JP2003247936A - Refractive index measuring sensor and its manufacturing method - Google Patents
Refractive index measuring sensor and its manufacturing methodInfo
- Publication number
- JP2003247936A JP2003247936A JP2002046861A JP2002046861A JP2003247936A JP 2003247936 A JP2003247936 A JP 2003247936A JP 2002046861 A JP2002046861 A JP 2002046861A JP 2002046861 A JP2002046861 A JP 2002046861A JP 2003247936 A JP2003247936 A JP 2003247936A
- Authority
- JP
- Japan
- Prior art keywords
- refractive index
- silica particles
- metal
- multilayer film
- measuring sensor
- 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.)
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/55—Specular reflectivity
- G01N21/552—Attenuated total reflection
- G01N21/553—Attenuated total reflection and using surface plasmons
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
- G01N21/4133—Refractometers, e.g. differential
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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)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、物質の状態変化等
の測定に用いられるバイオセンサ及びケミカルセンサに
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biosensor and a chemical sensor used for measuring changes in the state of substances.
【０００２】[0002]
【従来の技術】従来から屈折率の変化を測定すること
で、その屈折率の変化に応じた物質の状態変化を測定す
ることは知られている。この測定を行うために、金や銀
等の金属薄膜表面に発生する表面プラズモン共鳴現象を
利用して物質の状態測定を行うことが提案されている。
表面プラズモンとは、金属−誘電体界面に生じる電子の
疎密波の一種であり、その波数は試料の厚さや光学特性
（誘電率、屈折率）によって変化する。この変化を直接
測定することはできないため、表面プラズモン共鳴を利
用した測定方法では、プリズムの底面に金や銀等の金属
薄膜を形成し、その金属薄膜の表面に試料を直接接触さ
せた状態で、タングステンランプ、ハロゲンランプ、発
光ダイオード（ＬＥＤ）、スーパールミネッセントダイ
オード（ＳＬＤ）、レーザーなどの光を前記金属薄膜の
裏面、即ち、試料の反対面から当ててエバネッセント波
を発生させ、このエバネッセント波が表面プラズモンと
共鳴することに起因した減光により生じる暗線の角度の
角度変化から屈折率の変化を測定することで金属薄膜表
面に接触させた試料の状態変化を間接的に測定する装置
が提案され、既に実用化されている。2. Description of the Related Art Conventionally, it has been known to measure a change in the refractive index to measure a change in the state of a substance according to the change in the refractive index. In order to carry out this measurement, it has been proposed to measure the state of a substance by utilizing the surface plasmon resonance phenomenon generated on the surface of a metal thin film such as gold or silver.
The surface plasmon is a type of compressional wave of electrons generated at a metal-dielectric interface, and its wave number changes depending on the thickness of the sample and optical characteristics (dielectric constant, refractive index). Since this change cannot be directly measured, in the measurement method using surface plasmon resonance, a metal thin film such as gold or silver is formed on the bottom surface of the prism, and the sample is directly contacted with the surface of the metal thin film. , E.g., a tungsten lamp, a halogen lamp, a light emitting diode (LED), a super luminescent diode (SLD), or a laser, is applied from the back surface of the metal thin film, that is, the opposite surface of the sample to generate an evanescent wave. A device that indirectly measures the state change of the sample in contact with the metal thin film surface by measuring the change in the refractive index from the change in the angle of the dark line caused by the extinction caused by the wave resonating with the surface plasmon It has been proposed and already put into practical use.
【０００３】[0003]
【発明が解決しようとする課題】上記したように構成さ
れた従来の表面プラズモン共鳴センサは、ガラス基板上
に真空蒸着法で金属薄膜を形成する。このため、測定を
行うために試料毎に表面プラズモン共鳴が生じる入射角
を探す必要があるため光の入射角度が可変できるように
装置を組み立てる必要があり、装置が複雑になり、ま
た、測定も煩雑になるという問題点があった。本発明
は、上記した従来の問題点を解決し、入射角度に依存す
ることなく表面プラズモン共鳴現象を用いて物質の屈折
率を測定することができ、かつ、同時に回折光によって
も物質の屈折率を測定することができる屈折率測定用セ
ンサ及びその製造方法を提供することを目的としてい
る。In the conventional surface plasmon resonance sensor constructed as described above, a metal thin film is formed on a glass substrate by a vacuum deposition method. For this reason, it is necessary to find the incident angle at which surface plasmon resonance occurs for each sample in order to perform the measurement, so it is necessary to assemble the device so that the incident angle of light can be changed, and the device becomes complicated, and the measurement is also difficult. There was a problem that it became complicated. INDUSTRIAL APPLICABILITY The present invention solves the above-mentioned conventional problems, and can measure the refractive index of a substance by using the surface plasmon resonance phenomenon without depending on the incident angle, and at the same time, the refractive index of the substance can also be measured by diffracted light. It is an object of the present invention to provide a refractive index measuring sensor capable of measuring the above and a manufacturing method thereof.
【０００４】[0004]
【課題を解決するための手段】上記した目的を達成する
ために、本発明に係る屈折率測定用センサは、ガラス製
基板上に、表面が金属でコーティングされた同じサイズ
の複数のシリカ粒子を周期的に配列してなる多層膜を備
え、前記多層膜内のシリカ粒子間に測定すべき物質が入
り得る隙間を有することを特徴とするものである。前記
したシリカ粒子の表面をコーティングする金属は、好ま
しくは、金又は銀であるが、これに限定されることな
く、プラズモンを有する金属であれば任意の金属でよ
い。前記シリカ粒子の大きさは光回折と密接な関係があ
り、粒子サイズが大きければ大きいほど回折波長は長波
長側に移動する。従って、シリカ粒子の大きさは、測定
すべき試料や入射光の波長に応じて任意に設定すること
が可能であり、例えば、２００ｎｍ又は３００ｎｍであ
り得る。また、本発明に係る屈折率測定用センサの製造
方法は、ガラス基板上に、同じサイズの複数のシリカ粒
子が周期的に配列された多層膜を形成し、前記基板に形
成された多層膜を、金属及びポリマーを含有した溶液中
に入れ、前記溶液から多層膜を取り出して乾燥させた
後、ポリマーを焼却でき、かつ、金属の微粒子が凝集す
ることなく金属をシリカ粒子に固定することができる温
度で多層膜を焼成することで、個々のシリカ粒子の表面
に金属が固定され、かつ、個々のシリカ粒子間に微細な
隙間が形成された多層膜を形成することを特徴とするも
のである。前記焼成温度は、採用する金属に応じて、ポ
リマーを焼却でき、かつ、金属の微粒子が凝集すること
なく金属をシリカ粒子に固定することができる温度範囲
で任意に設定され得、例えば、金属として金を用いる場
合には、３００°〜４００°の範囲が好ましい。また、
シリカ粒子の多層膜は任意の方法で形成され得、例え
ば、垂直堆積法等の方法で形成され得る。In order to achieve the above-mentioned object, a sensor for measuring a refractive index according to the present invention comprises a glass substrate on which a plurality of silica particles of the same size, the surfaces of which are coated with a metal, are coated. It is characterized in that it comprises a multi-layered film arranged periodically, and has a gap between silica particles in the multi-layered film in which a substance to be measured can enter. The metal coating the surface of the silica particles is preferably gold or silver, but is not limited thereto, and any metal having plasmon may be used. The size of the silica particles is closely related to light diffraction, and the larger the particle size, the more the diffraction wavelength shifts to the long wavelength side. Therefore, the size of the silica particles can be arbitrarily set according to the sample to be measured and the wavelength of incident light, and can be, for example, 200 nm or 300 nm. Further, the method for manufacturing a sensor for measuring a refractive index according to the present invention, on a glass substrate, to form a multilayer film in which a plurality of silica particles of the same size are periodically arranged, the multilayer film formed on the substrate. It is possible to incinerate the polymer after putting it in a solution containing a metal and a polymer, taking out the multilayer film from the solution and drying it, and fixing the metal to the silica particles without agglomeration of the metal fine particles. By firing the multilayer film at a temperature, a metal is fixed on the surface of each silica particle, and a multilayer film in which fine gaps are formed between the individual silica particles is formed. . The firing temperature can be arbitrarily set in a temperature range in which the polymer can be incinerated, and the metal fine particles can be fixed to the silica particles without agglomeration, depending on the metal employed, for example, as a metal. When using gold, the range of 300 ° to 400 ° is preferable. Also,
The multilayer film of silica particles can be formed by any method, for example, a vertical deposition method or the like.
【０００５】[0005]
【発明の実施の形態】以下、添付図面に示した実施例を
参照して本発明に係る屈折率測定用センサの実施の形態
について説明していく。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of a refractive index measuring sensor according to the present invention will be described below with reference to the embodiments shown in the accompanying drawings.
【０００６】始めに図１及び図２を用いて本発明に係る
屈折率測定用センサの製造方法について説明していく。
まず、垂直堆積法で基板上にシリカ粒子の周期性多層膜
を作製する。垂直堆積法により形成された多層膜は、図
１に示すように同じサイズのシリカ粒子１が周期的に配
列されたものになっている。尚、図中２はシリカ粒子間
にあいた隙間を示している。次に図２（ａ）〜（ｅ）を
用いてガラス基板に形成された多層膜の各シリカ粒子の
表面を金でコーティングする工程について説明してい
く。図２（ａ）は、シリカ粒子の多層膜が形成されたガ
ラス基板を示している。始めに、金ナノ粒子４及びポリ
マー３を含有した溶液の中にガラス基板を浸ける（図２
（ｂ））。そして、溶液中に浸けられたガラス基板を２
ｍｍ／ｍｉｎの速度で引き上げて乾燥させる（図２
（ｂ）及び（ｃ））。そして、最後に、ポリマー３を焼
却でき、金ナノ粒子４が凝集することなく金をシリカ粒
子の表面に固定できる温度でガラス基板を焼成する（図
２（ｄ））。これにより、シリカ粒子の表面に金が固定
され、かつ、シリカ粒子１間の隙間２に混入していたポ
リマー３が焼却されてなくなるので、シリカ粒子１間に
微細な隙間２（ナノ空間）があいた屈折率測定用センサ
が完成する（図２（ｅ））。尚、図２中、符号５はシリ
カ粒子１の表面に固定された金膜を示している。First, a method for manufacturing the refractive index measuring sensor according to the present invention will be described with reference to FIGS.
First, a periodic multilayer film of silica particles is formed on a substrate by the vertical deposition method. The multilayer film formed by the vertical deposition method is one in which silica particles 1 of the same size are periodically arranged as shown in FIG. In the figure, 2 indicates a gap between the silica particles. Next, the step of coating the surface of each silica particle of the multilayer film formed on the glass substrate with gold will be described with reference to FIGS. FIG. 2A shows a glass substrate on which a multilayer film of silica particles is formed. First, a glass substrate is immersed in a solution containing gold nanoparticles 4 and polymer 3 (see FIG. 2).
(B)). Then, the glass substrate soaked in the solution 2
It is pulled up at a speed of mm / min and dried (Fig. 2).
(B) and (c)). Then, finally, the glass substrate is fired at a temperature at which the polymer 3 can be incinerated and the gold nanoparticles 4 can be fixed on the surface of the silica particles without agglomeration (FIG. 2 (d)). As a result, gold is fixed on the surface of the silica particles, and the polymer 3 mixed in the gaps 2 between the silica particles 1 is incinerated and disappears, so that fine gaps 2 (nano spaces) are formed between the silica particles 1. The open refractive index measuring sensor is completed (FIG. 2E). In FIG. 2, reference numeral 5 indicates a gold film fixed on the surface of the silica particle 1.
【０００７】上記したように構成された屈折率測定用セ
ンサを用いて、６種類の媒質（メタノール、エタノー
ル、イソプロパノール、テトラヒドロフラン、トルエ
ン、及び1,2-ジブロモブタン）の屈折率を測定した。図
３は測定実験に用いた装置の概略構成図である。測定に
用いた屈折率測定用センサは、直径３００ｎｍのシリカ
粒子の層を３層形成してなる多層膜をガラス基板に上に
形成したもので、各シリカ粒子の表面は金でコーティン
グされている。上記した屈折率測定用センサを、媒質が
入った透明容器中に浸け、基板の裏側（多層膜が形成さ
れてない側）から、白色光を入射し、センサを通過した
光を反対側で測定した。上記した条件で、屈折率が既知
の空気（屈折率1.000）、メタノール（屈折率1.329）、
エタノール（屈折率1.360）、イソプロパノール（屈折
率1.377）、テトラヒドロフラン（屈折率1.407）、トル
エン（屈折率1.496）、及び1,2-ジブロモブタン（屈折
率1.538）の各媒体を測定した結果を図４に示す。図４
中、符号ａは空気、符号ｂはメタノール、符号ｃはエタ
ノール、符号ｄはイソプロパノール、符号ｅはテトラヒ
ドロフラン、符号ｆはトルエン、及び符号ｇは1,2-ジブ
ロモブタンを各々示している。図面に示すように、測定
光の吸収には表面プラズモン共鳴によるピークと回折に
よるピークが二つ現れ、その値は媒質によって異なる。
これは測定すべき媒質が多層膜内のシリカ粒子間に存在
する隙間に入り込むことにより、表面プラズモン共鳴が
生じる波長及び回折が生じる波長が変化するからであ
る。各媒体のピーク値が生じる波長と屈折率との関係を
図５に示す。図中の符号ａ〜ｇは図４と同じ媒体を指
す。図面に示すように、表面プラズモン共鳴によるピー
ク値（ＬＳＰＲ）及び回折によるピーク値（Ｓｔｏｐ
ｂａｎｄ）が生じる波長は、共に媒体の持つ屈折率と比
例している。この測定実験結果により、本発明に係る屈
折率測定用センサを用いれば、表面プラズモン共鳴及び
回折の両方から屈折率の測定が可能であることが確認で
き、この特性を生かして、ケミカルセンサやバイオセン
サへの応用が可能であることが分かる。発明者は、多層
膜のシリカ粒子の直径を２００ｎｍにしたセンサを用い
て同じ条件で実験を行ったが、同様の結果が得られた。
上記したように本発明に係る屈折率測定用センサは、市
販の紫外可視分光器あるいはファイバー型分光器を用い
て屈折率を測定することが可能になる。また、本発明に
係る屈折率測定用センサによれば、一つの物質の屈折率
を表面プラズモン共鳴と回折との二つの現象を通して測
定することが可能になるので、より精密な測定が可能に
なる。Using the refractive index measuring sensor constructed as described above, the refractive indexes of six kinds of media (methanol, ethanol, isopropanol, tetrahydrofuran, toluene, and 1,2-dibromobutane) were measured. FIG. 3 is a schematic configuration diagram of the apparatus used for the measurement experiment. The refractive index measuring sensor used for the measurement is a multilayer film formed by forming three layers of silica particles having a diameter of 300 nm on a glass substrate, and the surface of each silica particle is coated with gold. . Immerse the above-mentioned refractive index measurement sensor in a transparent container containing a medium, inject white light from the back side of the substrate (the side where the multilayer film is not formed), and measure the light passing through the sensor on the opposite side. did. Under the above conditions, air with a known refractive index (refractive index 1.000), methanol (refractive index 1.329),
Figure 4 shows the results of measurements of ethanol (refractive index 1.360), isopropanol (refractive index 1.377), tetrahydrofuran (refractive index 1.407), toluene (refractive index 1.496), and 1,2-dibromobutane (refractive index 1.538). Shown in. Figure 4
In the above, the symbol a is air, the symbol b is methanol, the symbol c is ethanol, the symbol d is isopropanol, the symbol e is tetrahydrofuran, the symbol f is toluene, and the symbol g is 1,2-dibromobutane. As shown in the drawing, two peaks due to surface plasmon resonance and two peaks due to diffraction appear in the absorption of the measurement light, and the values differ depending on the medium.
This is because the medium to be measured enters the gap existing between the silica particles in the multilayer film, whereby the wavelength at which surface plasmon resonance occurs and the wavelength at which diffraction occurs change. FIG. 5 shows the relationship between the wavelength at which the peak value of each medium occurs and the refractive index. Reference numerals a to g in the figure indicate the same media as in FIG. As shown in the drawing, the peak value by surface plasmon resonance (LSPR) and the peak value by diffraction (Stop)
The wavelength that causes the band) is proportional to the refractive index of the medium. From this measurement experiment result, it can be confirmed that the refractive index can be measured from both surface plasmon resonance and diffraction by using the refractive index measuring sensor according to the present invention, and by utilizing this characteristic, a chemical sensor or a biosensor can be used. It can be seen that it can be applied to sensors. The inventor conducted an experiment under the same conditions using a sensor in which the silica particles in the multilayer film had a diameter of 200 nm, but similar results were obtained.
As described above, the refractive index measuring sensor according to the present invention can measure the refractive index using a commercially available UV-visible spectroscope or fiber type spectroscope. Further, according to the refractive index measuring sensor of the present invention, it is possible to measure the refractive index of one substance through the two phenomena of surface plasmon resonance and diffraction, which enables more precise measurement. .
【０００８】[0008]
【発明の効果】以上説明したように、本発明に係る屈折
率測定用センサは、ガラス製基板上に、表面が金属でコ
ーティングされた同じサイズの複数のシリカ粒子を周期
的に配列してなる多層膜を備え、前記多層膜内のシリカ
粒子間に測定すべき物質が入り得る隙間を有するので、
表面プラズモン共鳴現象が生じる波長と回折が生じる波
長の両方を測定することが可能になり、これらの波長か
ら、測定すべき物質の屈折率を測定することが可能にな
るという効果を奏する。また、本発明に係る屈折率測定
用センサによれば、上記した屈折率測定用センサを簡単
な方法で製造することが可能になる。As described above, the sensor for measuring the refractive index according to the present invention comprises a glass substrate, and a plurality of silica particles of the same size, the surfaces of which are coated with metal, arranged periodically. Since it is provided with a multilayer film and has a gap in which a substance to be measured can enter between silica particles in the multilayer film,
It is possible to measure both the wavelength at which the surface plasmon resonance phenomenon occurs and the wavelength at which diffraction occurs, and it is possible to measure the refractive index of the substance to be measured from these wavelengths. Further, according to the refractive index measuring sensor of the present invention, the above-described refractive index measuring sensor can be manufactured by a simple method.
【図１】 ガラス基板に形成されシリカ粒子の多層膜の
概略側面図である。FIG. 1 is a schematic side view of a multilayer film of silica particles formed on a glass substrate.
【図２】 （ａ）〜（ｅ）はガラス基板に形成された多
層膜の各シリカ粒子の表面を金でコーティングする工程
を示す概略図である。2A to 2E are schematic views showing a process of coating the surface of each silica particle of a multilayer film formed on a glass substrate with gold.
【図３】 本発明に係る屈折率測定センサの測定実験に
用いた装置の概略構成図である。FIG. 3 is a schematic configuration diagram of an apparatus used for a measurement experiment of the refractive index measurement sensor according to the present invention.
【図４】 本発明に係る屈折率測定センサを用いて７つ
の異なる媒体を測定した結果を示すグラフである。FIG. 4 is a graph showing the results of measuring seven different media using the refractive index measurement sensor according to the present invention.
【図５】 図４により得られた表面プラズモン共鳴が生
じる波長及び回折が生じる波長と、屈折率との関係を示
すグラフである。FIG. 5 is a graph showing a relationship between a wavelength at which surface plasmon resonance occurs and a wavelength at which diffraction occurs, which is obtained in FIG. 4, and a refractive index.
１ シリカ粒子 ２ 隙間（ナノ空間） ３ ポリマー ４ 金ナノ粒子 ５ 金粒子膜 1 silica particles 2 Gap (nano space) 3 polymer 4 gold nanoparticles 5 Gold particle film
フロントページの続き (72)発明者 顧 忠沢 神奈川県川崎市高津区溝口６−14−５ 第 一コーポラスみなみ201号 Ｆターム(参考） 2G059 AA02 BB04 EE02 GG10 KK01Continued front page (72) Inventor, Tadazawa 6-14-5 Mizoguchi, Takatsu-ku, Kawasaki City, Kanagawa Prefecture One Corpora Minami 201 F term (reference) 2G059 AA02 BB04 EE02 GG10 KK01
Claims (7)
リカ粒子を周期的に配列してなる多層膜を備え、 前記多層膜内のシリカ粒子間に測定すべき物質が入り得
る隙間を有することを特徴とする屈折率測定用センサ。1. A multilayer film comprising a glass substrate and a plurality of silica particles of the same size, the surface of which is coated with a metal, arranged periodically, the measurement being performed between the silica particles in the multilayer film. A refractive index measuring sensor having a gap into which a substance can enter.
項１に記載の屈折率測定用センサ。2. The refractive index measuring sensor according to claim 1, wherein the metal is gold.
項１に記載の屈折率測定用センサ。3. The refractive index measuring sensor according to claim 1, wherein the metal is silver.
カ粒子が周期的に配列された多層膜を形成し、 前記基板に形成された多層膜を、金属及びポリマーを含
有した溶液中に入れ、 前記溶液から多層膜を取り出して乾燥させた後、 ポリマーを焼却でき、かつ、金属の微粒子が凝集するこ
となく金属をシリカ粒子に固定することができる温度で
多層膜を焼成することで、 個々のシリカ粒子の表面に金属が固定され、かつ、個々
のシリカ粒子間に微細な隙間が形成された多層膜を形成
することを特徴とする屈折率測定用センサの製造方法。4. A multilayer film in which a plurality of silica particles of the same size are periodically arranged is formed on a glass substrate, and the multilayer film formed on the substrate is placed in a solution containing a metal and a polymer. By taking out the multilayer film from the solution and drying it, by firing the multilayer film at a temperature at which the polymer can be incinerated and the metal can be fixed to the silica particles without agglomeration of the metal fine particles, A method for producing a sensor for measuring a refractive index, which comprises forming a multilayer film in which a metal is fixed on the surface of silica particles and fine gaps are formed between individual silica particles.
項４に記載の製造方法。5. The manufacturing method according to claim 4, wherein the metal is gold.
ることを特徴とする請求項５に記載の製造方法。6. The manufacturing method according to claim 5, wherein the firing temperature range is 300 ° to 400 °.
項４に記載の製造方法。7. The manufacturing method according to claim 4, wherein the metal is silver.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1729112A1 (en) * | 2005-06-01 | 2006-12-06 | Canon Kabushiki Kaisha | Localized plasmon resonance sensor |
| JP2008538414A (en) * | 2005-04-22 | 2008-10-23 | 富士レビオ株式会社 | Sensor chip with bonded non-metallic particles including a metal coating |
-
2002
- 2002-02-22 JP JP2002046861A patent/JP2003247936A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008538414A (en) * | 2005-04-22 | 2008-10-23 | 富士レビオ株式会社 | Sensor chip with bonded non-metallic particles including a metal coating |
| US8288166B2 (en) | 2005-04-22 | 2012-10-16 | Fujirebio Inc. | Sensor chip with connected non-metallic particles comprising a metallic coating |
| EP1729112A1 (en) * | 2005-06-01 | 2006-12-06 | Canon Kabushiki Kaisha | Localized plasmon resonance sensor |
| US7599066B2 (en) | 2005-06-01 | 2009-10-06 | Canon Kabushiki Kaisha | Localized plasmon resonance sensor |
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