JP2007320798A - Solution for manufacturing ferroelectric thin film and method for preparing it - Google Patents
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- 239000010409 thin film Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 56
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- -1 alkyl titanate Chemical compound 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 28
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 150000007933 aliphatic carboxylic acids Chemical group 0.000 claims description 8
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical group [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical group [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 3
- 159000000009 barium salts Chemical class 0.000 claims 2
- 159000000008 strontium salts Chemical class 0.000 claims 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 4
- 229960005235 piperonyl butoxide Drugs 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- DOSGEBYQRMBTGS-UHFFFAOYSA-N 2-(3,6-dihydro-2h-pyran-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CCOCC1 DOSGEBYQRMBTGS-UHFFFAOYSA-N 0.000 description 1
- GRWPYGBKJYICOO-UHFFFAOYSA-N 2-methylpropan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] GRWPYGBKJYICOO-UHFFFAOYSA-N 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Ceramic Capacitors (AREA)
- Semiconductor Memories (AREA)
Abstract
Description
本発明は強誘電体薄膜作製溶液およびその製造方法に関する。更に詳しくは本発明は、強誘電体の薄膜を形成するために好適な強誘電体薄膜作製溶液およびその製造方法に関する。 The present invention relates to a ferroelectric thin film preparation solution and a method for manufacturing the same. More particularly, the present invention relates to a ferroelectric thin film preparation solution suitable for forming a ferroelectric thin film and a method for manufacturing the same.
ＤＲＡＭやノイズフィルタなどの半導体装置には強誘電体の薄膜が用いられており、強誘電体としては特定の金属酸化物が用いられている。
一般に、金属酸化物薄膜を作製する方法として、スパッタ法、蒸着法、化学的気相蒸着（ＣＶＤ）法等のドライ法や、ゾルゲル法、メッキ法、電解重合法等のウェット法により、薄膜を成形する方法が知られている。ドライ法では、結晶性の優れた均一な薄膜が、比較的良好に得られることが知られているが、装置が複雑かつ高価であるために製造コストが高くなり、また大面積の薄膜を得ることが難しいといった欠点がある。また、ウェット法は、比較的装置が簡単で大面積の薄膜を得ることができるものの、ウェット法として一般的に利用されているゾルゲル法においては、例えばチタニアゾルや有機チタネートを使用するが、用いるチタニアゾルや有機チタネートの安定性や透明性を保つため、有機溶媒を使用したり、塩酸や硝酸のような腐食性の酸を添加したりする必要があった。
そのため、有機溶媒の有害性が作業安全性から問題となったり、腐食性から製造装置が高価になってしまったりするなどの欠点があった。
Ferroelectric thin films are used in semiconductor devices such as DRAMs and noise filters, and specific metal oxides are used as the ferroelectrics.
In general, as a method for producing a metal oxide thin film, a thin film is formed by a dry method such as a sputtering method, a vapor deposition method or a chemical vapor deposition (CVD) method, or a wet method such as a sol-gel method, a plating method or an electrolytic polymerization method. A method of forming is known. It is known that a uniform thin film with excellent crystallinity can be obtained relatively well by the dry method. However, since the apparatus is complicated and expensive, the manufacturing cost is high, and a thin film having a large area is obtained. There is a drawback that it is difficult. In addition, although the wet method is relatively simple and can obtain a large-area thin film, in the sol-gel method generally used as the wet method, for example, titania sol or organic titanate is used. In order to maintain the stability and transparency of organic titanate, it was necessary to use an organic solvent or to add a corrosive acid such as hydrochloric acid or nitric acid.
For this reason, there is a drawback that the harmfulness of the organic solvent becomes a problem from the work safety, and the manufacturing apparatus becomes expensive due to the corrosiveness.
また、水溶性のチタン化合物を利用する方法も知られている（特許文献１参照）。この方法では、ヒドロキシカルボン酸を用いることにより安定性に優れた水溶性のチタン化合物を合成し、その化合物を用いて薄膜を作製している。しかし、この方法では、化合物の安定性が高すぎるために、次工程の加水分解、重縮合反応が進行しにくく、強固な薄膜を作製しにくい問題があった。
本発明の目的は、上記従来技術では達成し得なかった、強固な強誘電体薄膜を形成することのできる強誘電体薄膜作製溶液および強誘電体薄膜作製溶液の製造方法を提供することにある。 An object of the present invention is to provide a ferroelectric thin film preparation solution capable of forming a strong ferroelectric thin film and a method for manufacturing the ferroelectric thin film preparation solution, which could not be achieved by the above prior art. .
本発明者らは、上記従来技術に鑑み鋭意検討を重ねた結果、本発明を完成するに至った。
即ち、本発明の目的は、
チタン酸アルキル、水酸基を有さないカルボン酸類および水溶性金属塩を含む水溶液である、強誘電体薄膜作製溶液によって達成することができる。
As a result of intensive studies in view of the above prior art, the present inventors have completed the present invention.
That is, the object of the present invention is to
This can be achieved by a ferroelectric thin film preparation solution, which is an aqueous solution containing an alkyl titanate, a carboxylic acid having no hydroxyl group, and a water-soluble metal salt.
更に、本発明の他の目的は、
チタン酸アルキルと水酸基を有さないカルボン酸類とを混合する段階と、前記混合した溶液に水および水溶性金属塩を添加する段階からなる、強誘電体薄膜作製溶液の製造方法によって達成される。
Furthermore, another object of the present invention is to
This is achieved by a method for producing a ferroelectric thin film preparation solution comprising a step of mixing an alkyl titanate and a carboxylic acid having no hydroxyl group, and a step of adding water and a water-soluble metal salt to the mixed solution.
本発明によれば、強誘電体薄膜作製溶液を用いて、強固な強誘電体薄膜を容易に形成することができる。 According to the present invention, a strong ferroelectric thin film can be easily formed using a ferroelectric thin film preparation solution.
以下、本発明について詳細に説明する。
本発明の強誘電体薄膜作製溶液は、チタン酸アルキルと水酸基を有さないカルボン酸類と水溶性金属塩を含む水溶液である。
Hereinafter, the present invention will be described in detail.
The ferroelectric thin film preparation solution of the present invention is an aqueous solution containing an alkyl titanate, a carboxylic acid having no hydroxyl group, and a water-soluble metal salt.
ここで強誘電体とは、自発分極が存在し、外部電場によってその方向を変えられる材料のことであり、ＳｒＴｉＯ３、ＢａＴｉＯ３、ＰｂＴｉＯ３、ＣｄＴｉＯ３、ＫＮｂＯ３、Ｐｂ（Ｎｉ１／３Ｎｂ２／３）Ｏ３、Ｐｂ（Ｍｇ１／３Ｎｂ２／３）Ｏ３、Ｃｄ（Ｍｇ１／３Ｎｂ２／３）Ｏ３、ＬｉＮｂＯ３、ＬｉＴａＯ３、Ｃｄ２Ｎｂ２Ｏ７、ＰｂＮｂ２Ｏ６、Ｂｉ４Ｔｉ３Ｏ１２、Ｂｉ２ＷＯ６などが知られているが、中でも、材料の入手のし易さなどからチタン元素を含む材料からなることが好ましく、更に、チタン酸バリウム、チタン酸ストロンチウム、チタン酸ストロンチウムバリウムが好ましい。 Here, the ferroelectric material is a material that has spontaneous polarization and whose direction can be changed by an external electric field. SrTiO 3 , BaTiO 3 , PbTiO 3 , CdTiO 3 , KNbO 3 , Pb (Ni 1/3 Nb 2/3 ) O 3 , Pb (Mg 1/3 Nb 2/3 ) O 3 , Cd (Mg 1/3 Nb 2/3 ) O 3 , LiNbO 3 , LiTaO 3 , Cd 2 Nb 2 O 7 , PbNb 2 O 6 , Bi 4 Ti 3 O 12 , Bi 2 WO 6 and the like are known, and among these, it is preferable that the material is made of a material containing a titanium element because of the availability of the material, and further, barium titanate, Strontium titanate and barium strontium titanate are preferred.
ここで、強誘電体薄膜作製溶液とは、強誘電体薄膜を作製するための前駆体を含む溶液を指す。強誘電体薄膜作製溶液を用いた薄膜の作製方法としては、スプレーコーティング法、ディップコーティング法、フローコーティング法、スピンコーティング法、ロールコーティング法等の方法を任意に採用することができる。 Here, the ferroelectric thin film production solution refers to a solution containing a precursor for producing a ferroelectric thin film. As a method for producing a thin film using a ferroelectric thin film production solution, a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, or the like can be arbitrarily employed.
次に、チタン酸アルキルについて説明する。チタン酸アルキルには、チタンテトラメトキシド、チタンテトラエトキシド、チタンテトラノルマルプロポキシド、チタンテトライソプロポキシド、チタンテトラノルマルブトキシド、チタンテトラターシャリーブトキシドなどが挙げられるが、入手のしやすさより、チタンテトライソプロポキシド、チタンテトラノルマルブトキシドが好ましい。チタン酸アルキルは、構造体としたときの強誘電体を形成するものである。 Next, alkyl titanate will be described. Alkyl titanates include titanium tetramethoxide, titanium tetraethoxide, titanium tetranormal propoxide, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetratertiary butoxide, etc. Titanium tetraisopropoxide and titanium tetranormal butoxide are preferred. Alkyl titanate forms a ferroelectric when formed into a structure.
次に、水酸基を有さないカルボン酸類について説明する。本発明では、水酸基を有さないカルボン酸類をチタン酸アルキルの安定剤として使用するが、水酸基を有するカルボン酸類を使用した場合には、チタン酸アルキルと水酸基を有するカルボン酸類との反応により生成した化合物の安定性が高いために、次工程の加水分解、重縮合反応が進行しにくく、強固な薄膜を作製しにくい。水酸基を有さないカルボン酸類としては、脂肪族カルボン酸がチタン酸アルキルの安定化の程度が良好であることから好ましい。また、脂肪族カルボン酸としては、水溶性脂肪族カルボン酸であることが、溶液の均一性の点から好ましく。脂肪族カルボン酸としては、沸点が低く、次工程にて除去し易いことから、中でも酢酸が好ましい。また、ここでの水溶性とは、水と任意の割合で混合することを指す。 Next, carboxylic acids having no hydroxyl group will be described. In the present invention, a carboxylic acid having no hydroxyl group is used as an alkyl titanate stabilizer. When a carboxylic acid having a hydroxyl group is used, the carboxylic acid is produced by a reaction between an alkyl titanate and a carboxylic acid having a hydroxyl group. Since the stability of the compound is high, hydrolysis and polycondensation reactions in the next step are difficult to proceed, and it is difficult to produce a strong thin film. As the carboxylic acid having no hydroxyl group, an aliphatic carboxylic acid is preferable because the degree of stabilization of the alkyl titanate is good. The aliphatic carboxylic acid is preferably a water-soluble aliphatic carboxylic acid from the viewpoint of the uniformity of the solution. As the aliphatic carboxylic acid, acetic acid is preferable because it has a low boiling point and can be easily removed in the next step. Moreover, water solubility here refers to mixing with water in arbitrary ratios.
次に、強誘電体薄膜作製溶液に含まれる水酸基を有さないカルボン酸類の割合について説明する。チタン酸アルキル１当量に対する水酸基を有さないカルボン酸類の割合としては、２〜１００当量であることが好ましい。２当量より少ないと、溶液の安定が不十分であり水酸化チタンの生成が生じることから好ましくない。また、１００当量より多いと溶液中に含まれる有機物が多くなり、薄膜の均一性が低くなることから好ましくない。より好ましくは、３〜２０当量であり、５〜１０当量であることが更に好ましい。 Next, the ratio of carboxylic acids having no hydroxyl group contained in the ferroelectric thin film preparation solution will be described. The ratio of carboxylic acids having no hydroxyl group to 1 equivalent of alkyl titanate is preferably 2 to 100 equivalents. If the amount is less than 2 equivalents, the solution is not sufficiently stable and titanium hydroxide is produced, which is not preferable. On the other hand, when the amount is more than 100 equivalents, the organic matter contained in the solution is increased, and the uniformity of the thin film is lowered. More preferably, it is 3-20 equivalent, and it is still more preferable that it is 5-10 equivalent.
次に、水溶性金属塩について説明する。本発明の強誘電体薄膜作製溶液には、チタン元素以外の金属元素を水溶性金属塩によって添加する必要がある。水溶性の金属塩には、酢酸ストロンチウム、酢酸バリウム、酢酸カドミウム、酢酸鉛、酢酸リチウムなどが挙げられるが、チタン酸バリウム、チタン酸ストロンチウム、チタン酸ストロンチウムバリウムからなる強誘電体を作製するためには、酢酸ストロンチウム、酢酸バリウムが好ましい。 Next, the water-soluble metal salt will be described. To the ferroelectric thin film preparation solution of the present invention, it is necessary to add a metal element other than titanium element with a water-soluble metal salt. Examples of water-soluble metal salts include strontium acetate, barium acetate, cadmium acetate, lead acetate, and lithium acetate. In order to produce a ferroelectric material composed of barium titanate, strontium titanate, and barium titanate titanate. Is preferably strontium acetate or barium acetate.
次に、強誘電体薄膜作製溶液に含まれる水の割合について説明する。強誘電体薄膜作製溶液に含まれる水の割合としては、良好な薄膜が得られれば特に限定されないが、１０〜９０重量％であることが好ましい。より好ましくは、２０〜５０重量％である。 Next, the ratio of water contained in the ferroelectric thin film preparation solution will be described. The proportion of water contained in the ferroelectric thin film preparation solution is not particularly limited as long as a good thin film can be obtained, but is preferably 10 to 90% by weight. More preferably, it is 20 to 50% by weight.
また、本発明の強誘電体薄膜作製溶液は、溶液の安定性の程度において優れており、良好な薄膜が得られる。溶液の安定性の程度としては、作製から２〜３日間は透明な溶液が得られるが、室温において徐々に加水分解、重縮合反応が進行し、溶液粘度の上昇または白色の沈降物の生成が確認される程度の安定性であることが好ましい。 Moreover, the ferroelectric thin film preparation solution of the present invention is excellent in the degree of stability of the solution, and a good thin film can be obtained. As for the degree of stability of the solution, a transparent solution can be obtained for 2 to 3 days from the preparation, but the hydrolysis and polycondensation reaction gradually proceeds at room temperature, resulting in an increase in solution viscosity or generation of a white precipitate. It is preferable that the stability be confirmed.
また、本発明の強誘電体薄膜作製溶液は、チタン酸アルキルと水酸基を有さないカルボン酸類とを含む水溶液であるが、チタン酸アルキル、水酸基を有さないカルボン酸類、水以外に、溶液の粘度調整のために、増粘剤を添加しても良い。増粘剤としては、水溶性の有機高分子が挙げられ、ポリエチレンオキシド、ポリビニルアルコール、ポリビニルエステル、ポリビニルエーテル、ポリビニルピリジン、ポリアクリルアミド、エーテルセルロース、ペクチン、澱粉などが挙げられる。 The ferroelectric thin film preparation solution of the present invention is an aqueous solution containing an alkyl titanate and a carboxylic acid having no hydroxyl group. In addition to the alkyl titanate, the carboxylic acid having no hydroxyl group, and water, A thickener may be added to adjust the viscosity. Examples of the thickener include water-soluble organic polymers such as polyethylene oxide, polyvinyl alcohol, polyvinyl ester, polyvinyl ether, polyvinyl pyridine, polyacrylamide, ether cellulose, pectin, and starch.
次に、本発明の強誘電体薄膜作製溶液を製造するための態様について説明する。
本発明の強誘電体薄膜作製溶液を製造するには、前述の要件を同時に満足するような強誘電体薄膜作製溶液が得られる手法であればいずれも採用することができるが、チタン酸アルキルと水酸基を有さないカルボン酸類を混合する段階と、前記混合した溶液に水と水溶性金属塩を添加する段階からなる、強誘電体薄膜作製溶液の製造方法が好ましい一態様として挙げることができる。
Next, an embodiment for producing the ferroelectric thin film preparation solution of the present invention will be described.
In order to produce the ferroelectric thin film preparation solution of the present invention, any technique can be used as long as it can obtain a ferroelectric thin film preparation solution that simultaneously satisfies the above-mentioned requirements. A preferred embodiment is a method for producing a ferroelectric thin film preparation solution comprising a step of mixing a carboxylic acid having no hydroxyl group and a step of adding water and a water-soluble metal salt to the mixed solution.
このような段階を経ることによって、均一な溶液を作製することができる。まず、チタン酸アルキルと水酸基を有さないカルボン酸類を混合するが、この段階によってチタン酸アルキルと水酸基を有さないカルボン酸類とからなる錯体が形成される。この錯体を含む溶液に、水（または水と水溶性金属塩の混合物）を添加することによって、溶液が一旦ゲル化するが、攪拌を続けることにより均一な溶液を作製することができる。この手順によらず、例えばチタン酸アルキルと水（または水と水溶性金属塩の混合物）を添加した場合は、チタン酸アルキルの加水分解物からなる沈殿が生成するため、均一な溶液を作製することはできない。 By passing through such steps, a uniform solution can be produced. First, an alkyl titanate and a carboxylic acid having no hydroxyl group are mixed. At this stage, a complex composed of an alkyl titanate and a carboxylic acid having no hydroxyl group is formed. By adding water (or a mixture of water and a water-soluble metal salt) to the solution containing this complex, the solution once gels, but a uniform solution can be prepared by continuing stirring. Regardless of this procedure, for example, when an alkyl titanate and water (or a mixture of water and a water-soluble metal salt) are added, a precipitate composed of a hydrolyzate of the alkyl titanate is generated, so a uniform solution is prepared. It is not possible.
ここで、前記溶液が作製できれば特に限定されないが、水（または水と水溶性金属塩の混合物）を添加する段階で、０〜２０℃まで冷却した状態で添加することが、急激な反応を抑制する観点から好ましい。 Here, although it will not specifically limit if the said solution can be produced, In the stage which adds water (or mixture of water and water-soluble metal salt), adding in the state cooled to 0-20 degreeC suppresses a rapid reaction. From the viewpoint of
以下、本発明を実施例により更に具体的に説明するが、本発明は、これらの実施例により何等限定を受けるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
［実施例１］
チタンテトラノルマルブトキシド（和光純薬工業株式会社製、一級）１重量部と酢酸（和光純薬工業株式会社製、特級）１．３重量部を添加し均一な溶液を得た。この溶液にイオン交換水１．８重量部、酢酸バリウム（和光純薬工業株式会社製、特級）０．７５重量部を、混合させた溶液を攪拌しながら添加することにより溶液中にゲルが生成した。生成したゲルは、更に攪拌を続けることにより解離し、透明な溶液を調製することが出来た。作製した溶液を用いて、ディップコーティング法により薄膜形成性を確認したところ良好であった。
[Example 1]
1 part by weight of titanium tetranormal butoxide (manufactured by Wako Pure Chemical Industries, Ltd., first grade) and 1.3 parts by weight of acetic acid (made by Wako Pure Chemical Industries, Ltd., special grades) were added to obtain a uniform solution. By adding 1.8 parts by weight of ion-exchanged water and 0.75 parts by weight of barium acetate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) to this solution while stirring, a gel is formed in the solution. did. The produced gel was dissociated by further stirring, and a clear solution could be prepared. When the prepared solution was used to confirm thin film formation by dip coating, it was good.
［実施例２］
チタンテトラノルマルブトキシド（和光純薬工業株式会社製、一級）１重量部と酢酸（和光純薬工業株式会社製、特級）１．３重量部を添加し均一な溶液を得た。この溶液にイオン交換水２重量部、酢酸ストロンチウム０．５水和物（和光純薬工業株式会社製）０．６３重量部を、混合させた溶液を攪拌しながら添加することにより溶液中にゲルが生成した。生成したゲルは、更に攪拌を続けることにより解離し、透明な溶液を調製することが出来た。作製した溶液を用いて、ディップコーティング法により薄膜形成性を確認したところ良好であった。
[Example 2]
1 part by weight of titanium tetranormal butoxide (manufactured by Wako Pure Chemical Industries, Ltd., first grade) and 1.3 parts by weight of acetic acid (made by Wako Pure Chemical Industries, Ltd., special grades) were added to obtain a uniform solution. By adding 2 parts by weight of ion-exchanged water and 0.63 parts by weight of strontium acetate hemihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) to this solution while stirring, the gel is added to the solution. Generated. The produced gel was dissociated by further stirring, and a clear solution could be prepared. When the prepared solution was used to confirm thin film formation by dip coating, it was good.
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| JP2002029745A (en) * | 2000-07-18 | 2002-01-29 | Korea Advanced Inst Of Sci Technol | Method for producing crystalline barium titanate powder |
| JP2002356326A (en) * | 2001-04-09 | 2002-12-13 | Samsung Corning Co Ltd | Method for producing oxide powder |
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