JP2012052848A5 - Probe, microscope with probe - Google Patents
Probe, microscope with probe Download PDFInfo
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- JP2012052848A5 JP2012052848A5 JP2010193960A JP2010193960A JP2012052848A5 JP 2012052848 A5 JP2012052848 A5 JP 2012052848A5 JP 2010193960 A JP2010193960 A JP 2010193960A JP 2010193960 A JP2010193960 A JP 2010193960A JP 2012052848 A5 JP2012052848 A5 JP 2012052848A5
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Description
本発明は、プローブ、プローブを備えた顕微鏡に関し、特に近接場光を用いた分光装置等で用いるプローブおよびそのプローブを備えた顕微鏡に関するものである。 The present invention, probe relates microscope having a probe, to a microscope having a probe of probe and its used in particular near-field spectrometer using light or the like.
本発明は、上記課題に鑑み、従来の散乱型近接場光プローブのように電場増強を示す波長領域だけでなく、可視光の長波長領域においても電場増強を示すプローブおよびプローブを備えた顕微鏡の提供を目的とする。 In view of the above problems, not only the wavelength region showing the electric field enhancement as in the conventional scattering-type near-field optical probe, the probe and probe illustrating the electric field enhancement even in the long wavelength region of visible light and an object thereof is to provide a microscope equipped.
本発明のプローブは、先端部に金属単結晶を備え、
前記先端部に光を照射することで前記先端部に近接場光が発生することを特徴とする。
また、本発明の顕微鏡は、上記したプローブと、
試料を支持する支持部材と、
前記先端部に発生した近接場光と試料との相互作用によって生じる散乱光あるいは発光を検出する検出器と、有することを特徴とする。
Probes of the present invention comprises a metallic single crystal above end,
Near-field light, characterized in that generated in the tip portion by irradiating light to the front Kisaki end.
Further, the sensible Bikagami of the present invention includes a probe as described above,
A support member for supporting the sample;
And a detector for detecting scattered light or light emission generated by the interaction between the near-field light generated at the tip and the sample .
本発明によれば、従来の散乱型近接場光プローブのように電場増強を示す波長領域だけでなく、可視光の長波長領域においても電場増強を示すプローブおよびプローブを備えた顕微鏡を実現することができる。 According to the present invention, not only the wavelength region showing the electric field enhancement as in the conventional scattering-type near-field optical probe, sensible with the probe and probe illustrating the electric field enhancement even in the long wavelength region of visible light A micro-mirror can be realized.
次いで、溶液加熱手段１２としてマントルヒーター、溶液温度計測器１１としてテフロン（登録商標）をコートした熱電対を用い、溶液温度をモニターして溶液温度が９０℃で一定になるように温度調節器１３で調節しながら加熱した。
上記反応はドラフト内で行い、基板８上に形成される平板状の金単結晶１４が所望の大きさになるように反応時間、ドラフト排気量を調節し、基板８上に数十〜数百μｍの大きさの平板状の金単結晶１４を得た。
平板状の金単結晶１４は水洗後、５分間酸素プラズマ処理をした後、窒素雰囲気下において３０分間３００℃で熱処理した。
このようにして得た平板状の金単結晶のＳＥＭ像を、図１（ｃ）に示す。ここでは一辺が約２００μｍの大きさの正三角形の平板状の金単結晶が得られた。
Next, a mantle heater is used as the solution heating means 12, and a thermocouple coated with Teflon (registered trademark) is used as the solution temperature measuring device 11, and the temperature controller 13 is monitored so that the solution temperature becomes constant at 90 ° C. Heated while adjusting.
The above reaction is performed in a draft, and the reaction time and the draft exhaust amount are adjusted so that the flat gold single crystal 14 formed on the substrate 8 has a desired size. A plate-like gold single crystal 14 having a size of μm was obtained.
The flat gold single crystal 14 was washed with water, subjected to oxygen plasma treatment for 5 minutes, and then heat-treated at 300 ° C. for 30 minutes in a nitrogen atmosphere.
An SEM image of the flat gold single crystal thus obtained is shown in FIG. Here, an equilateral triangular flat gold single crystal having a side of about 200 μm was obtained.
このようにして作製した平板状の金単結晶の電場増強効果を検証した。
図６の図中に示す平板状の金単結晶は一辺が約５μｍの正三角形の形状をしている。
この平板状の金単結晶上に１ｗｔ％のポリスチレン溶液をスピンコーティングして約１００ｎｍの膜厚のポリスチレン薄膜を形成させ、平板状の金単結晶の（１１１）面上と結晶先端部においてラマン測定を行った。
測定には励起波長７８０ｎｍのレーザー、１００×ＮＡ０．９の対物レンズを使用し、露光時間２０ｓ、積算回数３回の条件でラマンスペクトルを取得した。
入射光は平板状の金単結晶の（１１１）面に垂直な方向から入射し、入射光の偏光方向は結晶の頂角を二等分する軸と平行な方向とした。
ポリスチレンは１０００ｃｍ -1 付近にベンゼン骨格振動の強いラマンピークが観測される。
平板状の金単結晶の（１１１）面上と結晶先端部で１０００ｃｍ -1 におけるラマン強度を比較すると、結晶先端部においてポリスチレンのラマン強度が約７．４倍強くなっていることが示された。
このように、正三角形の平板状の金単結晶を散乱型近接場光プローブとして用いることで、平板状の金単結晶先端において電場増強効果を得ることができることが実証できた。
平板状の金単結晶プローブは顕微鏡下でマイクロマニュピレータを使いて平板状の金単結晶をエポキシによりチューニングフォーク先端に固定することにより作製できる。
The electric field enhancement effect of the flat gold single crystal thus produced was verified.
The flat gold single crystal shown in FIG. 6 has an equilateral triangle shape with a side of about 5 μm.
A 1 wt% polystyrene solution is spin-coated on this flat gold single crystal to form a polystyrene thin film having a thickness of about 100 nm, and Raman measurement is performed on the (111) plane of the flat gold single crystal and at the tip of the crystal. Went.
For the measurement, a laser having an excitation wavelength of 780 nm and an objective lens of 100 × NA 0.9 were used, and a Raman spectrum was obtained under the conditions of an exposure time of 20 s and an integration number of three.
Incident light was incident from a direction perpendicular to the (111) plane of the flat gold single crystal, and the polarization direction of the incident light was parallel to the axis that bisects the apex angle of the crystal.
In polystyrene, a Raman peak with strong benzene skeleton vibration is observed in the vicinity of 1000 cm −1 .
Comparing the Raman intensity at 1000 cm −1 between the (111) plane of the flat gold single crystal and the crystal tip, it was shown that the Raman intensity of polystyrene was about 7.4 times stronger at the crystal tip. .
Thus, it was demonstrated that the electric field enhancement effect can be obtained at the tip of the flat gold single crystal by using the equilateral triangular flat gold single crystal as the scattering near-field optical probe.
A flat gold single crystal probe can be prepared by fixing a flat gold single crystal to the tip of a tuning fork with epoxy using a micromanipulator under a microscope.
［比較例１］
比較例１として、一般的に用いられる円錐形の金プローブと、本発明の平板状の金単結晶プローブを用いて色素（Ｏｉｌ Ｂｌｕｅ Ｎ）を添加したポリスチレン薄膜の近接場ラマン測定を行った例について説明する。
まず、５１４ｎｍ励起で近接場ラマン測定を行った。この測定では、添加した色素から蛍光が発生するため、どちらのプローブを用いた場合においてもポリスチレン固有のラマンスペクトルは確認しづらい。
そこで、蛍光を回避するために励起光を７８０ｎｍに変更した。
一般的に用いられる円錐形金プローブを用いた近接場ラマン測定においては色素からの蛍光を抑えることはできたものの、図３（ａ）に示すように７８０ｎｍにおいては電場増強効果がほとんど得られない。そのため、ポリスチレン薄膜からのラマン信号は微弱である。
一方、本発明の平板状の金単結晶プローブを用いた近接場ラマン測定においては、色素からの蛍光を抑え、かつ図３（ｂ）に示すように電場増強効果も得られるため、ポリスチレン薄膜からのラマン信号をＳ／Ｎよく検出することが可能となる。
[ Comparative Example 1 ]
As Comparative Example 1 , a near-field Raman measurement was performed on a polystyrene thin film to which a dye (Oil Blue N) was added using a commonly used conical gold probe and a flat gold single crystal probe of the present invention. Will be described.
First, near-field Raman measurement was performed with 514 nm excitation. In this measurement, fluorescence is generated from the added dye, so that it is difficult to confirm the Raman spectrum specific to polystyrene, regardless of which probe is used.
Therefore, in order to avoid fluorescence, the excitation light was changed to 780 nm.
In near-field Raman measurement using a commonly used conical gold probe, although fluorescence from the dye could be suppressed, as shown in FIG. 3 (a), almost no electric field enhancement effect was obtained at 780 nm. . Therefore, the Raman signal from the polystyrene thin film is weak.
On the other hand, in the near-field Raman measurement using the flat gold single crystal probe of the present invention, the fluorescence from the dye is suppressed and the electric field enhancement effect is also obtained as shown in FIG. Can be detected with good S / N.
［実施例２］
実施例２として、平板状の金単結晶の膜厚が電場増強度に与える影響についてＦＤＴＤ計算を行った例について説明する。
図７に、結晶を一辺１μｍの正三角形とし、膜厚を１０ｎｍ、２０ｎｍ、１００ｎｍと変えた時の、結晶先端における電場増強度をＦＤＴＤにより計算した結果を示す。
グラフの横軸は入射光の波長、縦軸はプローブ直下５ｎｍ位置における電場増強度｜Ｅ／Ｅ0｜2を示している。
これによると金単結晶の膜厚を薄くしていくと可視光の長波長側８００ｎｍ付近のプラズモン共鳴ピークが著しく増大することがわかった。
このように、可視光域の長波長側の励起光を用いて高感度な近接場ラマン分光を行う場合は、膜厚が薄い金単結晶を用いることが有利であることが示された。
[Example 2 ]
As Example 2 , an example in which the FDTD calculation is performed on the influence of the thickness of the flat gold single crystal on the electric field enhancement will be described.
FIG. 7 shows the results of calculating the electric field enhancement at the tip of the crystal by FDTD when the crystal is an equilateral triangle having a side of 1 μm and the film thickness is changed to 10 nm, 20 nm, and 100 nm.
The horizontal axis of the graph indicates the wavelength of incident light, and the vertical axis indicates the electric field enhancement intensity | E / E 0 | 2 at a position 5 nm directly below the probe.
According to this, it was found that as the thickness of the gold single crystal is reduced, the plasmon resonance peak near 800 nm on the long wavelength side of visible light is remarkably increased.
Thus, it has been shown that it is advantageous to use a gold single crystal with a small film thickness when performing high-sensitivity near-field Raman spectroscopy using excitation light on the long wavelength side in the visible light region.
Claims (8)
前記先端部に光を照射することで前記先端部に近接場光が発生することを特徴とするプローブ。 Comprising a metallic single crystal above end,
Features and to pulp lobes that near-field light is generated at the tip by irradiating light to the front Kisaki end.
試料を支持する支持部材と、
前記先端部に発生した近接場光と試料との相互作用によって生じる散乱光あるいは発光を検出する検出器と、有することを特徴とする顕微鏡。 And probe according to any one of 請 Motomeko 1 7,
A support member for supporting the sample;
Detector and, microscope you, comprising detecting the scattered light or light emitting caused by the interaction between the near-field light and the sample generated in the tip portion.
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| JP2010193960A JP2012052848A (en) | 2010-08-31 | 2010-08-31 | Scattering near-field optical probe and near-field optical microscope including the same |
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| JP2010193960A JP2012052848A (en) | 2010-08-31 | 2010-08-31 | Scattering near-field optical probe and near-field optical microscope including the same |
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| Publication Number | Publication Date |
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| JP2012052848A JP2012052848A (en) | 2012-03-15 |
| JP2012052848A5 true JP2012052848A5 (en) | 2013-10-10 |
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| JP6179905B2 (en) * | 2012-12-18 | 2017-08-23 | 学校法人早稲田大学 | Optical device and analyzer |
| KR101466807B1 (en) * | 2013-07-29 | 2014-11-28 | 포항공과대학교 산학협력단 | Tuning-fork based near field probe for mesuring spectral and near-field microscopy using the same, spectral analytical method using near-field microscopy |
| CN113406361B (en) * | 2021-03-22 | 2023-08-15 | 季华实验室 | Microscope needle tip for near field optical field regulation and preparation method thereof |
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| JPH10206435A (en) * | 1997-01-16 | 1998-08-07 | Canon Inc | Method for manufacturing probe and probe |
| JP4505596B2 (en) * | 2004-05-27 | 2010-07-21 | 独立行政法人産業技術総合研究所 | Biochip substrate manufacturing method, manufacturing apparatus thereof, and manufactured biochip |
| JP4451252B2 (en) * | 2004-09-02 | 2010-04-14 | エスアイアイ・ナノテクノロジー株式会社 | Near-field microscope probe, manufacturing method thereof, and scanning probe microscope using the probe |
| JP2007078451A (en) * | 2005-09-13 | 2007-03-29 | Canon Inc | Prism with metal membrane and spectral analyzer using the same |
| US7572300B2 (en) * | 2006-03-23 | 2009-08-11 | International Business Machines Corporation | Monolithic high aspect ratio nano-size scanning probe microscope (SPM) tip formed by nanowire growth |
| JP5256433B2 (en) * | 2007-12-25 | 2013-08-07 | ナノフォトン株式会社 | Scattering near-field microscope |
| JP2009150899A (en) * | 2009-01-30 | 2009-07-09 | Hitachi Ltd | Device for generating near-field light |
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