JPH05142605A - Nonlinear optical material and its production - Google Patents
Nonlinear optical material and its productionInfo
- Publication number
- JPH05142605A JPH05142605A JP30181891A JP30181891A JPH05142605A JP H05142605 A JPH05142605 A JP H05142605A JP 30181891 A JP30181891 A JP 30181891A JP 30181891 A JP30181891 A JP 30181891A JP H05142605 A JPH05142605 A JP H05142605A
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- optical material
- particles
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- fine particles
- metal
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非線形光学効果を利用
した光デバイスの基礎をなす、金属微粒子と光学的透明
物質との積層構造を有する非線形光学材料およびその製
造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nonlinear optical material having a laminated structure of fine metal particles and an optically transparent substance, which is the basis of an optical device utilizing the nonlinear optical effect, and a method for producing the same.
【０００２】[0002]
【従来の技術】金属微粒子をガラス中に分散させること
により、金属の３次の非線形感受率が増大し、光学的非
線形性が大きくなることがアプライド フィジックス
Ａ 第47巻第347 頁（Applied Physics A,vol.47,347(1
988)）に記載されている。BACKGROUND OF THE INVENTION Applied physics is that dispersion of fine metal particles in glass increases the third-order nonlinear susceptibility of the metal and increases optical nonlinearity.
A Vol. 47, p. 347 (Applied Physics A, vol.47,347 (1
988)).
【０００３】金属微粒子分散ガラスの製造方法として
は、溶融法によって作製した金を含有するケイ酸塩ガラ
スを熱処理して、ガラスマトリックス中に金微粒子を分
散させている。As a method for producing a glass containing dispersed fine metal particles, a silicate glass containing gold prepared by a melting method is heat-treated to disperse the fine gold particles in a glass matrix.
【０００４】[0004]
【発明が解決しようとする課題】このような、従来の方
法で製造した金属微粒子分散ガラスの３次の非線形感受
率は１０-14 〜１０-11ｅｓｕの値であり、非常に小さ
い。この原因は、ガラス中の金属微粒子が０．０１体積
％未満と非常に少ないためである。従来の製造方法で
は、金属含有量をこれ以上増やすと、溶融時に溶解限界
を越えて凝集し、バルク粒子として析出してしまうの
で、金属を微粒子としてガラス中に分散させることがで
きない。また、熱処理により金属微粒子の核生成・成長
を行なわせているため、熱力学的平衡に支配され、粒径
に分布が生じるのは避けられない。そのため非線形性に
ばらつきが生じ、非線形光学材料としての制御性が劣
る。The third-order nonlinear susceptibility of the metal fine particle-dispersed glass produced by the conventional method as described above is a value of 10 -14 to 10 -11 esu, which is very small. This is because the metal fine particles in the glass are very small, less than 0.01% by volume. In the conventional manufacturing method, if the metal content is increased more than this, the melting limit is exceeded and the particles are aggregated and precipitated as bulk particles during melting, so that the metal cannot be dispersed as fine particles in the glass. Further, since the nucleation and growth of the metal fine particles are performed by the heat treatment, it is unavoidable that they are governed by thermodynamic equilibrium and the particle size is distributed. Therefore, the non-linearity varies, and the controllability of the non-linear optical material is poor.
【０００５】本発明は、このような課題を解決するもの
で、光学的透明物質中に粒径のそろった金属微粒子が分
散した非線形感受率の大きな非線形光学材料および光学
的透明物質中に粒径をそろえて金属微粒子を多量に分散
し得る非線形感受率の大きな非線形光学材料を製造する
方法を提供することを目的とする。The present invention is intended to solve such a problem, and a non-linear optical material having a large non-linear susceptibility in which fine metal particles having a uniform particle size are dispersed in an optically transparent substance and a particle size in the optically transparent substance. It is an object of the present invention to provide a method for producing a non-linear optical material having a large non-linear susceptibility capable of dispersing a large amount of metal fine particles.
【０００６】[0006]
【課題を解決するための手段】前記目的を達成するため
に本発明の非線形光学材料は、光学的透明物質中に粒径
のそろった金属微粒子が層状に分散されてなる非線形光
学材料である。In order to achieve the above object, the non-linear optical material of the present invention is a non-linear optical material in which fine metal particles having a uniform particle size are dispersed in a layer in an optically transparent substance.
【０００７】前記構成においては、金属微粒子が金、
銀、銅、白金、あるいはパラジウムから選ばれた少なく
とも１種の金属であることが好ましい。本発明の非線形
光学材料の製造方法は、光学的透明物質中に金属微粒子
が分散されてなる非線形光学材料の製造方法において、
金属微粒子と光学的透明物質とを基板面上に交互に堆積
させることを特徴とする。In the above structure, the metal fine particles are gold,
It is preferably at least one metal selected from silver, copper, platinum, or palladium. The method for producing a nonlinear optical material of the present invention is a method for producing a nonlinear optical material in which fine metal particles are dispersed in an optically transparent substance,
It is characterized in that the metal fine particles and the optically transparent substance are alternately deposited on the surface of the substrate.
【０００８】前記製造方法に於いては、金属微粒子と光
学的透明物質とを基板面上に交互に堆積させる際、基板
面を加熱することにより、前記金属微粒子の形状を球形
とすることが好ましい。In the above manufacturing method, when the metal fine particles and the optically transparent substance are alternately deposited on the substrate surface, it is preferable to heat the substrate surface so that the metal fine particles have a spherical shape. ..
【０００９】[0009]
【作用】本発明の非線形光学材料は、光学的透明物質中
に粒径のそろった金属微粒子が層状に分散されているの
で、金属粒子が多量に分散されていても粒子がバルク状
に成長する恐れがなく効率の良い非線形光学材料が提供
できる。また、金属微粒子を用いているので、金属微粒
子の表面プラズモン共鳴吸収に伴う３次の非線形感受率
の増大を利用することができ、粒径をそろえることによ
り、プラズモン共鳴吸収が鋭くなり、３次の非線形感受
率を大きくすることができる。In the non-linear optical material of the present invention, since fine metal particles having a uniform particle size are dispersed in a layer in an optically transparent substance, the particles grow in bulk even if a large amount of the metal particles are dispersed. It is possible to provide a highly efficient nonlinear optical material without fear. Further, since the metal fine particles are used, it is possible to utilize the increase in the third-order nonlinear susceptibility associated with the surface plasmon resonance absorption of the metal fine particles. By making the particle diameters uniform, the plasmon resonance absorption becomes sharp and The non-linear susceptibility of can be increased.
【００１０】前記構成においては、金属微粒子が金、
銀、銅、白金、あるいはパラジウムから選ばれた少なく
とも１種の金属である好ましい構成とすることによりこ
れらの金属は複素誘電率の虚数部の値が小さく、表面プ
ラズモン共鳴振動数が光学的透明領域にあり、還元性が
高く金属微粒子として安定に存在し得るので、大きな３
次の非線形感受率を有する非線形光学材料を提供するこ
とができる。In the above structure, the fine metal particles are gold,
By adopting a preferred structure of at least one metal selected from silver, copper, platinum, or palladium, these metals have a small imaginary part of the complex permittivity, and the surface plasmon resonance frequency has an optically transparent region. In addition, since it is highly reducible and can stably exist as metal fine particles,
A non-linear optical material having the following non-linear susceptibility can be provided.
【００１１】本発明の非線形光学材料の製造方法は、光
学的透明物質中に金属微粒子が分散されてなる非線形光
学材料の製造方法において、金属微粒子と光学的透明物
質とを基板面上に交互に堆積さたので、金属微粒子の成
長による粒径の増大が防止でき、従って粒径のそろった
金属微粒子を多量に分散させることができる。The method for producing a non-linear optical material according to the present invention is a method for producing a non-linear optical material in which fine metal particles are dispersed in an optically transparent substance, wherein the fine metal particles and the optically transparent substance are alternately provided on the substrate surface. Since the particles are deposited, it is possible to prevent the particle size from increasing due to the growth of the metal particles, and therefore it is possible to disperse the metal particles having a uniform particle size in a large amount.
【００１２】前記製造方法に於いて、金属微粒子と光学
的透明物質とを基板面上に交互に堆積させる際、基板面
を加熱することにより、前記金属微粒子の形状を球形と
することにより前記金属微粒子の表面プラズモン共鳴吸
収ピークが鋭くなり、３次の非線形感受率を大きくする
ことができるので好ましい。In the above manufacturing method, when the metal fine particles and the optically transparent substance are alternately deposited on the substrate surface, the surface of the substrate is heated so that the metal fine particles have a spherical shape. The surface plasmon resonance absorption peak of the fine particles becomes sharp, and the third-order nonlinear susceptibility can be increased, which is preferable.
【００１３】[0013]
【実施例】本発明における非線形光学材料の断面構造を
図１に示す。図１に示したように、本発明の非線形光学
材料は、基板１上に、金属微粒子２と光学的透明物質３
とが交互に堆積した積層構造よりなるものである。EXAMPLE FIG. 1 shows the cross-sectional structure of a nonlinear optical material according to the present invention. As shown in FIG. 1, the non-linear optical material of the present invention comprises a substrate 1, a metal fine particle 2 and an optically transparent substance 3.
It has a laminated structure in which and are alternately deposited.
【００１４】本発明における非線形光学材料では、金属
薄膜作製時のごく初期過程に形成される島状成長物質が
微粒子であることに着目し、この島状成長物質を金属微
粒子２として、光学的透明物質３中へ多量に含有させる
ために積極的に利用しているものである。In the nonlinear optical material according to the present invention, attention is paid to the fact that the island-shaped growth substance formed in the very initial stage of the metal thin film formation is fine particles, and the island-shaped growth substance is used as the metal fine particles 2 to be optically transparent. It is actively used to contain a large amount in the substance 3.
【００１５】本発明において粒径のそろった球形の金属
微粒子２を光学的透明物質３中へ多量に含有させること
ができる理由を説明する。蒸発源（図示せず）から基板
１上に飛来した金属粒子は、基板１と垂直方向のエネル
ギーを短時間に失って基板１上に滞在する。しかし、気
相−固相間の遷移過程であり、この時点では熱力学的平
衡には達していないので、基板１表面上を動き回った
後、欠陥などの吸着点に捕らえられて基板１上に付着す
る。もし吸着点がなければ、蒸着粒子は再蒸発する。次
々に飛来してくる蒸着粒子によって、近傍の付着粒子が
いくつか集まり、それが結晶核となる。この結晶核が形
成された後に、島状構造が成長する。この時点で金属微
粒子が飛来するのを止めると、基板１上に金属島状微粒
子が分散することになる。この時の島状微粒子は、一般
に、基板と面接触しており、形状は半球状あるいは半回
転楕円体状であり、球状ではない。The reason why a large amount of spherical metal fine particles 2 having a uniform particle size can be contained in the optically transparent substance 3 in the present invention will be described. The metal particles flying from the evaporation source (not shown) onto the substrate 1 lose energy in the direction perpendicular to the substrate 1 in a short time and stay on the substrate 1. However, since it is a transition process between the gas phase and the solid phase, and since thermodynamic equilibrium has not been reached at this point, after moving around on the surface of the substrate 1, it is trapped on the substrate 1 by adsorption points such as defects. Adhere to. If there are no adsorption points, the vapor deposition particles will re-evaporate. By the vapor deposition particles that fly one after another, some adhering particles in the vicinity gather, and they become crystal nuclei. After the crystal nuclei are formed, the island structure grows. If the metal fine particles are prevented from flying at this point, the metal island fine particles are dispersed on the substrate 1. In this case, the island-shaped fine particles are generally in surface contact with the substrate and have a hemispherical or semi-spheroidal shape, not a spherical shape.
【００１６】次に、この上に光学的透明物質３の薄膜を
形成して、金属島状微粒子の表面を覆う。この時、飛来
する光学的透明物質３の蒸着粒子はその運動エネルギー
を熱エネルギーとして放出するため、金属島状微粒子と
の界面で新たな熱平衡状態への移行が起こる。ここで、
金属島状微粒子が光学的透明物質３との界面エネルギー
差を０にするに足りる熱エネルギーを受ければ、球状の
金属微粒子２となる。このエネルギーは、金属および光
学的透明物質３の種類により、表面エネルギーならびに
蒸着粒子の運動エネルギーが異なり、また蒸着条件によ
っても異なるが、スパッタリング法や真空蒸着法を用い
た場合、基板１面上を適当な温度に加熱することによ
り、微粒子が球状となるのに十分なエネルギーとなるの
で、好ましい。基板１の加熱温度としては上述の如く採
用条件や用いる物質の種類によって異なるので一概には
規定しがたいが、一般的には１００〜７００℃の範囲が
目安となる。通常、光学的透明物質３として有機高分子
重合体などの有機物を用いる場合は低い温度が採用さ
れ、また、石英ガラスの様に高温で溶融するような無機
化合物を用いる場合には、比較的高い温度が採用でき
る。Next, a thin film of the optically transparent substance 3 is formed on this to cover the surface of the metal island fine particles. At this time, the vapor-deposited particles of the optically transparent substance 3 coming in release their kinetic energy as heat energy, so that a transition to a new thermal equilibrium state occurs at the interface with the metal island-shaped fine particles. here,
When the metal island-shaped fine particles receive sufficient thermal energy to make the interface energy difference with the optically transparent substance 3 zero, the metal island-shaped fine particles 2 become spherical metal fine particles 2. This energy varies depending on the type of the metal and the optically transparent substance 3, the surface energy and the kinetic energy of the vapor deposition particles, and also depends on the vapor deposition conditions. However, when a sputtering method or a vacuum vapor deposition method is used, Heating to a suitable temperature provides sufficient energy to make the fine particles spherical, which is preferable. The heating temperature of the substrate 1 varies depending on the conditions used and the type of substance used as described above, so it is difficult to specify in a general manner, but generally a range of 100 to 700 ° C. is a standard. Usually, a low temperature is used when an organic substance such as an organic polymer is used as the optically transparent substance 3, and a relatively high temperature is used when an inorganic compound that melts at a high temperature such as quartz glass is used. Temperature can be adopted.
【００１７】金属微粒子２の粒径に等しい厚さよりも厚
く光学的透明物質３を堆積させたところで、光学的透明
物質３粒子の飛来を止めて、再び金属微粒子の蒸着を行
なう。この操作を繰り返し行なうことによって、光学的
透明物質３中に粒径のそろった球形の金属微粒子を層状
に分散させることができる。When the optically transparent substance 3 is deposited thicker than the particle size of the metal fine particles 2, the particles of the optically transparent substance 3 are stopped from flying and the metal fine particles are vapor-deposited again. By repeating this operation, it is possible to disperse spherical metal fine particles having a uniform particle size in the optically transparent substance 3 in layers.
【００１８】金属微粒子２の粒径は、蒸着量あるいは基
板１の加熱温度を変化させることによって制御でき、ま
た金属微粒子２が存在する層内での微粒子の面密度は、
蒸着粒子の運動エネルギーあるいは基板１の加熱温度を
変化させることによって制御できる。更に、本材料中の
金属微粒子２の密度は、光学的透明物質３の蒸着量を変
化させることによって制御できる。本実施例では、最大
で４０体積％と、従来の４０００倍以上の密度で金属微
粒子２を含有させることができた。The particle size of the metal fine particles 2 can be controlled by changing the deposition amount or the heating temperature of the substrate 1, and the surface density of the fine particles in the layer in which the metal fine particles 2 are present is
It can be controlled by changing the kinetic energy of vapor deposition particles or the heating temperature of the substrate 1. Furthermore, the density of the metal fine particles 2 in the present material can be controlled by changing the vapor deposition amount of the optically transparent substance 3. In this example, the metal fine particles 2 could be contained at a maximum density of 40% by volume, which is 4000 times or more that of the conventional one.
【００１９】金属微粒子２の粒径は局所的電場効果が現
われる程度に小さいことが必要であり、用いる金属の種
類などによって異なるが例えば５０ｎｍ以下、好ましく
は１〜１５ｎｍ程度の大きさが適当であった。微粒子の
大きさが１００ｎｍ以上になるとバルク的性質が顕著に
なるため、光学的非線形性は小さくなった。It is necessary that the particle size of the metal fine particles 2 is small enough to exhibit a local electric field effect, and it depends on the kind of the metal used and the like, but a size of, for example, 50 nm or less, preferably 1 to 15 nm is suitable. It was When the size of the fine particles is 100 nm or more, the bulk property becomes remarkable, and the optical nonlinearity becomes small.
【００２０】基板１として用いる材料は、光学的透明物
質３として用いる材料と同一のものであっても異なるも
のであってもよい。また、非線形光学材料を形成した
後、基板１から剥離して用いる場合、基板１は光学的に
透明な物質である必要はない。The material used for the substrate 1 may be the same as or different from the material used for the optically transparent substance 3. When the nonlinear optical material is formed and then peeled off from the substrate 1, the substrate 1 need not be an optically transparent substance.
【００２１】金属微粒子２として用いる物質は、金、
銀、銅、白金、あるいはパラジウムから選ばれた金属で
あることが好ましい。光学的透明物質３として用いる材
料は、非線形光学特性を得るのに必要な波長領域で光学
的に透明であれば、無機結晶物質であっても、ガラス物
質であっても、また有機高分子化合物であってもよい。
具体的には、例えば石英ガラス、フッ化マグネシウム、
ＬｉＦ、ＣａＦ2 、Ａｌ2 Ｏ3 、ＭｇＯ、ホウケイ酸ガ
ラス、アルミン酸ガラス、フッ化物ガラス、アクリル酸
樹脂、メタクリル酸樹脂、ポリスチレン、ポリエチレン
などが挙げられるがこれのみに限定されるものではな
い。The material used as the metal fine particles 2 is gold,
A metal selected from silver, copper, platinum, or palladium is preferable. The material used as the optically transparent substance 3 may be an inorganic crystalline substance, a glass substance, or an organic polymer compound as long as it is optically transparent in the wavelength region required to obtain the nonlinear optical characteristics. May be
Specifically, for example, quartz glass, magnesium fluoride,
Examples thereof include, but are not limited to, LiF, CaF 2 , Al 2 O 3 , MgO, borosilicate glass, aluminate glass, fluoride glass, acrylic acid resin, methacrylic acid resin, polystyrene, and polyethylene.
【００２２】光学的透明物質３中に分散させる金属微粒
子２の量は、通常０．０１〜５０体積％、好ましくは１
〜４０体積％程度であり、金属微粒子の体積占有率に比
例して３次非線形感受率が大きくなるので、通常は多い
ほど好ましい。本発明においては粒径のそろった金属微
粒子２が光学的透明物質３中に分散されているが、従来
の方法で得られた非線形光学材料の金属微粒子の粒径分
布に比べて粒径分布の標準偏差が小さい状態で分散され
ている場合（ただし平均粒径が同一の場合で比較する）
は粒径がそろっていると言える。The amount of the fine metal particles 2 dispersed in the optically transparent substance 3 is usually 0.01 to 50% by volume, preferably 1.
It is about 40% by volume, and the third-order nonlinear susceptibility increases in proportion to the volume occupancy of the metal fine particles. In the present invention, the metal fine particles 2 having a uniform particle size are dispersed in the optically transparent substance 3, but the particle size distribution is smaller than that of the metal fine particles of the nonlinear optical material obtained by the conventional method. When the standard deviations are small and dispersed (however, if the average particle size is the same, compare)
Can be said to have a uniform particle size.
【００２３】本発明の非線形光学材料の製造方法におい
ては、薄膜製造方法であるスパッタリング法や、真空蒸
着法などを用いることができる。スパッタリング法の場
合は通常スパッタリングガスとしてアルゴンガスが用い
られ１０-2〜１０Ｐａ程度の圧力下で行なわれ、また、
真空蒸着法１０-3Ｐａ〜１０-4Ｐａ程度の減圧力下で行
なわれる。どの方法を選定するか、またその条件などは
使用する金属および光学的透明物質の融点、蒸気圧、酸
化性などを考慮して選択することが好ましい。In the method of manufacturing the nonlinear optical material of the present invention, a sputtering method which is a thin film manufacturing method, a vacuum vapor deposition method, or the like can be used. In the case of the sputtering method, argon gas is usually used as the sputtering gas and the sputtering is performed under a pressure of about 10 -2 to 10 Pa.
The vacuum deposition method is performed under a reduced pressure of about 10 −3 Pa to 10 −4 Pa. It is preferable to select which method is to be selected and the conditions thereof in consideration of the melting point, vapor pressure, oxidizing property, etc. of the metal and the optically transparent substance used.
【００２４】また、金属微粒子の形状を球形にするため
には、基板加熱を行ない、適当な温度、例えば前述した
ように１００〜７００℃程度の温度に保つことが好まし
い。以下、具体的実施例を挙げて本発明をより詳細に説
明する。In order to make the shape of the metal fine particles spherical, it is preferable to heat the substrate and maintain it at an appropriate temperature, for example, a temperature of about 100 to 700 ° C. as described above. Hereinafter, the present invention will be described in more detail with reference to specific examples.
【００２５】実施例１ 図２に示すスパッタリング装置を用い、スパッタリング
法で本発明の非線形光学材料を製造した。スパッタ源は
石英（ＳｉＯ2 ）ガラスターゲット４と金（Ａｕ）ター
ゲット５とで構成した。基板６はヒーター７を備えた基
板ホルダ８に固定され、これに直結した回転軸により、
回転させることによってＳｉＯ2 ターゲット４またはＡ
ｕターゲット５のいずれかのターゲット上方に持ってく
ることができる。基板６の位置とターゲット上方での滞
在時間とは、コンピュータで制御されている。蒸着中の
コンタミネーションを防ぐため、各ターゲットにターゲ
ット周囲およびその延長上を覆う形のシールド板９を設
けている。基板６には石英ガラスを用いた。スパッタリ
ングガスにはアルゴンを用い、ガス導入口１０から流入
させ、ガス排出口１１を真空ポンプ（図示せず）に接続
して、ガス圧を１．０Ｐａ、基板温度は４００℃、Ｓｉ
Ｏ2 ターゲット４への印加電力は２５０Ｗ、Ａｕターゲ
ット５への印加電力は１０Ｗとした。Example 1 Using the sputtering apparatus shown in FIG. 2, the nonlinear optical material of the present invention was manufactured by the sputtering method. The sputtering source was composed of a quartz (SiO 2 ) glass target 4 and a gold (Au) target 5. The substrate 6 is fixed to a substrate holder 8 equipped with a heater 7, and by a rotary shaft directly connected to this,
By rotating the SiO 2 target 4 or A
It can be brought above any of the u targets 5. The position of the substrate 6 and the staying time above the target are controlled by a computer. In order to prevent contamination during vapor deposition, each target is provided with a shield plate 9 that covers the periphery of the target and its extension. Quartz glass was used for the substrate 6. Argon is used as the sputtering gas, the gas is introduced from the gas inlet 10, the gas outlet 11 is connected to a vacuum pump (not shown), the gas pressure is 1.0 Pa, the substrate temperature is 400 ° C., and Si is
The power applied to the O 2 target 4 was 250 W, and the power applied to the Au target 5 was 10 W.
【００２６】まず、基板６をＡｕターゲット５の上で５
秒間滞在させて、Ａｕ微粒子を堆積させた。次に、基板
６を回転させてＳｉＯ2 ターゲット４の上で５秒間滞在
させて、ＳｉＯ2 膜を堆積させた。ＡｕとＳｉＯ2 を基
板６に交互に堆積させる上記の操作を５００回繰り返し
て、ＳｉＯ2 ガラス中にＡｕ微粒子が層状に分散した積
層構造を有する非線形光学材料を形成した。First, the substrate 6 is placed on the Au target 5 by 5
After being left for a second, Au particles were deposited. Next, the substrate 6 was rotated and allowed to stay on the SiO 2 target 4 for 5 seconds to deposit a SiO 2 film. The above operation of alternately depositing Au and SiO 2 on the substrate 6 was repeated 500 times to form a nonlinear optical material having a laminated structure in which Au particles were dispersed in a layered form in SiO 2 glass.
【００２７】作製した非線形光学材料の膜厚は２μｍで
あり、球状Ａｕ微粒子の平均粒径は２ｎｍ、粒径分布の
標準偏差は０．４ｎｍ、Ａｕ微粒子が分散した層と層と
の間隔は４ｎｍ、Ａｕ微粒子の含有量は４０体積％であ
った。The thickness of the produced nonlinear optical material was 2 μm, the average particle size of the spherical Au particles was 2 nm, the standard deviation of the particle size distribution was 0.4 nm, and the distance between the layers in which the Au particles were dispersed was 4 nm. , The content of Au fine particles was 40% by volume.
【００２８】また、Ａｕターゲット５の上での滞在時間
を変化させて作製した非線形光学材料では、７秒間でＡ
ｕ微粒子の平均粒径が４ｎｍ、粒径分布の標準偏差は
０．７ｎｍ、１０秒間で平均粒径が７ｎｍ、標準偏差は
１ｎｍのものを得ることができた。In the case of a non-linear optical material produced by changing the staying time on the Au target 5, the A
It was possible to obtain an u particle having an average particle size of 4 nm, a standard deviation of particle size distribution of 0.7 nm, an average particle size of 7 nm and a standard deviation of 1 nm in 10 seconds.
【００２９】なお、Ａｕターゲット５を、銀（Ａｇ）、
銅（Ｃｕ）、白金（Ｐｔ）、あるいはパラジウム（Ｐ
ｄ）のターゲットに代えて作製しても、粒径１〜１０ｎ
ｍの金属微粒子が層状に分散した同様な非線形光学材料
が得られた。The Au target 5 is replaced with silver (Ag),
Copper (Cu), platinum (Pt), or palladium (P
Even if the target is manufactured in place of the target d), the particle size is 1 to 10 n.
A similar nonlinear optical material was obtained in which the metal fine particles of m were dispersed in layers.
【００３０】実施例２ 図２に示したスパッタリングターゲットの代わりに、蒸
発源をタングステンボートに乗せ、抵抗加熱で蒸発させ
る真空蒸着法を用いて本発明の非線形光学材料を製造し
た。基板部の構成は図２と同様であり、各蒸発源にシー
ルド板９を設けている点も同様である。光学的透明物質
として用いたのはフッ化マグネシウム（ＭｇＦ2 ）、金
属としてはＡｕを用いた。基板６には石英ガラスを用い
た。真空度は１０-4Ｐａ、基板温度は２００℃、ＭｇＦ
2 の乗ったボートへの印加電力は１２０Ｗ、Ａｕの乗っ
たボートへの印加電力は２００Ｗとした。Example 2 Instead of the sputtering target shown in FIG. 2, a non-linear optical material of the present invention was manufactured by using a vacuum evaporation method in which an evaporation source was placed on a tungsten boat and evaporation was performed by resistance heating. The structure of the substrate portion is the same as that in FIG. 2, and the point that the shield plate 9 is provided for each evaporation source is also the same. Magnesium fluoride (MgF 2 ) was used as the optically transparent substance, and Au was used as the metal. Quartz glass was used for the substrate 6. Vacuum degree is 10 −4 Pa, substrate temperature is 200 ° C., MgF
The power applied to the boat on which 2 was on was 120 W, and the power on the boat on which Au was on was 200 W.
【００３１】まず、基板をＡｕ蒸発源の上で２秒間滞在
させて、Ａｕ微粒子を堆積させた。次に、基板を回転さ
せてＭｇＦ2 蒸発源の上で５秒間滞在させて、ＭｇＦ2
膜を堆積させた。ＡｕとＭｇＦ2 を基板に交互に堆積さ
せる上記の操作を４００回繰り返して、ＭｇＦ2 中にＡ
ｕ微粒子が層状に分散した積層構造を有する非線形光学
材料を形成した。First, the substrate was left on the Au evaporation source for 2 seconds to deposit Au particles. Next, the substrate is rotated and allowed to stay on the MgF 2 evaporation source for 5 seconds, and then the MgF 2
The film was deposited. The above operation of alternately depositing Au and MgF 2 on the substrate was repeated 400 times to obtain A in MgF 2.
A non-linear optical material having a laminated structure in which u particles were dispersed in a layer was formed.
【００３２】作製した非線形光学材料の膜厚は２．４μ
ｍであり、球状Ａｕ微粒子の平均粒径は３ｎｍ、粒径分
布の標準偏差は０．５ｎｍ、Ａｕ微粒子が分散した層と
層との間隔は６ｎｍ、Ａｕ微粒子の含有量は４０体積％
であった。The thickness of the produced nonlinear optical material is 2.4 μm.
m, the average particle size of the spherical Au particles is 3 nm, the standard deviation of the particle size distribution is 0.5 nm, the spacing between the layers in which the Au particles are dispersed is 6 nm, and the content of the Au particles is 40% by volume.
Met.
【００３３】なお、Ａｕ以外にも、Ａｇ、Ｃｕ、Ｐｔ、
あるいはＰｄに代えて作製しても、粒径１〜１０ｎｍの
金属微粒子が層状に分散した同様な非線形光学材料が得
られた。Besides Au, Ag, Cu, Pt,
Alternatively, a similar non-linear optical material in which metal fine particles having a particle size of 1 to 10 nm are dispersed in a layer form was obtained even if it was produced in place of Pd.
【００３４】実施例３ 実施例１で作製した粒径２ｎｍのＡｕ微粒子が層状に分
散した非線形光学材料の３次の非線形感受率χ(3) を測
定したところ、波長５１５ｎｍにおいて４．８×１０-7
ｅｓｕであった。これに２枚の外部鏡をはさんでファブ
リペロー型共振器を構成し、光双安定素子とした。この
素子に波長５１５ｎｍのレーザ光をスポット径５μｍで
入射させ、入射光の強度と出射光の強度の関係を室温
（２５℃）にて測定したところ、光双安定特性を示し、
５ピコ秒以下の非常に高速のスイッチング速度を得た。Example 3 The third-order nonlinear susceptibility χ (3) of the nonlinear optical material prepared in Example 1 in which Au fine particles having a particle size of 2 nm were dispersed in a layer was measured, and it was 4.8 × 10 at a wavelength of 515 nm. -7
It was esu. A Fabry-Perot resonator was constructed by sandwiching this with two external mirrors, and was used as an optical bistable element. When a laser beam with a wavelength of 515 nm was made incident on this element with a spot diameter of 5 μm and the relationship between the intensity of the incident light and the intensity of the emitted light was measured at room temperature (25 ° C.), it showed an optical bistable characteristic.
Very fast switching speeds of less than 5 picoseconds were obtained.
【００３５】また同様に、実施例１で作製した平均粒径
５ｎｍ、粒径分布の標準偏差０．７ｎｍ、のＡｇ微粒子
を２５体積％含有させた非線形光学材料のχ(3) は波長
４００ｎｍにおいて、９．２×１０-8ｅｓｕであった。
この材料でファブリペロー型共振器を構成し、波長４０
０ｎｍのレーザ光をスポット径５μｍで入射させ、入射
光の強度と出射光の強度の関係を室温（２５℃）にて測
定したところ、光双安定特性を示し、５ピコ秒以下の非
常に高速のスイッチング速度を得た。Similarly, χ (3) of the nonlinear optical material prepared in Example 1 containing 25% by volume of Ag fine particles having an average particle size of 5 nm and a standard deviation of particle size distribution of 0.7 nm is 400 nm. , 9.2 × 10 −8 esu.
This material forms a Fabry-Perot resonator with a wavelength of 40
When a laser beam of 0 nm was made incident with a spot diameter of 5 μm and the relationship between the intensity of the incident light and the intensity of the emitted light was measured at room temperature (25 ° C), it showed optical bistable characteristics and was extremely fast at 5 picoseconds or less. Got the switching speed of.
【００３６】以上の結果から本発明の非線形光学材料
は、高速光スイッチとしての応用が可能であり、また他
の非線形光学特性を応用した素子としても適用できる効
果がある。From the above results, the nonlinear optical material of the present invention can be applied as a high-speed optical switch and can be applied as an element to which other nonlinear optical characteristics are applied.
【００３７】[0037]
【発明の効果】本発明の非線形光学材料は、効率の良い
３次の非線形感受率のすぐれた非線形光学材料を提供で
きる。INDUSTRIAL APPLICABILITY The nonlinear optical material of the present invention can provide an efficient nonlinear optical material having excellent third-order nonlinear susceptibility.
【００３８】また、金属微粒子が金、銀、銅、白金、あ
るいはパラジウムから選ばれた少なくとも１種の金属で
ある好ましい構成とすることにより、金属微粒子として
安定に存在し得、大きな３次の非線形感受率を有する非
線形光学材料を提供することができる。Further, by adopting a preferable structure in which the metal fine particles are at least one kind of metal selected from gold, silver, copper, platinum, or palladium, the metal fine particles can stably exist and have a large third-order nonlinearity. A nonlinear optical material having a susceptibility can be provided.
【００３９】本発明の非線形光学材料の製造方法によれ
ば、金属微粒子の成長による粒径の増大が防止でき、従
って粒径のそろった金属微粒子を多量に分散させること
ができる。According to the method for producing a non-linear optical material of the present invention, it is possible to prevent an increase in particle size due to the growth of metal particles, and therefore it is possible to disperse a large amount of metal particles having a uniform particle size.
【００４０】また、金属微粒子と光学的透明物質とを基
板面上に交互に堆積させる際、基板面を加熱することに
より、前記金属微粒子の形状を球形とすることにより前
記金属微粒子の表面プラズモン共鳴吸収ピークを鋭くし
て、３次の非線形感受率の大きい非線形光学材料の製造
方法を提供することができる。Further, when the metal fine particles and the optically transparent substance are alternately deposited on the surface of the substrate, the surface of the substrate is heated to make the shape of the metal fine particles spherical, whereby the surface plasmon resonance of the metal fine particles is formed. It is possible to provide a method for manufacturing a nonlinear optical material having a sharp absorption peak and a large third-order nonlinear susceptibility.
【図１】本発明の非線形光学材料の構造を示す断面図で
ある。FIG. 1 is a cross-sectional view showing the structure of a nonlinear optical material of the present invention.
【図２】本発明の一実施例で用いた線形光学材料の製造
装置の構成を示す略断面図である。FIG. 2 is a schematic cross-sectional view showing the structure of a linear optical material manufacturing apparatus used in an example of the present invention.
１ 基板 ２ 金属微粒子 ３ 光学的透明物質 ４ ＳｉＯ2 ターゲット ５ Ａｕターゲット ６ 基板 ７ ヒーター ８ 基板ホルダー ９ シールド板 １０ ガス導入口 １１ ガス排出口1 Substrate 2 Metal Fine Particles 3 Optically Transparent Material 4 SiO 2 Target 5 Au Target 6 Substrate 7 Heater 8 Substrate Holder 9 Shield Plate 10 Gas Inlet 11 Gas Outlet
───────────────────────────────────────────────────── フロントページの続き (72)発明者 真鍋 由雄 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 三露 常男 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshio Manabe 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Tsuneo Sanritsu 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co. Within
Claims (4)
微粒子が層状に分散されてなる非線形光学材料。1. A non-linear optical material in which fine metal particles having a uniform particle size are dispersed in layers in an optically transparent substance.
はパラジウムから選ばれた少なくとも１種の金属である
請求項１記載の非線形光学材料。2. The nonlinear optical material according to claim 1, wherein the fine metal particles are at least one metal selected from gold, silver, copper, platinum, and palladium.
れてなる非線形光学材料の製造方法において、金属微粒
子と光学的透明物質とを基板面上に交互に堆積させるこ
とを特徴とする非線形光学材料の製造方法。3. A method for producing a non-linear optical material in which fine metal particles are dispersed in an optically transparent substance, wherein the fine metal particles and the optically transparent substance are alternately deposited on the substrate surface. Material manufacturing method.
上に交互に堆積させる際、基板面を加熱することによ
り、前記金属微粒子の形状を球形としてなる請求項３記
載の非線形光学材料の製造方法。4. The non-linear optical material according to claim 3, wherein when the metal fine particles and the optically transparent substance are alternately deposited on the substrate surface, the shape of the metal fine particles becomes spherical by heating the substrate surface. Production method.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30181891A JPH05142605A (en) | 1991-11-18 | 1991-11-18 | Nonlinear optical material and its production |
| US08/495,186 US5817410A (en) | 1991-11-18 | 1995-06-27 | Nonlinear optical composites using linear transparent substances and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30181891A JPH05142605A (en) | 1991-11-18 | 1991-11-18 | Nonlinear optical material and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05142605A true JPH05142605A (en) | 1993-06-11 |
Family
ID=17901534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30181891A Pending JPH05142605A (en) | 1991-11-18 | 1991-11-18 | Nonlinear optical material and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05142605A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679888A (en) * | 1994-10-05 | 1997-10-21 | Matsushita Electric Industrial Co., Ltd. | Dynamic quantity sensor and method for producing the same, distortion resistance element and method for producing the same, and angular velocity sensor |
| JP2006208057A (en) * | 2005-01-25 | 2006-08-10 | Taiyo Yuden Co Ltd | Plasmon resonance structure, its control method and manufacturing method of metal domain |
| JP2006349532A (en) * | 2005-06-16 | 2006-12-28 | Takao Saito | Plasmon resonance structure and its manufacturing method |
| JP2009080311A (en) * | 2007-09-26 | 2009-04-16 | Toshiba Corp | Optical resonator |
| JP2013079442A (en) * | 2011-09-22 | 2013-05-02 | Sumitomo Chemical Co Ltd | Process for producing metallic particle assembly |
-
1991
- 1991-11-18 JP JP30181891A patent/JPH05142605A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679888A (en) * | 1994-10-05 | 1997-10-21 | Matsushita Electric Industrial Co., Ltd. | Dynamic quantity sensor and method for producing the same, distortion resistance element and method for producing the same, and angular velocity sensor |
| JP2006208057A (en) * | 2005-01-25 | 2006-08-10 | Taiyo Yuden Co Ltd | Plasmon resonance structure, its control method and manufacturing method of metal domain |
| JP2006349532A (en) * | 2005-06-16 | 2006-12-28 | Takao Saito | Plasmon resonance structure and its manufacturing method |
| JP2009080311A (en) * | 2007-09-26 | 2009-04-16 | Toshiba Corp | Optical resonator |
| JP2013079442A (en) * | 2011-09-22 | 2013-05-02 | Sumitomo Chemical Co Ltd | Process for producing metallic particle assembly |
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