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WO2019212043A1 - Substrat améliorant l'activité optique - Google Patents

Substrat améliorant l'activité optique Download PDF

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Publication number
WO2019212043A1
WO2019212043A1 PCT/JP2019/017931 JP2019017931W WO2019212043A1 WO 2019212043 A1 WO2019212043 A1 WO 2019212043A1 JP 2019017931 W JP2019017931 W JP 2019017931W WO 2019212043 A1 WO2019212043 A1 WO 2019212043A1
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WIPO (PCT)
Prior art keywords
optical activity
spiral
nanoflower
substrate
shape
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PCT/JP2019/017931
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English (en)
Japanese (ja)
Inventor
圭介 合田
振洲 程
廷▲輝▼ 肖
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University of Tokyo NUC
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University of Tokyo NUC
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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
    • G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
    • 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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering

Definitions

  • the present invention relates to an optical activity enhancement substrate.
  • ⁇ Chirality is the symmetry of molecules and determines the physical, chemical and biological properties of substances on a wide range of scales ranging from bulk crystals to nanomaterials and even biomolecules.
  • the chirality of a molecule is the ability of a chiral molecule to selectively interact with left-handed circularly polarized light (LCP) or right-handed circularly polarized light (RCP), which is expressed by optical activity. Is done.
  • a metal nanostructure as a basic component.
  • This metal nanostructure is artificially induced by inducing surface plasmon resonance (SPR) on the nanostructure. It has been demonstrated that large optical activity can be realized (see Non-Patent Documents 3 to 6 below).
  • SPR is resonant vibration due to free electrons in a metal coupled to an incident electromagnetic field. Since the electric field is strongly focused in the near-field region of the metal nanostructure due to the induction of SPR, the interaction between the metal nanostructure and the incident circularly polarized light is enhanced, and a large optical activity can be realized.
  • a helical propeller type, a helical type, a scaffold type, a supramolecular structure, a multilayer connection structure, a pseudochiral structure, and the like have been proposed.
  • Patent Documents 1 and 2 listed below disclose surface-enhanced Raman spectroscopy (SERS) that enhances Raman scattered light using metal nanostructures.
  • the metal materials that make up the metal nanostructures are low in energy efficiency and high heat generation due to their inherent high ohmic loss, so their performance and practicality, such as destruction of organic molecules to be observed and occurrence of alteration, etc. Was insufficient.
  • An object of the present invention is to provide an optical activity enhancement substrate having a high optical activity enhancement effect and a low ohmic loss.
  • the present invention includes the following embodiments:
  • the spiral nanoflower has a plurality of elliptical cylinders arranged between 4 and 8 around the cylinder, and a straight line connecting the center of the circle which is the cross section of the cylinder and the center of the ellipse which is the cross section of the elliptic cylinder
  • An optically active enhancement substrate having a pseudo-propeller shape in which the major axis of the ellipse is inclined 45 to 55 degrees clockwise with respect to the above.
  • CID (I R ⁇ I L ) / (I R + I L ) (2)
  • I R is the intensity of the scattered light RCP
  • I L is scattered light intensity of the LCP.
  • an optical activity enhancement substrate having a high optical activity enhancement effect and a low ohmic loss.
  • FIG. 1 shows a configuration example of the optical activity enhancement substrate according to the embodiment.
  • an optical activity enhancement substrate 100 includes a support substrate 10, an oxide layer 12 formed on one main surface of the support substrate 10, and a main surface on the opposite side of the oxide layer 12 from the support substrate 10. And the helical nanoflower 14 formed in the above.
  • the support substrate 10 is formed of a material selected from silicon dioxide, titanium oxide, silicon, metallic glass, polymer, and metal, and can be appropriately determined depending on the application as long as it has a flat plate shape.
  • the metal glass for example, Au 75 Si 25, alloys, such as chalcogenide glass can be used.
  • the polymer for example, an aromatic heterocyclic polymer such as polythiophene, a conjugated polymer such as polyacetylene, or the like can be used.
  • Au, Ag, Al etc. can be used, for example.
  • the oxide layer 12 is formed of a material containing silica and aluminum oxide. Moreover, TiO 2 may be included. This oxide layer 12 can be formed by thermal oxidation.
  • the spiral nanoflower 14 is made of a material (dielectric material) selected from silicon, germanium, titanium oxide, zinc telluride, and indium gallium arsenide, and is opposite to the support substrate 10 of the oxide layer 12. It is preferable to form a plurality on the main surface on the side. The shape and number of the spiral nanoflowers 14 will be described later.
  • FIGS. 2 (a) and 2 (b) show examples of the shape and arrangement of spiral nanoflowers.
  • Fig.2 (a) shows the example of the shape of a spiral nanoflower
  • FIG.2 (b) has shown the example of arrangement
  • the spiral nanoflower 14 includes a cylinder 16 and an elliptic cylinder 18 arranged around the cylinder 16.
  • a cylinder 16 and an elliptic cylinder 18 arranged around the cylinder 16.
  • six elliptical cylinders 18 are arranged, but the present invention is not limited to this, and a plurality of elliptical cylinders 18 can be arranged between four and eight.
  • the spiral nanoflower 14 has a major axis of the ellipse of 45 to 55 degrees clockwise with respect to a straight line connecting the center of the circle which is the cross section of the cylinder 16 and the center of the ellipse which is the cross section of the elliptic cylinder 18. More preferably, it has a pseudo propeller shape inclined by 50 degrees. As shown in FIG.
  • geometric parameters defining the shape of the spiral nanoflower 14 in this case include a major axis length a, a minor axis length b of the ellipse, a radius r of the circle,
  • the geometric parameter By making the geometric parameter the above numerical value, the contribution of the magnetic quadrupole of the spiral nanoflower 14 to the scattered light when the incident light is scattered by the spiral nanoflower 14 can be optimized, and the incident light Optical activity can be enhanced. That is, the spiral nanoflower 14 composed of the cylinder 16 and the elliptical column 18 has a shape in which electromagnetic resonance is excited, and can confine the electromagnetic field of light to vibrate and enhance it.
  • optical activity C is represented by the following formula (1).
  • E is an electric field
  • B is a magnetic field
  • ⁇ 0 is a dielectric constant
  • ⁇ 0 is a magnetic permeability.
  • Enhancing optical activity means increasing the value of optical activity represented by the above formula (1).
  • the spiral nanoflower 14 according to the embodiment is formed of a dielectric material, and the dielectric material has a low ohmic loss. Therefore, by utilizing this property, the optical activity enhancement substrate having a low ohmic loss is used. Can be realized.
  • spiral nanoflower 14 Other shapes include a spiral shape such as a spiral shape or a saddle shape formed of a spiral oligomer.
  • the arrangement of the spiral nanoflowers 14 is arranged as a square lattice array arranged at a constant period on the main surface of the oxide layer 12, and the optical activity enhancement substrate according to the embodiment. Is configured.
  • the period of the array is preferably 1 to 5 ⁇ m.
  • the inclination of the elliptic cylinder 18 is changed (for example, the center of the circle that is the cross section of the cylinder 16 and the center of the ellipse that is the cross section of the elliptic cylinder 18).
  • a scattered light with enhanced LCP can also be obtained.
  • FIG. 3 shows a manufacturing process of the optical activity enhancement substrate according to the embodiment.
  • a chip in which a support substrate 10, an oxide layer 12, and a dielectric material layer 20 are laminated in this order is prepared (I), and a negative resist film 22 is spin-coated on the dielectric material layer 20 (II). ).
  • the array pattern of spiral nanoflowers is transferred to the dielectric material layer 20 by inductively coupled plasma using a mixed gas such as CHF 3 and SF 6 , and the remaining negative resist film 22 is diluted with dilute hydrofluoric acid. Remove (IV).
  • the optical activity enhancement substrate according to the embodiment is manufactured.
  • optical activity enhancement substrate according to the example was manufactured by the method shown in FIG. The specific procedure is as follows.
  • a silicon-on-insulator (SOI) chip Soitec 8 inch (200 mm) wafer having a thickness of the upper silicon layer (dielectric material layer 20) of 340 nm was prepared, and a spin coater (SPS-Europe SPIN150i) was prepared. ) was applied by spin coating to a 300 nm thick HSQ negative resist film (manufactured by Tokyo Ohka Kogyo Co., Ltd.).
  • SOI silicon-on-insulator
  • an array pattern of spiral nanoflowers 40 ⁇ 40 square lattice array patterns were defined on an HSQ negative resist film by electron beam lithography using F7000S-VD02 manufactured by Advantest Corporation.
  • the period of the square lattice array was 5 ⁇ m.
  • the chip was developed with an NMD-3 solution (Tokyo Ohka Kogyo Co., Ltd., tetramethylammonium hydroxide solution) as a developer for 10 minutes and washed with pure water for 5 minutes.
  • NMD-3 solution Tokyo Ohka Kogyo Co., Ltd., tetramethylammonium hydroxide solution
  • etching is performed by inductively coupled plasma using a mixed gas of CHF 3 and SF 6 to form a square array pattern of spiral nanoflowers on the upper silicon. Transferred to the layer. Finally, the remaining HSQ negative resist was removed with dilute hydrofluoric acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) to obtain an optical activity enhancing substrate.
  • FIGS. 4A and 4B Scanning electron microscope (SEM manufactured by Hitachi, Ltd.) images of the surface on which the spiral nanoflowers of the obtained optical activity enhancement substrate are formed are shown in FIGS.
  • the scale bar displayed in FIG. 4A is 1 ⁇ m, and an array pattern of spiral nanoflowers is shown.
  • the scale bar displayed in FIG. 4B is 100 nm, and a single spiral nanoflower is shown.
  • FIGS. 4A and 4B it can be seen that a spiral nanoflower array is formed on the oxide layer of the optical activity enhancing substrate.
  • a spiral nanoflower array without the column 16 was also manufactured as a comparative example.
  • 5A and 5B show SEM images of the helical nanoflower array of the comparative example.
  • FIG. 6 shows the configuration of the measurement apparatus (dark field microscope).
  • a wide-area tungsten / halogen light source (SLS201L manufactured by Thorlabs) was used as a light source for incident light.
  • the circular polarization state of the incident light was adjusted by the combined use of a linear polarizing plate LP (Thorlabs LPVIS050) and an achromatic quarter-wave plate QWP (Thorlabs AQWP05M-980). Incident light was incident in the direction of the spiral nanoflower array (Chip) via the beam splitter BS1.
  • an objective lens with a low numerical aperture (Olympus UPLSAPO 10 ⁇ 0.40 NA) was used to focus the incident light on the spiral nanoflower array. .
  • the reflected beam was blocked using a beam blocker to form a dark field.
  • Scattered light from the helical nanoflower array was collected by an objective lens and then split into two beams by a beam splitter BS2.
  • One beam was incident on the alignment CCD camera via the lens L1, and the nanoflower array was imaged and aligned.
  • the other beam was sent to the spectrometer (CCS175, manufactured by Thorlabs) via the lens L2, and the scattering spectrum of the spiral nanoflower array was measured.
  • FIGS. 7A and 7B show the measurement results of the scattering spectrum of the spiral nanoflower array when RCP and LCP are incident, measured as described above.
  • FIG. 7A is a spectrum of scattered light intensity of the scattered spectrum
  • FIG. 7B is a circular intensity difference (CID) obtained from the spectrum of scattered light intensity by the following equation (2). Distribution.
  • CID (I R ⁇ I L ) / (I R + I L ) (2)
  • I R is the intensity of the scattered light RCP
  • the I L is scattered light intensity of the LCP.
  • the scattered light intensity of RCP is higher than the scattered light intensity of LCP.
  • the value of CID has a peak of 35% at a wavelength of 713 nm. This is an effect in which the geometric parameter of the spiral nanoflower is the above value.
  • the optical activity-enhancing substrate provided with the spiral nanoflower array has realized a huge optical activity.
  • FIG. 8 shows a measurement result of a scattering spectrum and a distribution of CID when RCP and LCP are incident on a substrate including a spiral nanoflower array according to a comparative example.
  • the maximum CID value is about 25%, which is lower than the maximum CID in the case of the optical activity enhancement substrate of the embodiment shown in FIG. 7B. This indicates that the optical activity has decreased.
  • the decrease in CID is due to the disappearance of interference between the central cylinder and the surrounding elliptic cylinder in the spiral nanoflower of the comparative example.
  • a measurement sample ((+) ⁇ -pinene) having chirality is placed in a cuvette having an optical path length of 0.75 mm, and the optical activity enhancing substrate according to the example is disposed so that the support substrate 10 is in contact with the inner wall in the cuvette. And immersed in a measurement sample.
  • the thickness of the measurement sample on the surface on which the spiral nanoflowers of the optical activity enhancing substrate are formed is 0.75 mm.
  • the cuvette was irradiated with excitation light, and the Raman optical activity of the measurement sample was measured.
  • a self-made measuring device was used for the measurement.
  • the excitation light is laser light having a wavelength of 561 nm generated by a semiconductor laser generator manufactured by Coherent INC.
  • FIG. 9 shows the configuration of the Raman optical activity measuring apparatus.
  • the semiconductor laser generator is used as a light source for incident light.
  • the circularly polarized state of incident light includes a linearly polarizing plate LP (Thorlabs LPVISC050), an achromatic quarter-wave plate QWP (Torlabs AQWP05M-561), a liquid crystal modulator LCM (Thorlabs LCC1411-A) and Techno. Adjustment was performed by using a half-wave plate with a rotary mount (WPQ05M-561, Thorlabs) R-HWP set in a hands motor, a hollow motor. Incident light was incident in the direction of the spiral nanoflower array (Chip) via the beam splitter BS.
  • WPQ05M-561, Thorlabs rotary mount
  • a measurement sample on the spiral nanoflower array is used to focus the incident light using a low numerical aperture objective lens (Olympus UPLSAPO 10 ⁇ 0.40 NA).
  • a low numerical aperture objective lens Opalympus UPLSAPO 10 ⁇ 0.40 NA.
  • Raman scattered light from the measurement sample enhanced by the helical nanoflower array is collected by the objective lens, then redirected by the beam splitter BS, through the notch filter, depolarizer, and through the lens L to the spectrometer (Oxford -It was sent to Kymera 193i Spectrograph & Andor Newton 920) manufactured by Instruments, and Raman scattered light was measured.
  • the same measurement sample as the above measurement sample was placed on a slide glass, and Raman optical activity was measured using the same measurement apparatus.
  • FIG. 10 shows the measurement results of the Raman optical activity of the optical activity enhancement substrate according to the example and the slide glass as a comparative example.
  • the Raman scattered light intensity is shown together with the Raman optical activity.
  • the Raman optical activity and the Raman scattered light intensity are enhanced about 10 times by the optical activity enhancing substrate according to the example as compared with the case of the slide glass.

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  • Health & Medical Sciences (AREA)
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Abstract

Le problème décrit par la présente invention est de fournir un substrat améliorant l'activité optique qui présente des effets d'amélioration élevés pour une activité optique et une faible perte ohmique. La solution selon l'invention porte sur un substrat d'amélioration d'activité optique qui est pourvu : d'un substrat de support 10 ; d'une couche d'oxyde 12 formée sur une surface principale du substrat de support 10 ; et d'une nanofleur en forme de spirale 14 formée sur une surface principale de la couche d'oxyde 12 sur le côté opposé au substrat de support 10. La nanofleur en forme de spirale 14 a une forme de pseudo-hélice où une pluralité de colonnes elliptiques 18 sont disposées autour d'une colonne circulaire 16, et par rapport à une ligne droite reliant le centre d'un cercle qui est la section transversale de la colonne circulaire 16, et le centre d'une ellipse qui est la section transversale de la colonne elliptique 18, l'axe long de l'ellipse est incliné dans le sens horaire de 45 degrés.
PCT/JP2019/017931 2018-04-30 2019-04-26 Substrat améliorant l'activité optique Ceased WO2019212043A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007187835A (ja) * 2006-01-12 2007-07-26 Ricoh Co Ltd 光処理素子および光処理装置
US20080246961A1 (en) * 2007-04-05 2008-10-09 The Board Of Trustees Of The University Of Illinois Biosensors with porous dielectric surface for fluorescence enhancement and methods of manufacture
JP2008292425A (ja) * 2007-05-28 2008-12-04 Ricoh Co Ltd バイオセンサ
JP2009210495A (ja) * 2008-03-06 2009-09-17 Tohoku Univ 円二色性を持つ媒体測定表面プラズモン共鳴センサー、円二色性測定法及び測定装置
WO2016159880A1 (fr) * 2015-03-31 2016-10-06 Agency For Science, Technology And Research Procédé de changement d'un spectre de dichroïsme circulaire d'une onde électromagnétique
US20170370923A1 (en) * 2016-06-23 2017-12-28 The University Court Of The University Of Glasgow Plasmonic device, method of manufacturing a plasmonic device and method of analysis using a plasmonic device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007187835A (ja) * 2006-01-12 2007-07-26 Ricoh Co Ltd 光処理素子および光処理装置
US20080246961A1 (en) * 2007-04-05 2008-10-09 The Board Of Trustees Of The University Of Illinois Biosensors with porous dielectric surface for fluorescence enhancement and methods of manufacture
JP2008292425A (ja) * 2007-05-28 2008-12-04 Ricoh Co Ltd バイオセンサ
JP2009210495A (ja) * 2008-03-06 2009-09-17 Tohoku Univ 円二色性を持つ媒体測定表面プラズモン共鳴センサー、円二色性測定法及び測定装置
WO2016159880A1 (fr) * 2015-03-31 2016-10-06 Agency For Science, Technology And Research Procédé de changement d'un spectre de dichroïsme circulaire d'une onde électromagnétique
US20170370923A1 (en) * 2016-06-23 2017-12-28 The University Court Of The University Of Glasgow Plasmonic device, method of manufacturing a plasmonic device and method of analysis using a plasmonic device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KUMAR, A. ET AL.: "Plasmonically engineered nanoprobes for biomedical applications", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 138, 10 October 2016 (2016-10-10), pages 14509 - 14525, XP055318390, DOI: 10.1021/jacs.6b09451 *
XIAO, T. H. ET AL.: "Giant optical activity in an all-dielectric spiral nanoflower", SMALL, vol. 14, no. 31, 1800485, 3 July 2018 (2018-07-03), pages 1 - 7, XP055651927 *

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