JP4670497B2 - Thin film electrode paste and method for manufacturing thin film electrode and thin film element - Google Patents

Thin film electrode paste and method for manufacturing thin film electrode and thin film element Download PDF

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JP4670497B2
JP4670497B2 JP2005175298A JP2005175298A JP4670497B2 JP 4670497 B2 JP4670497 B2 JP 4670497B2 JP 2005175298 A JP2005175298 A JP 2005175298A JP 2005175298 A JP2005175298 A JP 2005175298A JP 4670497 B2 JP4670497 B2 JP 4670497B2
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信幸 曽山
祐介 渡会
一祐 佐藤
貴博 宇野
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Mitsubishi Materials Corp
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本発明は、半導体記憶装置、薄膜コンデンサ、センサ、圧電素子、表面弾性波素子、フィルタ、表面弾性波光学導波管、光学記憶装置、空間光変調器等に用いられる薄膜素子の薄膜電極用のペースト並びにその薄膜電極の製造方法及びそれを利用した薄膜素子の製造方法に関するものである。   The present invention is for a thin film electrode of a thin film element used in a semiconductor memory device, a thin film capacitor, a sensor, a piezoelectric element, a surface acoustic wave element, a filter, a surface acoustic wave optical waveguide, an optical memory device, a spatial light modulator, etc. The present invention relates to a paste, a method for manufacturing the thin film electrode, and a method for manufacturing a thin film element using the paste.

従来、薄膜素子は、一般的に、多結晶体からなる誘電体材料膜と、この誘電体材料膜を挟んで配置される上部電極及び下部電極と、を備えた構造を有している。この誘電体材料膜の組成は、一般的に、チタン酸ジルコン酸鉛（以下、「ＰＺＴ」という）や、ペロブスカイト型の結晶構造を有するチタン酸バリウム系誘電物質（以下、「ＢＳＴ」という）が用いられ、この誘電体材料膜の製造に関しては、例えば、ゾルゲル法、レーザーアブレーション法及びＣＶＤ法等が用いられている。また、この薄膜素子における上部電極および下部電極を構成する材料としては、従来から白金、イリジウム、ルテニウム、チタン、金、ニッケル等、種々の導電体が使用されている。そして、上部電極および下部電極の従来の製造方法は、真空スパッタ法により成膜することにより上部電極および下部電極を製造していた（例えば、特許文献１参照。）。従って、従来では、下部電極を真空スパッタ法により製造した後、誘電体材料膜をその下部電極上に別工程からなるゾルゲル法、レーザーアブレーション法及びＣＶＤ法等で製造した後、得られた誘電体材料膜上に更に上部電極を真空スパッタ法により製造するという手順により得られていた。
特開平５−２８６１３１号公報 Conventionally, a thin film element generally has a structure including a dielectric material film made of a polycrystalline body, and an upper electrode and a lower electrode arranged with the dielectric material film interposed therebetween. The dielectric material film is generally composed of lead zirconate titanate (hereinafter referred to as “PZT”) or a barium titanate-based dielectric material (hereinafter referred to as “BST”) having a perovskite crystal structure. For the production of the dielectric material film, for example, a sol-gel method, a laser ablation method, a CVD method or the like is used. In addition, various conductors such as platinum, iridium, ruthenium, titanium, gold, and nickel have been conventionally used as materials constituting the upper electrode and the lower electrode in this thin film element. And the conventional manufacturing method of an upper electrode and a lower electrode manufactured the upper electrode and the lower electrode by forming into a film by a vacuum sputtering method (for example, refer patent document 1). Therefore, conventionally, after the lower electrode is manufactured by the vacuum sputtering method, the dielectric material film is manufactured on the lower electrode by a sol-gel method, a laser ablation method, a CVD method, or the like, which is a separate process. It was obtained by the procedure of further manufacturing the upper electrode on the material film by vacuum sputtering.
Japanese Patent Laid-Open No. 5-286131

しかし、下部電極を真空スパッタ法により製造した後、誘電体材料膜を別工程で製造し、その後更に上部電極を製造する薄膜素子の製造方法では、それぞれの成膜方法が異なり、製造方法が煩雑となる。このため、得られた薄膜素子の単価が押し上げられる不具合があった。この点を解消するために、電極に関しては金属粒子を含むペーストを所定の厚さに塗布して得られた膜を焼成することが考えられるが、その焼成温度が比較的高い場合には、電極を得るまでのタクトタイムも大きくなり、得られた薄膜素子の単価を更に押し上げる問題点もある。
本発明の目的は、薄膜素子の電極を低コストで、かつ短いタクトタイムで形成し、比較的安価な薄膜素子を得ることのできる薄膜電極用ペースト並びに薄膜電極の製造方法及び薄膜素子の製造方法を提供することにある。 However, in the thin film element manufacturing method in which the lower electrode is manufactured by a vacuum sputtering method, the dielectric material film is manufactured in a separate process, and then the upper electrode is further manufactured, each film forming method is different and the manufacturing method is complicated. It becomes. For this reason, there was a problem that the unit price of the obtained thin film element was pushed up. In order to eliminate this point, regarding the electrode, it is conceivable to fire a film obtained by applying a paste containing metal particles to a predetermined thickness. However, if the firing temperature is relatively high, the electrode There is also a problem that the tact time until obtaining is increased, and the unit price of the obtained thin film element is further increased.
An object of the present invention is to provide a thin film electrode paste, a thin film electrode manufacturing method, and a thin film element manufacturing method capable of forming a thin film element electrode at a low cost with a short tact time and obtaining a relatively inexpensive thin film element. Is to provide.

請求項１に係る発明は、Ｎｉメタルを気化させて、アルキルナフタレン系のオイルにポリアミンを添加した溶媒中に吹き込むことにより、粒径が１〜４０ｎｍのＮｉ粒子が分散したコロイド溶液を作製し、このコロイド溶液を固液分離した後、分離したＮｉからなる粒径が１〜４０ｎｍの金属微粒子を水に分散させてなる薄膜電極用ペーストである。
この請求項１に記載された薄膜電極用ペーストでは、粒径が１〜４０ｎｍの金属微粒子を水に分散させたので、４００〜９００℃の比較的低い温度で焼成することができ、薄膜電極を得るまでのタクトタイムを短縮させることができる。ここで、合金の粒径が１ｎｍ未満であると緻密な組織になりにくい不具合があり、その粒径が４０ｎｍを越えると低温での焼結が困難になるとともに基板へのアンカー効果による密着力が低下する不具合がある。そして、この合金の好ましい粒径は１〜１０ｎｍであり、２〜５ｎｍであることが更に好ましい。 The invention according to claim 1 vaporizes Ni metal and blows it into a solvent in which polyamine is added to an alkylnaphthalene-based oil to produce a colloidal solution in which Ni particles having a particle size of 1 to 40 nm are dispersed, after this the colloidal solution solid-liquid separation, Ni or Ranaru diameter separated is a thin film electrode paste obtained by dispersing fine metal particles 1~40nm water.
In the thin film electrode paste described in claim 1, since the metal fine particles having a particle diameter of 1 to 40 nm are dispersed in water, the thin film electrode can be fired at a relatively low temperature of 400 to 900 ° C. The tact time to obtain can be shortened. Here, when the particle size of the alloy is less than 1 nm, there is a problem that it is difficult to form a dense structure. When the particle size exceeds 40 nm, sintering at low temperature becomes difficult and adhesion due to the anchor effect to the substrate is difficult. There is a problem that decreases. And the preferable particle size of this alloy is 1-10 nm, and it is still more preferable that it is 2-5 nm.

請求項２に係る発明は、図１に示すように、請求項１記載の粒径が１〜４０ｎｍのＮｉからなる金属微粒子を水に分散させた薄膜電極用ペーストを準備する工程と、基板１１の上面にペーストを塗布して所定の厚さに成膜する工程と、熱処理によりペーストにおける水を除去して金属微粒子を焼成することにより基板１１上に薄膜電極１２を得る工程とを含む薄膜電極の製造方法である。
この請求項２に記載された薄膜電極の製造方法では、粒径が１〜４０ｎｍの金属微粒子を分散させたペーストを成膜して焼成するので、その焼成温度を比較的低く設定することにより薄膜電極を得るまでのタクトタイムを短縮させることができる。
請求項３に係る発明は、請求項２に係る発明であって、ペーストの塗布成膜がスピンコート法又はスプレー法又は液滴吐出法のいずれかによりなされる薄膜電極の製造方法である。
この請求項３に記載された薄膜電極の製造方法では、ペーストの塗布成膜を大気圧下において行うことができ、従来の真空スパッタ法により電極を製造する場合に比較して、薄膜電極を得るまでのタクトタイムを更に短縮させることができる。 As shown in FIG. 1, the invention according to claim 2 is a process for preparing a paste for a thin film electrode in which metal fine particles made of Ni having a particle diameter of 1 to 40 nm according to claim 1 are dispersed in water; A thin film electrode including a step of applying a paste to the upper surface of the substrate to form a film with a predetermined thickness, and a step of removing the water in the paste by heat treatment and firing the metal fine particles to obtain the thin film electrode 12 on the substrate 11 It is a manufacturing method.
In the method of manufacturing a thin film electrode according to claim 2, since a paste in which metal fine particles having a particle diameter of 1 to 40 nm are dispersed is formed and fired, the thin film electrode can be formed by setting the firing temperature relatively low. The tact time until the electrode is obtained can be shortened.
The invention according to claim 3 is the invention according to claim 2, and is a method of manufacturing a thin film electrode in which the coating film formation of the paste is performed by any one of a spin coating method, a spray method, and a droplet discharge method.
In the method of manufacturing a thin film electrode according to the third aspect, paste coating can be performed under atmospheric pressure, and a thin film electrode is obtained as compared with the case of manufacturing an electrode by a conventional vacuum sputtering method. It is possible to further shorten the tact time.

請求項４に係る発明は、請求項２又は３に係る発明であって、熱処理が大気圧雰囲気中において４００℃〜９００℃の温度によりなされる薄膜電極の製造方法である。
この請求項４に記載された薄膜電極の製造方法では、熱処理を４００〜９００℃の比較的低い温度で焼成するので、薄膜電極を得るまでのタクトタイムを更に短縮させることができ、比較的安価な薄膜電極を得ることができる。ここで、熱処理が４００℃未満であると十分に焼結しない不具合があり、その熱処理が９００℃を越えると成長が起こって密着力が低下する不具合がある。そして、この熱処理の好ましい温度範囲は４５０〜８００℃である。 The invention according to claim 4 is the invention according to claim 2 or 3, wherein the heat treatment is performed at a temperature of 400 ° C. to 900 ° C. in an atmospheric pressure atmosphere.
In the method of manufacturing a thin film electrode according to claim 4, since the heat treatment is performed at a relatively low temperature of 400 to 900 ° C., the tact time until the thin film electrode is obtained can be further shortened and is relatively inexpensive. A thin film electrode can be obtained. Here, when the heat treatment is less than 400 ° C., there is a problem that the sintering is not sufficiently performed, and when the heat treatment exceeds 900 ° C., there is a problem that the growth occurs and the adhesion force is lowered. And the preferable temperature range of this heat processing is 450-800 degreeC.

請求項５に係る発明は、請求項１記載の粒径が１〜４０ｎｍのＮｉからなる金属微粒子を水に分散させた薄膜電極用ペーストを基板１１の平坦な上面に塗布して所定の厚さに成膜した後に熱処理して金属微粒子を焼成することにより基板１１上に第１薄膜電極１２を形成する工程と、第１薄膜電極１２上にゾルゲル法により誘電体材料膜１３を形成する工程と、誘電体材料膜１３上に請求項１記載の粒径が１〜４０ｎｍのＮｉからなる金属微粒子を水に分散させた薄膜電極用ペーストを塗布して所定の厚さに成膜した後に熱処理して金属微粒子を焼成することにより誘電体材料膜１３上に第２薄膜電極１４を形成する工程とを含む薄膜素子の製造方法である。
この請求項５に記載された薄膜素子の製造方法では、薄膜素子の薄膜電極１２，１４を低コストで得ることができ、薄膜電極１２，１４及び誘電体材料膜１３が非真空状態で形成され得ることから電極を真空スパッタで行われる従来に比較してその製造工程を単純化させることができ、かつ比較的低温で薄膜電極１２，１４及び誘電体材料膜１３を形成し得ることから、短いタクトタイムで薄膜素子を得ることができ、その単価を安価なものとすることができる。 According to a fifth aspect of the present invention, a thin film electrode paste in which metal fine particles made of Ni having a particle diameter of 1 to 40 nm according to the first aspect are dispersed in water is applied to a flat upper surface of the substrate 11 to a predetermined thickness. Forming a first thin film electrode 12 on the substrate 11 by heat-treating the metal fine particles after the film is formed, and forming a dielectric material film 13 on the first thin film electrode 12 by a sol-gel method. The thin film electrode paste in which the metal fine particles made of Ni having a particle diameter of 1 to 40 nm according to claim 1 are applied to the dielectric material film 13 in water to form a predetermined thickness, followed by heat treatment. Forming a second thin film electrode 14 on the dielectric material film 13 by firing metal fine particles.
In the method of manufacturing the thin film element according to the fifth aspect, the thin film electrodes 12 and 14 of the thin film element can be obtained at low cost, and the thin film electrodes 12 and 14 and the dielectric material film 13 are formed in a non-vacuum state. Therefore, the manufacturing process can be simplified as compared with the conventional case where the electrodes are formed by vacuum sputtering, and the thin film electrodes 12 and 14 and the dielectric material film 13 can be formed at a relatively low temperature. A thin film element can be obtained in tact time, and the unit price can be reduced.

請求項７に係る発明は、粒径が１〜６０ｎｍの誘電体微粒子を溶媒に分散させた誘電体ペーストを準備する工程と、請求項２記載の方法により製造された第１薄膜電極１２の上面に誘電体ペーストを塗布して所定の厚さに成膜する工程と、熱処理により誘電体ペーストにおける溶媒を除去して誘電体微粒子を焼成することにより第１薄膜電極１２上に薄膜誘電体材料膜１３を形成する工程と、薄膜誘電体材料膜１３上にスパッタリング法、ＭＯＣＶＤ法、真空蒸着法又は請求項２記載の方法により第２薄膜電極１４を形成する工程とを含む薄膜素子の製造方法である。
この請求項７に記載された薄膜素子の製造方法では、粒径が１〜６０ｎｍの誘電体微粒子を溶媒に分散させた誘電体ペーストを成膜して焼成するので、その焼成温度を比較的低く設定することにより誘電体材料膜１３を得るまでのタクトタイムを短縮させることができる。ここで、誘電体微粒子の粒径が１ｎｍ未満であると緻密な組織になりにくい不具合があり、その粒径が６０ｎｍを越えると低温での焼結が困難になるとともに第１薄膜電極１２へのアンカー効果による密着力が低下する不具合がある。そして、この誘電体微粒子の好ましい粒径は１〜１０ｎｍであり、２〜５ｎｍであることが更に好ましい。 The invention according to claim 7 includes a step of preparing a dielectric paste in which dielectric fine particles having a particle diameter of 1 to 60 nm are dispersed in a solvent, and an upper surface of the first thin film electrode 12 manufactured by the method according to claim 2. A thin film dielectric material film is formed on the first thin film electrode 12 by applying a dielectric paste onto the first thin film electrode 12 by forming a film to a predetermined thickness, and removing the solvent in the dielectric paste by heat treatment and firing the dielectric fine particles. A method of forming a thin film element, and a step of forming a second thin film electrode 14 on the thin film dielectric material film 13 by a sputtering method, an MOCVD method, a vacuum deposition method or a method according to claim 2. is there.
In the method for manufacturing a thin film element described in claim 7, since the dielectric paste in which dielectric fine particles having a particle diameter of 1 to 60 nm are dispersed in a solvent is formed and fired, the firing temperature is relatively low. By setting, the tact time until the dielectric material film 13 is obtained can be shortened. Here, if the particle size of the dielectric fine particles is less than 1 nm, there is a problem that it is difficult to form a dense structure. If the particle size exceeds 60 nm, sintering at a low temperature becomes difficult and the first thin film electrode 12 is not easily sintered. There is a problem that the adhesion due to the anchor effect is reduced. And the preferable particle size of this dielectric fine particle is 1-10 nm, and it is still more preferable that it is 2-5 nm.

また、この請求項７に記載された薄膜素子の製造方法では、薄膜素子の薄膜電極１２，１４を低コストで得ることができ、薄膜電極１２，１４を真空スパッタで形成する従来に比較してその製造工程を単純化させることができ、かつ比較的低温で薄膜電極１２，１４及び誘電体材料膜１３を形成し得ることから、短いタクトタイムで薄膜素子を得ることができ、その単価を安価なものとすることができる。   Further, in the method of manufacturing a thin film element described in claim 7, the thin film electrodes 12 and 14 of the thin film element can be obtained at low cost, and compared with the conventional method in which the thin film electrodes 12 and 14 are formed by vacuum sputtering. Since the manufacturing process can be simplified and the thin film electrodes 12, 14 and the dielectric material film 13 can be formed at a relatively low temperature, a thin film element can be obtained with a short tact time, and the unit price is low. Can be.

本発明の薄膜電極用ペーストは、Ｎｉメタルを気化させて、アルキルナフタレン系のオイルにポリアミンを添加した溶媒中に吹き込むことにより、粒径が１〜４０ｎｍのＮｉ粒子が分散したコロイド溶液を作製し、このコロイド溶液を固液分離した後、分離したＮｉからなる粒径が１〜４０ｎｍの金属微粒子を水に分散させてなるので、４００〜９００℃の比較的低い温度で焼成することができ、薄膜電極を得るまでのタクトタイムを従来より短縮させることができる。
また、本発明の薄膜電極の製造方法では、上記粒径が１〜４０ｎｍのＮｉからなる金属微粒子を水に分散させた薄膜電極用ペーストを準備する工程と、基板の平坦な上面に前記ペーストを塗布して所定の厚さに成膜する工程と、熱処理によりペーストにおける水を除去して金属微粒子を焼成することにより基板上に薄膜電極を得る工程とを含むので、ペーストの焼成温度を比較的低く設定することにより薄膜電極を得るまでのタクトタイムを短縮させることができる。この際、ペーストの塗布成膜がスピンコート法又はスプレー法又は液滴吐出法のいずれかによりなされる場合には、ペーストの塗布成膜を大気圧下において行うことができ、従来の真空スパッタ法により電極を製造する場合に比較して、薄膜電極を得るまでのタクトタイムを更に短縮させることができる。そして、その熱処理が大気圧雰囲気中において４００℃〜９００℃の温度により行えば、薄膜電極を得るまでのタクトタイムを更に短縮させることができ、比較的安価な薄膜電極を得ることができる。 The paste for a thin film electrode of the present invention vaporizes Ni metal and blows it into a solvent in which polyamine is added to an alkylnaphthalene-based oil to produce a colloidal solution in which Ni particles having a particle size of 1 to 40 nm are dispersed. after this the colloidal solution solid-liquid separation, since the Ni or Ranaru diameter separated is formed by dispersing the fine metal particles 1~40nm water, be fired at a relatively low temperature of 400 to 900 ° C. In addition, the tact time for obtaining the thin film electrode can be shortened as compared with the prior art.
In the method for producing a thin film electrode of the present invention, a step of preparing a thin film electrode paste in which metal fine particles made of Ni having a particle size of 1 to 40 nm are dispersed in water, and the paste on a flat upper surface of a substrate. The method includes a step of applying and forming a film to a predetermined thickness, and a step of obtaining a thin film electrode on a substrate by removing water in the paste by heat treatment and firing metal fine particles, so that the firing temperature of the paste is relatively By setting it low, the tact time until the thin film electrode is obtained can be shortened. At this time, when the paste coating film is formed by any one of the spin coating method, the spray method, and the droplet discharge method, the paste coating film formation can be performed under atmospheric pressure, and the conventional vacuum sputtering method is used. As compared with the case of manufacturing an electrode, the tact time until obtaining a thin film electrode can be further shortened. If the heat treatment is performed at a temperature of 400 ° C. to 900 ° C. in an atmospheric pressure atmosphere, the tact time until the thin film electrode is obtained can be further shortened, and a relatively inexpensive thin film electrode can be obtained.

更に、本発明の薄膜素子の製造方法では、上記粒径が１〜４０ｎｍのＮｉからなる金属微粒子を水に分散させた薄膜電極用ペーストを基板の平坦な上面に塗布して所定の厚さに成膜した後に熱処理して金属微粒子を焼成することにより基板上に第１薄膜電極を形成する工程と、第１薄膜電極上にゾルゲル法により誘電体材料膜を形成する工程と、誘電体材料膜上に上記粒径が１〜４０ｎｍのＮｉからなる金属微粒子を水に分散させた薄膜電極用ペーストを塗布して所定の厚さに成膜した後に熱処理して金属微粒子を焼成することにより誘電体材料膜上に第２薄膜電極を形成する工程とを含むので、電極を低コストで得ることができ、かつ短いタクトタイムで電極及び誘電体材料膜を形成し得ることから、比較的安価な薄膜素子を得ることができる。
一方、本発明の薄膜素子の製造方法では、粒径が１〜６０ｎｍの誘電体微粒子を溶媒に分散させた誘電体ペーストを上述した方法で製造された第１薄膜電極の上面に塗布して成膜した後、焼成することにより薄膜誘電体材料膜を形成し、その薄膜誘電体材料膜上にスパッタリング法、ＭＯＣＶＤ法、真空蒸着法又は請求項２記載の方法により第２薄膜電極を形成するようにしてもよい。この場合における第２薄膜電極の形成をスパッタリング法、ＭＯＣＶＤ法、真空蒸着法又は上述した薄膜電極の製造方法により行わせれば、その単価を更に安価なものとすることができる。 Further, in the method of manufacturing a thin film element of the present invention, a thin film electrode paste in which metal fine particles made of Ni having a particle diameter of 1 to 40 nm are dispersed in water is applied to a flat upper surface of a substrate to have a predetermined thickness. Forming a first thin film electrode on the substrate by heat-treating the metal fine particles after the film formation and baking the fine metal particles; forming a dielectric material film on the first thin film electrode by a sol-gel method; and dielectric material film A dielectric is obtained by applying a thin film electrode paste in which metal fine particles made of Ni having a particle diameter of 1 to 40 nm are dispersed in water and forming a film with a predetermined thickness, followed by heat treatment and firing the metal fine particles. Forming the second thin film electrode on the material film, so that the electrode can be obtained at low cost and the electrode and the dielectric material film can be formed with a short tact time. Can get the element That.
On the other hand, in the method for manufacturing a thin film element of the present invention, a dielectric paste in which dielectric fine particles having a particle diameter of 1 to 60 nm are dispersed in a solvent is applied to the upper surface of the first thin film electrode manufactured by the above-described method. After the film is formed, a thin film dielectric material film is formed by firing, and a second thin film electrode is formed on the thin film dielectric material film by a sputtering method, an MOCVD method, a vacuum evaporation method or the method according to claim 2. It may be. If the formation of the second thin film electrode in this case is performed by the sputtering method, MOCVD method, vacuum vapor deposition method or the above-described thin film electrode manufacturing method, the unit price can be further reduced.

次に本発明を実施するための最良の形態を図面に基づいて説明する。
図１に示すように、本発明の薄膜素子１０の製造方法は、基板１１上に第１薄膜電極１２を形成する工程と、その第１薄膜電極１２上に誘電体材料膜１３を形成する工程と、その誘電体材料膜１３上に第２薄膜電極１４を形成する工程とを備える。ここで、第１薄膜電極１２を形成するための基板１１とは、シリコンからなる基板や、アルミナ（Ａｌ2Ｏ3）からなる基板等が挙げられる。第１薄膜電極１２は、薄膜電極用ペーストを基板１１の平坦な上面に塗布して所定の厚さに成膜した後に熱処理してそのペーストを焼成することにより得られる。 Next, the best mode for carrying out the present invention will be described with reference to the drawings.
As shown in FIG. 1, the method for manufacturing a thin film element 10 of the present invention includes a step of forming a first thin film electrode 12 on a substrate 11 and a step of forming a dielectric material film 13 on the first thin film electrode 12. And a step of forming the second thin film electrode 14 on the dielectric material film 13. Here, the substrate 11 for forming the first thin film electrode 12 includes a substrate made of silicon, a substrate made of alumina (Al 2 O 3 ), and the like. The first thin film electrode 12 is obtained by applying a thin film electrode paste on the flat upper surface of the substrate 11 to form a film having a predetermined thickness, and then heat-treating the paste.

この基板１１上に塗布される薄膜電極用ペーストは、Ｎｉの粒子が分散したコロイド溶液を作製し、このコロイド溶液を固液分離した後、分離したＮｉからなる粒径が１〜４０ｎｍの金属微粒子を水に分散させたペーストである。このような粒径が１〜４０ｎｍの金属微粒子を含むペーストの具体的な製造手順は、例えばＰｔが含まれる場合は、先ず塩化白金酸を水に溶解させて塩化白金酸の水溶液を調製する。この水溶液に分散剤を添加した後攪拌して混合する。その後還元剤を入れて白金イオンを還元して白金の粒子を析出させ、これにより粒径が１〜４０ｎｍの白金粒子が分散したコロイド溶液が作製される。一方、Ｎｉが含まれる場合は、真空蒸着によりＮｉメタルを気化させて、アルキルナフタレン系のオイルにポリアミンを添加した溶媒中に吹き込んでＮｉの粒子を析出させ、これにより、Ｎｉ粒子が分散したコロイド溶液が作製される。このコロイド溶液を遠心分離により固液分離し、固形分としての粒子を取り出し水と混合することにより粒径が１〜４０ｎｍの金属微粒子を含むペーストを調製できる。このような薄膜電極用ペーストでは、粒径が１〜４０ｎｍの金属微粒子を水に分散させることにより、４００〜９００℃の比較的低い温度で焼成することが可能になり、薄膜電極を得るまでのタクトタイムを短縮させることができる。 Thin film electrode paste is coated on the substrate 11, to prepare a colloidal solution of Ni particles are dispersed, after the colloidal solution solid-liquid separation, the separated Ni or Ranaru particle size of 1~40nm It is a paste in which metal fine particles are dispersed in water. For example, when Pt is contained in a specific manufacturing procedure of a paste containing metal fine particles having a particle diameter of 1 to 40 nm, first, chloroplatinic acid is first dissolved in water to prepare an aqueous solution of chloroplatinic acid. A dispersing agent is added to this aqueous solution and then mixed by stirring. Thereafter, a reducing agent is added to reduce platinum ions to precipitate platinum particles, thereby producing a colloidal solution in which platinum particles having a particle diameter of 1 to 40 nm are dispersed. On the other hand, when Ni is contained, Ni metal is vaporized by vacuum deposition, and blown into a solvent in which polyamine is added to an alkylnaphthalene-based oil to precipitate Ni particles, thereby colloid in which Ni particles are dispersed. A solution is made. The colloidal solution was centrifuged and the separated particles the particle size by mixing water outlet grain child as solids can be prepared a paste containing metal particles of from 1 to 40 nm. In such a thin film electrode paste, by dispersing metal fine particles having a particle size of 1 to 40 nm in water, it becomes possible to fire at a relatively low temperature of 400 to 900 ° C. until the thin film electrode is obtained. Tact time can be shortened.

次に、このように調製されたペーストを用いた第１薄膜電極１２の製造方法について説明する。上述したように粒径が１〜４０ｎｍの金属微粒子を水に分散させた薄膜電極用ペーストを準備した後、基板１１の平坦な上面にこのペーストを塗布して所定の厚さに成膜する。その後、熱処理によりペーストにおける水を除去して金属微粒子を焼成することにより基板１１上に薄膜電極を得る。そして、ペーストの塗布成膜はスピンコート法又はスプレー法又は液滴吐出法のいずれかによりなされ、熱処理は大気圧雰囲気中において４００℃〜９００℃の温度によりなされる。
即ち、この薄膜電極の製造方法では、ペーストの塗布成膜をスピンコート法又はスプレー法又は液滴吐出法のいずれかにより行うことにより、ペーストの塗布成膜を大気圧下において行うことができ、従来の真空スパッタ法により電極を製造する場合に比較して、薄膜電極を得るまでのタクトタイムを更に短縮させることができる。そして、ペーストは粒径が１〜４０ｎｍの金属微粒子を水に分散させているので、その焼成温度を比較的低く設定することができ、例えば、焼成させるための熱処理を４００〜９００℃の比較的低い温度にすることにより、薄膜電極を得るまでのタクトタイムを更に短縮させることができ、比較的安価な薄膜電極を得ることができる。 Next, the manufacturing method of the 1st thin film electrode 12 using the paste prepared in this way is demonstrated. As described above, after preparing a thin film electrode paste in which metal fine particles having a particle diameter of 1 to 40 nm are dispersed in water, this paste is applied to the flat upper surface of the substrate 11 to form a film with a predetermined thickness. Thereafter, the thin film electrode is obtained on the substrate 11 by removing the water in the paste by heat treatment and firing the fine metal particles. Then, the paste is formed by a spin coating method, a spray method, or a droplet discharge method, and the heat treatment is performed at a temperature of 400 ° C. to 900 ° C. in an atmospheric pressure atmosphere.
That is, in this thin film electrode manufacturing method, paste coating can be performed at atmospheric pressure by performing paste coating by either a spin coating method, a spray method, or a droplet discharge method. Compared to the case of manufacturing an electrode by a conventional vacuum sputtering method, the tact time until obtaining a thin film electrode can be further shortened. And since the paste is disperse | distributing the metal fine particle with a particle size of 1-40 nm in water, the baking temperature can be set comparatively low, for example, heat processing for baking is comparatively 400-900 degreeC. By setting the temperature lower, the tact time until the thin film electrode is obtained can be further shortened, and a relatively inexpensive thin film electrode can be obtained.

上述したように基板１１上に第１薄膜電極１２を形成した後、この第１薄膜電極１２上にはゾルゲル法により誘電体材料膜１３が形成される。誘電体材料としては従来から用いられているＰＺＴやＢＳＴの他に、ＰＬＺＴ系のいわゆるペロブスカイト型結晶構造を有する複合酸化物や、Ｂｉ層状ペロブスカイト型結晶構造を有する複合酸化物も適用できる。このような誘電体材料を用いてゾルゲル法により所定の厚さの誘電体材料膜１３を形成する。特に、この膜を形成する組成物がＢＳＴであるＢａ1-XＳｒXＴｉYＯ3であれば、これを塗布、乾燥して、４５０〜８００℃の比較的低い温度で焼成することができ、高誘電率かつ高絶縁性のＢａ1-XＳｒXＴｉYＯ3薄膜を更に容易に形成することができるので好ましい。 After the first thin film electrode 12 is formed on the substrate 11 as described above, the dielectric material film 13 is formed on the first thin film electrode 12 by the sol-gel method. As the dielectric material, besides PZT and BST which have been conventionally used, a complex oxide having a so-called perovskite crystal structure of a PLZT system or a complex oxide having a Bi layered perovskite crystal structure can be applied. Using such a dielectric material, a dielectric material film 13 having a predetermined thickness is formed by a sol-gel method. In particular, if the composition forming this film is Ba 1-X Sr X Ti Y O 3 which is BST, it can be applied, dried and fired at a relatively low temperature of 450 to 800 ° C. A high dielectric constant and high insulating Ba 1-X Sr X Ti Y O 3 thin film can be formed more easily, which is preferable.

そして、このように得られた誘電体材料膜１３上には上述した粒径が１〜４０ｎｍの金属微粒子を水に分散させた薄膜電極用ペーストを更に塗布して所定の厚さに成膜し、その後に熱処理して金属微粒子を焼成することにより誘電体材料膜１３上に第２薄膜電極１４を形成する。この第２薄膜電極１４の具体的な成膜手順は上述した第１薄膜電極１２の成膜手順と同一であり、このようにして第１薄膜電極１２と誘電体材料膜１３と第２薄膜電極１４を有する薄膜素子１０を得ることができる。
この薄膜素子１０の製造方法では、上述したように薄膜素子１０の電極を低コストで得ることができる。また、薄膜電極１２，１４及び誘電体材料膜１３が非真空状態で形成され得ることから電極を真空スパッタで行われる従来に比較してその製造工程を単純化させることができる。そして、比較的低温で薄膜電極１２，１４及び誘電体材料膜１３を形成し得ることから、短いタクトタイムで薄膜素子１０を得ることができ、その単価を安価なものとすることができる。 On the dielectric material film 13 thus obtained, a thin film electrode paste in which the metal fine particles having a particle diameter of 1 to 40 nm are dispersed in water is further applied to form a film having a predetermined thickness. Thereafter, the second thin film electrode 14 is formed on the dielectric material film 13 by baking the fine metal particles by heat treatment. The specific film formation procedure of the second thin film electrode 14 is the same as the film formation procedure of the first thin film electrode 12 described above, and thus the first thin film electrode 12, the dielectric material film 13, and the second thin film electrode. The thin film element 10 having 14 can be obtained.
In the method for manufacturing the thin film element 10, as described above, the electrode of the thin film element 10 can be obtained at low cost. Further, since the thin film electrodes 12 and 14 and the dielectric material film 13 can be formed in a non-vacuum state, the manufacturing process can be simplified as compared with the conventional case where the electrodes are formed by vacuum sputtering. Since the thin film electrodes 12 and 14 and the dielectric material film 13 can be formed at a relatively low temperature, the thin film element 10 can be obtained with a short tact time, and the unit price can be reduced.

なお、上述した実施の形態では、所定の厚さの誘電体材料膜１３をゾルゲル法により第１薄膜電極１２上に形成する場合を示したが、粒径が１〜６０ｎｍの誘電体微粒子を溶媒に分散させた誘電体ペーストを準備し、第１薄膜電極１２の上面にその誘電体ペーストを塗布して所定の厚さに成膜し、熱処理により誘電体ペーストにおける溶媒を除去して誘電体微粒子を焼成することにより第１薄膜電極１２上に薄膜誘電体材料膜１３を形成するようにしてもよい。このような薄膜素子の製造方法では、粒径が１〜６０ｎｍの誘電体微粒子を溶媒に分散させた誘電体ペーストを成膜して焼成するので、その焼成温度を比較的低く設定することにより誘電体材料膜１３を得るまでのタクトタイムを更に短縮させることができる。   In the above-described embodiment, the case where the dielectric material film 13 having a predetermined thickness is formed on the first thin film electrode 12 by the sol-gel method has been described. However, dielectric fine particles having a particle diameter of 1 to 60 nm are used as the solvent. A dielectric paste dispersed in the first thin film electrode 12 is prepared, and the dielectric paste is applied to the upper surface of the first thin film electrode 12 to form a predetermined thickness, and the solvent in the dielectric paste is removed by heat treatment to form dielectric fine particles. The thin film dielectric material film 13 may be formed on the first thin film electrode 12 by baking. In such a method of manufacturing a thin film element, a dielectric paste in which dielectric fine particles having a particle diameter of 1 to 60 nm are dispersed in a solvent is formed and fired. Therefore, the dielectric temperature can be set by setting the firing temperature relatively low. The tact time until the body material film 13 is obtained can be further shortened.

この場合、第２薄膜電極１４は、上述した本発明の薄膜電極の製造方法により得られたものに限らず、スパッタリング法、ＭＯＣＶＤ法、真空蒸着法により製造しても良い。このような方法により第２薄膜電極１４を得ることにより、薄膜電極１２，１４を真空スパッタで形成する従来に比較してその製造工程を単純化させることができ、かつ比較的低温で薄膜電極１２，１４及び誘電体材料膜１３を形成し得ることから、更に短いタクトタイムで薄膜素子を得ることができ、その単価を安価なものとすることができる。
ここで、スパッタリング法による薄膜電極の具体的な製造方法は、各電極材のスパッタリング用ターゲットを用い、ＤＣスパッタリング法にて各基板に成膜する方法である。また、ＭＯＣＶＤ法による薄膜電極の具体的な製造方法は、各金属のβジケトン錯体、シクロペンタジエン系錯体の固体昇華法で成膜するか、又はこれを有機溶剤に溶かした溶液を用いる液体供給法にて各基板に成膜する方法である。更に、真空蒸着法による薄膜電極の具体的な製造方法は、各金属を真空中で熔解し、各基板に成膜を行う方法である。 In this case, the second thin film electrode 14 is not limited to the one obtained by the thin film electrode production method of the present invention described above, and may be produced by a sputtering method, an MOCVD method, or a vacuum evaporation method. By obtaining the second thin film electrode 14 by such a method, the manufacturing process can be simplified as compared with the conventional method in which the thin film electrodes 12 and 14 are formed by vacuum sputtering, and the thin film electrode 12 can be obtained at a relatively low temperature. 14 and the dielectric material film 13 can be formed, so that a thin film element can be obtained with a shorter tact time and the unit price can be reduced.
Here, the specific manufacturing method of the thin film electrode by a sputtering method is a method of forming a film on each substrate by a DC sputtering method using a sputtering target of each electrode material. In addition, a specific method for producing a thin film electrode by MOCVD is a liquid supply method using a solid sublimation method of a β-diketone complex or a cyclopentadiene complex of each metal, or a solution obtained by dissolving this in an organic solvent. In this method, a film is formed on each substrate. Furthermore, the concrete manufacturing method of the thin film electrode by a vacuum evaporation method is a method of melting each metal in a vacuum and forming a film on each substrate.

次に、次の実施例１〜５により本発明の薄膜電極用ペーストが４００〜９００℃の比較的低い温度で焼成し得ることを確認した。
＜参考例１＞
Ｐｔ原料としてＨ2ＰｔＣｌ6，６Ｈ2Ｏを１グラム用意し、これを０．３リットルの水に溶解させてＰｔ含有水溶液を調製した。この水溶液に分散剤としてのＰＶＰ（Ｃ6Ｈ9ＮＯ）を１グラム添加した後攪拌して混合した。その後、その混合液に還元剤としてのＣ2Ｈ5ＯＨを１００グラム入れてＰｔイオンを還元してＰｔの粒子を析出させ、粒径が１〜４０ｎｍのＰｔ粒子が分散したコロイド溶液を作製した。このコロイド溶液を遠心分離により固液分離し、固形分としてのＰｔ粒子を取り出し水と混合することにより粒径が１〜４０ｎｍのＰｔ金属微粒子を含むペーストを調製した。このペーストを参考例１とした。 Next, it confirmed that the paste for thin film electrodes of this invention could be baked at the comparatively low temperature of 400-900 degreeC by the following Examples 1-5.
< Reference Example 1>
One gram of H 2 PtCl 6 , 6H 2 O was prepared as a Pt raw material and dissolved in 0.3 liter of water to prepare a Pt-containing aqueous solution. One gram of PVP (C 6 H 9 NO) as a dispersant was added to this aqueous solution, and then stirred and mixed. Thereafter, 100 g of C 2 H 5 OH as a reducing agent was added to the mixed solution, Pt ions were reduced to precipitate Pt particles, and a colloidal solution in which Pt particles having a particle size of 1 to 40 nm were dispersed was prepared. . This colloidal solution was subjected to solid-liquid separation by centrifugation, and Pt particles as a solid content were taken out and mixed with water to prepare a paste containing Pt metal fine particles having a particle diameter of 1 to 40 nm. This paste was designated as Reference Example 1.

＜参考例２＞
Ａｕ原料としてＨＡｕＣｌ4，４Ｈ2Ｏを１グラム用意し、これを０．３リットルの水に溶解させてＡｕ含有水溶液を調製した。この水溶液に分散剤としてのＮａ3Ｃ6Ｈ5Ｏ7を５グラム添加した後攪拌して混合した。その後、その混合液に還元剤としてのＮａ3Ｃ6Ｈ5Ｏ7を５グラム入れてＡｕイオンを還元してＡｕの粒子を析出させ、粒径が１〜４０ｎｍのＡｕ粒子が分散したコロイド溶液を作製した。このコロイド溶液を遠心分離により固液分離し、固形分としてのＡｕ粒子を取り出し水と混合することにより粒径が１〜４０ｎｍのＡｕ金属微粒子を含むペーストを調製した。このペーストを参考例２とした。 < Reference Example 2>
One gram of HAuCl 4 and 4H 2 O was prepared as an Au raw material, and this was dissolved in 0.3 liter of water to prepare an Au-containing aqueous solution. To this aqueous solution, 5 g of Na 3 C 6 H 5 O 7 as a dispersant was added and then stirred and mixed. Thereafter, 5 grams of Na 3 C 6 H 5 O 7 as a reducing agent is added to the mixed solution, Au ions are reduced to precipitate Au particles, and Au particles having a particle diameter of 1 to 40 nm are dispersed. Was made. This colloidal solution was subjected to solid-liquid separation by centrifugation, and Au particles as a solid content were taken out and mixed with water to prepare a paste containing Au metal fine particles having a particle diameter of 1 to 40 nm. This paste was used as Reference Example 2.

＜参考例３＞
Ａｇ原料としてＡｇＮＯ3を１グラム用意し、これを０．３リットルの水に溶解させてＡｇ含有水溶液を調製した。この水溶液に分散剤としてのＮａ3Ｃ6Ｈ5Ｏ7を５グラム添加した後攪拌して混合した。その後、その混合液に還元剤としてのＦｅＳＯ4を５グラム入れてＡｇイオンを還元してＡｇの粒子を析出させ、粒径が１〜４０ｎｍのＡｇ粒子が分散したコロイド溶液を作製した。このコロイド溶液を遠心分離により固液分離し、固形分としてのＡｇ粒子を取り出し水と混合することにより粒径が１〜４０ｎｍのＡｇ金属微粒子を含むペーストを調製した。このペーストを参考例３とした。 < Reference Example 3>
One gram of AgNO 3 was prepared as an Ag raw material and dissolved in 0.3 liter of water to prepare an Ag-containing aqueous solution. To this aqueous solution, 5 g of Na 3 C 6 H 5 O 7 as a dispersant was added and then stirred and mixed. Thereafter, 5 grams of FeSO 4 as a reducing agent was added to the mixed solution to reduce Ag ions to precipitate Ag particles, thereby preparing a colloidal solution in which Ag particles having a particle diameter of 1 to 40 nm were dispersed. This colloidal solution was subjected to solid-liquid separation by centrifugation, and Ag particles as a solid content were taken out and mixed with water to prepare a paste containing Ag metal fine particles having a particle diameter of 1 to 40 nm. This paste was designated as Reference Example 3.

＜参考例４＞
Ｐｄ原料としてＨ2ＰｄＣｌ4を１グラム用意し、これを０．３リットルの水に溶解させてＰｄ含有水溶液を調製した。この水溶液に分散剤としてのＰＶＰ（Ｃ6Ｈ9ＮＯ）を１グラム添加した後攪拌して混合した。その後、その混合液に還元剤としてのＣ2Ｈ5ＯＨを１００グラム入れてＰｄイオンを還元してＰｄの粒子を析出させ、粒径が１〜４０ｎｍのＰｄ粒子が分散したコロイド溶液を作製した。このコロイド溶液を遠心分離により固液分離し、固形分としてのＰｄ粒子を取り出し水と混合することにより粒径が１〜４０ｎｍのＰｄ金属微粒子を含むペーストを調製した。このペーストを参考例４とした。 < Reference Example 4>
One gram of H 2 PdCl 4 was prepared as a Pd raw material, and dissolved in 0.3 liter of water to prepare a Pd-containing aqueous solution. One gram of PVP (C 6 H 9 NO) as a dispersant was added to this aqueous solution, and then stirred and mixed. Thereafter, 100 g of C 2 H 5 OH as a reducing agent was added to the mixed solution, Pd ions were reduced to precipitate Pd particles, and a colloidal solution in which Pd particles having a particle size of 1 to 40 nm were dispersed was prepared. . This colloidal solution was subjected to solid-liquid separation by centrifugation, and Pd particles as a solid content were taken out and mixed with water to prepare a paste containing Pd metal fine particles having a particle diameter of 1 to 40 nm. This paste was designated as Reference Example 4.

＜実施例１＞
真空蒸着によりＮｉメタルを気化させて、アルキルナフタレン系のオイルにポリアミンを添加した溶媒中に吹き込んでＮｉ微粒子を析出させた。これにより、粒径が約１０ｎｍのＮｉ粒子が分散したコロイド溶液を作製した。このコロイド溶液を遠心分離により固液分離し、固形分としてのＮｉ粒子を取り出し水と混合することにより粒径が約１０ｎｍのＮｉ金属微粒子を含むペーストを調製した。このペーストを実施例１とした。 <Example 1>
Ni metal was vaporized by vacuum deposition, and Ni fine particles were precipitated by blowing into a solvent obtained by adding polyamine to an alkylnaphthalene-based oil. Thereby, a colloidal solution in which Ni particles having a particle size of about 10 nm were dispersed was produced. This colloidal solution was subjected to solid-liquid separation by centrifugation, and Ni particles as a solid content were taken out and mixed with water to prepare a paste containing Ni metal fine particles having a particle size of about 10 nm. This paste was designated as Example 1 .

＜評価試験１及び評価１＞
実施例１及び参考例１〜４におけるペーストの焼成温度をアルミナ基板上への塗布により調査した。その結果、参考例１のペーストは８００℃、参考例２のペーストは５００℃、参考例３のペーストは４００℃、参考例４のペーストは８００℃、実施例１のペーストは８００℃でそれぞれ焼結させることができた。よって、本発明の薄膜電極用ペーストでは、粒径が１〜４０ｎｍの金属微粒子を水に分散させることにより、４００〜９００℃の比較的低い温度で焼成することが可能になり、薄膜電極を得るまでのタクトタイムを短縮させることができることが判る。 <Evaluation Test 1 and Evaluation 1>
The firing temperature of the paste as in Example 1 and Reference Examples 1 to 4 were investigated by application to the alumina substrate. As a result, the paste of Reference Example 1 was baked at 800 ° C, the paste of Reference Example 2 was 500 ° C, the paste of Reference Example 3 was 400 ° C, the paste of Reference Example 4 was 800 ° C, and the paste of Example 1 was baked at 800 ° C. I was able to conclude. Therefore, the thin film electrode paste of the present invention can be fired at a relatively low temperature of 400 to 900 ° C. by dispersing metal fine particles having a particle diameter of 1 to 40 nm in water, thereby obtaining a thin film electrode. It can be seen that the tact time can be shortened.

次に、上述した薄膜電極用ペーストを用いて次の参考例５〜７により薄膜素子を製造した。
＜参考例５＞
参考例１で作製したＰｔペーストを用いて５００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉ上に塗布、乾燥を繰り返し、最後に８００℃で焼結し２００ｎｍのＰｔ電極膜を得た。この膜の上にさらに市販のＰＺＴゾルゲル液で２００ｎｍのＰＺＴ膜を形成し、先述の方法で更に上部電極として２００ｎｍのＰｔ電極膜を形成し、ＰＺＴ薄膜素子を得た。この薄膜素子を参考例５とした。 Next, the thin film element was manufactured by the following reference examples 5-7 using the paste for thin film electrodes mentioned above.
< Reference Example 5 >
Using the Pt paste prepared in Reference Example 1, a silicon wafer with a thermal oxide film of 500 nm: repeatedly applied and dried on SiO 2 (500 nm) / Si, and finally sintered at 800 ° C. to obtain a 200 nm Pt electrode film. It was. A 200 nm PZT film was further formed on this film with a commercially available PZT sol-gel solution, and a 200 nm Pt electrode film was further formed as an upper electrode by the above-described method to obtain a PZT thin film element. This thin film element was referred to as Reference Example 5 .

＜参考例６＞
参考例１で作製したＰｔペーストを用いて５００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉ上に塗布、乾燥を繰り返し、最後に８００℃で焼結し２００ｎｍのＰｔ電極膜を得た。この膜の上にさらに市販のＢＳＴゾルゲル液で２００ｎｍのＢＳＴ膜を形成し、先述の方法で更に上部電極として２００ｎｍのＰｔ電極膜を形成し、ＢＳＴ薄膜素子を得た。この薄膜素子を参考例６とした。 < Reference Example 6 >
Using the Pt paste prepared in Reference Example 1, a silicon wafer with a thermal oxide film of 500 nm: repeatedly applied and dried on SiO 2 (500 nm) / Si, and finally sintered at 800 ° C. to obtain a 200 nm Pt electrode film. It was. A 200 nm BST film was further formed on this film with a commercially available BST sol-gel solution, and a 200 nm Pt electrode film was further formed as the upper electrode by the above-mentioned method to obtain a BST thin film element. This thin film element was referred to as Reference Example 6 .

＜参考例７＞
参考例１で作製したＰｔペーストを用いて５００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉ上に塗布、乾燥を繰り返し、最後に８００℃で焼結し２００ｎｍのＰｔ電極膜を得た。この膜の上にさらに市販のＢＬＴゾルゲル液で２００ｎｍのＢＬＴ膜を形成し、先述の方法で更に上部電極として２００ｎｍのＰｔ電極膜を形成し、ＢＬＴ薄膜素子を得た。この薄膜素子を参考例７とした。 < Reference Example 7 >
Using the Pt paste prepared in Reference Example 1, a silicon wafer with a thermal oxide film of 500 nm: repeatedly applied and dried on SiO 2 (500 nm) / Si, and finally sintered at 800 ° C. to obtain a 200 nm Pt electrode film. It was. A 200 nm BLT film was further formed on this film with a commercially available BLT sol-gel solution, and a 200 nm Pt electrode film was further formed as an upper electrode by the above-described method to obtain a BLT thin film element. This thin film element was referred to as Reference Example 7 .

＜評価試験２及び評価２＞
参考例５における薄膜素子をラジアントテクノロジー社製強誘電体評価テスタＲＴ６０００で評価したところ、この参考例５の薄膜素子では、その残留分極値が２３．７ｕＣ／ｃｍ2であり、抗電界が４８．７ｋＶ／ｃｍであった。またＬＣＲメーターで比誘電率を測定したところ、１０４８であった。
また、参考例６の薄膜素子をＬＣＲメーターで評価し、ＢＳＴ膜の比誘電率を測定したところ、３５６であった。
更に、参考例７における薄膜素子をラジアントテクノロジー社製強誘電体評価テスタＲＴ６０００で評価したところ、この参考例７の薄膜素子では、残留分極値が１７．７ｕＣ／ｃｍ2であり、抗電界が５３．５ｋＶ／ｃｍであった。
よって、本発明の薄膜素子の製造方法では、薄膜電極及び誘電体材料膜が非真空状態で形成され得ることから電極を真空スパッタで行われる従来に比較してその製造工程を単純化させることができ、かつ比較的低温で薄膜電極１２，１４及び誘電体材料膜１３を形成し得ることから、短いタクトタイムで薄膜素子を得ることができることが判る。 <Evaluation Test 2 and Evaluation 2>
When the thin film element in Reference Example 5 was evaluated with a ferroelectric evaluation tester RT6000 manufactured by Radiant Technology, the thin film element of Reference Example 5 had a remanent polarization value of 23.7 uC / cm 2 and a coercive electric field of 48. It was 7 kV / cm. Moreover, it was 1048 when the dielectric constant was measured with the LCR meter.
The thin film element of Reference Example 6 was evaluated with an LCR meter, and the relative dielectric constant of the BST film was measured.
Furthermore, when the thin film element in Reference Example 7 was evaluated by a ferroelectric evaluation tester RT6000 manufactured by Radiant Technology, the thin film element of Reference Example 7 had a remanent polarization value of 17.7 uC / cm 2 and a coercive electric field of 53. 0.5 kV / cm.
Therefore, in the thin film element manufacturing method of the present invention, since the thin film electrode and the dielectric material film can be formed in a non-vacuum state, the manufacturing process can be simplified as compared with the conventional method in which the electrode is formed by vacuum sputtering. Since the thin film electrodes 12 and 14 and the dielectric material film 13 can be formed at a relatively low temperature, it can be seen that a thin film element can be obtained with a short tact time.

続いて、次の参考例８及び９により誘電体微粒子を溶媒に分散させた誘電体ペーストが比較的低い温度で焼成し得ることを確認した。
＜参考例８＞
平均粒径１μｍの市販のＢａＴｉＯ3粉末をエタノールを５：９５の重量比で混合し、ＺｒＯ2ボールを混ぜて７２時間ボールミルで粉砕し、平均粒径３０ｎｍのＢａＴｉＯ3粒子がエタノールに分散したペーストを調製した。この誘電体ペーストを参考例８とした。
＜参考例９＞
平均粒径１μｍの市販のＰｂＺｒ0.52Ｔｉ0.48Ｏ8粉末をエタノールを５：９５の重量比で混合し、ＺｒＯ2ボールを混ぜて７２時間ボールミルで粉砕し、平均粒径３０ｎｍのＰＺＴ粒子がエタノールに分散したペーストを調製した。この誘電体ペーストを参考例９とした。 Subsequently, it was confirmed in the following Reference Examples 8 and 9 that the dielectric paste in which the dielectric fine particles were dispersed in the solvent could be fired at a relatively low temperature.
< Reference Example 8 >
A paste in which commercially available BaTiO 3 powder with an average particle diameter of 1 μm is mixed with ethanol in a weight ratio of 5:95, mixed with ZrO 2 balls and pulverized with a ball mill for 72 hours, and BaTiO 3 particles with an average particle diameter of 30 nm are dispersed in ethanol. Was prepared. This dielectric paste was referred to as Reference Example 8 .
< Reference Example 9 >
Commercially available PbZr 0.52 Ti 0.48 O 8 powder with an average particle size of 1 μm is mixed with ethanol at a weight ratio of 5:95, mixed with ZrO 2 balls and pulverized with a ball mill for 72 hours. A dispersed paste was prepared. This dielectric paste was referred to as Reference Example 9 .

＜評価試験３及び評価３＞
参考例８及び９における誘電体ペーストの焼成温度をアルミナ基板上への塗布により調査した。その結果、参考例８の誘電体ペーストは９００℃、参考例９の誘電体ペーストは８００℃でそれぞれ焼結させることができた。よって、本発明の誘電体ペーストでは、粒径が１〜６０ｎｍの誘電体微粒子を溶媒に分散させることにより、比較的低い温度で焼成することが可能になり、更には完全緻密化する必要のない用途にはより低温での焼成も可能であり、誘電体材料膜を得るまでのタクトタイムを短縮させることができることが判る。 <Evaluation Test 3 and Evaluation 3>
The firing temperature of the dielectric paste in Reference Examples 8 and 9 was investigated by coating on an alumina substrate. As a result, the dielectric paste of Reference Example 8 could be sintered at 900 ° C., and the dielectric paste of Reference Example 9 could be sintered at 800 ° C., respectively. Therefore, the dielectric paste of the present invention can be fired at a relatively low temperature by dispersing dielectric fine particles having a particle diameter of 1 to 60 nm in a solvent, and further does not need to be completely densified. It can be seen that firing can be performed at a lower temperature for use, and the tact time until a dielectric material film is obtained can be shortened.

次に、誘電体微粒子を溶媒に分散させた誘電体ペーストを用いて、次の参考例１０〜５１により薄膜素子を製造した。
＜参考例１０＞
５００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉ上に常温によるスパッタリング法により２００ｎｍのＰｔ電極膜を得た。この膜の上に参考例８で作成したＢａＴｉＯ3粒子が分散した誘電体ペーストを塗布、乾燥した後に３００℃で焼結し厚さが３００ｎｍの誘電体材料膜を形成した。その後、この誘電体材料膜上にスパッタリング法により上部電極として２００ｎｍのＰｔ電極膜を形成して薄膜素子を得た。この薄膜素子を参考例１０とした。 Next, a thin film element was manufactured according to Reference Examples 10 to 51 below using a dielectric paste in which dielectric fine particles were dispersed in a solvent.
< Reference Example 10 >
A silicon wafer with a thermal oxide film of 500 nm: A Pt electrode film of 200 nm was obtained by sputtering at room temperature on SiO 2 (500 nm) / Si. On this film, the dielectric paste prepared in Reference Example 8 in which BaTiO 3 particles were dispersed was applied, dried, and then sintered at 300 ° C. to form a dielectric material film having a thickness of 300 nm. Thereafter, a 200-nm Pt electrode film was formed as an upper electrode on the dielectric material film by sputtering to obtain a thin film element. This thin film element was determined as Reference Example 10 .

＜参考例１１＞
Ｐｔ電極膜の上に塗布、乾燥したＢａＴｉＯ3粒子が分散した誘電体ペーストを５００℃で焼結させ厚さが３００ｎｍの誘電体材料膜を形成したことを除いて参考例１０と同一の条件及び手順で薄膜素子を得た。この薄膜素子を参考例１１とした。
＜参考例１２＞
Ｐｔ電極膜の上に塗布、乾燥したＢａＴｉＯ3粒子が分散した誘電体ペーストを７００℃で焼結させ厚さが３００ｎｍの誘電体材料膜を形成したことを除いて参考例１０と同一の条件及び手順で薄膜素子を得た。この薄膜素子を参考例１２とした。 < Reference Example 11 >
The same conditions as in Reference Example 10 except that a dielectric paste in which BaTiO 3 particles coated and dried on a Pt electrode film were dispersed was sintered at 500 ° C. to form a dielectric material film having a thickness of 300 nm. A thin film element was obtained by the procedure. This thin film element was referred to as Reference Example 11 .
< Reference Example 12 >
The same conditions as in Reference Example 10 except that a dielectric material film having a thickness of 300 nm was formed by sintering a dielectric paste dispersed with BaTiO 3 particles coated and dried on a Pt electrode film at 700 ° C. A thin film element was obtained by the procedure. This thin film element was determined as Reference Example 12 .

＜参考例１３＞
ＢａＴｉＯ3粒子が分散した誘電体ペーストを３００℃で焼結させることにより形成された誘電体材料膜上に、参考例１で作製したＰｔペーストを塗布、乾燥を繰り返した後に８００℃で焼結し２００ｎｍの上部電極としてのＰｔ電極膜を得たことを除いて参考例１０と同一の条件及び手順で薄膜素子を得た。この薄膜素子を参考例１３とした。
＜参考例１４＞
ＢａＴｉＯ3粒子が分散した誘電体ペーストを３００℃で焼結させることにより形成された誘電体材料膜上に、参考例２で作製したＡｕペーストを塗布、乾燥を繰り返した後に５００℃で焼結し２００ｎｍの上部電極としてのＡｕ電極膜を得たことを除いて参考例１０と同一の条件及び手順で薄膜素子を得た。この薄膜素子を参考例１４とした。 < Reference Example 13 >
The Pt paste produced in Reference Example 1 was applied on the dielectric material film formed by sintering the dielectric paste in which BaTiO 3 particles were dispersed at 300 ° C., and dried at 800 ° C. after repeated drying. A thin film element was obtained under the same conditions and procedures as in Reference Example 10 except that a Pt electrode film as a 200 nm upper electrode was obtained. This thin film element was referred to as Reference Example 13 .
< Reference Example 14 >
On the dielectric material film formed by sintering the dielectric paste in which BaTiO 3 particles are dispersed at 300 ° C., the Au paste prepared in Reference Example 2 is applied and dried, and then sintered at 500 ° C. A thin film element was obtained under the same conditions and procedure as in Reference Example 10 except that an Au electrode film as a 200 nm upper electrode was obtained. This thin film element was determined as Reference Example 14 .

＜参考例１５＞
ＢａＴｉＯ3粒子が分散した誘電体ペーストを３００℃で焼結させることにより形成された誘電体材料膜上に、参考例３で作製したＡｇペーストを塗布、乾燥を繰り返した後に４００℃で焼結し２００ｎｍの上部電極としてのＡｇ電極膜を得たことを除いて参考例１０と同一の条件及び手順で薄膜素子を得た。この薄膜素子を参考例１５とした。
＜参考例１６＞
ＢａＴｉＯ3粒子が分散した誘電体ペーストを３００℃で焼結させることにより形成された誘電体材料膜上に、参考例４で作製したＰｄペーストを塗布、乾燥を繰り返した後に８００℃で焼結し２００ｎｍの上部電極としてのＰｄ電極膜を得たことを除いて参考例１０と同一の条件及び手順で薄膜素子を得た。この薄膜素子を参考例１６とした。 < Reference Example 15 >
On the dielectric material film formed by sintering the dielectric paste in which BaTiO 3 particles are dispersed at 300 ° C., the Ag paste prepared in Reference Example 3 was applied, dried, and then sintered at 400 ° C. A thin film element was obtained under the same conditions and procedure as in Reference Example 10 except that an Ag electrode film as a 200 nm upper electrode was obtained. This thin film element was determined as Reference Example 15 .
< Reference Example 16 >
The Pd paste prepared in Reference Example 4 was applied on the dielectric material film formed by sintering the dielectric paste in which the BaTiO 3 particles were dispersed at 300 ° C., dried, and then sintered at 800 ° C. A thin film element was obtained under the same conditions and procedures as in Reference Example 10 except that a Pd electrode film as a 200 nm upper electrode was obtained. This thin film element was determined as Reference Example 16 .

＜参考例１７＞
ＢａＴｉＯ3粒子が分散した誘電体ペーストを３００℃で焼結させることにより形成された誘電体材料膜上に、実施例１で作製したＮｉペーストを塗布、乾燥を繰り返した後に５００℃で焼結し２００ｎｍの上部電極としてのＮｉ電極膜を得たことを除いて参考例１０と同一の条件及び手順で薄膜素子を得た。この薄膜素子を参考例１７とした。
＜参考例１８＞
参考例１で作製したＰｔペーストを用いて５００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉ上に塗布、乾燥を繰り返し、最後に８００℃で焼結し２００ｎｍのＰｔ電極膜を得た。この膜の上に参考例８で作成したＢａＴｉＯ3粒子が分散した誘電体ペーストを塗布、乾燥した後に３００℃で焼結し厚さが３００ｎｍの誘電体材料膜を形成した。その後、この誘電体材料膜上に、参考例１で作製したＰｔペーストを塗布、乾燥を繰り返した後に８００℃で焼結し２００ｎｍの上部電極としてのＰｔ電極膜を形成して薄膜素子を得た。この薄膜素子を参考例１８とした。 < Reference Example 17 >
On the dielectric material film formed by sintering the dielectric paste in which BaTiO 3 particles are dispersed at 300 ° C., the Ni paste prepared in Example 1 was applied, dried, and then sintered at 500 ° C. A thin film element was obtained under the same conditions and procedures as in Reference Example 10 except that a Ni electrode film as a 200 nm upper electrode was obtained. This thin film element was determined as Reference Example 17 .
< Reference Example 18 >
Using the Pt paste prepared in Reference Example 1, a silicon wafer with a thermal oxide film of 500 nm: repeatedly applied and dried on SiO 2 (500 nm) / Si, and finally sintered at 800 ° C. to obtain a 200 nm Pt electrode film. It was. On this film, the dielectric paste prepared in Reference Example 8 in which BaTiO 3 particles were dispersed was applied, dried, and then sintered at 300 ° C. to form a dielectric material film having a thickness of 300 nm. Thereafter, the Pt paste prepared in Reference Example 1 was applied on the dielectric material film, dried, and then sintered at 800 ° C. to form a Pt electrode film as a 200 nm upper electrode to obtain a thin film element. . This thin film element was determined as Reference Example 18 .

＜参考例１９＞
参考例２で作製したＡｕペーストを用いて５００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉ上に塗布、乾燥を繰り返し、最後に５００℃で焼結し２００ｎｍのＡｕ電極膜を得た。この膜の上に参考例８で作成したＢａＴｉＯ3粒子が分散した誘電体ペーストを塗布、乾燥した後に３００℃で焼結し厚さが３００ｎｍの誘電体材料膜を形成した。その後、この誘電体材料膜上に、参考例２で作製したＡｕペーストを塗布、乾燥を繰り返した後に５００℃で焼結し２００ｎｍの上部電極としてのＡｕ電極膜を形成して薄膜素子を得た。この薄膜素子を参考例１９とした。
＜参考例２０＞
参考例３で作製したＡｇペーストを用いて４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉ上に塗布、乾燥を繰り返し、最後に４００℃で焼結し２００ｎｍのＡｇ電極膜を得た。この膜の上に参考例８で作成したＢａＴｉＯ3粒子が分散した誘電体ペーストを塗布、乾燥した後に３００℃で焼結し厚さが３００ｎｍの誘電体材料膜を形成した。その後、この誘電体材料膜上に、参考例３で作製したＡｇペーストを塗布、乾燥を繰り返した後に４００℃で焼結し２００ｎｍの上部電極としてのＡｇ電極膜を形成して薄膜素子を得た。この薄膜素子を参考例２０とした。 < Reference Example 19 >
Using the Au paste prepared in Reference Example 2, a silicon wafer with a thermal oxide film of 500 nm: repeatedly applied and dried on SiO 2 (500 nm) / Si, and finally sintered at 500 ° C. to obtain a 200 nm Au electrode film. It was. On this film, the dielectric paste prepared in Reference Example 8 in which BaTiO 3 particles were dispersed was applied, dried, and then sintered at 300 ° C. to form a dielectric material film having a thickness of 300 nm. Thereafter, the Au paste prepared in Reference Example 2 was applied on the dielectric material film, dried, and then sintered at 500 ° C. to form an Au electrode film as an upper electrode of 200 nm to obtain a thin film element. . This thin film element was determined as Reference Example 19 .
< Reference Example 20 >
Using the Ag paste prepared in Reference Example 3, a silicon wafer with a 400 nm thermal oxide film: repeatedly coated and dried on SiO 2 (500 nm) / Si, and finally sintered at 400 ° C. to obtain a 200 nm Ag electrode film. It was. On this film, the dielectric paste prepared in Reference Example 8 in which BaTiO 3 particles were dispersed was applied, dried, and then sintered at 300 ° C. to form a dielectric material film having a thickness of 300 nm. Thereafter, the Ag paste prepared in Reference Example 3 was applied on the dielectric material film, dried, and then sintered at 400 ° C. to form an Ag electrode film as an upper electrode of 200 nm to obtain a thin film element. . This thin film element was referred to as Reference Example 20 .

＜参考例２１＞
参考例４で作製したＰｄペーストを用いて４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉ上に塗布、乾燥を繰り返し、最後に８００℃で焼結し２００ｎｍのＰｄ電極膜を得た。この膜の上に参考例８で作成したＢａＴｉＯ3粒子が分散した誘電体ペーストを塗布、乾燥した後に３００℃で焼結し厚さが３００ｎｍの誘電体材料膜を形成した。その後、この誘電体材料膜上に、参考例４で作製したＰｄペーストを塗布、乾燥を繰り返した後に８００℃で焼結し２００ｎｍの上部電極としてのＰｄ電極膜を形成して薄膜素子を得た。この薄膜素子を参考例２１とした。
＜実施例２＞
実施例１で作製したＮｉペーストを用いて４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉ上に塗布、乾燥を繰り返し、最後に５００℃で焼結し２００ｎｍのＮｉ電極膜を得た。この膜の上に参考例８で作成したＢａＴｉＯ3粒子が分散した誘電体ペーストを塗布、乾燥した後に３００℃で焼結し厚さが３００ｎｍの誘電体材料膜を形成した。その後、この誘電体材料膜上に、実施例１で作製したＮｉペーストを塗布、乾燥を繰り返した後に５００℃で焼結し２００ｎｍの上部電極としてのＮｉ電極膜を形成して薄膜素子を得た。この薄膜素子を実施例２とした。 < Reference Example 21 >
Using the Pd paste prepared in Reference Example 4, a silicon wafer with a 400 nm thermal oxide film: repeatedly coated and dried on SiO 2 (500 nm) / Si, and finally sintered at 800 ° C. to obtain a 200 nm Pd electrode film. It was. On this film, the dielectric paste prepared in Reference Example 8 in which BaTiO 3 particles were dispersed was applied, dried, and then sintered at 300 ° C. to form a dielectric material film having a thickness of 300 nm. Thereafter, the Pd paste prepared in Reference Example 4 was applied on the dielectric material film, dried, and then sintered at 800 ° C. to form a Pd electrode film as a 200 nm upper electrode to obtain a thin film element. . This thin film element was referred to as Reference Example 21 .
<Example 2 >
Using the Ni paste prepared in Example 1 , a silicon wafer with a 400 nm thermal oxide film: repeatedly coated and dried on SiO 2 (500 nm) / Si, and finally sintered at 500 ° C. to obtain a 200 nm Ni electrode film. It was. On this film, the dielectric paste prepared in Reference Example 8 in which BaTiO 3 particles were dispersed was applied, dried, and then sintered at 300 ° C. to form a dielectric material film having a thickness of 300 nm. Thereafter, the Ni paste prepared in Example 1 was applied on the dielectric material film, dried, and then sintered at 500 ° C. to form a Ni electrode film as an upper electrode of 200 nm to obtain a thin film element. . This thin film element was referred to as Example 2 .

＜参考例２２＞
ＳｉＯ2から成るシリコンウェーハ上に常温によるスパッタリング法により２００ｎｍのＩＴＯ（Indium Tin Oxide）電極膜を得た。この膜の上に参考例８で作成したＢａＴｉＯ3粒子が分散した誘電体ペーストを塗布、乾燥した後に２００℃で焼結し厚さが３００ｎｍの誘電体材料膜を形成した。その後、この誘電体材料膜上にスパッタリング法により上部電極として２００ｎｍのＩＴＯ電極膜を形成して薄膜素子を得た。この薄膜素子を参考例２２とした。
＜参考例２３＞
４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉに代えてＡｌ2Ｏ3から成る基板を用いたことを除いて参考例１８と同一の条件及び手順により薄膜素子を得た。この薄膜素子を参考例２３とした。 < Reference Example 22 >
A 200 nm ITO (Indium Tin Oxide) electrode film was obtained on a silicon wafer made of SiO 2 by sputtering at room temperature. On this film, the dielectric paste with dispersed BaTiO 3 particles prepared in Reference Example 8 was applied, dried and then sintered at 200 ° C. to form a dielectric material film having a thickness of 300 nm. Thereafter, a 200 nm ITO electrode film was formed as an upper electrode on the dielectric material film by sputtering to obtain a thin film element. This thin film element was determined as Reference Example 22 .
< Reference Example 23 >
Silicon wafer with 400 nm thermal oxide film: A thin film element was obtained under the same conditions and procedures as in Reference Example 18 except that a substrate made of Al 2 O 3 was used instead of SiO 2 (500 nm) / Si. This thin film element was determined as Reference Example 23 .

＜参考例２４＞
４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉに代えてＡｌ2Ｏ3から成る基板を用いたことを除いて参考例１９と同一の条件及び手順により薄膜素子を得た。この薄膜素子を参考例２４とした。
＜参考例２５＞
４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉに代えてＡｌ2Ｏ3から成る基板を用いたことを除いて参考例２０と同一の条件及び手順により薄膜素子を得た。この薄膜素子を参考例２５とした。 < Reference Example 24 >
Silicon wafer with 400 nm thermal oxide film: A thin film element was obtained under the same conditions and procedure as in Reference Example 19 except that a substrate made of Al 2 O 3 was used instead of SiO 2 (500 nm) / Si. This thin film element was determined as Reference Example 24 .
< Reference Example 25 >
Silicon wafer with 400 nm thermal oxide film: A thin film element was obtained under the same conditions and procedure as in Reference Example 20 except that a substrate made of Al 2 O 3 was used instead of SiO 2 (500 nm) / Si. This thin film element was determined as Reference Example 25 .

＜参考例２６＞
４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉに代えてＡｌ2Ｏ3から成る基板を用いたことを除いて参考例２１と同一の条件及び手順により薄膜素子を得た。この薄膜素子を参考例２６とした。
＜実施例３＞
４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉに代えてＡｌ2Ｏ3から成る基板を用いたことを除いて実施例２と同一の条件及び手順により薄膜素子を得た。この薄膜素子を実施例３とした。 < Reference Example 26 >
Silicon wafer with 400 nm thermal oxide film: A thin film element was obtained under the same conditions and procedure as in Reference Example 21 except that a substrate made of Al 2 O 3 was used instead of SiO 2 (500 nm) / Si. This thin film element was determined as Reference Example 26 .
<Example 3 >
Silicon wafer with 400 nm thermal oxide film: A thin film element was obtained under the same conditions and procedure as in Example 2 except that a substrate made of Al 2 O 3 was used instead of SiO 2 (500 nm) / Si. This thin film element was referred to as Example 3 .

＜参考例２７＞
４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉに代えてＹＳＺから成る基板を用いたことを除いて参考例１８と同一の条件及び手順により薄膜素子を得た。この薄膜素子を参考例２７とした。
＜参考例２８＞
４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉに代えてＹＳＺから成る基板を用いたことを除いて参考例１９と同一の条件及び手順により薄膜素子を得た。この薄膜素子を参考例２８とした。 < Reference Example 27 >
Silicon wafer with 400 nm thermal oxide film: A thin film element was obtained under the same conditions and procedure as in Reference Example 18 except that a substrate made of YSZ was used instead of SiO 2 (500 nm) / Si. This thin film element was determined as Reference Example 27 .
< Reference Example 28 >
Silicon wafer with 400 nm thermal oxide film: A thin film element was obtained under the same conditions and procedures as in Reference Example 19 except that a substrate made of YSZ was used instead of SiO 2 (500 nm) / Si. This thin film element was determined as Reference Example 28 .

＜参考例２９＞
４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉに代えてＹＳＺから成る基板を用いたことを除いて参考例２０と同一の条件及び手順により薄膜素子を得た。この薄膜素子を参考例２９とした。
＜参考例３０＞
４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉに代えてＹＳＺから成る基板を用いたことを除いて参考例２１と同一の条件及び手順により薄膜素子を得た。この薄膜素子を参考例３０とした。 < Reference Example 29 >
Silicon wafer with 400 nm thermal oxide film: A thin film element was obtained under the same conditions and procedures as in Reference Example 20 except that a substrate made of YSZ was used instead of SiO 2 (500 nm) / Si. This thin film element was determined as Reference Example 29 .
< Reference Example 30 >
400 nm silicon wafer with a thermal oxide film: A thin film element was obtained under the same conditions and procedure as in Reference Example 21 except that a substrate made of YSZ was used instead of SiO 2 (500 nm) / Si. This thin film element was referred to as Reference Example 30 .

＜実施例４＞
４００ｎｍの熱酸化膜付きシリコンウェーハ：ＳｉＯ2（５００ｎｍ）／Ｓｉに代えてＹＳＺから成る基板を用いたことを除いて実施例２と同一の条件及び手順により薄膜素子を得た。この薄膜素子を実施例４とした。
＜実施例５〜実施例７、参考例３１〜参考例５１＞
参考例８で作成したＢａＴｉＯ3粒子が分散した誘電体ペーストに代えて参考例９で作成したＰＺＴ粒子が分散した誘電体ペーストを用いたことを除き、実施例２〜実施例４、参考例１０〜参考例３０と同一の条件及び手順によりそれぞれ薄膜素子を得た。これらの薄膜素子を実施例５〜実施例７、参考例３１〜参考例５１とした。
上述した実施例２〜実施例７、参考例１０〜参考例５１の内容を表１及び表２に示す。 <Example 4 >
400 nm silicon wafer with a thermal oxide film: A thin film element was obtained under the same conditions and procedure as in Example 2 except that a substrate made of YSZ was used instead of SiO 2 (500 nm) / Si. This thin film element was referred to as Example 4 .
<Example 5 to Example 7, Reference Example 31 to Reference Example 51 >
Example 2 to Example 4 and Reference Example 10 except that the dielectric paste with dispersed PZT particles prepared in Reference Example 9 was used instead of the dielectric paste with dispersed BaTiO 3 particles prepared in Reference Example 8. -Thin film elements were obtained under the same conditions and procedures as in Reference Example 30 . These thin film elements were referred to as Example 5 to Example 7, and Reference Example 31 to Reference Example 51 .
Tables 1 and 2 show the contents of Examples 2 to 7 and Reference Examples 10 to 51 described above.

Figure 0004670497
Figure 0004670497

Figure 0004670497
Figure 0004670497

＜評価試験４及び評価４＞
実施例２〜実施例７、参考例１０〜参考例５１における薄膜素子の比誘電率をＬＣＲメータによりそれぞれ測定した。 <Evaluation Test 4 and Evaluation 4>
The relative dielectric constants of the thin film elements in Examples 2 to 7 and Reference Examples 10 to 51 were measured with an LCR meter.

その結果、実施例２〜実施例４、参考例１０〜参考例３０におけるＢａＴｉＯ3膜における比誘電率は１５０〜３７０の特性が得られた。また、実施例５〜実施例７、参考例３１〜５１におけるＰＺＴ膜における比誘電率は３５０〜１２００の特性が得られた。
この結果から、良好な薄膜素子が本発明の方法により得られることが判る。
よって、本発明の薄膜素子の製造方法では、従来に比較してその製造工程を単純化させることができ、かつ短いタクトタイムで薄膜素子を得ることができることが判る。 As a result, the dielectric constants of the BaTiO 3 films in Examples 2 to 4 and Reference Examples 10 to 30 were 150 to 370. Moreover, the characteristic of 350-1200 was obtained for the dielectric constant in the PZT film | membrane in Examples 5-7 and Reference Examples 31-51 .
From this result, it can be seen that a good thin film element can be obtained by the method of the present invention.
Therefore, it can be seen that the thin film element manufacturing method of the present invention can simplify the manufacturing process as compared with the conventional method, and can obtain the thin film element with a short tact time.

本発明実施形態の薄膜素子の構造を示す断面図である。It is sectional drawing which shows the structure of the thin film element of embodiment of this invention.

１０ 薄膜素子
１１ 基板
１２ 第１薄膜電極（薄膜電極）
１３ 誘電体材料膜
１４ 第２薄膜電極（薄膜電極）
10 Thin Film Element 11 Substrate 12 First Thin Film Electrode (Thin Film Electrode)
13 Dielectric material film 14 Second thin film electrode (thin film electrode)

Claims (8)

Ｎｉメタルを気化させて、アルキルナフタレン系のオイルにポリアミンを添加した溶媒中に吹き込むことにより、粒径が１〜４０ｎｍのＮｉ粒子が分散したコロイド溶液を作製し、前記コロイド溶液を固液分離した後、分離したＮｉからなる粒径が１〜４０ｎｍの金属微粒子を水に分散させてなる薄膜電極用ペースト。 A colloidal solution in which Ni particles having a particle size of 1 to 40 nm are dispersed is prepared by vaporizing Ni metal and blowing into a solvent in which polyamine is added to an alkylnaphthalene-based oil, and the colloidal solution is separated into solid and liquid. after the separated Ni or Ranaru particle size 1~40nm of the fine metal particles the thin film electrode paste obtained by dispersing in water. 請求項１記載の粒径が１〜４０ｎｍのＮｉからなる金属微粒子を水に分散させた薄膜電極用ペーストを準備する工程と、
基板(11)の上面に前記ペーストを塗布して所定の厚さに成膜する工程と、
熱処理により前記ペーストにおける水を除去して前記金属微粒子を焼成することにより前記基板上に薄膜電極(12)を得る工程と
を含む薄膜電極の製造方法。 Preparing a paste for a thin film electrode in which metal fine particles made of Ni having a particle diameter of 1 to 40 nm according to claim 1 are dispersed in water;
Applying the paste on the upper surface of the substrate (11) to form a film with a predetermined thickness;
Method of manufacturing a thin film electrode and a step of obtaining a thin film electrode (12) on the substrate by sintering the metal fine particles the water is removed in the paste by heat treatment. 前記ペーストの塗布成膜がスピンコート法又はスプレー法又は液滴吐出法のいずれかによりなされる請求項２記載の薄膜電極の製造方法。 3. The method for producing a thin film electrode according to claim 2, wherein the paste is formed by a spin coating method, a spray method, or a droplet discharge method. 前記熱処理が大気圧雰囲気中において４００℃〜９００℃の温度によりなされる請求項２又は３記載の薄膜電極の製造方法。 The method of manufacturing a thin film electrode according to claim 2 or 3, wherein the heat treatment is performed at a temperature of 400 ° C to 900 ° C in an atmospheric pressure atmosphere. 請求項１記載の粒径が１〜４０ｎｍのＮｉからなる金属微粒子を水に分散させた薄膜電極用ペーストを基板(11)の平坦な上面に塗布して所定の厚さに成膜した後に熱処理して前記金属微粒子を焼成することにより前記基板(11)上に第１薄膜電極(12)を形成する工程と、
前記第１薄膜電極(12)上にゾルゲル法により誘電体材料膜(13)を形成する工程と、
前記誘電体材料膜(13)上に請求項１記載の粒径が１〜４０ｎｍのＮｉからなる金属微粒子を水に分散させた薄膜電極用ペーストを塗布して所定の厚さに成膜した後に熱処理して前記金属微粒子を焼成することにより前記誘電体材料膜(13)上に第２薄膜電極(14)を形成する工程と
を含む薄膜素子の製造方法。 A thin film electrode paste in which metal fine particles made of Ni having a particle diameter of 1 to 40 nm according to claim 1 are dispersed in water is applied to a flat upper surface of a substrate (11) and formed into a predetermined thickness, followed by heat treatment. And forming the first thin film electrode (12) on the substrate (11) by firing the metal fine particles;
Forming a dielectric material film (13) on the first thin film electrode (12) by a sol-gel method;
A thin film electrode paste in which metal fine particles made of Ni having a particle diameter of 1 to 40 nm according to claim 1 are applied on the dielectric material film (13) and formed to a predetermined thickness. Forming a second thin film electrode (14) on the dielectric material film (13) by firing the metal fine particles by heat treatment. 請求項５記載の方法により作製された薄膜素子。   A thin film element manufactured by the method according to claim 5. 粒径が１〜６０ｎｍの誘電体微粒子を溶媒に分散させた誘電体ペーストを準備する工程と、
請求項２記載の方法により製造された第１薄膜電極(12)の上面に前記誘電体ペーストを塗布して所定の厚さに成膜する工程と、
熱処理により前記誘電体ペーストにおける溶媒を除去して誘電体微粒子を焼成することにより前記第１薄膜電極(12)上に薄膜誘電体材料膜(13)を形成する工程と、
前記薄膜誘電体材料膜(13)上にスパッタリング法、ＭＯＣＶＤ法、真空蒸着法又は請求項２記載の方法により第２薄膜電極(14)を形成する工程と
を含む薄膜素子の製造方法。 Preparing a dielectric paste in which dielectric fine particles having a particle diameter of 1 to 60 nm are dispersed in a solvent;
Applying the dielectric paste to an upper surface of the first thin film electrode (12) manufactured by the method according to claim 2, and forming a film with a predetermined thickness;
Forming a thin film dielectric material film (13) on the first thin film electrode (12) by removing the solvent in the dielectric paste by heat treatment and firing the dielectric fine particles;
Forming a second thin film electrode (14) on the thin film dielectric material film (13) by sputtering, MOCVD, vacuum deposition or the method according to claim 2. 請求項７記載の方法により作製された薄膜素子。   A thin film element produced by the method according to claim 7.
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