JP2010241638A - Thin film laminate with metal nanoparticle layer interposed - Google Patents
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本発明は、金属ナノ粒子層を挟んだ薄膜積層体に関する。 The present invention relates to a thin film laminate sandwiching metal nanoparticle layers.
ITO膜（Indium Tin Oxide膜)を使用した透明導電膜が知られている。ITO膜はスパッタリング粒子を２００℃以上に加熱して表面拡散を起こさせることによって結晶質層を形成し、その比抵抗値は２．５×１０−４Ωｃｍ以下になり得る。しかし、結晶化するためには基板温度を上げることが必要であるが、基板温度を上げて成膜すると低比抵抗値は得られない。 A transparent conductive film using an ITO film (Indium Tin Oxide film) is known. The ITO film forms a crystalline layer by heating the sputtered particles to 200 ° C. or more to cause surface diffusion, and the specific resistance value can be 2.5 × 10 −4 Ωcm or less. However, in order to crystallize, it is necessary to raise the substrate temperature. However, if the film is formed with the substrate temperature raised, a low specific resistance value cannot be obtained.
更に、ITO膜に使われているインジウムは希少金属であるため、このITO膜の代替金属として酸化亜鉛が有望視されている。しかし、低比抵抗値の酸化亜鉛膜は得られておらず、亜鉛の酸化膜である酸化亜鉛は透明であるが、透明導電膜としては使用できない。このため酸化亜鉛にＡｌなどをドープさせる方法が開発されているが、まだ十分に低い比抵抗値は得られていない。 Furthermore, since indium used in the ITO film is a rare metal, zinc oxide is promising as an alternative metal for the ITO film. However, a zinc oxide film having a low specific resistance value has not been obtained, and zinc oxide, which is a zinc oxide film, is transparent, but cannot be used as a transparent conductive film. For this reason, a method of doping zinc oxide with Al or the like has been developed, but a sufficiently low specific resistance value has not yet been obtained.
特開２０００−１２９４６４号公報は、二つの誘電体ベースのコーティング間に金属層を含み、金属層に接触する酸化亜鉛に基づいた薄膜積層体を開示している。赤外線反射特性を有した薄膜積層体に含有する金属層として、銀が有利であると述べている。実施例ではＡｌをドープしたＺｎＯを用いて、透過率７２％を得ているが、金属層は金属ナノ粒子層でなく、しかも薄膜積層体の比抵抗に触れておらず、対象の薄膜積層体が導電膜として利用できるか不明であり、薄膜積層体の構造に改良すべき点がある。 JP 2000-129464 discloses a thin-film stack based on zinc oxide that includes a metal layer between two dielectric-based coatings and contacts the metal layer. It states that silver is advantageous as the metal layer contained in the thin film laminate having infrared reflection characteristics. In the examples, ZnO doped with Al is used to obtain a transmittance of 72%, but the metal layer is not a metal nanoparticle layer, and the specific resistance of the thin film stack is not touched, and the target thin film stack Is unclear whether it can be used as a conductive film, and there is a point to be improved in the structure of the thin film laminate.
特開２００６―２０６４２４号公報は、透明基板の上に誘電体層と金属層（例．Ａｇ層）を２ｎ層以上に積層（ｎ≧１）した低反射率透明積層体を開示している。実施例に、透明基板としてのガラス板の上に、誘電体層としてのＺｎＯ層を、その上に金属層としてのＡｇ層を、更にその上に誘電体層としてのＺｎＯ層を積層した低反射率透明積層体を開示している。これによって日射遮蔽性、高断熱性が得られるという。しかし、実施例ではＡｌを2％含有するＺｎＯをターゲットとして得たＺｎＯにＡｌをドープしたAZO膜の積層体であり、ＺｎＯ膜を室温のような低温で積層体を構成した実施例もないし、Ａｇ層の詳細は不明であり、可視光透過率曲線にプラズモンによる効果が認められていないことからAg層は金属ナノ粒子層でなく、Ａｇの膜構造に改良すべき点がある。
Japanese Patent Application Laid-Open No. 2006-206424 discloses a low-reflectivity transparent laminate in which a dielectric layer and a metal layer (eg, Ag layer) are laminated on 2 n or more layers (n ≧ 1) on a transparent substrate. In the embodiment, a low reflection layer in which a ZnO layer as a dielectric layer is laminated on a glass plate as a transparent substrate, an Ag layer as a metal layer is laminated thereon, and a ZnO layer as a dielectric layer is further laminated thereon. A rate transparent laminate is disclosed. This is said to provide solar shading and high heat insulation. However, in the example, it is a laminated body of an AZO film obtained by doping ZnO containing 2% Al with ZnO as a target, and there is no example in which the laminated body is formed at a low temperature such as room temperature. Details of the Ag layer are unclear, and since the effect of plasmons is not recognized in the visible light transmittance curve, the Ag layer is not a metal nanoparticle layer, and there is a point that should be improved to the film structure of Ag.
発明者は、希少金属であるインジウムの代替金属として酸化亜鉛を使用しつつ、比抵抗値が低く、透明性がよい薄膜積層体を得るため鋭意検討した。 The inventors diligently studied to obtain a thin film laminate having a low specific resistance value and good transparency while using zinc oxide as a substitute metal for indium, which is a rare metal.
発明者は、上記課題を解決する下記の発明した。
１．基板上に、ＺｎＯ薄膜層、金属ナノ粒子層、ＺｎＯ薄膜層をこの順序に積層し、前記金属ナノ粒子層はAg、Al、Cu、Au、Ni、Pd、Pt、Zn、Cdの群から選ばれた１以上の金属ナノ粒子が結晶成長し相互に連結してナノ層を形成していることを特徴とする薄膜積層体
２．金属ナノ粒子が少なくともＡｇを含むナノ粒子であると効果的である。
３．金属ナノ粒子層の厚さが５ｎｍ〜１００ｎｍである前記１又は２に記載の薄膜積層体
４．ＺｎＯ、金属ナノ粒子層、およびＺｎＯの各薄膜層をDCマグネトロンスパッタリング法により室温において成膜した前記１、２又は３に記載の薄膜積層体
５．基板材料がガラス、セラミックス等の無機質板、熱可塑性樹脂、熱硬化性樹脂である前記１、２、３又は４に記載の薄膜積層体
６．基板材料が透明ガラスで、薄膜積層体の比抵抗が８．０×１０-４Ωｃｍ以下で、かつ紫外線域の波長を含んだ可視光透過率が７０％以上である前記１、２、３又は４に記載の薄膜積層体
The inventor has invented the following to solve the above problems.
1. A ZnO thin film layer, a metal nanoparticle layer, and a ZnO thin film layer are laminated in this order on a substrate, and the metal nanoparticle layer is selected from the group of Ag, Al, Cu, Au, Ni, Pd, Pt, Zn, and Cd 1. A thin film laminate in which at least one metal nanoparticle is grown and connected to each other to form a nanolayer. It is effective when the metal nanoparticles are nanoparticles containing at least Ag.
3. 3. The thin film laminate according to 1 or 2 above, wherein the thickness of the metal nanoparticle layer is 5 nm to 100 nm. 4. The thin film laminate according to the above 1, 2 or 3, wherein each thin film layer of ZnO, metal nanoparticle layer, and ZnO is formed at room temperature by a DC magnetron sputtering method. 5. The thin film laminate according to 1, 2, 3 or 4 above, wherein the substrate material is an inorganic plate such as glass or ceramics, a thermoplastic resin, or a thermosetting resin. The substrate material is transparent glass, the specific resistance of the thin film laminate is 8.0 × 10 −4 Ωcm or less, and the visible light transmittance including the wavelength in the ultraviolet region is 70% or more. 4. The thin film laminate according to 4
基板としては、（１）セラミックス膜（特に透明セラミックス膜）等の無機質板、（２）PP（ポリプロピレン）、PE（ポリエチレン）、PS（ポリスチレン）、PMMA（アクリル）、PET（ポリエチレンテレフタレート）、PPE（ポリフェニレンエーテル）、PA（ナイロン／ポリアミド）、PC（ポリカーボネイト）等の熱可塑性樹脂、（３）PF（フェノール樹脂）、MF（メラミン）等の熱硬化性樹脂が使用できる。透明かつ低抵抗の熱可塑性樹脂フィルム又はシート薄膜を基板に使用すると、ＰＤＰ、太陽電池、液晶のタッチパネルの電極、さらにはPDP、液晶の電磁波シールに使用できる。 Substrates include (1) inorganic plates such as ceramic films (especially transparent ceramic films), (2) PP (polypropylene), PE (polyethylene), PS (polystyrene), PMMA (acrylic), PET (polyethylene terephthalate), PPE Thermoplastic resins such as (polyphenylene ether), PA (nylon / polyamide), and PC (polycarbonate), and thermosetting resins such as (3) PF (phenol resin) and MF (melamine) can be used. When a transparent and low-resistance thermoplastic resin film or sheet thin film is used as a substrate, it can be used for electrodes of PDPs, solar cells, liquid crystal touch panels, PDPs, and liquid crystal electromagnetic waves.
本発明の構成要素であるＺｎＯ薄膜層、金属ナノ粒子層、ＺｎＯ薄膜層は透明性がよいので透明性を有する基板を使用して薄膜積層体を構成し透明性を必要とする用途に使用することが望ましいが、例えばUVレーザーとか、シートダイオードに使用するときは基板が透明性を有すことは必須でない。 Since the ZnO thin film layer, metal nanoparticle layer, and ZnO thin film layer, which are constituent elements of the present invention, have good transparency, a thin film laminate is formed using a transparent substrate and used for applications that require transparency. Desirably, however, it is not essential that the substrate be transparent, for example when used in UV lasers or sheet diodes.
金属ナノ粒子層のナノ粒子金属は、Ａｇ、Ａｌ、Ｃｕ、Ａｕ等の低抵抗の金属粒子単独で、またはそれらの金属ナノ粒子の組み合わせで使用できる。これらは表面プラズモン現象が発現しやすいからである。その中でも特にＡｇ又はＡｇと他の低抵抗の金属の組み合わせがよい。
金属ナノ粒子層は、金属ナノ粒子が電気的に連結されて形成されていることが好ましい。
金属ナノ粒子層の厚さは低比抵抗、透明性を確保できれば特に限定されるものではないが、実務的には５ｎｍ〜１００ｎｍ、好ましくは５ｎｍ〜５０ｎｍ、より好ましくは１０ｎｍ〜３０ｎｍがよい。連結して金属ナノ粒子層を形成する金属ナノ粒子の形状と大きさは上記金属ナノ粒子層の厚さ内に収まれば特に制限はない。
The nanoparticle metal of the metal nanoparticle layer can be used alone or in combination of metal particles with low resistance such as Ag, Al, Cu, Au. This is because the surface plasmon phenomenon is likely to occur. Among these, Ag or a combination of Ag and other low resistance metals is particularly preferable.
The metal nanoparticle layer is preferably formed by electrically connecting metal nanoparticles.
The thickness of the metal nanoparticle layer is not particularly limited as long as low specific resistance and transparency can be ensured, but in practice it is 5 nm to 100 nm, preferably 5 nm to 50 nm, more preferably 10 nm to 30 nm. The shape and size of the metal nanoparticles that are connected to form the metal nanoparticle layer are not particularly limited as long as they are within the thickness of the metal nanoparticle layer.
本発明の金属ナノ粒子層を挟んだ薄膜積層体は、基板上にＺｎＯ/金属ナノ粒子層/ＺｎＯの順に積層している。この薄膜積層体は、基板上に設けたＺｎＯ薄膜層の上に金属ナノ粒子層を形成した後、さらに、その上にＺｎＯ薄膜層を設けることで得られる。成膜成層方法はDCマグネトロンスパッタリング法が好ましいが、これに限定されるものではない。
DCマグネトロンスパッタリング法において傾斜対向したターゲット配置を採用すると、スパッタリング粒子やＡｒによる基板上に成膜するＺｎＯ薄膜層および金属ナノ粒子層の損傷を低減できる。
The thin film laminate sandwiching the metal nanoparticle layers of the present invention is laminated on the substrate in the order of ZnO / metal nanoparticle layer / ZnO. This thin film laminate can be obtained by forming a metal nanoparticle layer on a ZnO thin film layer provided on a substrate and further providing a ZnO thin film layer thereon. The film deposition method is preferably a DC magnetron sputtering method, but is not limited thereto.
Employing a target arrangement that is inclined and opposed in the DC magnetron sputtering method can reduce damage to the ZnO thin film layer and the metal nanoparticle layer formed on the substrate by sputtering particles or Ar.
本発明の薄膜積層体は、真空中で磁場で制御したスパッタリング法で、基板上に誘電体であるＺｎＯ薄膜層を室温において成膜し、その上に金属ナノ粒子層を結晶成長させた後、さらにその上にＺｎＯ薄膜層を積層して製造することが望ましい。ＺｎＯ薄膜層上に金属ナノ粒子層を形成させることにより、ＺｎＯ薄膜層を使用しているにも拘わらず比抵抗を低下させ、かつ透明性を高めたＺｎＯ薄膜層/金属ナノ粒子層/ＺｎＯ薄膜層からなる薄膜積層体が得られる。 The thin film laminate of the present invention is a sputtering method controlled by a magnetic field in a vacuum, a ZnO thin film layer that is a dielectric is formed on a substrate at room temperature, and after a metal nanoparticle layer is grown on the crystal, Furthermore, it is desirable to manufacture by laminating a ZnO thin film layer thereon. By forming a metal nanoparticle layer on the ZnO thin film layer, the specific resistance is lowered and the transparency is enhanced even though the ZnO thin film layer is used, and the transparency is improved. ZnO thin film layer / metal nanoparticle layer / ZnO thin film A thin film laminate comprising layers is obtained.
本発明の薄膜積層体は、金属ナノ粒子によってプラズモンを発生させ、透過率を向上させたことにも特徴がある。表面プラズモン現象は金属表面に光が照射されると、金属表面の約５０ｎｍ以下の表面層で光が生じる物理現象である。
透明な二つのＺｎＯ膜の間に、相互に連結した金属ナノ粒子からなる金属ナノ粒子を挟んだ本発明の薄膜積層体の表面プラズモン現象は、光の吸収と散乱の二つの因子が原因となって発現する。ＺｎＯ膜表面上に金属ナノ粒子層を堆積すると、表面プラズモン現象は金属ナノ粒子層の構造に依存して約５４０ｎｍ付近の波長領域において強く発現され、実用上使用できる光線の波長域を拡大させ、かつ可視光透過率を増大させる効果が高い。金属ナノ粒子層は、可視光域における光の散乱に強い影響を及ぼす。金属（例．Ａｇ）ナノ粒子の結晶成長の形態は、比抵抗の減少、かつ透明性の確保に影響がある。
The thin film laminate of the present invention is also characterized in that plasmons are generated by metal nanoparticles and the transmittance is improved. The surface plasmon phenomenon is a physical phenomenon in which light is generated in a surface layer of about 50 nm or less on the metal surface when the metal surface is irradiated with light.
The surface plasmon phenomenon of the thin film laminate of the present invention in which metal nanoparticles composed of interconnected metal nanoparticles are sandwiched between two transparent ZnO films is caused by two factors, light absorption and scattering. Expressed. When a metal nanoparticle layer is deposited on the surface of the ZnO film, the surface plasmon phenomenon is strongly expressed in a wavelength region near about 540 nm depending on the structure of the metal nanoparticle layer, and the wavelength region of light that can be used practically is expanded. In addition, the effect of increasing the visible light transmittance is high. The metal nanoparticle layer has a strong influence on light scattering in the visible light region. The form of crystal growth of metal (eg, Ag) nanoparticles has an effect on reduction of specific resistance and ensuring transparency.
基板を除く薄膜積層体全体の膜厚は特に制限はないが、４５ｎｍ〜２２５ｎｍ、好ましくは４５ｎｍ〜１１０ｎｍであることが望ましい。ＺｎＯ膜単独の膜厚が１１０ｎｍ越えることは成膜に多大な時間を要し、かつ透明性が劣るので、生産上好ましくない。 The film thickness of the entire thin film laminate excluding the substrate is not particularly limited, but is desirably 45 nm to 225 nm, preferably 45 nm to 110 nm. If the thickness of the ZnO film alone exceeds 110 nm, it takes a long time to form the film and is inferior in transparency, which is not preferable for production.
本発明の薄膜積層体のＺｎＯ薄膜層表面の凹凸の最大粗さは１０ｎｍ以下、好ましくは５ｎｍ以下の平滑性を持つことが望ましい。本発明の薄膜積層体は平滑性が要求される透明導電膜電極用および/または太陽光発電電極用、さらには電磁波シールド用の基板が主な用途になるからである。 The maximum roughness of the unevenness on the surface of the ZnO thin film layer of the thin film laminate of the present invention is desirably 10 nm or less, preferably 5 nm or less. This is because the thin film laminate of the present invention is mainly used for substrates for transparent conductive films and / or photovoltaic power generation electrodes that require smoothness, and for electromagnetic wave shielding.
誘電体である二つのＺｎＯ薄膜層の間に金属ナノ粒子層を挟んだ本発明のＺｎＯ/金属ナノ粒子層/ＺｎＯからなる薄膜積層体は、その比抵抗は８．０×１０―４Ωｃｍ以下、条件によっては９．０×１０-５Ωｃｍ以下にでき、更に紫外線領域の波長を含んだ可視光透過率が７０％以上、条件によっては８０％以上にできるので、従来にまして導電性が高く、かつ透明性の高い。本発明により透明導電膜としての酸化亜鉛薄膜の用途を広げることが可能になった。 The specific resistance of the thin film laminate of ZnO / metal nanoparticle layer / ZnO of the present invention in which the metal nanoparticle layer is sandwiched between two dielectric ZnO thin film layers is 8.0 × 10 −4 Ωcm or less. Depending on the conditions, it can be 9.0 × 10 −5 Ωcm or less, and the visible light transmittance including the wavelength in the ultraviolet region is 70% or more, and depending on the conditions, it can be 80% or more. And high transparency. The use of the zinc oxide thin film as the transparent conductive film can be expanded by the present invention.
本発明の薄膜積層体は、基板温度が室温であっても、二つの酸化亜鉛間に金属ナノ粒子層を挟んだ構造体からなる薄膜積層体を製造できる。本発明の薄膜積層体は、透明導電膜、太陽光発電電極、電磁波シールド材等として使用できる。 The thin film laminate of the present invention can produce a thin film laminate comprising a structure in which a metal nanoparticle layer is sandwiched between two zinc oxides even when the substrate temperature is room temperature. The thin film laminate of the present invention can be used as a transparent conductive film, a photovoltaic power generation electrode, an electromagnetic wave shielding material, and the like.
以下に本発明の実施の形態を説明する。
本発明の薄膜積層体は、図１に示す構造をしており、基板１の表面上に酸化亜鉛ＺｎＯ薄膜層２、その上に金属ナノ粒子層３、更にその上に酸化亜鉛ＺｎＯ薄膜層４がある。
本発明の薄膜積層体は、図２に示す傾斜対向ターゲット型DCマグネトロンスパッタリング装置を使って製造できる。
Embodiments of the present invention will be described below.
The thin film laminate of the present invention has a structure shown in FIG. 1, and a zinc oxide ZnO thin film layer 2 is formed on the surface of the substrate 1, a metal nanoparticle layer 3 is formed thereon, and a zinc oxide ZnO thin film layer 4 is formed thereon. There is.
The thin film laminate of the present invention can be manufactured using the inclined opposed target type DC magnetron sputtering apparatus shown in FIG.
ターゲットは基板に対して４５度の角度で設置しているため、シャッターを開けて基板を回転させながらコーティングを行う時に、スパッタリングされた粒子が基板に到着したときに起こすＺｎＯ薄膜の損傷を低減させることができる。そのため、この装置を使用すれば、コーティング時の基板温度は低くでき、室温でコーティングできる。製造したＺｎＯ薄膜表面上に金属ナノ粒子層を堆積すること、さらにその上にＺｎＯ薄膜層を成膜することにより、低比抵抗の導電性のよい薄膜積層体を得ることができる。その際、金属ナノ粒子層は、基板を固定させて加熱せずに短時間に成膜することが良い。 Since the target is set at an angle of 45 degrees with respect to the substrate, when coating is performed while the shutter is opened and the substrate is rotated, damage to the ZnO thin film caused when the sputtered particles arrive at the substrate is reduced. be able to. Therefore, if this apparatus is used, the substrate temperature at the time of coating can be lowered, and coating can be performed at room temperature. By depositing a metal nanoparticle layer on the surface of the manufactured ZnO thin film and further forming a ZnO thin film layer thereon, a thin film laminate having a low specific resistance and good conductivity can be obtained. At that time, the metal nanoparticle layer is preferably formed in a short time without fixing and heating the substrate.
本傾斜対向ターゲット型DCマグネトロンスパッタリング装置は、ターゲット材を４枚同時に設置することができる特徴を有している。ターゲットして酸化物ターゲット（酸化亜鉛）や金属ターゲットのいずれも使用可能である。ターゲットＴ１として金属１、ターゲットＴ２として金属２、ターゲットＴ３として金属３およびターゲットＴ４として金属４の純金属を同時に設置することができる。導電性の良い薄膜積層体を得るには、金属として電気抵抗が低い金属を使用することが望ましい。 This inclined opposed target type DC magnetron sputtering apparatus has a feature that four target materials can be installed simultaneously. As the target, either an oxide target (zinc oxide) or a metal target can be used. Metal 1 as target T1, metal 2 as target T2, metal 3 as target T3, and pure metal of metal 4 as target T4 can be simultaneously installed. In order to obtain a thin film laminate having good conductivity, it is desirable to use a metal having a low electrical resistance as the metal.
ＺｎＯ薄膜層の成膜にはターゲットＴ１に純亜鉛（９９．９９％）を設置し、スパッタガスとして酸素とアルゴンの混合ガスを用いてスパッタリングするのが望ましい。その際、チャンバー内の圧力を６．０×１０−１Ｐａ〜７．０×１０−１Ｐａにするのが良い。金属ナノ粒子層のコーティングに際して、金属ナノ粒子層単体の堆積には、ターゲットＴ３に純銀（９９．９９％）、純Ａｌ（９９．９９％）、純銅（９９．９９％）あるいは純金（９９．９９％）のいずれか一つを設置するのがよい。 For the formation of the ZnO thin film layer, it is desirable to place pure zinc (99.99%) on the target T1 and perform sputtering using a mixed gas of oxygen and argon as a sputtering gas. At that time, it is good to the pressure in the chamber to 6.0 × 10 -1 Pa~7.0 × 10 -1 Pa. When the metal nanoparticle layer is coated, pure silver (99.99%), pure Al (99.99%), pure copper (99.99%) or pure gold (99.99%) is deposited on the target T3. 99%) should be installed.
２種類の金属ナノ粒子がランダムに分布した金属ナノ粒子層を得る場合、例えばターゲットＴ２に純Ａｌ（９９．９９％）、純銅（９９．９９％）あるいは純金（９９．９９％）のいずれか一つ、ターゲットＴ３に純銀（９９．９９％）を設置するのが良い。３種類の金属ナノ粒子の金属ナノ粒子がランダムに分布した金属ナノ粒子層を得る場合、例えばターゲットＴ２として純銅（９９．９９％）または純金（９９．９９％）、ターゲットＴ３として純銀（９９．９９％）、ターゲットＴ４として純Ａｌ（９９．９％）を設置するのがよい。 When obtaining a metal nanoparticle layer in which two types of metal nanoparticles are randomly distributed, for example, either pure Al (99.99%), pure copper (99.99%), or pure gold (99.99%) is used as the target T2. One, it is good to install pure silver (99.99%) on the target T3. When obtaining a metal nanoparticle layer in which metal nanoparticles of three kinds of metal nanoparticles are randomly distributed, for example, pure copper (99.99%) or pure gold (99.99%) as the target T2, and pure silver (99.99%) as the target T3. 99%) and pure Al (99.9%) is preferably installed as the target T4.
チャンバー内の圧力は６．０×１０−１Ｐａ〜７．０×１０−１Ｐａにしてアルゴンガスを用いてスパッタリングするのが良い。堆積時間は特に制限はないが、金属ナノ粒子および金属ナノ膜が得られる５秒〜４５秒、好ましくは１０秒〜３０秒が良い。ＺｎＯ/金属ナノ粒子層/ＺｎＯからなる薄膜積層体の透明性と比抵抗は、二つのＺｎＯ間に挟まれた金属ナノ粒子層の構造（金属ナノ膜と金属ナノ粒子の大きさ、形状および密度等）の影響を受ける。 The pressure in the chamber is preferably 6.0 × 10 −1 Pa to 7.0 × 10 −1 Pa, and sputtering is performed using argon gas. The deposition time is not particularly limited, but is 5 seconds to 45 seconds, preferably 10 seconds to 30 seconds, from which metal nanoparticles and metal nanofilms can be obtained. The transparency and specific resistance of the thin film stack consisting of ZnO / metal nanoparticle layer / ZnO are the structure of the metal nanoparticle layer sandwiched between two ZnOs (size, shape and density of the metal nanofilm and metal nanoparticles). Etc.).
図２に示す傾斜対向型ＤＣマグネトロンスパッタリング装置を用いてＺｎＯ/Ａｇ/ＺｎＯの薄膜積層体を製造した。チャンバー内にあるターゲットＴ１およびターゲットＴ３の位置に、それぞれ純亜鉛（純度９９．９９％、３００×６２×５ｍｍ）板、および純銀（９９．９９％、３００×６２×５ｍｍ）板を予め取り付けた。また、ガラス基板は中心部の回転台に取り付けた。 A thin film laminate of ZnO / Ag / ZnO was manufactured using the inclined opposed DC magnetron sputtering apparatus shown in FIG. Pure zinc (purity 99.99%, 300 × 62 × 5 mm) plates and pure silver (99.99%, 300 × 62 × 5 mm) plates were previously attached to the positions of the target T1 and target T3 in the chamber, respectively. . Moreover, the glass substrate was attached to the turntable in the center.
その後、チャンバー内を３．０×１０−３Ｐａ〜３．３×１０−３Ｐａ以下になるまで真空にした。ガラス基板表面上にＺｎＯ膜を成膜する。まず、チャンバー内にＡｒ／Ｏ２の流量比が５０／３（ｓｃｃｍ）である混合ガスを流入させて、チャンバー内の圧力を６．０×１０−１Ｐａ〜７．０×１０−１Ｐａに調整した。基板を取り付けた回転台は回転速度５ｒｐｍで回転させながら、コイル電流５Ａ、アノード電圧２０V、バイアス電圧０Ｖ、純亜鉛ターゲットの電流は０．１Ａ、ターゲット電圧２５０Ｖ〜２６０Ｖの条件下でスパッタリングした。そのＺｎＯ膜の成膜速度は０．５１４ｎｍ/ｓであった。コーティング時間を１００分としてガラス基板表面上に膜厚５０ｎｍのＺｎＯ膜を得た。 Then, vacuum was applied until the chamber below 3.0 × 10 -3 Pa~3.3 × 10 -3 Pa. A ZnO film is formed on the glass substrate surface. First, by introducing the mixed gas flow ratio of Ar / O 2 is 50/3 (sccm) into the chamber, the pressure in the chamber 6.0 × 10 -1 Pa~7.0 × 10 -1 Pa Adjusted. Sputtering was performed under the conditions of a coil current of 5 A, an anode voltage of 20 V, a bias voltage of 0 V, a pure zinc target of 0.1 A, and a target voltage of 250 V to 260 V while the turntable on which the substrate was attached was rotated at a rotation speed of 5 rpm. The deposition rate of the ZnO film was 0.514 nm / s. A ZnO film having a thickness of 50 nm was obtained on the surface of the glass substrate with a coating time of 100 minutes.
次に得たＺｎＯ膜表面上にＡｇナノ粒子層を堆積するために、チャンバー内にＡｒガスを５０ｓｃｃｍの流量で流入させた。そのときのチャンバー内の圧力は、６．０×１０−１Ｐａ〜７．０×１０−１Ｐａとして、基板を取り付けた回転台は固定させた。コイル電流５Ａ、アノード電圧２０V、バイアス電圧０Ｖ、純銀ターゲットの電流は０．４Ａ、ターゲット電圧２７０Ｖ〜２８０Ｖの条件でＡｇナノ粒子層を堆積した。その堆積速度は０．４ｎｍ/ｓであった。堆積時間を１０秒〜４５秒に変えてＺｎＯ膜表面上に直接Ａｇナノ粒子層を堆積させた。 Next, in order to deposit an Ag nanoparticle layer on the surface of the obtained ZnO film, Ar gas was introduced into the chamber at a flow rate of 50 sccm. Pressure in the chamber at this time, as 6.0 × 10 -1 Pa~7.0 × 10 -1 Pa, turntable fitted with substrate was fixed. The Ag nanoparticle layer was deposited under the conditions of a coil current of 5 A, an anode voltage of 20 V, a bias voltage of 0 V, a pure silver target current of 0.4 A, and a target voltage of 270 V to 280 V. The deposition rate was 0.4 nm / s. The Ag nanoparticle layer was deposited directly on the ZnO film surface by changing the deposition time from 10 seconds to 45 seconds.
このＡｇナノ粒子層は、図３の電子顕微鏡写真が示すようにＺｎＯ膜表面上に直接堆積した金属ナノ膜上に金属ナノ粒子から構成されていた。Ａｇナノ粒子径は、２０ｎｍ〜５０ｎｍの範囲に分布しており、粒子径が３０ｎｍ〜４０ｎｍのＡｇナノ粒子が最も多かった。堆積時間が長くなっても、Ａｇナノ粒子径はほとんど同じであり、その密度は増加した。
得たＡｇナノ粒子層表面上にＺｎＯ膜を成膜した。その成膜条件は、上記のＺｎＯ膜の成膜条件と同一にした。得たＺｎＯ膜は、Ａｇナノ粒子間およびＡｇナノ粒子頂上に堆積した構造であった。薄膜積層体の成膜中の基板温度は３０℃とした。
The Ag nanoparticle layer was composed of metal nanoparticles on the metal nanofilm deposited directly on the surface of the ZnO film as shown in the electron micrograph of FIG. The Ag nanoparticle diameter was distributed in a range of 20 nm to 50 nm, and the Ag nanoparticle having a particle diameter of 30 nm to 40 nm was the largest. Even with a longer deposition time, the Ag nanoparticle size was almost the same and its density increased.
A ZnO film was formed on the surface of the obtained Ag nanoparticle layer. The film formation conditions were the same as those for the ZnO film. The obtained ZnO film had a structure deposited between Ag nanoparticles and on top of Ag nanoparticles. The substrate temperature during film formation of the thin film laminate was 30 ° C.
製造した薄膜積層体のガラス基板を含めた最大の可視光透過率は、図４に示すように、Ａｇナノ粒子の堆積時間が１０秒では７５％、１５秒では７８％、２０秒では８７％、２５秒では８０％、３０秒では８０％、３５秒では７４％、４０秒では７４％、４５秒では６８％であった。可視光透過率曲線が示すようにAgナノ粒子層の構造によって可視光透過率が変化し、かつその波長域が長波長域から短波長域に変化している。これはAgナノ粒子層の構造に基づく表面プラズモン現象の原因のうち散乱効果が強く現れたものと考えられる。また、紫外線領域の３７０ｎｍの透過率にピークが現れているが、これは表面プラズモンがAgナノ粒子による吸収効果に依存した現象と考えられる。製造した薄膜積層体の比抵抗は、図５に示すように７．４×１０―４Ωｃｍ（堆積時間＝１０秒）、５．３×１０―５Ωｃｍ（堆積時間＝２０秒）、１．８×１０―５Ωｃｍ（堆積時間＝３０秒）、１．４×１０―５Ωｃｍ（堆積時間＝４０秒）であった。この薄膜積層体のＸ線回折測定を行ったところ酸化亜鉛の（１００）を示す回折ピークとＡｇの（１１１）を示す回折ピークが観察され、室温で成膜したＺｎＯ薄膜層は結晶質であることが確認できた。また、原子間力顕微鏡より求めた薄膜積層体表面の凹凸は、平均粗さはＲａ＝０．６５５ｎｍー０．２３２ｎｍであり、最大粗さは約５．０ｎｍであった。 As shown in FIG. 4, the maximum visible light transmittance including the glass substrate of the manufactured thin film laminate is 75% for Ag nanoparticle deposition time of 10 seconds, 78% for 15 seconds, and 87% for 20 seconds. 80% at 25 seconds, 80% at 30 seconds, 74% at 35 seconds, 74% at 40 seconds, and 68% at 45 seconds. As shown by the visible light transmittance curve, the visible light transmittance varies depending on the structure of the Ag nanoparticle layer, and the wavelength region changes from the long wavelength region to the short wavelength region. This is considered to be due to the strong scattering effect among the causes of the surface plasmon phenomenon based on the structure of the Ag nanoparticle layer. In addition, a peak appears in the transmittance of 370 nm in the ultraviolet region, which is considered to be a phenomenon in which the surface plasmon depends on the absorption effect by Ag nanoparticles. The specific resistance of the manufactured thin film laminate is 7.4 × 10 −4 Ωcm (deposition time = 10 seconds), 5.3 × 10 −5 Ωcm (deposition time = 20 seconds), as shown in FIG. They were 8 × 10 −5 Ωcm (deposition time = 30 seconds) and 1.4 × 10 −5 Ωcm (deposition time = 40 seconds). When the X-ray diffraction measurement of this thin film laminate was performed, a diffraction peak showing (100) of zinc oxide and a diffraction peak showing (111) of Ag were observed, and the ZnO thin film layer formed at room temperature was crystalline. I was able to confirm. Further, the unevenness of the surface of the thin film laminate obtained from the atomic force microscope had an average roughness of Ra = 0.655 nm-0.232 nm and a maximum roughness of about 5.0 nm.
実施例１と同様に傾斜対向型ＤＣマグネトロンスパッタリング装置を使用して、ＺｎＯ/金属ナノ粒子層/ＺｎＯからなる薄膜積層体を製造した。金属ナノ粒子層として、Ａｇナノ粒子層単体、Ａｌナノ粒子層単体並びにＡｇおよびＡｌナノ粒子からなるものを別々に製造した。
チャンバー内のターゲットの位置に、ターゲットＴ１には純亜鉛（純度９９．９９％、３００×６２×５ｍｍ）板、ターゲットＴ３には純銀（９９．９９％、３００×６２×５ｍｍ）板、ターゲットＴ４には純Ａｌ（純度９９．９９％、３００×６２×５ｍｍ）板を取り付けた。ＺｎＯ膜のコーティング条件は、実施例１と同様な条件の下でＺｎＯ膜を成膜した。
In the same manner as in Example 1, a tilted opposed DC magnetron sputtering apparatus was used to manufacture a thin film laminate composed of ZnO / metal nanoparticle layer / ZnO. As the metal nanoparticle layer, an Ag nanoparticle layer alone, an Al nanoparticle layer alone, and Ag and Al nanoparticles were separately manufactured.
At the target position in the chamber, the target T1 has a pure zinc (purity 99.99%, 300 × 62 × 5 mm) plate, the target T3 has a pure silver (99.99%, 300 × 62 × 5 mm) plate, and the target T4. A pure Al (purity 99.99%, 300 × 62 × 5 mm) plate was attached. The ZnO film was formed under the same coating conditions as in Example 1.
金属ナノ粒子層は、Ａｇナノ粒子層単体あるいはＡｌナノ粒子層単体をＺｎＯ膜表面上に堆積した他、２つの金属ナノ粒子層からなる混合層をＺｎＯ膜表面上に直接堆積した。その堆積条件は実施例１と同じとした。ただし、純Ａｌターゲットの電流は０．２Ａ（堆積速度＝０．０８ｎｍ/sec、堆積時間＝１６秒）および０．４Ａ(堆積速度＝０．１５ｎｍ/sec、堆積時間＝１３秒)に変えた。金属ナノ粒子層の上にＺｎＯ膜を実施例１の条件と同様にして成膜した。 As the metal nanoparticle layer, a single Ag nanoparticle layer or an Al nanoparticle layer was deposited on the ZnO film surface, and a mixed layer composed of two metal nanoparticle layers was directly deposited on the ZnO film surface. The deposition conditions were the same as in Example 1. However, the current of the pure Al target was changed to 0.2 A (deposition rate = 0.08 nm / sec, deposition time = 16 seconds) and 0.4 A (deposition rate = 0.15 nm / sec, deposition time = 13 seconds). . A ZnO film was formed on the metal nanoparticle layer in the same manner as in Example 1.
製造した薄膜積層体のガラス基板を含めた最大の可視光透過率は、図６に示すように、Ａｇナノ粒子層単体では８７％、Ａｌナノ粒子層単体では７８％、Ａｇ＋Ａｌナノ粒子の混合ナノ粒子層では６０％（０．２Ａ）および６４％（０．４Ａ）であった。ＺｎＯ/金属ナノ粒子層/ＺｎＯからなる薄膜積層体の透明性は、薄膜積層体の間に挟んだ金属ナノ粒子の種類が、最大可視光透過率を変えた。この薄膜積層体の比抵抗値は、Ａｇナノ粒子層単体（堆積時間＝２０秒）；５．６×１０―５Ωｃｍ、Ａｌナノ粒子単体（堆積時間＝３分）；１２Ωｃｍ、Ａｇ+Ａｌナノ粒子混合層（堆積時間＝１６秒）；７．６×１０―４Ωｃｍ、Ａｇ＋Ａｌナノ粒子混合層（堆積時間＝１３秒）；１．８×１０―３Ωｃｍであった。 As shown in FIG. 6, the maximum visible light transmittance of the manufactured thin film laminate including the glass substrate is 87% for the Ag nanoparticle layer alone, 78% for the Al nanoparticle layer alone, and mixed nanoparticles of Ag + Al nanoparticles. The particle layer was 60% (0.2 A) and 64% (0.4 A). As for the transparency of the thin film laminate composed of ZnO / metal nanoparticle layer / ZnO, the type of metal nanoparticles sandwiched between the thin film laminates changed the maximum visible light transmittance. The specific resistance value of this thin film laminate was as follows: Ag nanoparticle layer alone (deposition time = 20 seconds); 5.6 × 10 −5 Ωcm, Al nanoparticle alone (deposition time = 3 minutes); 12Ωcm, Ag + Al nanoparticle Particle mixed layer (deposition time = 16 seconds); 7.6 × 10 −4 Ωcm, Ag + Al nanoparticle mixed layer (deposition time = 13 seconds); 1.8 × 10 −3 Ωcm.
実施例１と同様に傾斜対向型ＤＣマグネトロンスパッタリング装置を使用してＺｎＯ/Ｃｕ/ＺｎＯからなる薄膜積層体を製造した。ターゲットＴ１として純亜鉛（純度９９．９９％、３００×６２×５ｍｍ）板を設置した他に、ターゲットＴ３には純銅（９９．９９％、３００×６２×５ｍｍ）板を取り付けた以外は、成膜条件は実施例１と同様にした。
Ｃｕナノ粒子層は、ＺｎＯ膜表面上に直接堆積した。その堆積条件は、純Ａｇと同じにして堆積時間を３５秒、７０秒、１０５秒および１４０秒に変えた。再度、その上にＺｎＯ膜を実施例１の条件と同様にして成膜した。
In the same manner as in Example 1, a thin film laminate made of ZnO / Cu / ZnO was manufactured using a tilted opposed DC magnetron sputtering apparatus. In addition to installing a pure zinc (purity 99.99%, 300 × 62 × 5 mm) plate as the target T1, the target T3 is composed of a pure copper (99.99%, 300 × 62 × 5mm) plate, except that it is attached. The film conditions were the same as in Example 1.
The Cu nanoparticle layer was deposited directly on the ZnO film surface. The deposition conditions were the same as pure Ag, and the deposition time was changed to 35 seconds, 70 seconds, 105 seconds and 140 seconds. Again, a ZnO film was formed thereon in the same manner as in Example 1.
製造した薄膜積層体のガラス基板を含めた最大の可視光透過率は、図７に示すように、堆積時間が３５秒で７９％、７０秒で７０％、１０５秒で６０％、１４０秒で５３％であった。この薄膜積層体の比抵抗値は、３．８×１０―２Ωｃｍ（３５秒）、２．９×１０―３Ωｃｍ（７０秒）、６．１×１０―４Ωｃｍ（１０５秒）、５．４×１０―４Ωｃｍ（１４０秒）であった。 As shown in FIG. 7, the maximum visible light transmittance including the glass substrate of the manufactured thin film laminate is 79% at 35 seconds, 70% at 70 seconds, 60% at 105 seconds, and 140 seconds. 53%. The specific resistance of this thin film laminate was 3.8 × 10 −2 Ωcm (35 seconds), 2.9 × 10 −3 Ωcm (70 seconds), 6.1 × 10 −4 Ωcm (105 seconds), 5 4 × 10 −4 Ωcm (140 seconds).
１ 基板
２ 酸化亜鉛ＺｎＯ薄膜層
３ 金属ナノ粒子層
４ 酸化亜鉛ＺｎＯ薄膜層
Ｔ１ ターゲット
Ｔ２ ターゲット
Ｔ３ ターゲット
Ｔ４ ターゲット
DESCRIPTION OF SYMBOLS 1 Substrate 2 Zinc oxide ZnO thin film layer 3 Metal nanoparticle layer 4 Zinc oxide ZnO thin film layer T1 Target T2 Target T3 Target T4 Target
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| JP2009092037A JP2010241638A (en) | 2009-04-06 | 2009-04-06 | Thin film laminate with metal nanoparticle layer interposed |
| CN2009202722401U CN201816254U (en) | 2009-04-06 | 2009-11-20 | Film laminated structure with metal nano particle interlayer |
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| CN102199755A (en) * | 2011-04-27 | 2011-09-28 | 南开大学 | Method for growing hydrogenated Ga-Ti codoped ZnO-TCO thin film and application |
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| JP2006206424A (en) * | 2004-12-27 | 2006-08-10 | Central Glass Co Ltd | Ag FILM FORMING METHOD AND LOW-EMISSIVITY GLASS |
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2009
- 2009-04-06 JP JP2009092037A patent/JP2010241638A/en active Pending
- 2009-11-20 CN CN2009202722401U patent/CN201816254U/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006206424A (en) * | 2004-12-27 | 2006-08-10 | Central Glass Co Ltd | Ag FILM FORMING METHOD AND LOW-EMISSIVITY GLASS |
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