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JPH06167443A - Measuring apparatus utilizing surface plasmon resonance - Google Patents

Measuring apparatus utilizing surface plasmon resonance

Info

Publication number
JPH06167443A
JPH06167443A JP4286189A JP28618992A JPH06167443A JP H06167443 A JPH06167443 A JP H06167443A JP 4286189 A JP4286189 A JP 4286189A JP 28618992 A JP28618992 A JP 28618992A JP H06167443 A JPH06167443 A JP H06167443A
Authority
JP
Japan
Prior art keywords
surface plasmon
thin film
sample
microscope
plasmon resonance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP4286189A
Other languages
Japanese (ja)
Inventor
Nobuyoshi Tajima
信芳 田島
Etsuo Shinohara
悦夫 篠原
Seiji Kondo
聖二 近藤
Kiyozo Koshiishi
喜代三 越石
Masatsugu Shimomura
政嗣 下村
Ichiro Yamaguchi
一郎 山口
Takayuki Okamoto
隆之 岡本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Olympus Corp
RIKEN
Original Assignee
Olympus Optical Co Ltd
RIKEN
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Olympus Optical Co Ltd, RIKEN filed Critical Olympus Optical Co Ltd
Priority to JP4286189A priority Critical patent/JPH06167443A/en
Publication of JPH06167443A publication Critical patent/JPH06167443A/en
Pending legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55Specular reflectivity
    • G01N21/552Attenuated total reflection
    • G01N21/553Attenuated total reflection and using surface plasmons
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/645Specially adapted constructive features of fluorimeters
    • G01N21/648Specially adapted constructive features of fluorimeters using evanescent coupling or surface plasmon coupling for the excitation of fluorescence
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Length Measuring Devices By Optical Means (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

(57)【要約】 【目的】 表面プラズモン共鳴を利用した測定装置にお
いて、刺激に対する試料の状態変化を測定できる表面プ
ラズモン共鳴を利用した測定装置を提供する。 【構成】 表面プラズモン顕微鏡(2,21)と化学・バイオ
センサ(41,42,51,52,53)、または表面プラズモン顕微鏡
および化学・バイオセンサと外部刺激手段(3,31,32,11
1) および/または他の測定手段(61,71,81,91,101) 、
あるいは表面プラズモン顕微鏡と外部刺激手段および/
または他の測定手段とを設けて試料を測定・分析する。
(57) [Summary] [Object] To provide a measuring apparatus using surface plasmon resonance, which can measure a state change of a sample with respect to a stimulus in the measuring apparatus using surface plasmon resonance. [Structure] Surface plasmon microscope (2,21) and chemical / biosensor (41,42,51,52,53), or surface plasmon microscope and chemical / biosensor and external stimulator (3,31,32,11)
1) and / or other measuring means (61,71,81,91,101),
Or surface plasmon microscope and external stimulation means and /
Alternatively, another measuring means is provided to measure and analyze the sample.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】この発明は、誘電体物質の表面近
傍の情報や誘電体薄膜の膜厚分布を高感度で測定する表
面プラズモン共鳴を利用した測定装置に関するものであ
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a measuring apparatus utilizing surface plasmon resonance for measuring information near the surface of a dielectric substance and film thickness distribution of a dielectric thin film with high sensitivity.

【0002】[0002]

【従来の技術】近年、誘電体物質の表面近傍の情報や誘
電体薄膜の膜厚分布を高感度で測定するものとして、表
面プラズモン共鳴を利用した顕微鏡がいくつか開発され
ている。例えば、「Thin Solid Films,187,(1990)349-3
56」には、ラングミュアーブロジェット膜(LB)膜を
試料として、平行光で表面プラズモン共鳴を誘起させ、
その反射光の強度分布を検出してLB膜の膜厚分布を観
察したことが報告されている。また、「光学,19,(1990)
682-686 」には、玉葱を試料として、収束光で表面プラ
ズモンを誘起させ、その反射光強度の角度分布を1次元
イメージセンサを用いて求めると共に、試料をX−Yス
テージで2次元走査しながら角度分布を色分けしてマッ
ピングすることで、玉葱の表皮細胞を擬似カラー像とし
て観察したことが報告されている。
2. Description of the Related Art In recent years, several microscopes utilizing surface plasmon resonance have been developed to measure the information near the surface of a dielectric substance and the film thickness distribution of a dielectric thin film with high sensitivity. For example, `` Thin Solid Films, 187, (1990) 349-3
56 ”is a sample of Langmuir-Blodgett film (LB) film, which induces surface plasmon resonance by parallel light,
It is reported that the intensity distribution of the reflected light was detected and the film thickness distribution of the LB film was observed. Also, `` Optics, 19, (1990)
682-686 ", a surface plasmon is induced by converging light using an onion as a sample, and the angular distribution of the reflected light intensity is obtained using a one-dimensional image sensor, and the sample is two-dimensionally scanned by an XY stage. However, it is reported that the onion epidermal cells were observed as a pseudo-color image by mapping the angular distribution by color.

【0003】一方、表面プラズモン共鳴は、境界の誘電
的・幾何学的変化に対して高い感度を持っていることか
ら、表面上での物質の反応や濃度を検出する化学・バイ
オセンサへ応用した研究が盛んに行われている。例え
ば、「電子情報通信学会論文誌,J74-C-2,5,(1991)443-4
49」には、免疫反応を示す物質を用いて表面プラズモン
の共鳴角を検出することで、抗原・抗体反応を測定する
バイオセンサが報告されている。また、本出願人らも
「特願平3−195052号」において、イオン感応を
示すLB膜を用いて表面プラズモンの共鳴角を検出する
ことで、イオン濃度を測定するイオンセンサを提案して
いる。
On the other hand, the surface plasmon resonance has a high sensitivity to the dielectric and geometrical changes of the boundary, and therefore, it was applied to a chemical / biosensor for detecting the reaction or concentration of a substance on the surface. Research is actively carried out. For example, "Journal of the Institute of Electronics, Information and Communication Engineers, J74-C-2,5, (1991) 443-4
49 ”, a biosensor that measures an antigen-antibody reaction by detecting the resonance angle of surface plasmons using a substance exhibiting an immune reaction is reported. Further, the present applicants have also proposed in Japanese Patent Application No. 3-195052, an ion sensor for measuring the ion concentration by detecting the resonance angle of the surface plasmon using an LB film exhibiting ion sensitivity. .

【0004】[0004]

【発明が解決しようとする課題】表面プラズモン共鳴を
利用した顕微鏡は、生体膜、合成二分子膜やLB膜のよ
うな擬似生体膜、液晶性の配向膜等の状態を高感度で観
察することができる。このような有機膜は、加熱による
結晶−液晶相転移や相分離等の状態変化、電場の印加に
よる配向変化、あるいは酸化還元反応による状態変化等
の刺激応答性を示すものが多い。
A microscope utilizing surface plasmon resonance is capable of observing with high sensitivity the state of a biological membrane, a pseudo-biological membrane such as a synthetic bilayer membrane or an LB membrane, and a liquid crystal alignment layer. You can Many of such organic films exhibit stimulus responsiveness such as state change such as crystal-liquid crystal phase transition or phase separation due to heating, orientation change due to application of an electric field, or state change due to redox reaction.

【0005】しかしながら、上記の文献「Thin Solid F
ilms,187,(1990)349-356」および「光学,19,(1990)682-
686 」に記載された技術では、試料を単に基板に固定し
て観察するものであるため、上述した加熱や電場等の刺
激を与えた場合の試料の状態変化を測定することができ
ないという問題がある。
However, the above-mentioned document "Thin Solid F
ilms, 187, (1990) 349-356 '' and `` Optics, 19, (1990) 682-
In the technique described in "686", since the sample is simply fixed to the substrate for observation, there is a problem in that the state change of the sample cannot be measured when a stimulus such as heating or an electric field is applied. is there.

【0006】さらに、試料表面に誘起される表面プラズ
モン共鳴のみを検出し、試料表面を直接観察する手段が
ないため、試料の目的の部位の表面プラズモン共鳴を正
確に観察しているかどうかを確認することができないと
いう問題があった。
Furthermore, since there is no means for detecting only the surface plasmon resonance induced on the sample surface and directly observing the sample surface, it is confirmed whether the surface plasmon resonance at the target site of the sample is accurately observed. There was a problem that I could not.

【0007】そこで、この発明は、薄膜に対して、刺激
を加え、その刺激による状態変化を測定することのでき
るよう適切に構成した表面プラズモン共鳴を利用した測
定装置を提供することを目的とする。
Therefore, an object of the present invention is to provide a measuring apparatus utilizing surface plasmon resonance, which is appropriately configured so that a stimulus is applied to a thin film and a state change due to the stimulus can be measured. .

【0008】[0008]

【課題を解決するための手段】上記目的を達成するた
め、この発明では、金属薄膜の一方の面に誘電体試料を
接触させるとともに、この金属薄膜の他方の面に全反射
の条件で偏光光を入射して表面プラズモン共鳴を誘起さ
せ、その反射光を検出することで、前記誘電体試料の状
態を測定する表面プラズモン測定手段と、前記誘電体試
料に物理的又は化学的な刺激を加える刺激手段と、この
刺激手段により刺激された前記誘電体試料の状態変化を
前記表面プラズモン測定手段により測定するように構成
したものである。
In order to achieve the above object, according to the present invention, a dielectric sample is brought into contact with one surface of a metal thin film and polarized light is polarized on the other surface of the metal thin film under the condition of total reflection. To induce surface plasmon resonance and detect the reflected light to measure the state of the dielectric sample, and a stimulus that applies a physical or chemical stimulus to the dielectric sample. And means for measuring the state change of the dielectric sample stimulated by the stimulating means by the surface plasmon measuring means.

【0009】[0009]

【作用】このような構成の測定装置によれば、誘電体試
料に刺激を加え、この刺激による試料の状態変化を検出
することができる。
According to the measuring device having such a configuration, it is possible to apply a stimulus to the dielectric sample and detect a change in the state of the sample due to the stimulus.

【0010】さらに、誘電体試料の表面を観察する観察
手段を備えることにより、表面プラズモン測定を行って
いる試料の測定位置における試料の状態変化について、
表面プラズモン共鳴による情報以外の情報を得ることが
できるので、試料のより正確な情報を得ることもでき
る。
Further, by providing an observing means for observing the surface of the dielectric sample, the change of the state of the sample at the measurement position of the sample for which the surface plasmon is being measured,
Since information other than information by surface plasmon resonance can be obtained, more accurate information of the sample can be obtained.

【0011】[0011]

【実施例】図1は、この発明の第1実施例を示す断面図
である。この測定装置1は、表面プラズモン顕微鏡2と
加熱ヒータ3とを具え、誘電体物質からなる測定試料4
の加熱に伴う状態変化の観察を可能にしたものである。
表面プラズモン顕微鏡2は、透明基板5の一方の表面に
測定試料4を接触保持する金属薄膜6を、他方の表面に
マッチングオイル7を介して光学プリズム8を設け、単
色光レーザ光源9から偏光板10、ビームエキスパンダ
11、絞り12、集光レンズ13、光学プリズム8、マ
ッチングオイル7、透明基板5を経て金属薄膜6にP偏
光の収束光を入射させ、その反射光をNDフィルタ14
およびシリンドリカルレンズ15を経て焦平面に平行に
配置したフォトダイオードアレイ16で受光して反射光
強度の角度依存性を求めるよう構成する。
1 is a sectional view showing a first embodiment of the present invention. This measuring apparatus 1 comprises a surface plasmon microscope 2 and a heater 3, and a measurement sample 4 made of a dielectric substance.
It is possible to observe the change of state with the heating of.
The surface plasmon microscope 2 is provided with a thin metal film 6 for holding the measurement sample 4 in contact with one surface of a transparent substrate 5 and an optical prism 8 on the other surface through a matching oil 7 so that a monochromatic laser light source 9 can be used as a polarizing plate. 10, P-polarized convergent light is made incident on the metal thin film 6 via the beam expander 11, the diaphragm 12, the condenser lens 13, the optical prism 8, the matching oil 7, and the transparent substrate 5, and the reflected light is reflected by the ND filter 14.
The photodiode array 16 arranged parallel to the focal plane through the cylindrical lens 15 receives the light and determines the angle dependence of the reflected light intensity.

【0012】かかる構成において、全反射の条件で金属
薄膜6にP偏光を入射しても、表面プラズモンが誘起さ
れると、その誘起された角度では反射率が極端に減少す
る。したがって、フォトダイオードアレイ16をシリン
ドリカルレンズ15の焦平面に平行に配置してその各素
子を光の反射角に対応させれば、その出力から表面プラ
ズモン共鳴により発生した暗線、すなわち最低の反射率
に対応する素子を検知することができ、その素子位置か
ら吸収ピークの反射角を求めることにより、表面プラズ
モン共鳴が生じる入射角つまり共鳴角を検出することが
できる。
In such a structure, even if P-polarized light is incident on the metal thin film 6 under the condition of total reflection, when the surface plasmon is induced, the reflectance is extremely reduced at the induced angle. Therefore, if the photodiode array 16 is arranged in parallel with the focal plane of the cylindrical lens 15 and each element thereof is made to correspond to the reflection angle of light, the dark line generated by the surface plasmon resonance from the output, that is, the minimum reflectance is obtained. The corresponding element can be detected, and the incident angle at which the surface plasmon resonance occurs, that is, the resonance angle can be detected by obtaining the reflection angle of the absorption peak from the element position.

【0013】透明基板5は、パルスモータ(図示せず)
によってX−Yステージ17により2次元走査する。こ
こで、走査範囲がそれほど大きくない場合には、光学プ
リズム8を透明基板5と一体に移動させても入射角変動
の問題は少ないが、走査範囲が大きい場合には、入射角
を保証するために入射面とX−Yステージ17に対する
光学プリズム8との位置合わせ精度に厳密さが要求され
る。そこで、この実施例では、プリズム固定部材18を
用いて2次元走査時に光学プリズム8を光学系に対して
固定し、透明基板5のみを移動させるようにする。な
お、この動作を円滑に行わせるためには、マッチングオ
イル7は、好適には測定部周辺の極一部に限定して使用
する。
The transparent substrate 5 is a pulse motor (not shown).
Two-dimensional scanning is performed by the XY stage 17. Here, when the scanning range is not so large, the problem of incident angle fluctuation is small even if the optical prism 8 is moved integrally with the transparent substrate 5, but when the scanning range is large, the incident angle is guaranteed. In addition, strictness is required in alignment accuracy between the incident surface and the optical prism 8 with respect to the XY stage 17. Therefore, in this embodiment, the prism fixing member 18 is used to fix the optical prism 8 with respect to the optical system during two-dimensional scanning, and only the transparent substrate 5 is moved. In order to smoothly perform this operation, the matching oil 7 is preferably used only in a very small part around the measuring part.

【0014】パルスモータは、パーソナルコンピュータ
によって制御し、その位置情報と共鳴角との角度分布を
色分けによりマッピングして、CRT(図示せず)に濃
淡像や擬似カラー像として表示する。なお、共鳴角は、
フォトダイオードアレイ16からの信号をA/D変換し
た後、パーソナルコンピュータに取込んで、演算により
求める。
The pulse motor is controlled by a personal computer, and the angular distribution between the position information and the resonance angle is mapped by color coding and displayed as a grayscale image or a pseudo color image on a CRT (not shown). The resonance angle is
After the signal from the photodiode array 16 is A / D converted, it is taken into a personal computer and calculated.

【0015】加熱ヒータ3は、測定試料4を保持する金
属薄膜6を加熱するように設け、その温度をサーミスタ
19により制御するようにする。この加熱ヒータ3は、
任意のものを使用することができるが、この実施例では
絶縁性のシート状のもの、例えばシリコンラバーヒータ
等を用いる。
The heater 3 is provided so as to heat the metal thin film 6 holding the measurement sample 4, and its temperature is controlled by the thermistor 19. This heater 3 is
Although any material can be used, an insulating sheet-shaped material such as a silicon rubber heater is used in this embodiment.

【0016】金属薄膜6は、「表面」20,6,(1982)289-3
04, に記載されているように、複素誘電率の実部が負で
大きな、Ag,Au,Cu,Zn,Al,Kが望まし
く、虚部との大きさの関係から、特にPd,Ni,Fe
は好ましくない。また、金属薄膜6は、合金組成で構成
することもできるが、AgにPdを混合した場合には、
表面プラズモン共鳴が消失するため、この合金の使用は
好ましくない。さらに、金属薄膜6は、透明基板5への
密着性を向上させるために、例えばその表面にCr膜を
極めて薄く形成し、その上にAu膜等を形成した多層構
造をもって構成することもできる。
The metal thin film 6 is "surface" 20,6, (1982) 289-3.
As described in 04, it is desirable that Ag, Au, Cu, Zn, Al, and K whose real part of complex permittivity is negative and large, and especially Pd, Ni, Fe
Is not preferable. The metal thin film 6 may be made of an alloy composition, but when Ag is mixed with Pd,
The use of this alloy is not preferred because the surface plasmon resonance disappears. Further, the metal thin film 6 may have a multi-layer structure in which, for example, a Cr film is formed extremely thin on the surface thereof, and an Au film or the like is formed thereon, in order to improve the adhesion to the transparent substrate 5.

【0017】単色光レーザ光源9は、ランダム偏光ある
いは直線偏光の光を放射する任意の光源を用いることが
できると共に、直線偏光の光を放射する光源を用いる場
合には、偏光板10は省略してもよい。また、光源は、
白色光をモノクロメータで単色光にするものを用いるこ
ともできる。なお、絞り12、NDフィルタ14および
シリンドリカルレンズ15は省略することができる。
The monochromatic laser light source 9 may be any light source that emits randomly polarized light or linearly polarized light. If a light source that emits linearly polarized light is used, the polarizing plate 10 is omitted. May be. Also, the light source is
It is also possible to use a device that converts white light into monochromatic light with a monochromator. The diaphragm 12, the ND filter 14, and the cylindrical lens 15 can be omitted.

【0018】この実施例によれば、測定試料4を加熱ヒ
ータ3により加熱しながら、その表面状態を表面プラズ
モン顕微鏡2で観察することができるので、測定試料4
が加熱により結晶−液晶相転移を示す物質であれば、相
転移に伴う状態の変化を観察することができる。また、
測定試料4が加熱により相分離を示す物質であれば、そ
の相分離の変化およびクラスターサイズを観察すること
ができる。したがって、生体膜、または合成二分子膜や
LB膜のような擬似生体膜のように、結晶−液晶相転移
や相分離を示す誘電体物質の状態変化を容易に観察する
ことができる。
According to this embodiment, the surface condition of the measurement sample 4 can be observed by the surface plasmon microscope 2 while the measurement sample 4 is being heated by the heater 3.
If is a substance that exhibits a crystal-liquid crystal phase transition by heating, it is possible to observe a change in state associated with the phase transition. Also,
If the measurement sample 4 is a substance that exhibits phase separation by heating, changes in the phase separation and cluster size can be observed. Therefore, it is possible to easily observe the state change of the dielectric substance exhibiting the crystal-liquid crystal phase transition or the phase separation like the biological film or the pseudo biological film such as the synthetic bilayer film and the LB film.

【0019】図2は、この発明の第2実施例を示す断面
図である。この測定装置20は、第1実施例と同様に、
表面プラズモン顕微鏡21と加熱ヒータ3とを具え、誘
電体物質からなる測定試料4の加熱に伴う状態変化の観
察を可能にしたものである。この実施例では、表面プラ
ズモン顕微鏡21を、図1に示した表面プラズモン顕微
鏡2において、集光レンズ13、シリンドリカルレンズ
15およびフォトダイオードアレイ16を省略し、フォ
トダイオードアレイ16の位置にCCDカメラ22を設
けて構成する。
FIG. 2 is a sectional view showing a second embodiment of the present invention. This measuring device 20, like the first embodiment,
The surface plasmon microscope 21 and the heater 3 are provided to enable observation of the state change associated with the heating of the measurement sample 4 made of a dielectric substance. In this embodiment, the surface plasmon microscope 21 is the same as the surface plasmon microscope 2 shown in FIG. 1 except that the condenser lens 13, the cylindrical lens 15 and the photodiode array 16 are omitted, and the CCD camera 22 is provided at the position of the photodiode array 16. Provide and configure.

【0020】このようにして、単色光レーザ光源9から
の光を、偏光板10、ビームエキスパンダ11、絞り1
2、光学プリズム8、マッチングオイル7および透明基
板5を経て金属薄膜6にP偏光の平行光として入射して
表面プラズモン共鳴を誘起させ、その反射光をNDフィ
ルタ14を経てその焦平面に平行に配置したCCDカメ
ラ22で検出して、反射光の強度分布を検出する。
In this manner, the light from the monochromatic laser light source 9 is polarized by the polarizing plate 10, the beam expander 11 and the diaphragm 1.
2, through the optical prism 8, the matching oil 7 and the transparent substrate 5 is incident on the metal thin film 6 as P-polarized parallel light to induce surface plasmon resonance, and the reflected light is passed through the ND filter 14 and parallel to its focal plane. The intensity distribution of the reflected light is detected by the CCD camera 22 arranged.

【0021】また、この実施例では、測定試料4の表面
状態をCCDカメラ22で直接観察するため、透明基板
5は2次元走査することなく、固定ステージ23に設け
る。その他の構成については、図1と同様に構成する。
したがって、この実施例においても、図1に示した実施
例と同様の効果を得ることができる。
In this embodiment, since the surface state of the measurement sample 4 is directly observed by the CCD camera 22, the transparent substrate 5 is provided on the fixed stage 23 without two-dimensional scanning. The other configurations are the same as those in FIG.
Therefore, also in this embodiment, the same effect as that of the embodiment shown in FIG. 1 can be obtained.

【0022】図3は、この発明の第3実施例を示すもの
である。この測定装置30は、図1に示した測定装置1
において、測定試料4の透明基板5とは反対側の表面に
接して電極31を設けると共に、表面プラズモン励起用
金属薄膜6を対電極に兼用して、これら電極31および
金属薄膜6間に直流電源32から直流電圧を印加するよ
うにしたものである。電極31は、電圧印加によって測
定試料4と反応しないもの、例えばPt,Au,Al,
ITOガラス等の薄板や、ガラス基板に蒸着、スパッタ
等の既知の方法で形成した厚さ100Å以上の導電性薄
膜等をもって構成する。なお、加熱ヒータ3は、X−Y
ステージ17と電極31との間に配置して、測定試料4
を電極31を介して加熱するようにすると共に、その温
度を透明基板5上に設けたサーミスタ19で制御するよ
うにする。
FIG. 3 shows a third embodiment of the present invention. This measuring device 30 is the measuring device 1 shown in FIG.
In addition, the electrode 31 is provided in contact with the surface of the measurement sample 4 opposite to the transparent substrate 5, and the surface plasmon exciting metal thin film 6 is also used as a counter electrode, and a DC power supply is provided between the electrode 31 and the metal thin film 6. A DC voltage is applied from 32. The electrode 31 does not react with the measurement sample 4 when a voltage is applied, such as Pt, Au, Al,
It is composed of a thin plate such as ITO glass or a conductive thin film having a thickness of 100 Å or more formed on a glass substrate by a known method such as vapor deposition or sputtering. The heater 3 is XY
The measurement sample 4 is placed between the stage 17 and the electrode 31.
Is heated via the electrode 31, and its temperature is controlled by the thermistor 19 provided on the transparent substrate 5.

【0023】このように、測定試料4に対して電圧を印
加する手段を付加すれば、液晶のように電場によって配
向変化を生じる測定試料4の表面状態の変化を、表面プ
ラズモン顕微鏡2によって容易に観察することができ
る。
As described above, if a means for applying a voltage to the measurement sample 4 is added, the surface plasmon microscope 2 can easily change the surface state of the measurement sample 4 which causes an orientation change due to an electric field like liquid crystal. Can be observed.

【0024】図4は、この発明の第4実施例を示すもの
である。この測定装置40は、図3に示した測定装置3
0において、金属薄膜6と電極31との間にセル枠41
を設けてセル42を形成し、このセル42内に支持電解
質溶液を保持し得るようにしたものである。なお、この
場合の電極31は、電圧印加により測定試料4や支持電
解質中の成分と反応しないもの、例えばPt,Au,I
TOガラス等の薄板や、ガラス基板に蒸着、スパッタ等
の既知の方法で形成した厚さ100Å以上の導電性薄膜
等をもって構成する。
FIG. 4 shows a fourth embodiment of the present invention. This measuring device 40 is the measuring device 3 shown in FIG.
0, the cell frame 41 is provided between the metal thin film 6 and the electrode 31.
Is provided to form a cell 42, and the supporting electrolyte solution can be held in the cell 42. The electrode 31 in this case is one that does not react with the components in the measurement sample 4 or the supporting electrolyte when a voltage is applied, such as Pt, Au, I.
It is composed of a thin plate such as TO glass or a conductive thin film having a thickness of 100 Å or more formed on a glass substrate by a known method such as vapor deposition or sputtering.

【0025】この実施例によれば、測定試料4がフェロ
セン基やビオロゲン基を有する有機薄膜の場合に、セル
42内の支持電解質溶液に酸化剤を加えて直流電源32
による印加電圧を掃引することにより、測定試料4の酸
化還元に伴う相変化の状態変化を表面プラズモン顕微鏡
2によって容易に観察することができる。
According to this embodiment, when the measurement sample 4 is an organic thin film having a ferrocene group or a viologen group, an oxidizing agent is added to the supporting electrolyte solution in the cell 42 and the DC power source 32 is added.
By sweeping the applied voltage by, the state change of the phase change accompanying the redox of the measurement sample 4 can be easily observed by the surface plasmon microscope 2.

【0026】図5は、この発明の第5実施例を示すもの
である。この測定装置50は、図4に示した測定装置4
0において、セル枠41に注入管51および排出管52
を設けて、セル42をフローセル構造にすると共に、測
定試料4に代えて、気体又は液体の特定成分と相互作用
を示す機能性薄膜を用いた例を示したものである。この
例は、機能性薄膜として、特定物質に感応するイオン感
応膜または免疫反応膜よりなる物質センシング機能を有
する薄膜状の誘電体物質53を設けて、フローセル内に
流した液体の特定のイオン濃度または免疫物質を、表面
プラズモン顕微鏡2により表面プラズモンの共鳴角を検
出することで測定する化学・バイオセンサの機能を付加
したものである。
FIG. 5 shows a fifth embodiment of the present invention. This measuring device 50 is the same as the measuring device 4 shown in FIG.
0, the cell frame 41 has an injection pipe 51 and an exhaust pipe 52.
Is provided, the cell 42 has a flow cell structure, and a functional thin film that interacts with a specific component of gas or liquid is used instead of the measurement sample 4. In this example, as a functional thin film, a thin film dielectric material 53 having a substance sensing function composed of an ion sensitive film or an immunoreactive film sensitive to a specific substance is provided, and a specific ion concentration of the liquid flown in the flow cell is provided. Alternatively, a chemical / biosensor function for measuring an immunological substance by detecting the resonance angle of the surface plasmon with the surface plasmon microscope 2 is added.

【0027】なお、上記機能性薄膜とは、特定の原子又
は分子に対して物理的、化学的、電気化学的な作用を生
ずる薄膜であり、特異な例としては特定のイオンと感応
するもの、特定の抗体又は抗原に免疫反応を示すもの、
特定の基質に酵素反応を示すものなどがある。
The functional thin film is a thin film that causes a physical, chemical or electrochemical action on a specific atom or molecule, and a specific example is a film which is sensitive to a specific ion. Those that show an immune reaction to a specific antibody or antigen,
For example, there are those that show an enzymatic reaction with a specific substrate.

【0028】表面プラズモン共鳴を利用したセンサにつ
いては、上述した「特願平3−195052号」および
「電子情報通信学会論文誌,J74-C-2,5,(1991)443-449」
において提案されており、新しいタイプのセンサとして
注目されている。しかしながら、表面プラズモン共鳴を
利用したセンサにおいては、感応膜の表面状態によっ
て、検出される結果が大きく左右されるため、正確なセ
ンシングを行うためには、センサとして測定を行う前お
よび測定後に、その感応膜の状態をそれぞれ観察するこ
とが必要になる。
Regarding the sensor using the surface plasmon resonance, the above-mentioned "Japanese Patent Application No. 3-195052" and "Journal of the Institute of Electronics, Information and Communication Engineers, J74-C-2,5, (1991) 443-449".
Have been proposed as a new type of sensor. However, in a sensor using surface plasmon resonance, the surface state of the sensitive film has a great influence on the detected result.Therefore, in order to perform accurate sensing, before and after the measurement as a sensor, It is necessary to observe the state of each sensitive film.

【0029】この実施例によれば、上述したように表面
プラズモン顕微鏡に化学・バイオセンサ機能を付加して
いるので、センサとして測定する前および測定後におい
て、感応膜としての誘電体物質53の表面状態を単一の
測定装置50で測定することができる。したがって、セ
ンサの研究開発を遂行する上で極めて有効となる。
According to this embodiment, since the surface plasmon microscope is provided with the chemical / biosensor function as described above, the surface of the dielectric substance 53 as a sensitive film is measured before and after measurement as a sensor. The condition can be measured with a single measuring device 50. Therefore, it is extremely effective in carrying out the research and development of the sensor.

【0030】なお、この実施例において、電極31は免
疫センサ等に用いる場合には使用しないが、酸化還元反
応を応用したセンサ等では必要となる場合がある。この
電極31は、上述したと同様に、電圧印加により誘電体
物質53や電解質溶液中の成分と反応しないもの、例え
ばPt,Au,ITOガラス等の薄板や、ガラス基板に
蒸着、スパッタ等の既知の方法で形成した厚さ100Å
以上の導電性薄膜等をもって構成する。また、電圧の印
加や掃引は、ポテンショスタットやガルバノスタット等
を用いて行うようにする。
In this embodiment, the electrode 31 is not used when it is used in an immunosensor or the like, but it may be necessary in a sensor that applies a redox reaction. Similar to the above, the electrode 31 does not react with the dielectric substance 53 or components in the electrolyte solution when a voltage is applied, for example, a thin plate of Pt, Au, ITO glass or the like, or a known vapor deposition or sputtering method on a glass substrate. 100 Å formed by the method
It is configured by the above-mentioned conductive thin film and the like. Further, the voltage application and the sweep are performed using a potentiostat, a galvanostat, or the like.

【0031】図6は、この発明の第6実施例を示すもの
である。この測定装置60は、図1に示した表面プラズ
モン顕微鏡2と赤外分光光度計61とを設けて、測定試
料4の表面状態を観察すると同時に、測定試料4の赤外
線吸収スペクトルを分析し得るようにしたものである。
赤外分光光度計61は、全反射法を採用する場合には、
図6に示すように、測定試料4の金属薄膜6とは反対側
の表面に接してATRプリズム62を設け、このATR
プリズム62を介して赤外光光源63からの赤外光を測
定試料4に全反射の条件で入射させ、その反射光をAT
Rプリズム62を介して検知器64で検出して、測定試
料4の赤外線吸収スペクトルを測定するよう構成し、高
感度反射法を採用する場合には、上記構成においてAT
Rプリズム62を省略して構成する。なお、赤外分光分
析法については、例えば「FT−IRの基礎と実際」、
田隅三生著、東京化学同人、(1986)P47-82,P92-113、に
詳しく説明されている。
FIG. 6 shows a sixth embodiment of the present invention. This measuring device 60 is provided with the surface plasmon microscope 2 and the infrared spectrophotometer 61 shown in FIG. 1 to observe the surface state of the measurement sample 4 and at the same time analyze the infrared absorption spectrum of the measurement sample 4. It is the one.
When the infrared spectrophotometer 61 adopts the total reflection method,
As shown in FIG. 6, an ATR prism 62 is provided in contact with the surface of the measurement sample 4 opposite to the metal thin film 6, and the ATR prism 62 is provided.
The infrared light from the infrared light source 63 is incident on the measurement sample 4 via the prism 62 under the condition of total reflection, and the reflected light is transmitted to the AT.
In the case where the infrared absorption spectrum of the measurement sample 4 is measured by the detector 64 through the R prism 62 and the high-sensitivity reflection method is adopted, the
The R prism 62 is omitted in the configuration. Regarding the infrared spectroscopic analysis method, for example, "Basics and practice of FT-IR",
It is described in detail in Mitsuo Tasumi, Tokyo Kagaku Dojin, (1986) P47-82, P92-113.

【0032】この実施例によれば、表面プラズモン顕微
鏡2による観察と同時に、赤外分光光度計61を用いる
ことによって、全反射法によりATRプリズム62に接
した測定試料4の表面近傍の状態を、また高感度反射法
により金属薄膜6上の薄膜状の測定試料4の状態を、定
性的・定量的に分析することができ、さらに測定試料4
が配向した膜の場合には、その配向状態を知ることがで
きる。また、加熱ヒータ3をも付加しているので、測定
試料4が配向した膜の場合には、これを加熱ヒータ3で
加熱することにより、加熱に伴った相転移、相分離等の
状態変化やそれに伴う膜の配向状態を同時に測定するこ
とができる。
According to this embodiment, by using the infrared spectrophotometer 61 at the same time as the observation by the surface plasmon microscope 2, the state near the surface of the measurement sample 4 in contact with the ATR prism 62 by the total reflection method, Further, the state of the thin film-shaped measurement sample 4 on the metal thin film 6 can be qualitatively and quantitatively analyzed by the high-sensitivity reflection method.
In the case of an oriented film, the orientation state can be known. Further, since the heater 3 is also added, in the case where the measurement sample 4 is an oriented film, by heating this with the heater 3, the state change such as phase transition and phase separation due to heating, It is possible to simultaneously measure the orientation state of the film associated therewith.

【0033】図7は、この発明の第7実施例を示すもの
である。この測定装置70は、図5に示した測定装置5
0に、レーザラマン分光光度計71を設けたものであ
る。レーザラマン分光光度計71は、測定試料4の金属
薄膜6とは反対側にレーザ光源72および分光検知器7
3を配置して、レーザ光源72から電極31を経て測定
試料4に強い単色光を入射し、これによって分子の振動
のうち分子の分極率の変化を起こすものに起因して入射
光が受ける波数変化(ラマン散乱)を分光検知器73で
検出するよう構成する。なお、ラマンスペクトル法につ
いては、例えば「機器分析」、田中誠之、飯田芳男著、
裳華房、P104-109、に記されている。
FIG. 7 shows a seventh embodiment of the present invention. This measuring device 70 is the same as the measuring device 5 shown in FIG.
0 is provided with a laser Raman spectrophotometer 71. The laser Raman spectrophotometer 71 includes a laser light source 72 and a spectral detector 7 on the side of the measurement sample 4 opposite to the metal thin film 6.
3 is arranged, and strong monochromatic light is made incident on the measurement sample 4 from the laser light source 72 via the electrode 31, and the number of waves received by the incident light is caused by one of the vibrations of the molecule that causes a change in the polarizability of the molecule. A change (Raman scattering) is detected by the spectroscopic detector 73. Regarding the Raman spectrum method, for example, “Instrument analysis”, Masayuki Tanaka, Yoshio Iida,
It is written in Sokabo, P104-109.

【0034】この実施例によれば、化学・バイオセンサ
として測定する前および測定後において、感応膜として
の誘電体物質53の状態を観察および分析することがで
き、より正確なセンシングが可能となる。また、レーザ
ラマン分光光度計71は、可視光を用いるので、水によ
る吸収の大きい赤外光を用いる場合に比べ、水溶液系の
測定も可能になる。
According to this embodiment, the state of the dielectric substance 53 as the sensitive film can be observed and analyzed before and after the measurement as the chemical / biosensor, and more accurate sensing is possible. . Further, since the laser Raman spectrophotometer 71 uses visible light, it is possible to measure an aqueous solution system as compared with the case of using infrared light which is highly absorbed by water.

【0035】図8は、この発明の第8実施例を示すもの
である。この測定装置80は、図1に示した測定装置1
に既知の光学顕微鏡81を設けて、測定試料4のある一
定の部位を二つの手段で同時に観察し得るようにしたも
のである。光学顕微鏡81は、測定試料4の金属薄膜6
に接していない表面側に対物レンズ82を配置して、表
面プラズモン顕微鏡2と同時に同じ部位を観察できるよ
うにする。なお、対物レンズ82は、構成上の点からは
長焦点のものを用いる。
FIG. 8 shows an eighth embodiment of the present invention. This measuring device 80 is the measuring device 1 shown in FIG.
In addition, a known optical microscope 81 is provided to allow a certain part of the measurement sample 4 to be observed simultaneously by two means. The optical microscope 81 uses the metal thin film 6 of the measurement sample 4.
The objective lens 82 is arranged on the surface side not in contact with the surface plasmon microscope 2 so that the same portion can be observed simultaneously with the surface plasmon microscope 2. The objective lens 82 has a long focus from the point of view of the configuration.

【0036】この実施例によれば、表面プラズモン顕微
鏡2で観察する測定試料4の目的の部位を光学顕微鏡8
1で観察しながら調整することが可能となる。例えば、
一般に表面プラズモン顕微鏡2のX−Yステージ17の
走査範囲は、200μm×200μm程度であるので、
光学顕微鏡81の視野範囲内に存在する。したがって、
光学顕微鏡81で測定試料4の所望の部位を決めて光学
顕微鏡像を観察した後、X−Yステージ17を走査して
表面プラズモン像を得ることができる。なお、測定試料
4が透明な生体物質試料等の場合には、その試料を蛍光
物質で染色し、光学顕微鏡81を蛍光顕微鏡とすること
により観察することができる。
According to this embodiment, the target portion of the measurement sample 4 observed by the surface plasmon microscope 2 is the optical microscope 8
It becomes possible to adjust while observing with 1. For example,
Generally, since the scanning range of the XY stage 17 of the surface plasmon microscope 2 is about 200 μm × 200 μm,
It exists within the visual field range of the optical microscope 81. Therefore,
After deciding a desired portion of the measurement sample 4 with the optical microscope 81 and observing the optical microscope image, the surface plasmon image can be obtained by scanning the XY stage 17. When the measurement sample 4 is a transparent biological material sample or the like, it can be observed by staining the sample with a fluorescent substance and using the optical microscope 81 as a fluorescence microscope.

【0037】図9は、この発明の第9実施例を示すもの
である。この測定装置90は、図1に示した測定装置1
に走査型トンネル顕微鏡91を設けて、測定試料4のあ
る一定の部位を二つの手段で同時に観察し得るようにし
たものである。走査型トンネル顕微鏡91は、測定試料
4の金属薄膜6に接していない表面側に探針92と圧電
体93とを配置して、探針92と金属薄膜6との間に直
流電源94により所要の電圧を印加し、これにより表面
プラズモン顕微鏡2と同時に同じ部位を走査型トンネル
顕微鏡91で測定できるようにする。したがって、この
場合の測定試料4は、トンネル電流が流れる超薄膜誘電
体に限定される。
FIG. 9 shows a ninth embodiment of the present invention. This measuring device 90 is the measuring device 1 shown in FIG.
A scanning tunneling microscope 91 is provided in the above, so that a certain part of the measurement sample 4 can be simultaneously observed by two means. The scanning tunneling microscope 91 arranges a probe 92 and a piezoelectric body 93 on the surface side of the measurement sample 4 which is not in contact with the metal thin film 6, and requires a DC power supply 94 between the probe 92 and the metal thin film 6. Voltage is applied so that the same portion can be measured by the scanning tunneling microscope 91 at the same time as the surface plasmon microscope 2. Therefore, the measurement sample 4 in this case is limited to the ultra-thin film dielectric through which the tunnel current flows.

【0038】この実施例によれば、表面プラズモン励起
状態におけるトンネル電流効果またはトンネル電流発生
時における表面プラズモン状態の変化を測定することが
できるので、薄膜を構成する物質の原子レベルの物性を
調べることができる。すなわち、表面プラズモン励起前
に測定試料4にトンネル電流を流しておき、表面プラズ
モン励起によるトンネル電流の変化や表面プラズモン励
起前後のトンネル顕微鏡像の比較等を行うことができ
る。
According to this embodiment, since the tunnel current effect in the surface plasmon excited state or the change in the surface plasmon state when the tunnel current is generated can be measured, the physical properties of the substance constituting the thin film at the atomic level can be investigated. You can That is, a tunnel current is passed through the measurement sample 4 before the surface plasmon excitation, and a change in the tunnel current due to the surface plasmon excitation and a comparison of tunnel microscope images before and after the surface plasmon excitation can be performed.

【0039】図10は、この発明の第10実施例を示す
ものである。この測定装置100は、図1に示した測定
装置1に走査型原子間力顕微鏡101を設けて、測定試
料4のある一定の部位を二つの手段で同時に観察し得る
ようにしたものである。走査型原子間力顕微鏡101
は、測定試料4の金属薄膜6に接していない表面側にカ
ンチレバー102と圧電体93とを配置して、表面プラ
ズモン顕微鏡2と同時に同じ部位を走査型原子間力顕微
鏡101で測定できるようにする。したがって、この場
合の測定試料4は、表面プラズモンを励起するエバネッ
セント波の波長以下の厚みの超薄膜誘電体に限定され
る。
FIG. 10 shows a tenth embodiment of the present invention. In this measuring apparatus 100, a scanning atomic force microscope 101 is provided in the measuring apparatus 1 shown in FIG. 1 so that a certain portion of a measurement sample 4 can be observed simultaneously by two means. Scanning atomic force microscope 101
Arranges the cantilever 102 and the piezoelectric body 93 on the surface side of the measurement sample 4 which is not in contact with the metal thin film 6 so that the same site can be measured by the scanning atomic force microscope 101 at the same time as the surface plasmon microscope 2. . Therefore, the measurement sample 4 in this case is limited to the ultrathin film dielectric having a thickness equal to or less than the wavelength of the evanescent wave that excites the surface plasmon.

【0040】この実施例によれば、表面プラズモン励起
時における原子間力の変化を測定することができるの
で、薄膜を構成する原子レベルの物性を調べることがで
きる。すなわち、表面プラズモン励起前に測定試料4と
カンチレバー102との間に原子間力を生じさせてお
き、表面プラズモン励起による原子間力の変化や表面プ
ラズモン励起前後の原子間力顕微鏡像の比較等を行うこ
とができる。
According to this embodiment, the change in interatomic force during surface plasmon excitation can be measured, so that the physical properties at the atomic level constituting the thin film can be investigated. That is, an atomic force is generated between the measurement sample 4 and the cantilever 102 before the surface plasmon excitation, and a change in the atomic force due to the surface plasmon excitation or a comparison of atomic force microscope images before and after the surface plasmon excitation is performed. It can be carried out.

【0041】図11は、この発明の第11実施例を示す
ものである。この測定装置110は、図3に示した測定
装置30に磁気コイル111を設けて、測定試料4の磁
場の印加に伴う状態変化の観察を可能にしたものであ
る。磁気コイル111は、測定試料4の金属薄膜6に接
していない表面側に配置して、測定試料4に磁場を印加
するようにする。
FIG. 11 shows an eleventh embodiment of the present invention. This measuring apparatus 110 is provided with a magnetic coil 111 in the measuring apparatus 30 shown in FIG. 3 to enable observation of a state change associated with the application of the magnetic field of the measurement sample 4. The magnetic coil 111 is arranged on the surface side of the measurement sample 4 which is not in contact with the metal thin film 6 so that a magnetic field is applied to the measurement sample 4.

【0042】この実施例によれば、磁場によって配向変
化を生じる測定試料4の表面状態の変化を、表面プラズ
モン顕微鏡2によって容易に観察することができる。
According to this embodiment, the surface plasmon microscope 2 can easily observe the change in the surface state of the measurement sample 4 which causes the orientation change due to the magnetic field.

【0043】なお、この発明は、上述した実施例にのみ
限定されるものではなく、幾多の変形または変更が可能
である。例えば、上述した各実施例では、表面プラズモ
ン顕微鏡を上方に配置したが、これを下方、あるいは横
方向等の任意の方向に配置することができる。また、第
3〜11実施例においては、表面プラズモン顕微鏡を第
1実施例と同様に構成したが、これを第2実施例のもの
と同様に構成することができると共に、加熱ヒータ3を
省略することもできる。
It should be noted that the present invention is not limited to the above-described embodiments, and many variations and modifications are possible. For example, in each of the above-described embodiments, the surface plasmon microscope is arranged above, but it can be arranged below or in any direction such as the lateral direction. Further, in the third to eleventh embodiments, the surface plasmon microscope has the same structure as that of the first embodiment, but it may have the same structure as that of the second embodiment and the heater 3 is omitted. You can also

【0044】さらに、第8実施例に示す光学顕微鏡81
は、第2〜6実施例の測定装置に付加することもでき
る。ただし、第3〜6実施例の測定装置に付加する場合
には、電極31を透明電極をもって構成する。また、第
9実施例に示す走査型トンネル顕微鏡91を、第2およ
び6実施例の測定装置に付加することもできるし、同様
に第10実施例に示す走査型原子間力顕微鏡101を、
第2および6実施例の測定装置に付加することもでき
る。ただし、第6実施例の測定装置に走査型トンネル顕
微鏡91や走査型原子間力顕微鏡101を付加する場合
には、赤外分光光度系61をATRプリズム62を用い
ない高感度法で構成する。
Further, the optical microscope 81 shown in the eighth embodiment.
Can also be added to the measuring devices of the second to sixth embodiments. However, when it is added to the measuring devices of the third to sixth embodiments, the electrode 31 is composed of a transparent electrode. Further, the scanning tunneling microscope 91 shown in the ninth embodiment can be added to the measuring devices of the second and sixth embodiments, and similarly, the scanning atomic force microscope 101 shown in the tenth embodiment is
It can also be added to the measuring devices of the second and sixth embodiments. However, when the scanning tunneling microscope 91 or the scanning atomic force microscope 101 is added to the measuring apparatus of the sixth embodiment, the infrared spectrophotometric system 61 is constructed by the high sensitivity method without using the ATR prism 62.

【0045】また、第11実施例に示す磁気コイル11
1は、第1,2,4〜8実施例の測定装置に付加するこ
ともできる。さらに、外部刺激手段としては、上述した
熱的、電気的および磁気的手段に限らず、音波を作用さ
せる手段を付加することもできる。
Further, the magnetic coil 11 shown in the eleventh embodiment.
1 can also be added to the measuring devices of the first, second, fourth to eighth embodiments. Furthermore, the external stimulating means is not limited to the above-mentioned thermal, electrical and magnetic means, and means for applying a sound wave may be added.

【0046】さらに、この発明は、表面プラズモン顕微
鏡に、上述した各種の外部刺激手段および/または測定
手段を任意に組み合わせて構成することができる。とこ
ろで、上記実施例では表面プラズモン顕微鏡に、上述し
た各種の刺激手段にさらに、試料表面を観察する観察手
段を合わせて設けているが、刺激手段を設けなくても、
観察手段を有していれば、試料表面の目的の箇所を観察
したり、測定したりすることができるので、測定位置の
確認や、表面プラズモン共鳴による情報以外の各種の測
定データを比較することが可能になり、試料に対する情
報をより正確に求めることができる。
Further, the present invention can be constructed by arbitrarily combining the surface plasmon microscope with the above-mentioned various external stimulating means and / or measuring means. By the way, in the above embodiment, the surface plasmon microscope, in addition to the various stimulating means described above, is further provided with an observing means for observing the sample surface.
If you have an observing means, you can observe and measure the target area on the sample surface, so you can confirm the measurement position and compare various measurement data other than information by surface plasmon resonance. This makes it possible to more accurately obtain information about the sample.

【0047】さらに、前記刺激手段としては、前記誘電
体試料に対して、熱、音波、電界、磁界、化学反応、電
気化学反応などのうちの1つ又は複数の刺激を組み合わ
せて加える手段であればよく、また、前記観察手段とし
ては、赤外分光光度計、ラマン分光光度計、光学顕微
鏡、走査型トンネル顕微鏡(STM)、走査型原子間力
顕微鏡(AFM)など各種の手段のうちの1つ又は複数
を組み合わせて用いることができる。
Further, the stimulating means may be a means for applying a combination of one or a plurality of stimuli of heat, sound wave, electric field, magnetic field, chemical reaction, electrochemical reaction and the like to the dielectric sample. As the observation means, one of various means such as an infrared spectrophotometer, a Raman spectrophotometer, an optical microscope, a scanning tunneling microscope (STM), and a scanning atomic force microscope (AFM) is used. One or more can be used in combination.

【0048】[0048]

【発明の効果】以上のように、この発明によれば、表面
プラズモン共鳴を利用した測定装置において、表面プラ
ズモン測定手段に、刺激手段を設けたので、刺激を加え
たときの試料の状態変化を測定することができ、試料に
対する種々の情報を正確に得ることができる。
As described above, according to the present invention, in the measuring apparatus utilizing the surface plasmon resonance, since the surface plasmon measuring means is provided with the stimulating means, the change of the state of the sample when the stimulus is applied is suppressed. It can be measured, and various information about the sample can be accurately obtained.

【0049】さらに、誘電体試料の表面を観察する観察
手段を設けることにより、表面プラズモン測定を行って
いる試料の測定位置における試料の状態変化について、
表面プラズモン共鳴による情報以外の情報を得ることが
できるので、試料のより正確な情報を得ることもでき
る。
Further, by providing an observing means for observing the surface of the dielectric sample, the change of the state of the sample at the measuring position of the sample for which the surface plasmon is being measured,
Since information other than information by surface plasmon resonance can be obtained, more accurate information of the sample can be obtained.

【図面の簡単な説明】[Brief description of drawings]

【図1】この発明の第1実施例を示す断面図である。FIG. 1 is a sectional view showing a first embodiment of the present invention.

【図2】同じく第2実施例を示す断面図である。FIG. 2 is a sectional view showing a second embodiment of the same.

【図3】同じく第3実施例を示す断面図である。FIG. 3 is a sectional view showing a third embodiment of the same.

【図4】同じく第4実施例を示す断面図である。FIG. 4 is a sectional view showing a fourth embodiment of the same.

【図5】同じく第5実施例を示す断面図である。FIG. 5 is a sectional view showing a fifth embodiment of the same.

【図6】同じく第6実施例を示す断面図である。FIG. 6 is a sectional view showing a sixth embodiment of the same.

【図7】同じく第7実施例を示す断面図である。FIG. 7 is a sectional view showing a seventh embodiment of the same.

【図8】同じく第8実施例を示す断面図である。FIG. 8 is a sectional view showing an eighth embodiment of the same.

【図9】同じく第9実施例を示す断面図である。FIG. 9 is a sectional view showing a ninth embodiment of the same.

【図10】同じく第10実施例を示す断面図である。FIG. 10 is a sectional view showing a tenth embodiment.

【図11】同じく第11実施例を示す断面図である。FIG. 11 is a sectional view showing an eleventh embodiment.

【符号の説明】[Explanation of symbols]

1,20,30,40,50,60,70,80,9
0,100,110 測定装置 2,21 表面プラズモン顕微鏡 3 加熱ヒータ 4 測定試料 5 透明基板 6 金属薄膜 7 マッチングオイル 8 光学プリズム 9 単色光レーザ光源 10 偏光板 11 ビームエキスパンダ 12 絞り 13 集光レンズ 14 NDフィルタ 15 シリンドリカルレンズ 16 フォトダイオードアレイ 17 X−Yステージ 18 プリズム固定部材 19 サーミスタ 22 CCDカメラ 23 固定ステージ 31 電極 32 直流電源 41 セル枠 42 セル 51 注入管 52 排出管 53 誘電体物質 61 赤外分光光度計 62 ATRプリズム 63 赤外光光源 64 検知器 71 レーザラマン分光光度計 72 レーザ光源 73 分光検知器 81 光学顕微鏡 82 対物レンズ 91 走査型トンネル顕微鏡 92 探針 93 圧電体 94 直流電源 101 走査型原子間力顕微鏡 102 カンチレバー 111 磁気コイル
1, 20, 30, 40, 50, 60, 70, 80, 9
0,100,110 Measuring device 2,21 Surface plasmon microscope 3 Heating heater 4 Measurement sample 5 Transparent substrate 6 Metal thin film 7 Matching oil 8 Optical prism 9 Monochromatic laser light source 10 Polarizing plate 11 Beam expander 12 Aperture 13 Condensing lens 14 ND filter 15 Cylindrical lens 16 Photodiode array 17 XY stage 18 Prism fixing member 19 Thermistor 22 CCD camera 23 Fixed stage 31 Electrode 32 DC power supply 41 Cell frame 42 Cell 51 Injection pipe 52 Discharge pipe 53 Dielectric substance 61 Infrared spectroscopy Photometer 62 ATR prism 63 Infrared light source 64 Detector 71 Laser Raman spectrophotometer 72 Laser light source 73 Spectral detector 81 Optical microscope 82 Objective lens 91 Scanning tunneling microscope 92 Probe 93 Piezoelectric body 94 Straight Power 101 Scanning atomic force microscope 102 cantilever 111 magnetic coil

───────────────────────────────────────────────────── フロントページの続き (72)発明者 近藤 聖二 東京都渋谷区幡ヶ谷2丁目43番2号 オリ ンパス光学工業株式会社内 (72)発明者 越石 喜代三 神奈川県相模原市元橋本町7−32 (72)発明者 下村 政嗣 東京都小金井市中町2−24−48−103 (72)発明者 山口 一郎 埼玉県和光市広沢2番1号 理化学研究所 内 (72)発明者 岡本 隆之 埼玉県和光市広沢2番1号 理化学研究所 内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Seiji Kondo 2-43-2 Hatagaya, Shibuya-ku, Tokyo Inside Olympus Optical Co., Ltd. (72) Inventor Kiyozo Koshiishi 7 Motomachi Hashimachi, Sagamihara-shi, Kanagawa 32 (72) Inventor Masatsugu Shimomura 2-24-48-103 Nakamachi, Koganei-shi, Tokyo (72) Inventor Ichiro Yamaguchi 2-1, Hirosawa, Wako-shi, Saitama RIKEN (72) Inventor Takayuki Okamoto Wako, Saitama 2-1, Hirosawa City, RIKEN

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】 金属薄膜の一方の面に誘電体試料を接触
させるとともに、この金属薄膜の他方の面に全反射の条
件で偏光光を入射して表面プラズモン共鳴を誘起させ、
その反射光を検出することで、前記誘電体試料の状態を
測定する表面プラズモン測定手段と、 前記誘電体試料に物理的又は化学的な刺激を加える刺激
手段とを備え、 この刺激手段により刺激された前記誘電体試料の状態変
化を前記表面プラズモン測定手段により測定するように
構成したことを特徴とする表面プラズモン共鳴を利用し
た測定装置。
1. A dielectric sample is brought into contact with one surface of a metal thin film, and polarized light is incident on the other surface of the metal thin film under conditions of total reflection to induce surface plasmon resonance.
The surface plasmon measuring means for measuring the state of the dielectric sample by detecting the reflected light, and the stimulating means for physically or chemically stimulating the dielectric sample are provided, and are stimulated by the stimulating means. A measuring apparatus using surface plasmon resonance, characterized in that the state change of the dielectric sample is measured by the surface plasmon measuring means.
【請求項2】 請求項1記載の測定装置において、前記
誘電体試料の前記金属薄膜と接触していない側の表面を
観察する観察手段をさらに備えたことを特徴とする表面
プラズモン共鳴を利用した測定装置。
2. The measurement apparatus according to claim 1, further comprising an observation means for observing a surface of the dielectric sample that is not in contact with the metal thin film, wherein surface plasmon resonance is used. measuring device.
【請求項3】 請求項1記載の測定装置において、前記
誘電体試料が気体又は液体の特定成分に対して相互作用
を生じる材料からなる機能性薄膜であり、 この薄膜に生じる相互作用を測定することにより前記気
体又は液体の特定成分の濃度を検出する検出手段を備え
たことを特徴とする表面プラズモン共鳴を利用した測定
装置。
3. The measuring device according to claim 1, wherein the dielectric sample is a functional thin film made of a material that interacts with a specific component of gas or liquid, and the interaction that occurs in the thin film is measured. Accordingly, a measuring device utilizing surface plasmon resonance, comprising a detection means for detecting the concentration of the specific component of the gas or liquid.
JP4286189A 1992-10-23 1992-10-23 Measuring apparatus utilizing surface plasmon resonance Pending JPH06167443A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4286189A JPH06167443A (en) 1992-10-23 1992-10-23 Measuring apparatus utilizing surface plasmon resonance

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4286189A JPH06167443A (en) 1992-10-23 1992-10-23 Measuring apparatus utilizing surface plasmon resonance

Publications (1)

Publication Number Publication Date
JPH06167443A true JPH06167443A (en) 1994-06-14

Family

ID=17701107

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4286189A Pending JPH06167443A (en) 1992-10-23 1992-10-23 Measuring apparatus utilizing surface plasmon resonance

Country Status (1)

Country Link
JP (1) JPH06167443A (en)

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