JP2005047752A - Method for controlling film structure of zinc oxide film - Google Patents
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Abstract
Description
本発明は、還元析出によって酸化亜鉛膜を形成する方法において、酸化亜鉛膜の配向性、析出状態などの皮膜構造を制御する方法に関する。 The present invention relates to a method for controlling the film structure such as the orientation and deposition state of a zinc oxide film in a method for forming a zinc oxide film by reduction deposition.
酸化亜鉛（ZnO）は、ガス・温度センサー、バリスタ、透明導電膜、表面弾性波素子、圧電素子などの広い分野で応用されており工業的に重要な材料である。これらの応用分野の中で、特に、圧電素子、表面弾性波素子などに酸化亜鉛膜を適用する際には、酸化亜鉛結晶の配向性の制御が重要である。 Zinc oxide (ZnO) is an industrially important material that is applied in a wide range of fields such as gas / temperature sensors, varistors, transparent conductive films, surface acoustic wave elements, and piezoelectric elements. Among these application fields, especially when a zinc oxide film is applied to a piezoelectric element, a surface acoustic wave element, etc., it is important to control the orientation of the zinc oxide crystal.
酸化亜鉛膜を還元析出させる方法としては、亜鉛イオン、硝酸イオン及びボラン−アミンコンプレックスを含む水溶液を用い、この水溶液に各種の基材を浸漬する方法が知られている（例えば、下記特許文献１参照）。この方法では、還元析出により酸化亜鉛膜を形成することは可能であるが、析出する酸化亜鉛の配向性を制御することができないために特定の優先配向性を有する酸化亜鉛膜を形成することはできない。 As a method for reducing and depositing a zinc oxide film, a method is known in which an aqueous solution containing zinc ions, nitrate ions and borane-amine complex is used, and various substrates are immersed in this aqueous solution (for example, Patent Document 1 below). reference). In this method, it is possible to form a zinc oxide film by reduction deposition, but since the orientation of the deposited zinc oxide cannot be controlled, it is not possible to form a zinc oxide film having a specific preferred orientation. Can not.
酸化亜鉛膜の配向性を制御する方法としては、Ｓｎ，Ａｇ及びＰｄを特定の割合で含む触媒層が形成された被処理物を用い、ボラン系還元剤の濃度範囲を調整する方法が報告されている（例えば、下記特許文献２参照）。 As a method for controlling the orientation of the zinc oxide film, a method for adjusting the concentration range of the borane-based reducing agent using an object to be treated on which a catalyst layer containing Sn, Ag and Pd in a specific ratio is formed has been reported. (For example, see Patent Document 2 below).
しかしながら、ボラン系還元剤は、高価な還元剤であり、その添加量を調整する方法では、添加量を増加させるとコストが大きく上昇し、更に、浴安定性が低下して浴分解が生じ易くなる。しかも、この方法は、使用できる触媒層が限定されるために、汎用性に乏しい方法である。
本発明は、上記した従来技術に鑑みてなされたものであり、その主な目的は、特殊な触媒物質を用いることなく、簡単な方法で酸化亜鉛膜の配向性や析出状態などの皮膜構造を制御できる方法を提供することである。 The present invention has been made in view of the above-described prior art, and its main purpose is to form a coating structure such as the orientation and precipitation state of a zinc oxide film by a simple method without using a special catalyst substance. It is to provide a method that can be controlled.
本発明者は、上記した目的を達成すべく鋭意研究を重ねた結果、亜鉛イオン、硝酸イオン及びアミンボラン化合物を含む酸化亜鉛膜形成用組成物を用いて還元析出によって酸化亜鉛膜を形成する方法において、亜鉛イオン及び硝酸イオンの濃度を特定の範囲に制御する方法や液温を制御する方法などによれば、非常に簡単な方法で酸化亜鉛膜の配向性や析出状態を制御できることを見出し、ここに本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned object, the present inventor, in a method of forming a zinc oxide film by reduction deposition using a composition for forming a zinc oxide film containing zinc ions, nitrate ions and amine borane compounds. The method of controlling the concentration of zinc ions and nitrate ions to a specific range and the method of controlling the liquid temperature have found that the orientation and precipitation state of the zinc oxide film can be controlled by a very simple method. The present invention has been completed.
即ち、本発明は、下記の酸化亜鉛膜の皮膜構造の制御方法を提供するものである。
１． 亜鉛イオン、硝酸イオン及びアミンボラン化合物を含み、亜鉛イオン濃度が０．０１〜０．０５モル／ｌであって、硝酸イオンのモル濃度が亜鉛イオンのモル濃度の１〜３倍の範囲内にある水溶液からなる酸化亜鉛膜形成用組成物を被処理物に接触させることによって、（００１）面に優先配向したポーラス構造の酸化亜鉛膜を形成することを特徴とする酸化亜鉛膜の皮膜構造の制御方法。
２． 亜鉛イオン、硝酸イオン及びアミンボラン化合物を含み、亜鉛イオン濃度が０．０６〜０．０７５モル／ｌであって、硝酸イオンのモル濃度が亜鉛イオンのモル濃度の１〜３倍の範囲内にある水溶液からなる酸化亜鉛膜形成用組成物を被処理物に接触させることによって、（００１）面に優先配向した緻密な構造の酸化亜鉛膜を形成することを特徴とする酸化亜鉛膜の皮膜構造の制御方法。
３． 亜鉛イオン、硝酸イオン及びアミンボラン化合物を含み、亜鉛イオン濃度が０．０７５〜０．１モル／ｌであって、硝酸イオンのモル濃度が亜鉛イオンのモル濃度の１〜３倍の範囲内にある水溶液からなる酸化亜鉛膜形成用組成物を、７０〜９０℃の液温で被処理物に接触させることによって、（００１）面に優先配向した緻密な構造の酸化亜鉛膜を形成することを特徴とする酸化亜鉛膜の皮膜構造の制御方法。
４． 亜鉛イオン、硝酸イオン及びアミンボラン化合物を含み、亜鉛イオン濃度が０．０１〜０．０５モル／ｌであって、硝酸イオンのモル濃度が亜鉛イオンのモル濃度の１〜３倍の範囲内にある水溶液からなる酸化亜鉛膜形成用組成物を被処理物に接触させた後、亜鉛イオン、硝酸イオン及びアミンボラン化合物を含み、亜鉛イオン濃度が０．０８〜０．１モル／ｌであって、硝酸イオンのモル濃度が亜鉛イオンのモル濃度の１〜３倍の範囲内にある水溶液からなる酸化亜鉛膜形成用組成物を被処理物に接触させることによって、（００１）面に優先配向した緻密な構造の酸化亜鉛膜を形成することを特徴とする酸化亜鉛膜の皮膜構造の制御方法。
５． 上記項１〜４の方法によって皮膜構造を制御して形成される酸化亜鉛膜。
That is, the present invention provides the following method for controlling the coating structure of a zinc oxide film.
1. Including zinc ion, nitrate ion and amine borane compound, the zinc ion concentration is 0.01 to 0.05 mol / l, and the molar concentration of nitrate ion is in the range of 1 to 3 times the molar concentration of zinc ion. Control of the coating structure of a zinc oxide film, wherein a zinc oxide film having a porous structure preferentially oriented on the (001) plane is formed by bringing a composition for forming a zinc oxide film made of an aqueous solution into contact with an object to be processed Method.
2. Including zinc ion, nitrate ion and amine borane compound, the zinc ion concentration is 0.06-0.075 mol / l, and the molar concentration of nitrate ion is in the range of 1-3 times the molar concentration of zinc ion. By forming a zinc oxide film having a dense structure preferentially oriented on the (001) plane by bringing a composition for forming a zinc oxide film made of an aqueous solution into contact with an object to be processed, Control method.
3. Contains zinc ions, nitrate ions and amine borane compounds, the zinc ion concentration is 0.075 to 0.1 mol / l, and the molar concentration of nitrate ions is in the range of 1 to 3 times the molar concentration of zinc ions. A zinc oxide film having a dense structure preferentially oriented on the (001) plane is formed by bringing a composition for forming a zinc oxide film made of an aqueous solution into contact with an object to be processed at a liquid temperature of 70 to 90 ° C. A method for controlling the film structure of a zinc oxide film.
4). Including zinc ion, nitrate ion and amine borane compound, the zinc ion concentration is 0.01 to 0.05 mol / l, and the molar concentration of nitrate ion is in the range of 1 to 3 times the molar concentration of zinc ion. After the composition for forming a zinc oxide film made of an aqueous solution is brought into contact with the object to be treated, it contains zinc ions, nitrate ions and amine borane compounds, and the zinc ion concentration is 0.08 to 0.1 mol / l, By bringing the composition for forming a zinc oxide film made of an aqueous solution having a molar concentration of ions in the range of 1 to 3 times the molar concentration of zinc ions into contact with the object to be processed, the densely oriented layer preferentially oriented on the (001) plane A method for controlling a coating structure of a zinc oxide film, comprising forming a zinc oxide film having a structure.
5. 5. A zinc oxide film formed by controlling the film structure by the method of items 1 to 4 above.
本発明で使用する酸化亜鉛膜形成用組成物は、亜鉛イオン、硝酸イオン及びアミンボラン化合物を含む水溶液である。 The composition for forming a zinc oxide film used in the present invention is an aqueous solution containing zinc ions, nitrate ions and an amine borane compound.
亜鉛イオンイオン源となる化合物としては、水溶性亜鉛塩を用いればよく、その具体例として、硝酸亜鉛、硫酸亜鉛、塩化亜鉛、酢酸亜鉛、リン酸亜鉛、ピロリン酸亜鉛、炭酸亜鉛等を挙げることができる。 As a compound serving as a zinc ion source, a water-soluble zinc salt may be used. Specific examples thereof include zinc nitrate, zinc sulfate, zinc chloride, zinc acetate, zinc phosphate, zinc pyrophosphate, and zinc carbonate. Can do.
硝酸イオン源としては、硝酸、水溶性硝酸塩等を用いることができ、硝酸塩の具体例として、硝酸亜鉛、硝酸アンモニウム、硝酸ナトリウム、硝酸カリウム、硝酸リチウム、硝酸尿素等を挙げることができる。 As the nitrate ion source, nitric acid, water-soluble nitrate and the like can be used, and specific examples of nitrate include zinc nitrate, ammonium nitrate, sodium nitrate, potassium nitrate, lithium nitrate, urea nitrate and the like.
亜鉛イオン源となる化合物及び硝酸イオン源となる化合物は、それぞれ、一種単独又は二種以上混合して用いることができ、また、亜鉛イオン及び硝酸イオンの両方のイオン源として、硝酸亜鉛を単独で用いても良い。特に、硝酸亜鉛を単独で用いる場合には、浴中に不要な成分が多く存在することがなく、水酸化亜鉛の形成なども抑制されて、純度の高い酸化亜鉛膜を広い濃度範囲で形成することが可能となる。 The compound serving as the zinc ion source and the compound serving as the nitrate ion source can be used singly or in combination of two or more, respectively, and zinc nitrate alone can be used as both the zinc ion and nitrate ion sources. It may be used. In particular, when zinc nitrate is used alone, there are not many unnecessary components in the bath, formation of zinc hydroxide and the like are suppressed, and a high-purity zinc oxide film is formed in a wide concentration range. It becomes possible.
アミンボラン化合物としては、水溶性の化合物であればいずれも用いることができ、具体例として、ジメチルアミンボラン、トリメチルアミンボラン等を挙げることができる。特に、トリメチルアミンボランを用いる場合には、浴の安定性が良好となり、良好な酸化亜鉛膜を長期間継続して形成できる。 As the amine borane compound, any water-soluble compound can be used, and specific examples include dimethylamine borane, trimethylamine borane and the like. In particular, when trimethylamine borane is used, the stability of the bath is improved and a good zinc oxide film can be formed continuously for a long period of time.
第一方法
本発明の第一方法は、上記した酸化亜鉛膜形成用組成物に含まれる亜鉛イオン濃度を０．０１〜０．０５モル／ｌ程度とし、硝酸イオンのモル濃度を亜鉛イオンのモル濃度の１〜３倍程度、好ましくは１．５〜２．５倍程度に調整した組成物を用いる方法である。上記した非常に狭い濃度範囲の亜鉛イオンと硝酸イオンを含む組成物を用いることによって、（００１）面に優先配向したポーラス構造の酸化亜鉛膜を形成することができる。この場合には、比較的粒径の小さい六角柱形状の酸化亜鉛が成長し、その結晶間がポーラス構造となり、通常、基材表面の２０〜６０％程度が露出した状態となる。
First method In the first method of the present invention, the zinc ion concentration contained in the composition for forming a zinc oxide film is set to about 0.01 to 0.05 mol / l, and the molar concentration of nitrate ions is set. This is a method using a composition adjusted to about 1 to 3 times, preferably about 1.5 to 2.5 times the molar concentration of zinc ions. By using the composition containing zinc ions and nitrate ions in a very narrow concentration range as described above, a porous zinc oxide film preferentially oriented in the (001) plane can be formed. In this case, hexagonal column-shaped zinc oxide having a relatively small particle size grows, and a porous structure is formed between the crystals, and usually about 20 to 60% of the substrate surface is exposed.
アミンボラン化合物の添加量については、広い範囲で調整することが可能であり、例えば、０．００１〜０．５モル／ｌ程度とすることができるが、０．０１〜０．１モル／ｌ程度とすることが好ましい。この様にアミンボラン化合物の添加量は、広い範囲で調整できるので、例えば、低コストとするためには、アミンボラン化合物の添加量を比較的低い濃度とすればよい。この場合には、析出速度は若干の低下があるものの、目的とする（００１）面に優先的に配向したポーラス構造の酸化亜鉛膜を形成することは可能である。 The addition amount of the amine borane compound can be adjusted in a wide range, for example, about 0.001 to 0.5 mol / l, but about 0.01 to 0.1 mol / l. It is preferable that Thus, the amount of amine borane compound added can be adjusted over a wide range. For example, in order to reduce the cost, the amount of amine borane compound added may be set to a relatively low concentration. In this case, although the deposition rate is slightly reduced, it is possible to form a zinc oxide film having a porous structure preferentially oriented on the target (001) plane.
酸化亜鉛膜形成用組成物のｐＨについては、特に限定されるものではないが、ｐＨが低い場合には浴の安定性は向上するものの成膜速度が低下し、一方、ｐＨが高い場合には、成膜速度は向上するが浴の安定性が低下して沈殿が生成し易くなり、酸化亜鉛膜を得ることが困難となる。これらの点から、該組成物のｐＨは４〜７程度とすることが好ましい。 The pH of the composition for forming a zinc oxide film is not particularly limited. However, when the pH is low, the stability of the bath is improved, but the film formation rate is reduced, while when the pH is high. Although the film formation rate is improved, the stability of the bath is lowered and precipitation is easily generated, making it difficult to obtain a zinc oxide film. From these points, the pH of the composition is preferably about 4 to 7.
酸化亜鉛膜形成用組成物の液温については、特に限定的ではなく、４０〜９０℃程度の広い範囲とすることができるが、特に、５５〜９０℃程度とすることが好ましい。 The liquid temperature of the composition for forming a zinc oxide film is not particularly limited, and can be in a wide range of about 40 to 90 ° C., but is preferably about 55 to 90 ° C.
酸化亜鉛膜を形成する方法としては、被処理物を上記した酸化亜鉛膜形成用組成物に接触させればよく、通常は、酸化亜鉛膜形成用組成物に被処理物を浸漬すればよい。浸漬する際には、該組成物は、無撹拌及び撹拌状態のいずれでも良く、撹拌法としては、公知の攪拌方法を適宜採用できる。形成される酸化亜鉛膜の膜厚は浸漬時間とともに増加するので、浸漬時間を適宜設定することによって、目的とする膜厚の酸化亜鉛膜を形成することができる。 As a method for forming the zinc oxide film, the object to be processed may be brought into contact with the above-described composition for forming a zinc oxide film, and usually the object to be processed may be immersed in the composition for forming a zinc oxide film. When dipping, the composition may be in a non-stirred state or in a stirred state, and a known stirring method can be appropriately employed as a stirring method. Since the thickness of the zinc oxide film to be formed increases with the immersion time, a zinc oxide film having a target thickness can be formed by appropriately setting the immersion time.
酸化亜鉛膜を形成した後、水洗、乾燥等の通常の後処理を行うことができる。 After forming the zinc oxide film, normal post-treatment such as washing with water and drying can be performed.
酸化亜鉛膜を形成するための基材の種類は特に限定されず、酸化亜鉛膜形成用組成物中に浸漬した場合に変質しない材料であればどのような材料も使用可能であり、導電性及び非導電性のいずれの材料であってもよい。その具体例としては、銅、鉄、アルミニウム等の金属材料、ＮＥＳＡガラス、ＩＴＯガラス等の導電性ガラス、ソーダライムガラス、無アルカリガラス（コーニング７０５９ガラス）などの非導電性ガラス材料、セラミックス材料、プラスチックス材料などを挙げることができる。 The kind of base material for forming the zinc oxide film is not particularly limited, and any material can be used as long as it does not change in quality when immersed in the composition for forming a zinc oxide film. Any non-conductive material may be used. Specific examples thereof include metal materials such as copper, iron and aluminum, conductive glasses such as NESA glass and ITO glass, non-conductive glass materials such as soda lime glass and alkali-free glass (Corning 7059 glass), ceramic materials, Examples include plastics materials.
基材としてガラス、セラミック、プラスチックス等を用いる場合には、基材を酸化亜鉛膜形成用組成物に浸漬する前に、無電解めっき皮膜を形成する際に行われている触媒付与方法と同様にして、触媒金属を付与すればよい。触媒付与処理の具体的な方法としては、無電解めっき皮膜を形成する際に行われている公知の方法をいずれも適用できる。一般的には、パラジウムを付与する方法が広く行われており、例えば、センシタイジング−アクチベーション法、キャタリスト−アクセレレーター法、アルカリキャタリスト法等により触媒を付与すればよい。 When glass, ceramic, plastics, etc. are used as the base material, the same method as the catalyst application method used when forming the electroless plating film before immersing the base material in the composition for forming a zinc oxide film Thus, the catalyst metal may be added. As a specific method of the catalyst application treatment, any known method that is used when forming an electroless plating film can be applied. In general, a method for imparting palladium is widely performed. For example, a catalyst may be imparted by a sensitizing-activation method, a catalyst-accelerator method, an alkaline catalyst method, or the like.
その他、触媒金属としては、例えば、銀を用いることもできる。銀触媒を付与する方法については、特に限定はないが、例えば、特開平１−６８４７８号公報に記載されている銀ヒドロゾルを用いて触媒を付与する方法、特開平１０−３０１８８号公報に記載されている銀塩０．０１〜１００ミリモル／ｌ、陰イオン界面活性剤０．０１〜０．５重量％、及び銀塩に対して０．１〜０．８倍モルの還元剤を含有する水溶液を用いる方法、特開２０００−８１８０号公報に記載されている、２価の錫イオンを含むセンシタイジング溶液と接触させてセンシタイジング処理を行った後、銀イオンを含有する溶液と接触させることによって銀触媒を付与する方法などを適用できる。 In addition, as a catalyst metal, for example, silver can be used. The method for applying the silver catalyst is not particularly limited. For example, the method for applying the catalyst using a silver hydrosol described in JP-A-1-68478, described in JP-A-10-30188. Aqueous solution containing 0.01 to 100 mmol / l of silver salt, 0.01 to 0.5% by weight of an anionic surfactant, and 0.1 to 0.8 times mol of the reducing agent relative to the silver salt , A method comprising using a sensitizing solution described in JP-A-2000-8180, contacting with a sensitizing solution containing divalent tin ions, and then contacting with a solution containing silver ions A method for applying a silver catalyst can be applied.
更に、無電解めっき皮膜を形成する際に用いられるその他の触媒、例えば、鉄、コバルト、ニッケル、白金等の触媒金属を付与してもよい。また、上記した触媒金属を二種類以上併用してもよい。 Furthermore, you may provide other catalysts used when forming an electroless-plating film, for example, catalytic metals, such as iron, cobalt, nickel, and platinum. Two or more kinds of the above-described catalyst metals may be used in combination.
第二方法
本発明の第二方法は、亜鉛イオン濃度を０．０６〜０．０７５モル／ｌ程度とし、硝酸イオンのモル濃度を亜鉛イオンのモル濃度の１〜３倍程度、好ましくは１．５〜２．５倍程度とした酸化亜鉛膜形成用組成物を用いる方法である。亜鉛イオン濃度と硝酸イオン濃度を上記した非常に狭い範囲に調整した組成物を用いることによって、析出粒子の直径が大きくなり、ポアーなどの欠陥がほとんどなく、基材表面の露出の無い緻密な酸化亜鉛膜を形成することができる。この場合にも、（００１）面に優先配向した酸化亜鉛膜が形成される。
Second method In the second method of the present invention, the zinc ion concentration is about 0.06 to 0.075 mol / l, the molar concentration of nitrate ions is about 1 to 3 times the molar concentration of zinc ions, Preferably, it is a method using a zinc oxide film forming composition of about 1.5 to 2.5 times. By using a composition in which the zinc ion concentration and nitrate ion concentration are adjusted to the above-mentioned very narrow ranges, the diameter of the precipitated particles is increased, and there is almost no defects such as pores. A zinc film can be formed. Also in this case, a zinc oxide film preferentially oriented on the (001) plane is formed.
アミンボラン化合物の添加量については、広い範囲で調整することが可能であり、例えば、０．００１〜０．５モル／ｌ程度とすることができるが、０．０１〜０．１モル／ｌ程度とすることが好ましい。 The addition amount of the amine borane compound can be adjusted in a wide range, for example, about 0.001 to 0.5 mol / l, but about 0.01 to 0.1 mol / l. It is preferable that
酸化亜鉛膜形成用組成物のｐＨ、浴温、及び酸化亜鉛膜を形成する方法については、上記した第一方法と同様とすればよい。 The pH of the composition for forming a zinc oxide film, the bath temperature, and the method for forming the zinc oxide film may be the same as the first method described above.
第三方法
本発明の第三方法では、上記した酸化亜鉛膜形成用組成物に含まれる亜鉛イオン濃度を０．０７５〜０．１モル／ｌ程度、好ましくは０．０８〜０．１モル／ｌ程度とし、硝酸イオンのモル濃度を亜鉛イオンのモル濃度の１〜３倍程度、好ましくは１．５〜２．５倍程度とした組成物を用いる。第三方法は、この様に亜鉛イオン濃度及び硝酸イオン濃度を、第一方法及び第二方法と比較して高い範囲に設定し、酸化亜鉛膜を形成する際の液温を７０〜９０℃とする方法である。
Third method In the third method of the present invention, the zinc ion concentration contained in the composition for forming a zinc oxide film is about 0.075 to 0.1 mol / l, preferably 0.08 to 0. A composition in which the molar concentration of nitrate ions is about 1 to 3 times, preferably about 1.5 to 2.5 times the molar concentration of zinc ions, is used. In the third method, the zinc ion concentration and the nitrate ion concentration are set to a higher range as compared with the first method and the second method, and the liquid temperature when forming the zinc oxide film is set to 70 to 90 ° C. It is a method to do.
この際のアミンボラン化合物の添加量については、広い範囲で調整することが可能であり、例えば、０．００１〜０．５モル／ｌ程度とすることができるが、０．０１〜０．１モル／ｌ程度とすることが好ましい。 The amount of the amine borane compound added at this time can be adjusted in a wide range, for example, about 0.001 to 0.5 mol / l, but 0.01 to 0.1 mol / L is preferable.
第三方法によれば、（００１）面に優先的に配向し、ポアーなどの欠陥がほとんどない緻密な酸化亜鉛膜であって、非常に配向性の高い酸化亜鉛膜を形成することができる。この場合、配向性の程度は、浴温を上昇させることにより強くすることができ、例えば、酸化亜鉛膜を析出させる際の浴温が８０℃程度の場合には、（００１）面に平行する面である（００２）面の回折強度は、（１０１）面の回折強度の約１０倍となり、浴温が９０℃の場合には、（００２）面の回折強度は、（１０１）面の回折強度の約２０倍となり、（００１）面の配向性が非常に高くなる。従って、第三方法によれば、処理液の液温を適宜設定することによって、優先配向の程度を調整することが可能である。 According to the third method, it is possible to form a dense zinc oxide film that is preferentially oriented in the (001) plane and has almost no defects such as pores and has a very high orientation. In this case, the degree of orientation can be increased by increasing the bath temperature. For example, when the bath temperature when depositing the zinc oxide film is about 80 ° C., it is parallel to the (001) plane. The diffraction intensity of the (002) plane is about 10 times the diffraction intensity of the (101) plane, and when the bath temperature is 90 ° C., the diffraction intensity of the (002) plane is the diffraction of the (101) plane. The strength is about 20 times, and the orientation of the (001) plane becomes very high. Therefore, according to the third method, it is possible to adjust the degree of priority orientation by appropriately setting the temperature of the treatment liquid.
尚、酸化亜鉛膜形成用組成物のｐＨ及び酸化亜鉛膜を形成する方法については、上記した第一方法と同様とすればよい。 The pH of the composition for forming a zinc oxide film and the method for forming the zinc oxide film may be the same as the first method described above.
第四方法
本発明の第四方法は、まず、第一工程として、亜鉛イオン濃度を０．０１〜０．０５モル／ｌ程度とし、硝酸イオンのモル濃度を亜鉛イオンのモル濃度の１〜３倍程度、好ましくは１．５〜２．５倍程度の範囲に調整した酸化亜鉛膜形成用組成物を被処理物に接触させた後、第二工程として、この被処理物を、亜鉛イオン濃度を０．０８〜０．１モル／ｌ程度とし、硝酸イオンのモル濃度を亜鉛イオンのモル濃度の１〜３倍程度、好ましくは１．５〜２．５倍程度の範囲に調整した酸化亜鉛膜形成用組成物に接触させる方法である。この方法によれば、第一工程において、（００１）面に優先配向したポーラス構造の酸化亜鉛膜が形成され、次いで、第二工程において、第一工程で形成されたポーラス構造の酸化亜鉛膜のポアー部分に酸化亜鉛粒子が成長して粒子間のポアーが消滅し、（００１）面に優先的に配向し、しかも緻密な構造の酸化亜鉛膜が形成される。特に、第四方法によれば、（００１）面の配向性が非常に高い酸化亜鉛膜を形成することができる。
Fourth method In the fourth method of the present invention, first, as a first step, the zinc ion concentration is set to about 0.01 to 0.05 mol / l, and the molar concentration of nitrate ions is set to the molar concentration of zinc ions. After the zinc oxide film forming composition adjusted to about 1 to 3 times, preferably about 1.5 to 2.5 times, is brought into contact with the object to be treated, the object to be treated is used as a second step. The zinc ion concentration is about 0.08 to 0.1 mol / l, and the molar concentration of nitrate ions is about 1 to 3 times, preferably about 1.5 to 2.5 times the molar concentration of zinc ions. It is a method of contacting with the adjusted composition for forming a zinc oxide film. According to this method, a porous zinc oxide film preferentially oriented in the (001) plane is formed in the first step, and then in the second step, the porous zinc oxide film formed in the first step is formed. Zinc oxide particles grow in the pores, and the pores between the particles disappear, and a zinc oxide film having a dense structure is formed that is preferentially oriented in the (001) plane. In particular, according to the fourth method, it is possible to form a zinc oxide film having a very high (001) plane orientation.
この方法で用いる酸化亜鉛膜形成用組成物についても、アミンボラン化合物の添加量は広い範囲で調整することが可能であり、第一工程で用いる酸化亜鉛膜形成用組成物と第二工程で用いる酸化亜鉛膜形成用組成物のいずれについても、０．００１〜０．５モル／ｌ程度とすることができ、０．０１〜０．１モル／ｌ程度とすることが好ましい。酸化亜鉛膜形成用組成物のｐＨについても、第一方法で用いる組成物と同様に、特に限定されるものではないが、ｐＨ４〜７程度とすることが好ましい。 Also for the zinc oxide film forming composition used in this method, the amount of amine borane compound added can be adjusted in a wide range, and the zinc oxide film forming composition used in the first step and the oxidation used in the second step. For any of the compositions for forming a zinc film, it can be about 0.001 to 0.5 mol / l, and preferably about 0.01 to 0.1 mol / l. Similarly to the composition used in the first method, the pH of the composition for forming a zinc oxide film is not particularly limited, but is preferably about pH 4 to 7.
処理時間については、目的とする膜厚のポーラス構造の酸化亜鉛膜が形成されるまで第一工程の処理を行い、次いで、粒子間のポアーが消滅するまで第二工程の処理を行えばよい。例えば、第一工程において、５〜３０分間程度処理を行った場合には、第二工程において、１０〜６０分間程度の処理を行えばよい。 With respect to the treatment time, the treatment in the first step may be performed until a porous zinc oxide film having a desired film thickness is formed, and then the treatment in the second step may be performed until the pores between the particles disappear. For example, when processing is performed for about 5 to 30 minutes in the first step, processing may be performed for about 10 to 60 minutes in the second step.
この方法では、処理温度は、第一工程及び第二工程共に、４０〜９０℃程度、好ましくは５５〜９０℃程度とすることができる。特に、この方法は、５５〜７０℃程度、更には、５５〜６５℃程度という第三方法よりかなり低い処理液温度において、（００１）面に優先配向した緻密な酸化亜鉛膜を形成することができるので、処理液の安定性が低下することが少ない点で有利である。 In this method, the treatment temperature can be about 40 to 90 ° C., preferably about 55 to 90 ° C. in both the first step and the second step. In particular, this method can form a dense zinc oxide film preferentially oriented on the (001) plane at a treatment liquid temperature of about 55 to 70 ° C., further about 55 to 65 ° C., which is considerably lower than the third method. Therefore, it is advantageous in that the stability of the treatment liquid is hardly lowered.
本発明によれば、還元析出によって酸化亜鉛膜を形成する際に、酸化亜鉛の配向性や析出状態を簡単に制御することができる。 According to the present invention, when a zinc oxide film is formed by reduction precipitation, the orientation and precipitation state of zinc oxide can be easily controlled.
従って、本発明方法を利用して、酸化亜鉛膜の配向性や析出状態を制御することによって、圧電素子、表面弾性波素子などの使用目的に適した特定の皮膜構造の酸化亜鉛膜を、比較的簡単な方法によって形成することができる。 Therefore, by using the method of the present invention, the zinc oxide film having a specific coating structure suitable for the purpose of use such as a piezoelectric element and a surface acoustic wave element is compared by controlling the orientation and precipitation state of the zinc oxide film. It can be formed by a simple method.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
大きさ５×５ｃｍのソーダライムガラス板を被処理物として用い、脱脂剤（商標名：テクノクリア-CL、奥野製薬工業（株）製）の40g/ｌ水溶液中に６５℃で５分間浸漬して脱脂処理を行った後、Ｓｎ触媒（商標名：テクノクリア-SN、奥野製薬工業（株）製）の１００ｍｌ／ｌ水溶液に２５℃で２分浸漬し、Ａｇ触媒（商標名：テクノクリア-AG、奥野製薬工業（株）製）の２０ｍｌ／ｌ水溶液に２５℃で１分浸漬し、次いでＰｄ触媒（商標名：テクノクリア-PD、奥野製薬工業（株）製）の１００ｍｌ／ｌ水溶液に２５℃で１分浸漬する工程により、還元析出用の触媒を付与した。尚、上記各処理の間には、水洗を行った。 A soda lime glass plate with a size of 5 x 5 cm is used as the object to be treated, and immersed in a 40 g / l aqueous solution of a degreasing agent (trade name: Techno Clear-CL, manufactured by Okuno Pharmaceutical Co., Ltd.) at 65 ° C for 5 minutes. After degreasing treatment, the catalyst was immersed in a 100 ml / l aqueous solution of Sn catalyst (trade name: Techno Clear-SN, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25 ° C. for 2 minutes, and Ag catalyst (trade name: Techno Clear— AG, manufactured by Okuno Seiyaku Kogyo Co., Ltd.) for 20 minutes at 25 ° C. and then immersed in a 100 ml / l aqueous solution of Pd catalyst (trade name: Techno Clear-PD, Okuno Pharmaceutical Co., Ltd.). A catalyst for reduction deposition was applied by a step of immersing at 25 ° C. for 1 minute. In addition, it washed with water between each said process.
次いで、下記表１に示す配合量の硝酸亜鉛（Ｚｎ（ＮＯ3）2）及びジメチルアミンボラン（ＤＭＡＢ）を含む水溶液からなる酸化亜鉛膜形成用組成物中に、上記した方法で触媒を付与した被処理物を液温６５℃で１時間浸漬して酸化亜鉛膜を形成した。 Next, a catalyst was applied to the composition for forming a zinc oxide film comprising an aqueous solution containing zinc nitrate (Zn (NO 3 ) 2 ) and dimethylamine borane (DMAB) in the blending amounts shown in Table 1 below. The object to be treated was immersed for 1 hour at a liquid temperature of 65 ° C. to form a zinc oxide film.
形成された酸化亜鉛膜について、皮膜構造を走査型電子顕微鏡で観察し、更に、Ｘ線回折を行った。その結果を下記表１に示す。回折強度比としては、回折強度の最も高いものを１００とした場合の相対強度を示す。 About the formed zinc oxide film | membrane, the film | membrane structure was observed with the scanning electron microscope, and also X-ray diffraction was performed. The results are shown in Table 1 below. As the diffraction intensity ratio, the relative intensity when the highest diffraction intensity is 100 is shown.
以上の結果から明らかなように、Ｚｎ（ＮＯ3）2濃度が０．０１又は０．０５モル／ｌの場合には、粒子径が小さい酸化亜鉛が析出し、ポーラス構造の酸化亜鉛膜が形成され、０．０７５モル／ｌ以上では、粒子径が大きくなり緻密な酸化亜鉛膜が形成された。また、酸化亜鉛膜の配向性については、Ｚｎ（ＮＯ3）2濃度が０．０７５モル／ｌ以下では、（００２）面の回折強度が高く、（００１）面に優先配向（ｃ軸配向）する傾向が強くなった。 As is clear from the above results, when the Zn (NO 3 ) 2 concentration is 0.01 or 0.05 mol / l, zinc oxide having a small particle size is precipitated, and a zinc oxide film having a porous structure is formed. At 0.075 mol / l or more, the particle size increased and a dense zinc oxide film was formed. Regarding the orientation of the zinc oxide film, when the Zn (NO 3 ) 2 concentration is 0.075 mol / l or less, the diffraction intensity of the (002) plane is high, and the preferred orientation (c-axis orientation) is on the (001) plane. The tendency to do became strong.
実施例１と同様にしてソーダライムガラス板に触媒を付与した後、硝酸亜鉛を０．１モル／ｌとジメチルアミンボランを０．０１モル／ｌ含む水溶液からなる酸化亜鉛膜形成用組成物中に被処理物を浸漬して酸化亜鉛膜を形成した。処理液の温度については、６５℃、７０℃、８０℃及び９０℃の４種類の温度とした。形成された各酸化亜鉛膜について、Ｘ線回折強度比を求めた結果を下記表２に示す。 In the composition for forming a zinc oxide film comprising an aqueous solution containing 0.1 mol / l zinc nitrate and 0.01 mol / l dimethylamine borane after applying a catalyst to a soda lime glass plate in the same manner as in Example 1. The object to be treated was immersed in a zinc oxide film. About the temperature of the process liquid, it was set as four types of temperatures, 65 degreeC, 70 degreeC, 80 degreeC, and 90 degreeC. Table 2 below shows the results of obtaining the X-ray diffraction intensity ratio for each of the formed zinc oxide films.
表２から明らかなように、Ｚｎ（ＮＯ3）2濃度が０．１モル／ｌの酸化亜鉛膜形成用組成物を用いた場合には、７０℃以上の処理液温度において、（００１）面に優先配向した酸化亜鉛膜が形成された。これらの場合、形成された酸化亜鉛膜は、何れも、ポアー等の欠陥のない緻密な構造であった。 As is apparent from Table 2, when a composition for forming a zinc oxide film having a Zn (NO 3 ) 2 concentration of 0.1 mol / l is used, the (001) plane is obtained at a treatment liquid temperature of 70 ° C. or higher. A zinc oxide film preferentially oriented was formed. In these cases, each of the formed zinc oxide films had a dense structure free from defects such as pores.
実施例１と同様にしてソーダライムガラス板に触媒を付与した後、下記表３に示す条件で、二工程の処理を行い、酸化亜鉛膜を形成した。 After applying the catalyst to the soda lime glass plate in the same manner as in Example 1, two-step treatment was performed under the conditions shown in Table 3 below to form a zinc oxide film.
表３から明らかなように、Ｚｎ（ＮＯ3）2濃度０．０１〜０．０５モル／ｌという低濃度の酸化亜鉛膜形成用組成物を用いて酸化亜鉛膜を形成した後、Ｚｎ（ＮＯ3）2濃度０．０８〜０．１モル／ｌという比較的高い濃度の酸化亜鉛膜形成用組成物を用いて酸化亜鉛を析出させることにより、ポアー等の欠陥のない緻密な構造であって、（００１）面に優先配向した酸化亜鉛膜が形成された。この場合、処理液の温度は６０〜６５℃と比較的低温度であり、浴安定性が阻害されることが少ない点で有利であった。 As is apparent from Table 3, after forming a zinc oxide film using a zinc oxide film forming composition having a low concentration of Zn (NO 3 ) 2 of 0.01 to 0.05 mol / l, Zn (NO 3 ) 3 ) Precipitation of zinc oxide using a composition for forming a zinc oxide film having a relatively high concentration of 2 to 0.08 to 0.1 mol / l, resulting in a dense structure free from defects such as pores. , A zinc oxide film preferentially oriented on the (001) plane was formed. In this case, the temperature of the treatment liquid was relatively low at 60 to 65 ° C., which was advantageous in that the bath stability was hardly hindered.
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| JP2007126743A (en) * | 2005-10-04 | 2007-05-24 | Okuno Chem Ind Co Ltd | Pretreatment method for electroless plating and method for forming electroless plating film |
| JP2008098637A (en) * | 2006-10-12 | 2008-04-24 | Xerox Corp | Thin-film transistor |
| JP2008169053A (en) * | 2007-01-09 | 2008-07-24 | National Institute Of Advanced Industrial & Technology | ZnO SELF-SUPPORTED CRYSTAL FILM HAVING HIGH C-AXIS ORIENTATION AND HIGH SPECIFIC SURFACE AREA AND METHOD OF MANUFACTURING THE SAME |
| JP2008297168A (en) * | 2007-05-31 | 2008-12-11 | National Institute Of Advanced Industrial & Technology | ZnO WHISKER FILM AND ITS PREPARATION METHOD |
| JP2009013039A (en) * | 2007-07-09 | 2009-01-22 | National Institute Of Advanced Industrial & Technology | Zn5(CO3)2(OH)6 SELF-SUPPORTED CRYSTAL FILM AND ITS PRODUCTION METHOD |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007126743A (en) * | 2005-10-04 | 2007-05-24 | Okuno Chem Ind Co Ltd | Pretreatment method for electroless plating and method for forming electroless plating film |
| JP2008098637A (en) * | 2006-10-12 | 2008-04-24 | Xerox Corp | Thin-film transistor |
| JP2008169053A (en) * | 2007-01-09 | 2008-07-24 | National Institute Of Advanced Industrial & Technology | ZnO SELF-SUPPORTED CRYSTAL FILM HAVING HIGH C-AXIS ORIENTATION AND HIGH SPECIFIC SURFACE AREA AND METHOD OF MANUFACTURING THE SAME |
| JP4665175B2 (en) * | 2007-01-09 | 2011-04-06 | 独立行政法人産業技術総合研究所 | High c-axis oriented high specific surface area ZnO crystal free-standing film and method for producing the same |
| JP2008297168A (en) * | 2007-05-31 | 2008-12-11 | National Institute Of Advanced Industrial & Technology | ZnO WHISKER FILM AND ITS PREPARATION METHOD |
| JP2009013039A (en) * | 2007-07-09 | 2009-01-22 | National Institute Of Advanced Industrial & Technology | Zn5(CO3)2(OH)6 SELF-SUPPORTED CRYSTAL FILM AND ITS PRODUCTION METHOD |
| JP2013019041A (en) * | 2011-07-14 | 2013-01-31 | Toppan Printing Co Ltd | Method for forming zinc oxide film |
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