WO2007072418A2 - Augmentation de la densite d'energie dans des grilles de fils de sous longueur d'onde - Google Patents

Augmentation de la densite d'energie dans des grilles de fils de sous longueur d'onde Download PDF

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Publication number
WO2007072418A2
WO2007072418A2 PCT/IB2006/054943 IB2006054943W WO2007072418A2 WO 2007072418 A2 WO2007072418 A2 WO 2007072418A2 IB 2006054943 W IB2006054943 W IB 2006054943W WO 2007072418 A2 WO2007072418 A2 WO 2007072418A2
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WIPO (PCT)
Prior art keywords
wire
grid
reflector
slits
light
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PCT/IB2006/054943
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English (en)
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WO2007072418A3 (fr
Inventor
Derk J. W. Klunder
Maarten M. J. W. Van Herpen
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Koninklijke Philips Electronics N.V.
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Publication of WO2007072418A2 publication Critical patent/WO2007072418A2/fr
Publication of WO2007072418A3 publication Critical patent/WO2007072418A3/fr

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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
    • G01N21/62—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
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/645—Specially adapted constructive features of fluorimeters
    • G01N21/648—Specially adapted constructive features of fluorimeters using evanescent coupling or surface plasmon coupling for the excitation of fluorescence
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • 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
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • 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
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/645—Specially adapted constructive features of fluorimeters
    • G01N21/6452—Individual samples arranged in a regular 2D-array, e.g. multiwell plates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/107—Subwavelength-diameter waveguides, e.g. nanowires
    • 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
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G01N21/03—Cuvette constructions
    • G01N2021/0346—Capillary cells; Microcells
    • 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
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G01N21/03—Cuvette constructions
    • G01N21/05—Flow-through cuvettes
    • 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
    • G01N21/21—Polarisation-affecting properties
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/06—Illumination; Optics
    • G01N2201/063—Illuminating optical parts
    • G01N2201/0636—Reflectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/06—Illumination; Optics
    • G01N2201/063—Illuminating optical parts
    • G01N2201/0638—Refractive parts

Definitions

  • the present invention relates to luminescence sensors, for example luminescence biosensors or luminescence chemical sensors, and to a method for the detection of luminescence radiation generated by one or more luminophores present in such a luminescence sensor.
  • Biosensing through luminescence imaging is a technique used in detecting target analytes such as toxins or bacteria, or in testing the binding affinity of target compounds.
  • bio molecules are deposited in a pattern on a surface on or near an optical waveguide.
  • a solution containing target analytes is flown over the pattern and analytes attach to the bio molecules if there is a match.
  • the matched sites are either designed to become fluorescent, or are made so by introducing fluorescently labelled compounds (luminophores) that bind to matched sites with a high degree of specificity.
  • laser light are directed through the waveguide, whereby the evanescent field will excite fluorescent states at the matched sites.
  • the fluorescent signal is filtered to remove the exciting wavelengths and is monitored by a CCD imaging system.
  • the spatial variation is typically obtained by having different bio molecules in different parts of the pattern or in flowing different target analytes over different parts of the pattern.
  • the reason for using the evanescent field from a waveguide is to ensure that the field excites only luminophores bound to biomolecules on the surface. Free luminophores in the solution are only excited to a very limited degree, and will therefore not contribute to the background noise.
  • the wire-grid biosensors has an advantage over luminescence biosensors relying on evanescent fields emanating from waveguides in that the excitation radiation can easily be homogenously applied over a large area.
  • the present invention provides a luminescence sensor comprising a wire-grid formed by one or more slits arranged, preferably in a periodical array, in a plane sheet and a first reflector arranged in parallel with the plane sheet and in overlap with the wire-grid, wherein - a first transverse dimension of the slits is smaller than a diffraction limit of light with a first predetermined wavelength; a second transverse dimension of the slits, perpendicular to the first transverse dimension, is larger than a diffraction limit of light with the first predetermined wavelength; and - material compositions forming the plane sheet and the first reflector have complex refractive indices with a non-zero imaginary component.
  • a sub-wavelength wire-grid is a plane material sheet, preferably of sub- wavelength thickness, having slits with one transverse dimensions smaller than the diffraction limit the excitation radiation and one transverse dimension larger than the diffraction limit of the excitation radiation.
  • the wavelength or diffraction limit is the wavelength or diffraction limit in the medium that fill the slits, typically a liquid such as water.
  • the first reflector is in overlap with the wire-grid, meaning that when observing the wire-grid along a direction normal to the plane sheet, the first reflector covers the wire-grid. It may be preferred that a thickness, D, of the plane sheet and a distance between the plane sheet and the first reflector are smaller than the first predetermined wavelength. If the plane sheet is a top layer in a layered structure, the slits merely form grooves in the layered structure; if the plane sheet is self-supporting, the slits form openings in the plane sheet. Unless otherwise stated, the terms "grid”, “slit” and “wire-grid” refer to a sub-wavelength wire-grid as described above.
  • the light with the first predetermined wavelength is preferably the excitation radiation, typically light having vacuum wavelengths in the range 300 nm - 800 nm. In relation to the sub-wavelength wire-grid, it is the wavelength in the medium surrounding the wire-grid, which is referred to.
  • the energy density is the time-averaged energy density (energy per unit volume).
  • the transition rate for excitation of a lower (ground) state to an upper (excited) state of a luminophore is proportional (among other parameters) to intensity of the excitation light.
  • surface parts in the slits either have an enhanced binding capacity towards luminophores or biomolecules, or may have be provided with biomolecules.
  • An enhanced binding capacity may e.g. be provided by a surface treatment, e.g. by treating the surface to make it hydrophobic or hydrophilic.
  • a luminophore is a molecule or group of molecules that emits light, such as through fluorescence or phosphorescence, when illuminated by the excitation radiation.
  • a biomolecule is a molecule of a compound produced by or important to a biological organism, e.g. a protein, carbohydrate, lipid, etc.
  • the front side of the luminescence sensor is the side from which the excitation radiation is to be applied; the backside is the side opposite the front side.
  • the first reflector is provided on the backside. It is an important realization in the present invention, that by providing the first reflector and by using exciting radiation that is TM polarized instead of TE polarized, an increased energy density in the volume of the slits may be obtained.
  • the luminescence sensor according to the first aspect further comprises a polarizer positioned in front of the wire-grid and oriented to transmit only light having a polarization with an electrical component perpendicular to the second transverse dimension of the slits (TM polarized light).
  • the luminescence sensor further comprises a fluid handling system for providing a fluid flow over, or through, the wire-grid.
  • a fluid handling system typically comprises fluid channels formed as an integrated part of the sensor, optionally comprising the slits of the wire-grid.
  • the luminescence sensor according to first aspect further comprises a second reflector arranged in parallel with the plane sheet and in overlap with the wire-grid opposite the first reflector, i.e. on the front side of the sensor.
  • the material composition of the second reflector should be at least substantially transparent for the excitation radiation.
  • a distance between the wire-grid and the second reflector is smaller than the first wavelength.
  • the wire-grid of the luminescence sensor may be formed in a surface part of the first reflector or in a surface part of the second reflector facing the first reflector. Either of these options has the advantage of providing a durable structure in which the slits can be formed by well-established techniques such as lithography.
  • the wire grid may also be a self- supporting structure that may or may not abut the first/second reflector. This option has the advantage that it opens up for fluid transport through the wire-grid.
  • the structure of the slits of the luminescence sensor may be seen as sophisticated Fabry-Perot interferometers where:
  • each slit of the wire-grid may be modeled as a waveguide
  • the interfaces between the wire-grid and the surrounding environment at the front/backside may be seen as reflectors where a fraction of the light in the slits (i.e. resonant modes in the waveguides) is reflected.
  • the reflectivity at the backside interface is substantially increased by providing an efficient reflector at the output of the slits.
  • the second reflector at the front side interface may substantially increase the reflectivity at the other end of the optical resonators formed by the slits.
  • the dimensions and material properties of the second reflector may be used to tune the phase shift at the front side to improve the resonance conditions in the slits.
  • a thickness of the second reflector in a direction normal to the plane layer and a refractive index of the material composition of the second reflector are chosen to provide for a maximum or near-maximum energy density in the slits or pinholes upon illumination of the wire-grid with the excitation radiation.
  • the invention provides a method for choosing the thickness and the refractive index (i.e. the material composition) of the second reflector in accordance with the embodiment described in the previous paragraph.
  • the method comprises the steps of: providing electronic data representing a model of the luminescence sensor according to claim 1, the model containing at least the dimensions of the wire-grid and the refractive indices of the material compositions of the wire-grid and the first reflector, - providing electronic data representing a model of a second reflector arranged in parallel with the plane sheet and in overlap with the wire-grid opposite the first reflector, the second reflector having a thickness, Dl, in a direction normal to the plane sheet and a material composition with refractive index n 2 , which is at least substantially transparent for light with the first predetermined wavelength, - in the electronic data representation, varying values of the refractive index n 2 and the thickness Dl, for each value of the refractive index n 2 and the thickness Dl, calculating an energy density in at least one s
  • the invention relates to the use of a wire-grid and a first reflector arranged in parallel and in overlap with the wire-grid as a luminescence sensor in luminescence imaging.
  • the wire-grid is formed by slits arranged in a plane sheet, a first transverse dimension of the slits is smaller than a diffraction limit of the exciting radiation; a second transverse dimension of the slits, perpendicular to the first transverse dimension, is larger than a diffraction limit of the exciting radiation; and - material compositions forming the plane sheet and the first reflector having complex refractive indices with a non-zero imaginary component.
  • the use according to the third aspect involves illuminating the wire grid with excitation radiation having a polarization with an electrical component perpendicular to the second transverse dimension of the slits (TM polarized light)
  • the invention provides a method for biosensing using a wire-grid luminescence sensor with enhanced excitation energy density of light with a first wavelength, ⁇ l s the method comprising the steps of: providing a wire-grid luminescence sensor formed by one or more slits arranged in a plane sheet wherein: a first transverse dimension of the slits is smaller than a diffraction limit of light with ⁇ i; and a second transverse dimension of the slits, perpendicular to the first transverse dimension, is larger than a diffraction limit of light with ⁇ i; providing a first reflector arranged in parallel with the plane sheet and in overlap with the wire-grid; providing bio molecules on the wire-grid; illuminating the
  • the basic idea of the present invention is to increase the excitation energy density in the binding area of the slits by using TM polarized excitation light and providing a reflector on the backside of the wire-grid. Illuminating the wire-grid with TM polarized excitation light (which is transmitted through wire-grid) means that a uniform distribution of the excitation light inside the slits is obtained, giving a larger effective excitation volume inside the slits. Providing the reflector means that a Q-value of the small optical resonators formed between the front and backsides of the slits is increased, resulting in longer photon lifetime in the slits and thereby an increased energy density.
  • the problem solved by the present invention may be formulated as how to find a scenario for a sub-wavelength (in at least two dimensions relating to the polarization and direction of propagation of the light) excitation volume having: 1. increased useful excitation volume and binding area (only locations with sufficient excitation intensity are useful), and
  • the scenario allows easy integration of the optical excitation and detection path; e.g. nano-fluidic channels.
  • Fig. 1 is a graph showing the calculated energy density for normal incident TE and TM polarized light at the center line of slits in a wire-grid without a reflector at the backside.
  • Fig. 2 is a graph showing the calculated energy density along the center line of slit in a wire-grid having a first reflector according to the invention.
  • Fig. 3 is a graph showing the calculated energy density as a function of depth of slit for: (32) a reflector at backside of slit; (34) slit without reflector, and (36) reflector without slit (reference).
  • Fig. 4 is an intensity map showing the calculated energy density distribution inside an Aluminum wire grid (depth of slits are 85 nm) in a water environment with an Aluminum reflector at the output/back side. Scale runs from low energy density (dark) to high energy density (light) with a lower and upper cap in the energy density to suppress the high energy densities at the corners of the Aluminum regions. The map shows the difference between the regions inside the slit and in front of the wire-grid.
  • Figs. 5 and 6 are cross-sectional illustrations of luminescence sensors according to the invention, without and with a second reflector at the front side, respectively.
  • Fig. 7 is a graph showing calculated energy densities 71 and 72 as a function of thickness Dl of the second reflector for different material compositions.
  • Figs. 8 through 11 are illustrations showing different scenarios for forming the wire-grid and the reflectors.
  • Fig. 12 is an illustration of the luminescence sensor with a fluid handling system and a polarizer, together with a source of exciting radiation and a light detector.
  • an analysis of the energy density in various designs are provided. In the analysis, an Aluminum wire-grid in a water environment with, in some scenarios, an infinitely thick Aluminum reflector at the backside of the wire-grid is considered.
  • the calculation parameters are: Wavelength (in vacuum) 650 nm
  • FIG. 1 is a graph showing the calculated energy density (E/V) for TE (16) and TM (18) polarized light incident at prior art wire-grids; with the energy density normalized to the energy density of the incident light.
  • the curve 20 illustrates the region 12 inside the slit, whereas regions 10 and 14 are the front- and backside respectively. From Figure 1 , it can be seen that the energy density for TM polarized light inside the slit is indeed substantially higher than for TE polarized light. On the other hand, the steep decay of the energy density inside the slit for TE polarized light is absent for TM polarized light.
  • FIG 2 a wire-grid with an Aluminum reflector at the backside of the slits is considered.
  • the denominations are as in Figure 1 , except that here, the backside region 22 is now the Aluminum reflector.
  • Curve 20 shows the energy density for normally incident TM polarized light. It should be noted that since the interfaces between the wire-grid and the water can be considered as reflectors with relatively low reflectivity, a slight enhancement, ⁇ 60%, in the energy density inside the slit for TM polarized light can be seen in Figure 1. However, with the Aluminum reflector at the backside of the wire-grid, a much more significant increase of - 590% in the energy density can be observed.
  • the enhancement of the energy density inside the slit was estimated by calculating the average energy density inside the slit as a function of the depth of the slit.
  • the results are shown in Figure 3 where curve 32 shows the energy density for the scenario with a reflector at backside of the slit; curve 34 shows the energy density for the scenario with a slit without reflector, and curve 34 shows the energy density for the scenario with a reflector alone (i.e. without slit) as a reference.
  • the light is reflected at the front-and backsides due to the interface between the slit and the water environment (this results in a relatively low reflection).
  • the light is reflected due to the interface between the slit and Aluminum surface, and the magnitude of this reflection is significantly larger than the reflection at the front side.
  • FIG. 4 shows the energy density distribution inside a wire-grid 41 formed in a plane sheet 43 of thickness D with a reflector 40 at the backside.
  • the low (dark) energy density in front of the wire grid stands in contrast to the high (light) energy density inside slits 42. From Figure 4, it also follows that the energy distribution is reasonably constant inside the slit (apart from the corner regions at the front side of the grid).
  • Figures 5 and 6 illustrate the working principle of different embodiments of the luminescence sensor in accordance with the first, third and fourth aspects of the invention - the figures are not to scale.
  • a reflector 40 formed in a material composition having a complex refractive index with a non-zero imaginary component.
  • the reflector is typically formed in a metal slab such as Aluminum, but depending on the design, it could lust as well be a thin metal layer on a dielectric substrate, e.g. a Gold or Silver film.
  • the wire-grid 41 is formed as a periodic array of elongate grooves or slits 42 in the metal slab of reflector 40, the grooves or slits 42 having sub-wavelength width and depth.
  • each slit provides a small optical resonator 54 for the incoming excitation radiation 56, the appropriate dimensions being determined e.g. from calculations as provided in relation to Figures 2 and 3.
  • the front side "end-mirror" is provided by the transition from the medium inside of the slit to the medium in front of the wire-grid..
  • the luminous radiation 59 can be separated from reflected excitation radiation
  • the first reflector preferably has an as high as possible reflection.
  • the material compositions can be the same as for the wire grid, which allows definition of wire-grid in the reflector luminophore 58 that absorbs excitation light and start to emit (this can be fluorescence but other processes like Raman, two-Photon absorption followed by emission at wavelengths around half the excitation wavelength are also possible) - TM polarized normal incident excitation light 56, although normal incidence is not a requirement
  • a second reflector 61 is provided on the front side of the wire-grid 41.
  • the second reflector 61 is at least substantially transparent to the (first) wavelength of the exciting radiation 56.
  • the front side "end-mirrors" of the resonators 54 formed in the slits are provided by the second reflector.
  • the selection of dimensions and material composition of the second reflector 61 can be used to tune the resonance of resonators 54.
  • Curves 71 and 72 of Figure 7 shows calculated energy densities inside the slit as a function of thickness Dl of the second reflector for different material compositions.
  • the second reflector 61 which: preferably has a large refractive index difference with water (resulting in larges reflection) - should be transparent for the excitation light is preferably also transparent for the luminescence light Has a thickness chosen such that the excitation energy inside the slit is maximum; For example, a thickness of 170-180 nm for a material with a refractive index of 2.
  • Figures 8 through 11 show different scenarios for forming wire-grid of the luminescence sensor.
  • the plane sheet 43 in which wire-grid 41 is formed is a self- supporting free-standing structure that only abuts first and second reflectors 40 and 61 at some sections 81.
  • This scenario has the advantage of allowing fluid transport through the wire-grid 41.
  • the wire-grid 41 can be formed by milling or etching grooves or slits in a metal layer deposited on either of first or second reflector 40 and 61. After formation of the wire grid, the structure is sandwiched with the other of the second/first reflector to make the luminescence sensor.
  • the sandwich structure can be formed with a gap at either of the front- or backside ( Figures 9 and 10) or without gaps ( Figure 11).
  • the gaps allows for easier fluid transport over the wire grid.
  • each slit can form a nano- fluidic channel for liquid transport. Preferably, the gaps are small: i.e., in the order of the wavelength of the excitation light.
  • Figure 12 shows an illustration of a luminescence sensor 90 comprising a wire-grid 41, first and second reflectors 40 and 61 sandwiching the wire-grid, a fluid handling system comprising a fluid reservoir 82 and channels 83 for transporting fluid to the wire-grid, a light source 84, a polarizer 85, a light detector 86 and a wavelength selective filter 87.
  • the polarizer 85 may be provided in relation the light source as shown, or may be provided as an integrated part of the sandwich structure.
  • the polarizer may e.g. consist of a second wire-grid with the same orientation as the wire-grid 41, formed on the second reflector opposite wire-grid 41.
  • the channels 83 forming the fluid handling system can provide fluid evenly over the entire surface of the wire-grid.

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Abstract

L'invention se rapporte à des capteurs de luminescence à grille de fils, à une conception et à un procédé permettant d'augmenter la densité d'énergie dans des fentes, ou nano cavités, de sous longueur d'onde de la grille de fils. En utilisant un premier réflecteur, ou miroir, sur l'arrière, où la sortie, de la fente et en utilisant une lumière d'excitation polarisée TM, chaque fente forme un petit résonateur optique présentant une densité d'énergie accrue. En utilisant un second réflecteur à l'avant, ou à l'entrée, la densité d'énergie peut même être encore augmentée. La densité d'énergie accrue dans les fentes conduites à un volume d'excitation et une zone de liaison utiles accrus.
PCT/IB2006/054943 2005-12-22 2006-12-19 Augmentation de la densite d'energie dans des grilles de fils de sous longueur d'onde WO2007072418A2 (fr)

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EP05112700 2005-12-22
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Cited By (7)

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WO2008050274A1 (fr) * 2006-10-24 2008-05-02 Koninklijke Philips Electronics N.V. Détection de molécules cibles dans un échantillon
WO2008053442A2 (fr) * 2006-10-31 2008-05-08 Koninklijke Philips Electronics N.V. Biodétecteur utilisant des grilles de fil pour augmenter l'énergie de cavité
WO2008078264A1 (fr) * 2006-12-21 2008-07-03 Koninklijke Philips Electronics N.V. Guide d'onde à grille
WO2009083884A1 (fr) * 2007-12-26 2009-07-09 Koninklijke Philips Electronics N.V. Dispositif de capteur microélectronique
EP2221605A1 (fr) * 2009-02-12 2010-08-25 Koninklijke Philips Electronics N.V. Capteur de treillis
WO2015078755A1 (fr) * 2013-11-29 2015-06-04 Koninklijke Philips N.V. Régulation optique d'une réaction chimique
JP2021081214A (ja) * 2019-11-14 2021-05-27 株式会社豊田中央研究所 試料ホルダ、赤外線吸収分光光度計及び赤外線吸収スペクトルの測定方法

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