JP5626066B2 - Observation device - Google Patents
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- JP5626066B2 JP5626066B2 JP2011071679A JP2011071679A JP5626066B2 JP 5626066 B2 JP5626066 B2 JP 5626066B2 JP 2011071679 A JP2011071679 A JP 2011071679A JP 2011071679 A JP2011071679 A JP 2011071679A JP 5626066 B2 JP5626066 B2 JP 5626066B2
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- 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
Description
本発明は、観察装置に関する。 The present invention relates to an observation apparatus.
ナノデバイスの開発においては、例えば、分子構造の０．１レーヤー程度の精度で、ナノデバイスの形成プロセス中の状況を観察しながら製作し、その観察情報を更なる高性能デバイスの開発プロセスにフィードバックするといったことが必要とされる。しかし、分子構造レベルの微細な構造の観察手段が乏しいため、開発の実態は、先ずナノデバイスを完成し、性能評価をして、それを次の完成品製作に反映しながらレベルアップを図るといった開発手段をとらざるを得ない。この結果、ナノデバイスの開発や、その製造工程の確立に多くの時間と費用を必要としている。 In the development of nanodevices, for example, with the accuracy of about 0.1 layer of the molecular structure, it is manufactured while observing the situation during the nanodevice formation process, and the observation information is fed back to the development process of further high-performance devices. It is necessary to do. However, since there are few means for observing the fine structure at the molecular structure level, the actual state of development is to first complete the nanodevice, evaluate the performance, and improve the level while reflecting it in the production of the next finished product. I have to take development measures. As a result, much time and money are required for the development of nanodevices and the establishment of their manufacturing processes.
分子や分子構造の特定方法の一つとして、例えば、原子間の結合における熱振動を観察する方法がある。熱振動の周波数の値は、原子の結合構造の変化に敏感に反応して変わるため、熱振動の周波数が検出できれば分子構造の知見を得ることができる。 As one of methods for specifying molecules and molecular structures, for example, there is a method of observing thermal vibration in bonds between atoms. Since the value of the frequency of thermal vibration changes sensitively in response to changes in the bonding structure of atoms, knowledge of the molecular structure can be obtained if the frequency of thermal vibration can be detected.
熱振動周波数の観察手段として、赤外線領域の吸収特性の測定や反射分光特性の測定、また可視光・紫外光で励起されたラマン散乱光の分光特性の測定などの方法が、従来から用いられてきた。また、電子線を観察手段と用いられるものに、ＥＥＬＳ（Ｅｌｅｃｔｒｏｎ Ｅｎａｅｒｇｙ Ｌｏｓｓ Ｓｐｅｃｔｒｏｓｃｏｐｙ；電子エネルギー損失分光法）が知られている。しかし、上記のいずれの方法も、検出感度の課題があり、１レーヤー以下のレベルの分子構造の検出を行うことは困難であった。 Methods for observing the thermal vibration frequency include methods such as measurement of absorption characteristics in the infrared region, measurement of reflection spectral characteristics, and measurement of spectral characteristics of Raman scattered light excited by visible light and ultraviolet light. It was. Further, EELS (Electron Energy Loss Spectroscopy) is known as an electron beam observation means. However, any of the above methods has a problem of detection sensitivity, and it has been difficult to detect a molecular structure at a level of one layer or less.
一方、ＳＴＭ（Ｓｃａｎｎｉｎｇ Ｔｕｎｎｅｌ Ｍｉｃｒｏｓｃｏｐｅ；走査型トンネル顕微鏡）のＩ−Ｖ特性を解析することで、ＥＥＬＳと同様な結果が、１個の分子に対しても知ることができるとの報告もある。この方法は、超高真空化と、熱雑音の発生と熱膨張を抑えるための極低温状態化が必要で、適用するには多くの制限がある。 On the other hand, there is a report that by analyzing the IV characteristics of STM (Scanning Tunnel Microscope), the same result as EELS can be obtained for one molecule. This method requires an ultra-high vacuum and a very low temperature state to suppress the generation of thermal noise and thermal expansion, and there are many limitations to its application.
これらと異なり、全反射プリズムの反射面下に試料および金属を配し、これに光を反射させて、金属に誘起されるプラズモン共鳴によって増強された光を用いて光吸収を測定するといった方法が提案されている。例えば、全反射プリズムの反射面下に網状金属を設け、この網状金属に接するように試料を配して、この試料での赤外吸収スペクトルを測定する方法、金属上に試料を配置し、かつ試料上方に空気を介し光学プリズムを配置する計測装置、また、光学プリズムの反射面に金属薄膜を形成し、金属薄膜下に試料を配置する測定装置などが提案されている。 Unlike these, there is a method in which a sample and a metal are arranged under the reflection surface of the total reflection prism, light is reflected on this, and light absorption is measured using light enhanced by plasmon resonance induced in the metal. Proposed. For example, a method in which a net-like metal is provided below the reflecting surface of the total reflection prism, a sample is arranged so as to be in contact with the net-like metal, and an infrared absorption spectrum of the sample is measured, the sample is arranged on the metal, and There have been proposed a measuring device in which an optical prism is arranged above a sample via air, a measuring device in which a metal thin film is formed on a reflection surface of the optical prism, and a sample is arranged under the metal thin film.
他方、分子構造の研究に関連し、シリコン表面に付着する各種分子成分の分析に関連する報告として、例えば、シリコン表面を水素化する方法に関する報告や、そのような、シリコン表面上に付着した水素とシリコンの結合に起因する吸収波数特性を多重反射ＡＴＲ（Ａｔｔｅｎｕａｔｅｄ Ｔｏｔａｌ Ｒｅｆｌｅｃｔｉｏｎ；減衰全反射）法で測定した報告などがなされている。 On the other hand, as a report related to the study of molecular structure and related to the analysis of various molecular components adhering to the silicon surface, for example, a report on a method of hydrogenating the silicon surface and such a hydrogen adhering to the silicon surface. There have been reports of measuring the absorption wave number characteristics resulting from the bond between silicon and silicon by the multiple reflection ATR (Attenuated Total Reflection) method.
そのような従来のプラズモン共鳴による光吸収測定による観察方法では、例えば、１原子層以下の存在量を有する分子などの検出を行うことは容易ではない。また、例えば上記のような存在量の小さな分子等の試料を金属に接し、設けることも困難である。 In such a conventional observation method based on optical absorption measurement using plasmon resonance, it is not easy to detect molecules having an abundance of one atomic layer or less, for example. In addition, for example, it is difficult to provide a sample such as a molecule having a small abundance as described above in contact with a metal.
そこで本発明の観察装置の課題は、より高い検出感度を有する観察装置を提供することにある。 Accordingly, an object of the observation apparatus of the present invention is to provide an observation apparatus having higher detection sensitivity.
本発明の観察装置は、
観察対象である観察面を有する第１部品と、
前記観察面から距離をおいて設けられた第２部品と、
前記観察面に対向した前記第２部品の面上に、複数の金属粒子が前記第２部品の材料によって互いに離間して形成された金属粒子形成部と
光を、前記第１部品を介して前記観察面に照射する照射部と、
前記観察面を反射した前記光から、前記観察面上ないしその近傍の状態観察をする観察部と、
を備え、
前記第１部品および前記第２部品は、前記観察面と前記金属粒子形成部が前記光の電磁場内となるように、前記観察面および前記金属粒子形成部を保持することを特徴とする。
The observation apparatus of the present invention is
A first part having an observation surface to be observed;
A second component provided at a distance from the observation surface;
On the surface of the second part facing the observation surface, a plurality of metal particles are formed by being separated from each other by the material of the second part, and light is transmitted through the first part. An irradiation unit for irradiating the observation surface;
From the light reflected from the observation surface, an observation unit for observing the state on or near the observation surface; and
With
The first component and the second component hold the observation surface and the metal particle formation portion so that the observation surface and the metal particle formation portion are in an electromagnetic field of the light.
本発明の観察装置によって、基本的な観察装置に比べ、５〜７倍のより検出感度の高い観察装置を得ることができる。 With the observation device of the present invention, it is possible to obtain an observation device with a detection sensitivity that is 5 to 7 times higher than that of a basic observation device.
以下に、本発明の実施の形態を、添付図を参照しつつ説明する。 Embodiments of the present invention will be described below with reference to the accompanying drawings.
本発明者は、先ず、比較実施例として、次に示すような、観察装置（これを、ここでは金属粒子型観察装置と呼称する）を検討した。
（比較実施例）
図１に、その金属粒子型観察装置の一部断面の模式図を示す。金属粒子型観察装置１００は、観察セル１０１、照射部１０２および観察部１０３を備えている。観察セル１０１は、第１部品１０４、互いに離間した複数の金属粒子１０５および第２部品１０６を備えている。第１部品１０４は観察面１０７を有し、光学プリズムである。観察面１０７において光１０８が全反射する観察面１０７が観察対象であり、そこで、観察面１０７の表面状態や観察面１０７に設置した試料の状態を観察するなど、観察面１０７上ないしその近傍の状態を観察可能とする。
The inventor first examined an observation apparatus (hereinafter referred to as a metal particle type observation apparatus) as shown below as a comparative example.
(Comparative Example)
FIG. 1 shows a schematic diagram of a partial cross section of the metal particle type observation apparatus. The metal particle type observation apparatus 100 includes an observation cell 101, an irradiation unit 102, and an observation unit 103. The observation cell 101 includes a first part 104, a plurality of metal particles 105 spaced apart from each other, and a second part 106. The first component 104 has an observation surface 107 and is an optical prism. The observation surface 107 on which the light 108 is totally reflected on the observation surface 107 is an observation target. Therefore, the surface state of the observation surface 107 and the state of the sample placed on the observation surface 107 are observed, for example, on or near the observation surface 107. The state can be observed.
照射部１０２では、観察に必要な波長や偏光の光を第１部品に照射し、観察部では、反射して来た光の強度などを測定する。 The irradiation unit 102 irradiates the first component with light having a wavelength or polarized light necessary for observation, and the observation unit measures the intensity of the reflected light or the like.
互いに離間した複数の粒子からなる金属粒子１０５は、第１部品１０４の観察面１０５に、距離Ｇおいて、相対して設けられた第２部品１０６の表面上に設けられる。金属粒子１０５は、例えば金（Ａｕ）であり、例えば、１００ｎｍ以下の直径を有する粒子が離散して配置される。 The metal particles 105 composed of a plurality of particles spaced apart from each other are provided on the surface of the second component 106 that is provided opposite to the observation surface 105 of the first component 104 at a distance G. The metal particles 105 are, for example, gold (Au). For example, particles having a diameter of 100 nm or less are discretely arranged.
互いに離間した複数の金属粒子１０５は、光１０８が観察面１０７において全反射する際に、エバネッセント波が金属粒子１０５全体を含むように設けられる。すなわち、第１部品１０４と第２部品１０６の距離Ｇは、光１０８の波長以下である。従って、金属粒子１０５の大きさは、上記の様に、光１０８の波長以下のナノサイズである。照射部１０２は、第１部品１０４を介して観察面１０７に光１０８を照射し、観察部１０３は、観察面１０７で反射した光１０８から観察面１０７上ないしその近傍の状態を観察する。 The plurality of metal particles 105 separated from each other are provided so that the evanescent wave includes the entire metal particles 105 when the light 108 is totally reflected on the observation surface 107. That is, the distance G between the first component 104 and the second component 106 is equal to or less than the wavelength of the light 108. Therefore, the size of the metal particle 105 is nano-sized less than the wavelength of the light 108 as described above. The irradiation unit 102 irradiates the observation surface 107 with light 108 via the first component 104, and the observation unit 103 observes the state on or near the observation surface 107 from the light 108 reflected by the observation surface 107.
このような構成の金属粒子型観察装置１００において、第１部品１０４および第２部品１０６は、観察面１０７およびナノサイズの互いに離間している金属粒子１０５が、光１０８のエバネッセント波の電磁波内になるように、観察面１０７および金属粒子１０５の距離Ｇを持続的に保持することにより、互いに離間している複数の金属粒子１０５において生じた局在（表面）プラズモンとエバネッセント波の電場とのカップリングが発生し、局在（表面）プラズモン共鳴（Ｓｕｒｆａｃｅ Ｐｌａｓｍａ Ｒｅｓｏｎａｎｓｅ；ＳＰＲ）が起き、プラズモンポラリトンが励起する。これにより、観察面１０７の状態（観察面上ないしその近傍の状態）に起因して、観察部１０３で観察される光１０８の吸収に関する波長依存性を測定すると、特定波数において吸収が増大する。このように、金属粒子１０５における局在（表面）プラズモンとエバネッセント波の電場のカップリングをより増大させることにより、観察面の状態観察感度を向上することができる。 In the metal particle type observation apparatus 100 having such a configuration, the first component 104 and the second component 106 are configured such that the observation surface 107 and the nano-sized metal particles 105 are separated from each other in the electromagnetic wave of the evanescent wave of the light 108. As described above, by maintaining the distance G between the observation surface 107 and the metal particles 105 continuously, a cup of localized (surface) plasmons generated in the plurality of metal particles 105 that are separated from each other and the electric field of the evanescent wave. A ring is generated, a localized (surface) plasmon resonance (SPR) occurs, and plasmon polaritons are excited. Thereby, due to the state of the observation surface 107 (on the observation surface or in the vicinity thereof), when the wavelength dependency regarding the absorption of the light 108 observed by the observation unit 103 is measured, the absorption increases at a specific wave number. Thus, the state observation sensitivity of the observation surface can be improved by further increasing the coupling of the electric field of the localized (surface) plasmon and the evanescent wave in the metal particle 105.
図１に示した金属粒子型観察装置の構成により、測定を実施した。具体的には、第１部品１０４、第２部品１０６に、シリコン（Ｓｉ）を用い、観察面１０７はＳｉの（１１１）面を使用した。金属粒子１０５は金（Ａｕ）の微粒子を使用し、この金（Ａｕ）の微粒子は、成長速度を遅くした電子ビーム蒸着法で、個々の微粒子が互いに離間するように形成して、その個々の大きさは、数１０ｎｍ以下であった。照射部１０２からの光１０８は、分光された赤外光を用い、全反射光を観察部１０３の検出器で受光した。 Measurement was carried out with the configuration of the metal particle type observation apparatus shown in FIG. Specifically, silicon (Si) was used for the first component 104 and the second component 106, and the Si (111) surface was used for the observation surface 107. Gold (Au) fine particles are used as the metal particles 105. The gold (Au) fine particles are formed so that the individual fine particles are separated from each other by an electron beam evaporation method with a slow growth rate. The size was several tens of nm or less. As the light 108 from the irradiation unit 102, spectral infrared light was used, and the totally reflected light was received by the detector of the observation unit 103.
第１部品１０４の観察面１０７と、第２部品の金属粒子１０５が形成された面との距離Ｇの制御は、第１部品１０４と第２部品１０６を外側から圧力Ｐｒを、図示しない、万力でトルクを加える方式を用い、この圧力Ｐｒの変化で距離Ｇを変化させた。 The control of the distance G between the observation surface 107 of the first component 104 and the surface of the second component on which the metal particles 105 are formed is performed by controlling the pressure Pr between the first component 104 and the second component 106 from the outside. A method of applying torque by force was used, and the distance G was changed by changing the pressure Pr.
観察対象として、第１部品１０４のシリコン（Ｓｉ）の観察面１０７の（１１１）表面に、水素（Ｈ）を付加させた状態のものを用いた。 As the observation target, the one in which hydrogen (H) was added to the (111) surface of the silicon (Si) observation surface 107 of the first component 104 was used.
図２に、その測定結果を示す。図２の横軸は波数（Ｗａｖｅｎｕｍｂｅｒ）で、縦軸は
万力にトルクを加えたときの状態での出力光強度（Ｒ）を、万力にトルクを加えない状態、つまり距離Ｇが十分離れているときでの出力光強度（Ｒ０）で規格化した値を示す。実線はＰ偏光（Ｐ−ｐｏｌ．）の光を示し、点線はＳ偏光（Ｓ−ｐｏｌ．）の光を示す。図１において、光１０８の進行方向の垂直で、観察面１０７に対し交差する方向の偏光がＰ偏光で、光１０８の進行方向に垂直で、観察面１０７に対し平行な方向の偏光がＳ偏光である。
FIG. 2 shows the measurement results. The horizontal axis in FIG. 2 is the wave number, and the vertical axis is the output light intensity (R) when the torque is applied to the vise, and the state where the torque is not applied to the vise, that is, the distance G is sufficiently separated. The value normalized by the output light intensity (R0) when A solid line indicates P-polarized (P-pol.) Light, and a dotted line indicates S-polarized (S-pol.) Light. In FIG. 1, the polarized light in the direction perpendicular to the traveling direction of the light 108 and intersecting the observation surface 107 is P-polarized light, and the polarized light perpendicular to the traveling direction of the light 108 and parallel to the observed surface 107 is S-polarized light. It is.
図２から解るように、Ｓ偏光では信号は観察されないが、Ｐ偏光では約２０８０ｃｍ−１付近において吸収信号Ｍが、また約２２５０ｃｍ−１付近において吸収信号ＭＯ３が観察された。 As can be seen from Figure 2, but the signal was observed in the S-polarized light, absorption signal M in the vicinity of about 2080cm -1 in P-polarized light, also absorption signal MO3 in the vicinity of about 2250 cm -1 was observed.
図３（ａ）および図３（ｂ）は、分子の構造を模式的に示した図である。吸収信号Ｍは、先に本発明者が報告している、多重反射ＡＴＲ法によって検出され信号と同じ波数である。これにより、吸収信号Ｍは、図３（ａ）に示すように、シリコン結晶１１０の（１１１）面のテラスを構成するシリコン原子１１１に、（１１１）面に垂直に結合した水素原子１１２の（１１１）面に垂直な熱振動に対応した信号と考えられる。 FIG. 3A and FIG. 3B are diagrams schematically showing the molecular structure. The absorption signal M has the same wave number as that of the signal detected by the multiple reflection ATR method previously reported by the present inventor. Thereby, as shown in FIG. 3 (a), the absorption signal M is generated from the hydrogen atoms 112 bonded to the silicon atoms 111 constituting the terrace of the (111) plane of the silicon crystal 110 perpendicularly to the (111) plane ( The signal corresponds to thermal vibration perpendicular to the (111) plane.
吸収信号ＭＯ３は、図３（ｂ）に示すように、シリコン結晶１１０の（１１１）面より飛び出したシリコン原子１１１に、（１１１）面に垂直に水素原子１１２が結合し、シリコン原子１１１とシリコン結晶１１０との間に３つの酸素原子１１３が結合した構造において、水素原子１１２の（１１１）面に垂直な熱振動に対応した信号と考えられる。なお、吸収信号ＭＯ３は、多重反射ＡＴＲ法では観察されない。 As shown in FIG. 3B, the absorption signal MO3 is obtained by bonding a silicon atom 111 protruding from the (111) plane of the silicon crystal 110 to a hydrogen atom 112 perpendicular to the (111) plane. In a structure in which three oxygen atoms 113 are bonded to the crystal 110, it is considered that the signal corresponds to thermal vibration perpendicular to the (111) plane of the hydrogen atom 112. The absorption signal MO3 is not observed by the multiple reflection ATR method.
このように、観察面１０７を反射した光１０８の吸収スペクトルから、観察面１０７の状態（この場合は、シリコンに付着した水素の状態）を観察することができる。Ｐ偏光の光によって観察面１０７の状態が観察できたということは、Ｐ偏光の光は観察面１０７と金属粒子１０５の配置方向に偏光した光を含んでいるため、観察面１０７に垂直な方向に分極したプラズモンポラリトンが励起され、観察面１０７に垂直な方向の動的分極（ｄｙｎａｍｉｃ ｐｏｌａｒｉｚａｔｉｏｎ）を有する構造が電場増強される。よって、観察面１０７に垂直な方向の構造分子の熱振動を効率的に観察することができる。他方Ｓ偏光の光では電場増強が無いため、吸収スペクトルが現れて来ない。
（実施例その１）
本発明者は、上記の比較実施例より更なる検出感度の向上を目指して検討を進めた。
Thus, the state of the observation surface 107 (in this case, the state of hydrogen attached to silicon) can be observed from the absorption spectrum of the light 108 reflected from the observation surface 107. The fact that the state of the observation surface 107 can be observed by the P-polarized light means that the P-polarized light includes light polarized in the arrangement direction of the observation surface 107 and the metal particles 105, and thus the direction perpendicular to the observation surface 107. The polarized plasmon polaritons are excited, and the structure having dynamic polarization in the direction perpendicular to the observation surface 107 is enhanced by the electric field. Therefore, the thermal vibration of the structural molecule in the direction perpendicular to the observation surface 107 can be efficiently observed. On the other hand, the absorption spectrum does not appear in S-polarized light because there is no electric field enhancement.
(Example 1)
The present inventor has proceeded with studies aiming at further improvement in detection sensitivity as compared with the comparative example described above.
図４、本発明の観察装置（その１）の、一部断面の模式図を示す。本発明の観察装置（その１）２００は、基本的な構成は、図１に示した金属粒子型観察装置１００と同様であるが、第１部品１０４の観察面１０７と距離Ｇを隔てて相対する、第２部品１０６の面に形成された、複数の粒子からなる混成金属粒子２０１と、これを含む本発明の観察セル（その１）２０２の個所が異なる。 FIG. 4 shows a schematic diagram of a partial cross section of the observation apparatus (part 1) of the present invention. The observation apparatus (No. 1) 200 of the present invention has the same basic configuration as that of the metal particle type observation apparatus 100 shown in FIG. 1, but is relatively separated from the observation surface 107 of the first component 104 by a distance G. The location of the hybrid metal particle 201 made of a plurality of particles formed on the surface of the second component 106 and the observation cell (No. 1) 202 of the present invention including the same are different.
観察装置（その１）２００の実施構成は、第１部品１０４、第２部品１０６に、シリコン（Ｓｉ）を用い、観察面１０７はＳｉの（１１１）面を使用した。第１部品１０４の観察面１０７に相対する、第２部品１０６の表面に混成金属粒子２０１が形成される。 In the implementation configuration of the observation apparatus (part 1) 200, silicon (Si) was used for the first component 104 and the second component 106, and the Si surface (111) was used for the observation surface 107. Hybrid metal particles 201 are formed on the surface of the second part 106, which is opposed to the observation surface 107 of the first part 104.
混成金属粒子２０１の拡大図（ａ）、（ｂ）を、図４の左下に示す。混成金属粒子２０１の形成は、先ず、第２部品１０６と同じ材料のシリコン（Ｓｉ）を、成長速度を遅くした電子ビーム蒸着法で形成して、その個々の大きさが数１０ｎｍ以下であるのシリコン（Ｓｉ）微粒子２０４を付着させ、次に、成長速度を遅くした電子ビーム蒸着法で形成して、その個々の大きさが数１０ｎｍ以下である金（Ａｕ）微粒子２０３を、シリコン（Ｓｉ）微粒子２０４付着面上に付着させた。このとき、金（Ａｕ）微粒子２０３はシリコン（Ｓｉ）微粒子２０４で互いに離間されるようにし、例えば、拡大図（ａ）の様に、シリコン（Ｓｉ）微粒子２０４の隙間のシリコン表面へ挟まるように金（Ａｕ）微粒子２０３が付着するのが好ましい。また拡大図（ｂ）の様に、シリコン表面上のシリコン（Ｓｉ）微粒子２０４の隙間や一部積層したシリコン（Ｓｉ）微粒子２０４上へ挟まるように金（Ａｕ）微粒子２０３が形成される状態などが混在した場合でも、金（Ａｕ）微粒子２０３がシリコン（Ｓｉ）微粒子２０４で互いに離間されるようになっていることが好ましい。 Enlarged views (a) and (b) of the hybrid metal particle 201 are shown in the lower left of FIG. The hybrid metal particles 201 are formed by first forming silicon (Si), which is the same material as the second component 106, by an electron beam evaporation method with a slow growth rate, and each size is several tens of nm or less. Silicon (Si) fine particles 204 are attached, and then formed by an electron beam evaporation method with a slow growth rate. Gold (Au) fine particles 203 each having a size of several tens of nanometers or less are formed into silicon (Si). It was made to adhere on the fine particle 204 adhesion surface. At this time, the gold (Au) fine particles 203 are separated from each other by the silicon (Si) fine particles 204, and, for example, are sandwiched between the silicon surfaces in the gaps of the silicon (Si) fine particles 204 as shown in the enlarged view (a). It is preferable that gold (Au) fine particles 203 adhere. Further, as shown in the enlarged view (b), a state in which the gold (Au) fine particles 203 are formed so as to be sandwiched between the silicon (Si) fine particles 204 on the silicon surface or the partially laminated silicon (Si) fine particles 204, etc. Even in the case where gold is mixed, it is preferable that the gold (Au) fine particles 203 are separated from each other by the silicon (Si) fine particles 204.
こうして形成した、本発明の観察装置（その１）で、比較実施例において述べたものと同様に、観察対象として、シリコン（Ｓｉ）の観察面１０７の（１１１）表面に、水素（Ｈ）を付加させた状態のものを用いて、光吸収スペクトル特性を観察した。 In the observation apparatus (part 1) of the present invention formed in this way, hydrogen (H) was applied to the (111) surface of the observation surface 107 of silicon (Si) as the observation object, as in the comparative example. The light absorption spectrum characteristics were observed using the added state.
図５に、その本発明の観測装置（その１）＜混成金属粒子使用＞での観測結果と、比較実施例での金属粒子型観測装置での観測結果とを同時に示した。図５において、横軸は波数で、縦軸は、万力にトルクを加えたときの状態での出力光強度（Ｒ）を、万力にトルクを加えない状態での出力光強度（Ｒ０）で規格化した値を用いて、−ｌｏｇ（Ｒ／Ｒ０）を用いている。このときの光はＰ偏光したものを入射している。図中太線Ａは、本発明の
観測装置（その１）＜混成金属粒子使用＞によるもので、細線Ｂは、比較実施例での金属粒子型観測装置＜金属粒子使用＞によるものである。
FIG. 5 shows the observation results of the observation apparatus (part 1) <use of mixed metal particles> of the present invention and the observation results of the metal particle type observation apparatus in the comparative example at the same time. In FIG. 5, the horizontal axis is the wave number, and the vertical axis is the output light intensity (R) when torque is applied to the vise, and the output light intensity (R0) when torque is not applied to the vise. -Log (R / R0) is used using the value normalized by. At this time, the P-polarized light is incident. In the figure, the thick line A is due to the observation apparatus (part 1) <use of mixed metal particles> of the present invention, and the thin line B is due to the metal particle type observation apparatus <use of metal particles> in the comparative example.
図５に示されているように、両線のベースラインがほぼ一致しており、これは、第１部品と第２部品間に圧力をかけ、距離Ｇが光波長レベルになるようにして状態観測をしたとき、両観測装置の観測面と金属粒子形成面との距離Ｇが略一致した状態で観測が行われていることを示している。その状況下で比較した結果は、同じ波長帯で、ＭおよびＭＯ３が観察されるが、太線Ａのほうが５〜７倍ピークが高い。即ち、本発明の観測装置（その１）＜混成金属粒子使用＞によるもののほうが、検出感度が向上していることが解る。 As shown in FIG. 5, the baselines of both lines are substantially coincident, which is a state where pressure is applied between the first part and the second part so that the distance G is at the optical wavelength level. When observed, it is shown that the observation is performed in a state where the distance G between the observation surface of both the observation devices and the metal particle formation surface is substantially the same. As a result of comparison under the circumstances, M and MO3 are observed in the same wavelength band, but the thick line A has a peak 5 to 7 times higher. That is, it can be seen that the detection sensitivity of the observation apparatus (part 1) <use of mixed metal particles> of the present invention is improved.
こうした本発明の観察装置における検出感度の向上の効果は、第２部品の材料および同時に混成金属粒子を形成する材料として、上記のシリコン（Ｓｉ）のほかに、ゲルマニウム（Ｇｅ）、セレン化亜鉛（ＺｎＳｅ）、臭化カリウム（ＫＢｒ）などを適用することが可能である。また、混成金属粒子における金属としては、上記の金（Ａｕ）以外に白金（Ｐｔ）も適用できる。 The effect of improving the detection sensitivity in the observation apparatus of the present invention is that, in addition to the silicon (Si) described above, germanium (Ge), zinc selenide ( ZnSe), potassium bromide (KBr), or the like can be used. In addition to the above gold (Au), platinum (Pt) can also be applied as the metal in the hybrid metal particles.
本発明の観察装置の検出感度の向上は、図５のような第２部品の材料の微粒子と金属微粒子で混成金属粒子を作って行う方法以外に、第２部品中に離散して金属粒子を半ば埋め込み、金属粒子が一部露出しつつ第２部品の材料中に存在するようにしても良い。
（実施例その２）
図６に、そうした、本発明の観察装置（その２）３００の、一部断面の模式図を示す。本発明の観察装置（その２）３００は、基本的な構成は、図１で示した金属粒子型観察装置１００および本発明の観察装置（その１）２００と同様であるが、第１部品１０４の観察面１０７と距離Ｇを隔てて相対する、第２部品１０６の面に形成された、複数の粒子からなる、埋め込み金属粒子３０１と、これを含む本発明の観察セル（その２）３０２の個所が異なる。
The improvement of the detection sensitivity of the observation apparatus of the present invention is not limited to the method of making the mixed metal particles with the fine particles of the second part material and the metal fine particles as shown in FIG. You may make it exist in the material of 2nd components, partially embedding and a part of metal particle exposing.
(Example 2)
FIG. 6 shows a schematic diagram of a partial cross section of the observation apparatus (part 2) 300 of the present invention. The observation apparatus (part 2) 300 of the present invention has the same basic configuration as the metal particle type observation apparatus 100 and the observation apparatus (part 1) 200 of the present invention shown in FIG. Of the embedded metal particle 301 composed of a plurality of particles formed on the surface of the second part 106 facing the observation surface 107 with a distance G, and the observation cell (part 2) 302 of the present invention including the embedded metal particle 301 The location is different.
本発明の観察装置（その２）３００の実施構成は、第１部品１０４、第２部品１０６に、シリコン（Ｓｉ）を用い、観察面１０７はＳｉの（１１１）面を使用した。第１部品１０４の観察面１０７に相対する、第２部品１０６の表面に埋め込み金属粒子３０１が形成される。 In the implementation configuration of the observation apparatus (part 2) 300 of the present invention, silicon (Si) was used for the first component 104 and the second component 106, and the Si surface (111) was used for the observation surface 107. Embedded metal particles 301 are formed on the surface of the second part 106, which is opposed to the observation surface 107 of the first part 104.
埋め込み金属粒子３０１の拡大図（ａ）、（ｂ）を図６の左下に示す。埋め込み金属粒子３０１の形成は、例えば、拡大図（ａ）の様に、第２部品１０６の表面を、ウエットあるいはドライエッチングなどの手法で作成された離間する多数の微小半球形の開口部に、埋め込み用金属粒子３０３を埋め込む手法や、拡大図（ｂ）の様に、第２部品１０６の表面に間隔を空けた複数のＶ溝３０４を形成し、その中に離間して埋め込み用金属粒子３０３をはめ込む手法などが適用可能である。 Enlarged views (a) and (b) of the embedded metal particles 301 are shown in the lower left of FIG. For example, as shown in the enlarged view (a), the embedded metal particle 301 is formed by separating the surface of the second component 106 into a large number of spaced apart micro hemispherical openings created by a technique such as wet or dry etching. As shown in a method of embedding the embedding metal particles 303 or an enlarged view (b), a plurality of V-grooves 304 spaced apart are formed on the surface of the second component 106, and the embedding metal particles 303 are spaced apart from each other. It is possible to apply a method of fitting.
観察装置（その２）３００においても、観察装置（その１）３００と同様に、複数の金属粒子が第２部品の材料によって互いに離間して形成された構成をとることで、図５で示したのと同様な、高い検出感度を有する観察装置を実現することができる。 In the observation apparatus (part 2) 300, as in the observation apparatus (part 1) 300, a configuration in which a plurality of metal particles are formed apart from each other by the material of the second part is shown in FIG. It is possible to realize an observation apparatus having high detection sensitivity similar to the above.
図７は、本発明の観察装置が、比較実施例のそれに比べ、検出感度の向上が見られる現象を検討するための図である。図７（ａ）は、比較実施例の場合で、金属粒子１０５は第２部品１０６の表面上に接して形成されていて、観察面１０７からのエバネッセント波と金属粒子中に局在するプラズモンと結合して共鳴する過程において、垂直方向の結合度合い係数ＲＶと水平方向の結合度合い係数Ｒｈとがほほ同等になっているとみられる。上記共鳴強度即ち吸収スペクトル検出感度は垂直方向結合のみの効果である。 FIG. 7 is a diagram for examining a phenomenon in which the observation apparatus of the present invention shows an improvement in detection sensitivity as compared with that of the comparative example. FIG. 7A shows a comparative example in which the metal particle 105 is formed in contact with the surface of the second component 106, and an evanescent wave from the observation surface 107 and a plasmon localized in the metal particle. In the process of coupling and resonance, the vertical coupling degree coefficient RV and the horizontal coupling degree coefficient Rh are considered to be approximately equal. The resonance intensity, that is, the absorption spectrum detection sensitivity is an effect of only the vertical coupling.
図７（ｂ−１）は、本発明の観察装置（その１）２００の混成金属粒子２０１の部分拡大図であり、図７（ｂ−２）は、本発明の観察装置（その２）３００の埋め込み金属粒子３０１の部分拡大図である。金属粒子２０３、２０４それぞれに隣接するものは、第２部品の材料の粒子２０４あるいは第２部品１０６そのものである。その結果、垂直方向の結合度合い係数ＲＶのほうが水平方向のそれに比し、より増大するといった効果が生じ、共鳴強度即ち吸収スペクトル検出感度は垂直方向のみの効果であることと相俟って、検出感度の大幅向上がなされたものと考えることができよう。
（実施例・観察装置システム）
図８に、本発明の観察装置（その１）あるいは観察装置（その２）を用い、自動的ないしは効率的に、微細な分子構造などの状態観察を、局在プラズモン共鳴の吸収スペクトルを通して、高感度に観察可能な観察装置システム４００の構成を示す。
FIG. 7 (b-1) is a partially enlarged view of the hybrid metal particle 201 of the observation apparatus (part 1) 200 of the present invention, and FIG. 7 (b-2) shows the observation apparatus (part 2) 300 of the present invention. It is the elements on larger scale of the embedded metal particle 301 of. Adjacent to each of the metal particles 203 and 204 is the particle 204 of the material of the second part or the second part 106 itself. As a result, there is an effect that the vertical coupling degree coefficient RV is larger than that in the horizontal direction, and the resonance intensity, that is, the absorption spectrum detection sensitivity is the effect only in the vertical direction. It can be considered that the sensitivity has been greatly improved.
(Example / observation system)
FIG. 8 shows an observation apparatus (part 1) or an observation apparatus (part 2) of the present invention, which automatically or efficiently observes the state of a fine molecular structure through a local plasmon resonance absorption spectrum. The structure of the observation apparatus system 400 which can be observed to a sensitivity is shown.
観察装置システム４００は、大別して、例えば、観察セル（その１）２０２を用いた本発明の観察装置（その１）（または本発明の観察装置（その２））、システム全体と個別装置とを制御する制御装置４０１、光の分光検出関係を行う赤外分光装置４０２、および第１部品１０４と第２部品１０６間の距離Ｇを、例えば万力などで圧力Ｐｒを加えて制御する距離制御装置４０３からなる。赤外分光装置４０２は赤外光源４０４から得た光を分光器４０５で分波し、かつ偏光制御装置４０６で偏光した光１０８を本発明の観察装置に入射させる。観察面１０７で全反射した光を検出器４０７で受けることで、任意の波長の任意の偏光波の検出器到達光強度を測定できる。こうして、制御装置でシステム全体を制御し、距離制御装置を制御して、例えば、圧力無し、即ち万力強度０、よって距離Ｇが波長レベルより離れている状態の検出光強度Ｒ０と、圧力をかけ距離Ｇが波長レベル以下の、共鳴が生じている状態の検出光強度Ｒを得れば、先に図５に示したデータを得ることができ、その吸収波長から観察面１０７上ないし近傍の状態を観察することができる。 The observation apparatus system 400 is roughly divided into, for example, an observation apparatus (part 1) of the present invention using an observation cell (part 1) 202 (or an observation apparatus (part 2) of the present invention), the entire system, and individual apparatuses. A control device 401 for controlling, an infrared spectroscopic device 402 for performing spectral detection of light, and a distance control device for controlling the distance G between the first component 104 and the second component 106 by applying pressure Pr with, for example, a vise 403. The infrared spectroscopic device 402 demultiplexes the light obtained from the infrared light source 404 by the spectroscope 405 and makes the light 108 polarized by the polarization control device 406 enter the observation device of the present invention. By receiving the light totally reflected by the observation surface 107 by the detector 407, the intensity of light reaching the detector of an arbitrary polarized wave having an arbitrary wavelength can be measured. In this way, the entire system is controlled by the control device, and the distance control device is controlled. For example, the detected light intensity R0 in the state where there is no pressure, that is, the vise intensity is 0, that is, the distance G is separated from the wavelength level, and the pressure If the detection light intensity R in a state where resonance occurs with the applied distance G equal to or less than the wavelength level, the data shown in FIG. 5 can be obtained, and the observation wavelength 107 on or near the observation surface 107 can be obtained from the absorption wavelength. The state can be observed.
なお、図８に示した赤外分光装置４０２は、回折格子を用いた分散型赤外分光装置をイメージした構成を示してが、この赤外分光装置４０２として、レーザ光による波数モニタ、移動鏡をもつ干渉計およびコンピュータ処理部を有するフーリエ変換型赤外分光装置についても適用可能であることは言うまでも無い。 The infrared spectroscopic device 402 shown in FIG. 8 shows a configuration in the image of a dispersive infrared spectroscopic device using a diffraction grating. As the infrared spectroscopic device 402, a wave number monitor using a laser beam, a moving mirror, and the like. Needless to say, the present invention can also be applied to a Fourier transform infrared spectroscopic apparatus having an interferometer with a computer processing unit.
以上の実施例を含む実施の形態に関し、以下の付記を開示する。
（付記１）
観察対象である観察面を有する第１部品と、
前記観察面から距離をおいて設けられた第２部品と、
前記観察面に対向した前記第２部品の面上に、複数の金属粒子が前記第２部品の材料によって互いに離間して形成された金属粒子形成部と
光を、前記第１部品を介して前記観察面に照射する照射部と、
前記観察面を反射した前記光から、前記観察面上ないしその近傍の状態観察をする観察部と、
を備え、
前記第１部品および前記第２部品は、前記観察面と前記金属粒子形成部が前記光の電磁場内となるように、前記観察面および前記金属粒子形成部を保持することを特徴とする観察装置。
（付記２）
前記金属粒子形成部は、前記複数の金属粒子が、前記第２部品の材料中に一部表出するように埋め込まれることによって互いに離間して形成されていることを特徴とする付記１記載の観察装置。
（付記３）
前記観察部は、前記光のうち前記観察面と前記金属粒子形成部との配置方向に偏光した光から前記状態観察をすることを特徴とする付記１または２記載の観察装置。
（付記４）
前記光は、前記第１部品を通過した後前記観察面で全反射し、前記全反射した前記光は前記第１部品を通過した後、前記観察部に至ることを特徴とする付記１または２記載の観察装置。
（付記５）
前記第１部品および前記第２部品は、前記観察面および前記金属粒子形成部を前記光のエバネッセント場内に保持することを特徴とする付記４記載の観察装置。
（付記６）
前記観察部は、前記観察面を反射した前記光の吸収スペクトルから前記観察面上ないしその近傍の状態観察をすることを特徴とする付記１ないし５のいずれかに記載の観察装置。
（付記７）
前記金属粒子は、金（Ａｕ）または白金（Ｐｔ）であることを特徴とする付記１ないし６のいずれかに記載の観察装置。
（付記８）
前記第１部品の材料は、シリコン（Ｓｉ）、ゲルマニウム（Ｇｅ）、セレン化亜鉛（ＺｎＳｅ）、臭化カリウム（ＫＢｒ）のうちの１つであることを特徴とする付記１ないし７のいずれかに記載の観察装置。
The following additional notes are disclosed regarding the embodiments including the above examples.
(Appendix 1)
A first part having an observation surface to be observed;
A second component provided at a distance from the observation surface;
On the surface of the second part facing the observation surface, a plurality of metal particles are formed by being separated from each other by the material of the second part, and light is transmitted through the first part. An irradiation unit for irradiating the observation surface;
From the light reflected from the observation surface, an observation unit for observing the state on or near the observation surface; and
With
The first component and the second component hold the observation surface and the metal particle forming portion so that the observation surface and the metal particle forming portion are in an electromagnetic field of the light. .
(Appendix 2)
The metal particle forming portion is formed to be separated from each other by being embedded so that the plurality of metal particles are partially exposed in the material of the second component. Observation device.
(Appendix 3)
The observation apparatus according to claim 1 or 2, wherein the observation unit performs the state observation from light polarized in an arrangement direction of the observation surface and the metal particle forming unit in the light.
(Appendix 4)
The light is totally reflected by the observation surface after passing through the first part, and the light that has been totally reflected passes through the first part and then reaches the observation part. The observation apparatus described.
(Appendix 5)
The observation apparatus according to appendix 4, wherein the first part and the second part hold the observation surface and the metal particle forming portion in an evanescent field of the light.
(Appendix 6)
The observation device according to any one of appendices 1 to 5, wherein the observation unit performs state observation on or near the observation surface from an absorption spectrum of the light reflected from the observation surface.
(Appendix 7)
7. The observation apparatus according to any one of appendices 1 to 6, wherein the metal particles are gold (Au) or platinum (Pt).
(Appendix 8)
Any one of appendices 1 to 7, wherein the material of the first component is one of silicon (Si), germanium (Ge), zinc selenide (ZnSe), and potassium bromide (KBr). The observation apparatus described in 1.
１００ 金属粒子型観察装置
１０１ 観察セル
１０２ 照射部
１０３ 観察部
１０４ 第１部品
１０５ 金属粒子
１０６ 第２部品
１０７ 観察面
１０８ 光
１１０ シリコン結晶
１１１ シリコン原子
１１２ 水素原子
１１３ 酸素原子
２００ 本発明の観察装置（その１）
２０１ 混成金属粒子
２０２ 本発明の観測セル（その１）
３００ 本発明の観察装置（その２）
３０１ 埋め込み金属粒子
３０２ 本発明の観測セル（その２）
３０３ 埋め込み用金属粒子
３０４ Ｖ溝
４００ 観察装置システム
４０１ 制御装置
４０２ 赤外分光装置
４０３ 距離制御装置
４０４ 赤外光源
４０５ 分光器
４０６ 偏光制御装置
４０７ 検出器
DESCRIPTION OF SYMBOLS 100 Metal particle type observation apparatus 101 Observation cell 102 Irradiation part 103 Observation part 104 1st part 105 Metal particle 106 2nd part 107 Observation surface 108 Light 110 Silicon crystal 111 Silicon atom 112 Hydrogen atom 113 Oxygen atom 200 Observation apparatus of this invention ( 1)
201 Hybrid metal particle 202 Observation cell of the present invention (Part 1)
300 Observation apparatus of the present invention (2)
301 Embedded metal particles 302 Observation cell of the present invention (2)
303 Metal particle for embedding 304 V groove 400 Observation device system 401 Control device 402 Infrared spectroscopic device 403 Distance control device 404 Infrared light source 405 Spectroscope 406 Polarization control device 407 Detector
Claims (5)
前記観察面から距離をおいて設けられた第２部品と、
前記観察面に対向した前記第２部品の面上に、複数の金属粒子が前記第２部品の材料によって互いに離間して形成された金属粒子形成部と、
光を前記第１部品を介して前記観察面に照射する照射部と、
前記観察面を反射した前記光から、前記観察面上ないしその近傍の状態観察をする観察部と、
を備え、
前記第１部品および前記第２部品は、前記観察面と前記金属粒子形成部が前記光の電磁場内となるように、前記観察面および前記金属粒子形成部を保持するとともに、
前記光は、前記第１部品を通過した後前記観察面で全反射し、前記全反射した前記光は前記第１部品を通過した後、前記観察部に至ることを特徴とする観察装置。 A first part having an observation surface to be observed;
A second component provided at a distance from the observation surface;
A plurality of metal particles formed on the surface of the second component facing the observation surface, the metal particles being separated from each other by the material of the second component ;
An irradiation unit that irradiates the observation surface with light through the first component;
From the light reflected from the observation surface, an observation unit for observing the state on or near the observation surface; and
With
The first component and the second component hold the observation surface and the metal particle formation portion so that the observation surface and the metal particle formation portion are in the electromagnetic field of the light ,
The light is totally reflected by the observation surface after passing through the first component, and the totally reflected light reaches the observation unit after passing through the first component .
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