能である。 The composition for forming a ferroelectric thin film of the present invention, the method for forming a ferroelectric thin film, and the ferroelectric thin film formed by the method are excellent in basic characteristics as a capacitor, and are used for a high-capacity density thin film capacitor. Is available. In addition, it has excellent basic characteristics as an IPD. IPD, DRAM memory capacitor, multilayer capacitor, transistor gate insulator, nonvolatile memory, pyroelectric infrared detector, piezoelectric element, electro-optical element, actuator, resonator It can be used for composite electronic parts such as ultrasonic motors or LC noise filter elements.
Claims (8)
一般式:(PbxLay)(ZrzTi(1-z))O3(式中0.9<x<1.3、0≦y<0.1、0≦z<0.9)で示される複合金属酸化物Aに、Smを含む複合金属酸化物Bが混合した混合複合金属酸化物の形態をとる薄膜を形成するための液状組成物であり、
前記複合金属酸化物Aを構成するための原料並びに前記複合金属酸化物Bを構成するための原料が上記一般式で示される金属原子比を与えるような割合で、かつ、BとAとのモル比B/Aが0.005≦B/A<0.03の範囲内になるように、有機溶媒中に溶解している有機金属化合物溶液からなる
ことを特徴とする強誘電体薄膜形成用組成物。 In the ferroelectric thin film forming composition for forming one kind of ferroelectric thin film selected from the group consisting of PLZT, PZT and PT,
General formula: (Pb x La y ) (Zr z Ti (1-z) ) O 3 (where 0.9 <x <1.3, 0 ≦ y <0.1, 0 ≦ z <0.9) Is a liquid composition for forming a thin film in the form of a mixed composite metal oxide in which a composite metal oxide B containing Sm is mixed with the composite metal oxide A shown by
The raw material for constituting the composite metal oxide A and the raw material for constituting the composite metal oxide B are in such a ratio that gives the metal atomic ratio represented by the above general formula, and the moles of B and A A composition for forming a ferroelectric thin film comprising an organometallic compound solution dissolved in an organic solvent such that the ratio B / A is in the range of 0.005 ≦ B / A <0.03 object.
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JP2002234709A (en) * | 2001-02-06 | 2002-08-23 | Mitsubishi Materials Corp | Surface structure of substrate of perovskite type oxide film, the substrate and the perovskite type oxide film |
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JPH07252664A (en) * | 1994-03-14 | 1995-10-03 | Texas Instr Japan Ltd | Formation of ferroelectric film by sol-gel method, manufacture of capacitor using the same, solution of starting material therefor and preparation of solution |
JP2003002647A (en) * | 2000-12-27 | 2003-01-08 | Mitsubishi Materials Corp | Plzt ferroelectric thin film, composition for forming the same, and producing method for the same |
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