EP3350575A1 - Élément de réflexion atr et procédé de spectroscopie atr - Google Patents

Élément de réflexion atr et procédé de spectroscopie atr

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Publication number
EP3350575A1
EP3350575A1 EP16762824.7A EP16762824A EP3350575A1 EP 3350575 A1 EP3350575 A1 EP 3350575A1 EP 16762824 A EP16762824 A EP 16762824A EP 3350575 A1 EP3350575 A1 EP 3350575A1
Authority
EP
European Patent Office
Prior art keywords
layer
atr
structural elements
reflection element
hollow
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16762824.7A
Other languages
German (de)
English (en)
Inventor
Lorenz Sykora
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP3350575A1 publication Critical patent/EP3350575A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55—Specular reflectivity
    • G01N21/552—Attenuated total reflection
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
    • A61B5/1455—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using optical sensors, e.g. spectral photometrical oximeters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/12—Generating the spectrum; Monochromators
    • G01J3/14—Generating the spectrum; Monochromators using refracting elements, e.g. prisms
    • 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
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
    • 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
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR

Definitions

  • the invention relates to an ATR reflection element for the reinforcement of
  • Attenuated Total Reflection Infrared Spectroscopy is an established and widely used method for the analysis of analytes and liquids, in particular of substances that are largely free from one another, ie those substances. which complicate or prevent conventional transmission measurement.
  • ATR spectrometers and structures for infrared spectroscopy regularly use so-called ATR reflection elements. These must, according to the underlying physical effects, have a higher refractive index for the radiation used than the medium to be investigated.
  • the ATR reflection elements usually have surface finishes for coupling in and surface areas for decoupling the radiation used. In addition, they have surface areas for contact with the medium to be examined. At the last mentioned surface areas the total reflection takes place.
  • the ATR reflection elements can be used as single or
  • ATR reflection elements are made of materials with a high refractive index for the radiation used. Typically, zinc selenide becomes. Diamond,
  • ATR spectrometers regularly have a radiation source, for example an infrared laser and / or a black body emitter (glow wire), and a detector for the reflected radiation with downstream electronics for visualization, processing and evaluation of the measurements.
  • a radiation source for example an infrared laser and / or a black body emitter (glow wire)
  • a detector for the reflected radiation with downstream electronics for visualization, processing and evaluation of the measurements.
  • a thin, transparent layer with a high refractive index is arranged on a substrate with a lower refractive index.
  • the radiation is coupled into the thin layer via the substrate.
  • the radiation undergoes multiple total reflection in this thin layer at the boundaries to the medium to be examined, and to the substrate. Due to the small thickness of the layer, the optical path through the ATR reflection element is kept short despite the large number of reflections.
  • Blood components e.g. the measurement of blood sugar.
  • Projections are arranged on the surface, which should improve the contact, such as with the lip of the subject, and allow displacement of the saliva between the reflection element and lip.
  • the reflection element is designed as a triple reflection element.
  • the object of the present invention is to overcome the disadvantages of the prior art.
  • it is the object of the invention, the signal-to-Rau Silicon- ratio and thus the efficiency over the conventional ATR reflection elements. especially for measurements on weakly absorbent samples.
  • an ATR reflection element in particular an ATR-1R reflection element, comprising a base body with a first effective one
  • Refractive index » a transmission layer the transmission layer being a
  • first layer boundary in particular plane, first layer boundary and an opposite, in particular planar, preferably parallel to the first layer boundary, second layer boundary
  • the transmission layer is designed and adapted to receive a fluid over the second layer boundary, in particular wherein the second layer boundary is permeable to a fluid
  • the transmission layer is connected to the base body, in particular to a first interface area of the base body, the boundary between
  • Transmisshus and Grandenia is formed by the first layer boundary, wherein the transmission layer at the second layer boundary a second effective
  • the first effective refractive index is greater than the second effective refractive index and the second effective refractive index is greater than 1
  • the first and the second effective refractive index are each in vacuum at 25 ° C in the
  • Time length A TR to be determined wherein ⁇ ATR is selected from a Wellenatnbercich of 2 ⁇ to 20 ⁇ .
  • the ATR Reflexionselemcnt thus fulfills at least one
  • Wavelength of the said wavelength range the properties mentioned.
  • the properties for all wavelengths of the well are satisfied at from 2 ⁇ to 20 ⁇ .
  • the results observed for the first embodiment of the invention are associated with the following possible mechanism. If a fluid is applied to the transmission layer, in particular measuring layer,
  • Electromagnetic radiation which penetrates from the main body into the transmission layer during the measuring process, experiences when passing through the transmission layer Transmission through the fluid and / or by analytes, which with the fluid in the
  • analyte or analytes are those substances contained in a sample or fluid that are to be said upon measurement, d. h, in particular molecules or mixtures of molecules thereof
  • Absorption spectrum should be determined. It is also conceivable that the fluid is removed before the measurement and only the analyte or analytes to be examined remain.
  • an analyte-containing fluid may be used, with the fluid evaporating prior to measurement.
  • the transmission of electromagnetic radiation during the measurement takes place only by the analytes within the transmission layer.
  • the fluid itself, for example, a gas, be the subject of the measurement.
  • the first interface area is usually the same as the first layer boundary.
  • the former denotes the corresponding side surface of the base body, while the latter shuts off the boundary to the transmission layer, which adjoins the first interface region.
  • the transmission layer is thus located on the first interface area or adjoins it.
  • An interface region in the sense of the present invention represents a boundary surface of the base body, thus determines its extent and shape in conjunction with other interface areas of the body, Preferably, the various interface areas of the body are plan designed and in particular connected.
  • IR radiation in the context of the present invention is electromagnetic radiation having a wavelength in the wavelength range of 780 nm to 1 mm, wherein the wavelength range of 2 to 20 ⁇ is preferably meant.
  • Light in the sense of the present invention is equivalent to electromagnetic radiation.
  • IR radiation in particular the wavelength range of 2 to 20 ⁇ understood.
  • a transmission layer in the sense of the present invention, if at a layer thickness of 1 mm and an irradiation of the light along the surface normal of an interface or surface
  • Transmission layer of the majority, in particular at least 50%, preferably at least 75%, of the IR light of a wavelength of 2 ⁇ and / or 20 ⁇ is transmitted when measured in a vacuum.
  • interface areas for the coupling and decoupling of the electromagnetic radiation used in order to reduce reflection losses of the light or of this radiation when entering the ATR reflection element may be the same interface area or spaced from one another, in one embodiment there are second interface areas for coupling and third interface areas for coupling out, preferably spaced apart from each other. However, it is also conceivable that there are second interface areas for coupling and decoupling. In one embodiment, the minimum distance between the second and third. Interfacial areas greater than the respective maximum extent of the second and third Renzflambachen Symposium. It is also preferred if said second and third interface areas are inclined in different directions, in particular with regard to a plane orthogonal to the second layer boundary. In particular, it is preferred if the second and third interface areas are planar, so that mathematical planes can be assigned to them these planes preferably converging and intersecting on the side of the second layer boundary on which the base body is encountered.
  • the ATR reflection element has at least one second interface region of the main body for coupling in electromagnetic radiation, and at least one third interface region, of the main body for decoupling, of electromagnetic radiation which is opposite to the
  • Transmission layer and / or the first interface region are arranged.
  • the second and third interface areas are arranged in parallel, in particular preferably within the same mathematical plane.
  • the first and second interface areas are not arranged in parallel, but have different inclinations. The latter embodiment allows a more effective inhibition of the total reflection upon the emission of radiation from the ATR reflection element at the third boundary surface areas.
  • the first and second layer boundary are arranged in parallel, in particular plane-parallel. This facilitates the calculation of the beam path and ensures uniform incidence, refraction and reflection angles. It has also been shown that the efficiency of total reflection in this case at the second
  • the transmission layer delimited by the first and the second layer boundaries is distinguished in a preferred embodiment in that it has at least one cross-sectional area parallel and / or at least one cross-sectional area orthogonal to the first and / or second layer boundary which, in particular a multiplicity,
  • the hollow regions of the at least one cross-sectional area orthogonal to the first and / or second layer boundary are open to said second layer boundary.
  • the opening of the hollow regions towards the second layer boundary allows a penetration of a fluid into said hollow regions beyond the second schizhlite boundary
  • Cross-sectional areas of massive and hollow areas form volumes in three-dimensional space, which are three-dimensional, massive first elements of the structure or three-dimensional hollow first structure elements open towards the second layer boundary
  • At least one of the two can be heard.
  • at least one of the two can be heard.
  • Layer boundaries parallel cross-sectional area massive and open to the second layer boundary hollow areas at regular average distances, in particular periodic mean distances on.
  • a fluid may preferably enter via the second layer boundary and be incorporated into the transmission layer.
  • the transmission layer comprises or is formed from a multiplicity of massive first structural elements spaced apart from one another and / or a multiplicity of hollow first structural elements open to the second layer boundary.
  • the hollow and / or solid first structural elements of the transmission layer open toward the second layer boundary are arranged periodically or aperiodically, preferably such that at least one cross-sectional area, in particular a plurality of cross-sectional areas, between the first and second layer boundaries, in particular parallel and spaced from the first and second layer boundary, wherein said cross-sectional area identically formed periodically or aperiodisch, in particular periodically arranged massive areas of the massive first structural elements and / or hollow, the second Schichet border open areas of the second layer boundary open comprises hollow first structural elements, in particular wherein these hollow and these massive areas are arranged alternately.
  • SWS sub-wavelength structure
  • the transmission layer in the sense of the present invention therefore preferably represents a layer containing sub-wavelength structures, in particular sub-wavelength structures for wavelengths of> 20 ⁇ m, preferably of> 2 ⁇ m.
  • One speaks also of a SWS layer. Are the extent and mean distance of the solid and / or hollow first open to the second layer boundary
  • Structural elements in all spatial directions greater than the measuring wavelength used they ' do not form a sub-wavelength structure (SWS) for this wavelength.
  • the light or the electromagnetic radiation can dissolve the individual massive and the individual hollow first structural elements which are open towards the second layer boundary, so that it is not an effective refractive index that is set but different ones
  • a sub-wavelength structure is present as or in the transmission layer, that is to say the
  • SWS sub-wavelength structure
  • An alternative embodiment comprises aperiodically arranged solid and / or hollow regions open toward the second layer boundary, in particular porous structures formed of these aperiodically arranged solid and / or hollow, first structural elements open towards the second layer boundary.
  • the first and second effective refractive indices in the sense of the present invention are the refractive indices which the light of the measuring wavelength, in particular IR wavelength ⁇ ⁇ , experiences, wherein ⁇ ATR is preferably selected from a wavelength range from 2 to 20 ⁇ .
  • These effective refractive indices may be for example Material mixtures of two materials with two different refractive indices result.
  • grooves or columns in a material can affect the effective refractive index.
  • an effective refractive index within the meaning of the present invention is to be determined at 25 ° C. and under vacuum in the absence of a fluid, unless explicitly stated otherwise. Whether the refractive index is an effective refractive index for a given wavelength can be easily determined by the person skilled in the art by irradiating a light beam, in particular a laser light beam, of said wavelength into the body.
  • the irradiation takes place during the determination of the respective effective refractive index, in particular of the effective second refractive index, preferably at an angle of 70 °, particularly preferably below 45 °, to the said schizlite boundary. If this light beam is diffracted in different directions, areas with different refraction are present in the body or in the transmission layer. If the light beam diffracted in one direction only, the body has an effective refractive index, which experimentally in the above
  • Wavelength from the wavelength range 2 to 20 pm is determined at 1 5 ⁇ , in particular 10 pm, preferably 5 pm, more preferably 2 pm.
  • a transmission layer may also comprise or be formed from mixtures of the previously described embodiments of the solid and / or hollow first structural elements which are open towards the second layer boundary. Especially in the case of the aperiodic arrangement of the first
  • Structural elements are also provided porous solid and / or to the second layer boundary open hollow first structural elements.
  • Strakturieri can have a variety of geometric shapes. Embodiments of the elevations and depressions, in particular columns and / or holes and / or blocks and / or grooves, having a substantially square, rectangular, round or polygonal cross-sectional area in at least one direction, in particular parallel or orthogonal to the second layer boundary, are preferred.
  • the solid first structural elements may substantially also include cylinders and / or cuboids and / or cubes and / or cones and / or truncated cones and / or pyramids and / or truncated pyramids and / or spherical segments and / or spherical layers and / or spherical discs.
  • first structural elements which are open towards the second layer boundary, in particular columns, cubes, cuboids or grooves which have a mean height or average depth which is greater, in particular many times greater, than the mean distance between neighboring massive first. Structural elements or between adjacent to the second layer boundary open hollow first
  • Structural elements in particular between adjacent columns or, between adjacent holes or grooves. Particularly preferred are also massive and / or hollow first
  • Structural elements in particular columns, holes or grooves, which have a maximum height or maximum depth which is greater, in particular many times greater, than the minimum distance between adjacent solid and / or second layer boundary open hollow first structural elements, in particular between adjacent columns or between adjacent holes or grooves.
  • a multiple is to be understood in an embodiment in that the height or depth is at least three times, at least five times, or at least ten times greater than the average distance, the determination of the heights of the massive first structural elements and depths of The hollow first structural element of the transmission layer which is open toward the second layer boundary is preferably orthogonal to the first and / or second layer boundary.
  • the height of the columns or the depth of the grooves is in particular determined orthogonal .to the first and / or second layer boundary.
  • the mean distance is the average distance, after which the solid and / or the hollow first stress element open towards the second layer boundary repeats itself. It should be noted that there are always distances between massive
  • Structural elements or distances between hollow structural elements distances between a hollow and an adjacent solid structural element are not meant, in this sense, the distance between adjacent hollow and / or solid Structural elements interpreted as the distance between each adjacent solid structural elements or the distance between each adjacent hollow S tru ct urel ten or as the distance between each adjacent solid structural elements and the distance between each adjacent hollow structural elements, but not as the distance between a hollow Structural element to the adjacent massive
  • Structural element In the case of periodically arranged hollow and / or massive first
  • Structure elements corresponds to the mean distance of the so-called lattice constant in the corresponding spatial direction. Accordingly, the dimension of the respective solid and / or hollow first structural elements for the average distance is generally not critical, but the distance of the respective closest, in particular similar, first structural elements. For room-filling massive and / or hollow first elements of the structure, the mean distance can be very small and the mean distance
  • the mean distance corresponds, for example, to the average distance between the axes of rotation of adjacent cylinders or cylindrical holes. For example, if two columns have a radius of 1 ⁇ and a diameter of 2 ⁇ and the distance of the axes of rotation is 2.5 ⁇ , the average distance between the two columns is 2.5 ⁇ and the average distance of said columns 0.5 ⁇ . at
  • the extent and the average distance of the first structural elements are usually always smaller than the average distance of the first structural elements
  • the mean distance of the first structure element is the relevant quantity.
  • mean distance is generally not necessary since the values are identical (the outer surfaces coincide with the object itself).
  • the lattice constants are known to give the lengths needed to describe the smallest unit of a lattice, especially a unit cell.
  • a substantially two-dimensional grid is described (structuring of an interface)
  • the lattice constants comprise two lengths and an angle, preferably of 90 ° or 60 ° as a rule.
  • parallel grooves on the other hand, it is a one-dimensional grid arranged on the two-dimensional surface.
  • the two lengths are identical, ie two lattice constants are identical.
  • a lattice constant is sufficient to describe the periodic arrangement of the stressors corresponding to the mean distance between the grooves or lobes and determined orthogonally to the course of the grooves or lobes.
  • the lattice constant of a structural element in the sense of the present invention corresponds to the lattice constant, which corresponds to the lattice of the
  • Periodic arrangement of the said structural element is assigned.
  • the lattice constant is the distance of the grooves measured orthogonal to the grooves
  • Aperiodic arranged structural elements have a
  • Lattice constant does not open.
  • the average distance preferably corresponds to at least one lattice constant, in particular a Bravais lattice constant, i. the lattice constant of a Bravais lattice. in one possible embodiment, the massive and / or the second
  • Layer boundary open hollow first structural elements in particular the massive first Strukturelemeiite in the form of elevations, each having a first outer surface, a second orthogonal thereto second outer surface and the first outer surface opposite third outer surface, which is also preferably arranged orthogonal to the second outer surface. It may preferably be provided that the first and third outer surface is curved.
  • the second outer surface is preferably planar, in particular plane-parallel to and / or concurrently with the second layer boundary.
  • the solid first structural elements each represent cylindrical columns. In a suitable.
  • Embodiment meets at least one lattice constant, in particular at least one Bravais Gitterkon staute, preferably all lattice constants, the periodically arranged, massive and / or open to the second Scliiclitumble hollow first structural elements and / or the average distance of the periodically or aperiodically arranged massive and / or second layer boundary open hollow first structural elements the condition (la) (la)
  • all the lattice constants of the periodic bulk and / or hollow first structural elements open to the second layer boundary satisfy the relation Ia, in particular Ib, Ic, Pmax is the value for the purposes of the present invention which is assigned to the lattice constant and / or the mean distance,
  • the solid and / or the hollow first open to the second layer boundary.
  • Structural elements lattice constants and / or average distances with p max > 0.1 ⁇ , particularly preferably lattice constants and / or average distances, with p max > 0.4 ⁇ , in particular lattice constants and / or average distances of p max > 0.7 ⁇ on ,
  • the solid and / or hollow first openings open towards the second layer boundary
  • Structural elements lattice constants or average distances with p max ⁇ 4 ⁇ , particularly preferably lattice constants, and / or average distances with p mux ⁇ 2 ⁇ , in particular lattice constants and / or average distances, of p max ⁇ 1.3 ⁇ on, In a whole Particularly preferred embodiment, the massive and / or the second
  • Layer boundary towards open hollow first elements of the structure lattice coordinates and / or average distances with 0.1 ⁇ ⁇ p max ⁇ 4 ⁇ , particularly preferably lattice constants and / or average distances with 0.4 ⁇ ⁇ p max ⁇ 2 ⁇ , in particular lattice constants and / or mean Distances of 0.7 ⁇ ⁇ p max ⁇ 1.3 ⁇ on.
  • These mean distances and / or lattice constants allow measurements even in the shortwave infrared range.
  • a filter effect can be achieved. If particles of different sizes are present in the fluid, a suitable embodiment of the hollow regions of the transmission layer allows penetration into this transmission layer only from particles up to a certain size.
  • the cellular components of human blood have, for example, different sizes Human leukocytes have an average diameter of 7 to 20 ⁇ , menschliehe erythrocytes an average diameter of 6 to 8 ⁇ and human platelets an average diameter of only 1, 5 to 3 ⁇ .
  • the mean distances of the hollow regions of the transmission layer can be designed such that only erythrocytes and platelets or only thrombocytes together with the blood serum or even the blood serum can penetrate into the transmission layer and undergo transmission.
  • the usually upstream separation of the blood can be omitted in its components.
  • a selective IR measurement of specific analytes under suitable conditions is possible, preferably
  • Impurities are not or only with reduced intensity in the measurement signal incorporated.
  • US Pat. No. 4,648,988 discloses ATR spectrometers in which the second layer boundary of the transmission layer in generic use of the ATR reflection element or the ATR spectrometer comprises or represents a sample receiving surface, for which in particular direct measurement of solid analytes contained in fluids is used.
  • inventive ATR reflection element as well as the ATR spectrometer according to the invention, in which in each case the second Layer boundary of the transmission layer in the generic use of the ATR reflection element or the ATR spectrometer include or represent a Probenauf ahme modeling, is used not only for the measurement of penetrated into the transmission layer or analytes present, but also for the separation of the present in fluids solid analytes with different diameters, such as with the fluid applied to the transmission layer as the sample receiving surface.
  • the transmission layer preferably has an im in its entire layer thickness
  • the fill factor of the transmission layer is in the range of 1 to 85%, preferably in the range of 3 to 30%, and more preferably in the range of 10 to 20%.
  • Fill factor is the volume fraction of the transmission layer, which is occupied by the massive areas. The larger the fill factor, the more volume of the transmission layer is occupied by the solid areas and the less volume of the transmission layer is occupied by the hollow areas. For the above-mentioned ranges, a considerable amplification of the absorption signal can be detected while at the same time ensuring the structural integrity.
  • the transmission layer preferably has an average thickness in the range from 0.1 to 50 ⁇ m, more preferably in the range from 1 to 20 ⁇ m, very particularly preferably in the range from 4 to 6 ⁇ m, the average thickness preferably being determined orthogonal to the first layer boundary , Particularly preferably, the mean thickness corresponds to the mean distance between the first and second layer boundary c.
  • Layer boundary toward open hollow first structural elements orthogonal to the first and / or second Schichet limit at least two, in particular at least 20, substantially
  • a preferred embodiment is also preferred in which the solid first and / or the first hollow hollow space open to the second layer are preferred
  • Layer boundary each have substantially at least one same cross-sectional area.
  • the solid or the hollow first structural elements which are open toward the second layer boundary are preferably of substantially similar design, ie. have the same dimensions and shapes in terms of manufacturing and measuring accuracy.
  • the main body and the solid first structural elements are made of a material and are in particular formed in one piece.
  • the first structural elements may be grooves or pillars formed in a silicon crystal.
  • the solid regions of the transmission layer may also comprise materials other than those of the base body, preferably materials with similar absorption behavior and / or similar refractive index. Similarly, if, the absorption coefficients and / or
  • the ATR reflection element and / or the base body preferably comprise or is formed by a crystal, in particular a single crystal.
  • the ATR reflection element comprises silicon and / or germanium and / or zinc selenide and / or diamond and / or thallium bromide iodide and / or AMTIR, in particular consisting thereof.
  • the ATR reflection element preferably comprises silicon, germanium, zinc selenide, diamond, thallium bromide iodide or AMTIR, in particular silicon, germanium or zinc selenide.
  • the second and / or third interface areas of the main body for coupling and uncoupling are not arranged on the side of the ATR reflection element on which the transmission layer is present, but especially on the side opposite to the transmission layer.
  • the second interface area of the main body for coupling and uncoupling is not arranged on the side of the ATR reflection element on which the transmission layer is present, but especially on the side opposite to the transmission layer.
  • Base body for coupling and / or the third G enz vombereieh for coupling the electromagnetic radiation second structural elements, in particular solid and / or open hollow second structural elements. It may, even a separate fourth
  • Interface area in particular for coupling and decoupling of light, be provided, which comprises solid and / or open hollow second Strukturelemeiite.
  • Structural elements are present.
  • These solid and / or these hollow second structural elements are preferably as periodic elevations and / or depressions, particularly preferably as. in particular V-shaped, grooves or elongated, in particular, tapering in the direction of the second layer boundary ,, surveys formed.
  • Second structural elements differ from the first structural elements described above preferably in that the average distance and / or the mean distance between the solid structural elements, preferably elevations, in particular columns, cones or walls, is greater than in the first Strukturelemeiite, preferably at least twice large, in particular at least five times or ten times as large.
  • Second structural elements differ from the first structural elements described above alternatively or additionally preferably in that the average distance and / or the mean distance between the particularly open hollow structural elements, preferably recesses, in particular grooves or indentations, is greater than those for the second layer boundary open hollow first structural elements, preferably at least twice as large, in particular at least five times or ten times as large.
  • hollow structural elements are basically open in the sense of the present document. Open means that the affected hollow
  • Structural element does not have a closed cavity, but this is open, preferably open to receive a fluid. This does not exclude that instead or in addition, for example, closed pores may be present, but there are not massive structural elements which are open.
  • Hollow first and / or second structural elements in the sense of the present invention are not filled with material, i. they are, in contrast to massive first and second respectively
  • first and / or second structural elements are only in
  • said material-filled areas can be a massive continuous layer or massive
  • first structural elements in particular elevations, e.g. Pillars, be.
  • the transmission layer is solid, the massive areas being continuously connected to one another.
  • These continuously interconnected areas do not constitute massive first structural elements, wherein said first structural elements are isolated, and / or delimitable.
  • massive and. hollow first structural elements together represent or form the transmission layer.
  • a checkerboard pattern with square elevations and corner adjacent square depressions is conceivable.
  • grooves which are delimited by ramparts or elongated elevations are conceivable.
  • the grooves in this case are hollow open first structural elements and. the elongated elevations massive first structural elements.
  • Massive in the sense of the present invention means in particular the presence of material, while hollow the
  • this is the material from which the base body is formed.
  • the transmission layer periodically arranged massive first structural elements which extend from the first layer boundary to the second layer boundary, wherein between the solid first structural elements is a continuous material-free region.
  • a multiplicity of hollow first structural elements which are open from solid, and / or to the second layer boundary, lie on the ATR surface. Reflection element or in the transmission layer of the same before.
  • Structural elements on the ATR reflection element or in the transmission layer thereof are present.
  • the number of hollow first structural elements, for example columns, of the transmission layer of the ATR reflection element, per area is preferably many times greater than the number of solid and / or hollow second structural elements, for example grooves as present on the second and / or third and or fourth interface areas on the same area.
  • at least five, in particular at least ten times, more first structural elements per area in the transmission layer exist as second structural elements per area on the second and / or third interface areas of the ATR reflection element.
  • the solid and / or hollow first structural elements open to the second visual boundary are referred to as fine structures having a first mean distance and the solid and / or said hollow second structural elements as coarse structures having a second mean distance, the first mean distance being smaller as the second mean distance.
  • the middle distances affect the distance of the massive ones
  • the first mean distance is at least a factor of 5, in particular by a factor of 10, preferably by a factor of 100, smaller than the second mean distance.
  • the lattice constant and / or the average distance of said hollow and / or solid second structural elements is in the range 30-3000 ⁇ , particularly preferably in the range of 100 to 1000 ⁇ , in particular in the range of 400 to 600 ⁇ ⁇ ⁇ . At these distances, an effective refractive index does not occur at a plane layer boundary towards the vacuum at a wavelength of 20 ⁇ m.
  • the hollow and / or solid second structural elements do not form any sub-measuring wavelength structures, in particular with regard to the wavelengths of the range from 2 to 20 ⁇ m, preferably 2 ⁇ m. It is preferred if these hollow and / or solid second structural elements, even in the determination of the refractive index in the said wavelength range, in contrast to the first structural elements, do not have a planar layer boundary with an effective refractive index. Rather, each massive second structural element preferably has an effective refractive index at 2 ⁇ and 25 ° C in a vacuum, which may coincide with adjacent massive structural elements, but not continuously over the distances, in particular hollow structural elements, between these massive second
  • Structural elements extends across. If the limit to the vacuum assigned to a third layer boundary, which is the height of the second. Structural elements results, so this third layer boundary different refractive indices in different areas, preferably so that in some areas of the refractive index corresponds to that of the body and in other areas, the refractive index of the vacuum corresponds.
  • the base body and the solid second structural elements are made of a material and are in particular formed in one piece.
  • the hollow second structural elements can be grooves, in particular V-shaped grooves, which are formed in a silicon crystal, wherein the walls of the grooves represent the outer surface of adjacent solid structural elements made of silicon remaining silicon crystal of the main body are connected.
  • the solid and 'or to the second layer boundary open hollow first structural elements at least partially have steeper flanks as the solid and / or said hollow second structural elements, wherein the
  • the transmission layer has solid and / or hollow first structural elements which are open towards the second layer boundary and which at least partially have a pitch of 90 °, ie are oriented at least in sections orthogonally to the first layer boundary or to the first interface area.
  • the slope less than 60 '°, in particular less than 50 °, preferably less than 37 °, with respect to the underlying interface region of the base body, in particular of the underlying second and / or third interface region of the grandfather.
  • the ATR reflection element is as
  • the ATR reflection element is designed as a multiple reflection element. However, it has been shown that with the inventive ATR reflection element due to the higher
  • the ATR reflection element or provided in the generic use beam path of the ATR reflection element is formed so that no more than five, especially not more than four, preferably not more than three total reflections of a transmitti erteil photon done at the second layer boundary.
  • recesses of hollow second structural elements in particular grooves, preferably substantially V-shaped grooves, have a depth in the range of 15 to 1517 ⁇ m, particularly preferably a depth in the range of 50 to 500 m, in particular a depth in the range from 100 to 200 ⁇ on.
  • a mask region is generally the region of an interface which is covered by the photomask during a lithography step and thus is not exposed to any exposure. Accordingly, for the purposes of this invention, the mask region is in particular those areas of the boundary surface to be provided with solid and / or hollow second structural elements in which there are no elevations or depressions. These areas are then also referred to as plateau areas and preferably correspond to the maximum height, in particular the maximum distance from the main body.
  • the plateau regions are planar, and / or concurrently with the second.
  • the area or areal extent of the mask area is less than 50%, particularly preferably less than 5%, in particular 0%, of the surface area of the interface provided with second structural elements, in particular the second, third and / or fourth interface.
  • a mask area of 0% means that the rising flank borders a V-shaped groove directly on the falling flank of the adjacent flute. This will be a
  • ATR spectrometer comprising at least one ATR reflection element according to the invention.
  • Said ATR spectrometer comprises at least one light source, in particular at least one infrared light source, at least one detector, in particular designed, and. arranged for the detection of infrared radiation, optical elements, in particular mirrors and / or lenses, for guiding the beam generated by the light source, as well as at least one inventive ATR reflection element as described above.
  • the light source is preferably an infrared laser and / or a black body emitter (glow wire). Particularly suitable in connection with the first structural elements of the transmission layer are infrared lasers. According to the invention, the light source is arranged such that the light or at least part of the light strikes the first layer boundary of the ATR reflection element at an angle .alpha.
  • the second layer boundary is preferably the, in particular exposed, sample space of the ATR spectrometer.
  • the first and the second layer boundary are arranged plane-parallel and the Transmission layer of the AI R reflection element uiriutzt the massive and / or open to the second layer boundary hollow first structural elements, which are preferably arranged periodically,
  • At least one lattice constant in particular a Bravais lattice constant, preferably all lattice constants, and / or the mean distance of these solid and / or hollow first structural elements open towards the second layer boundary, satisfy the relationship (II) ATR2 in a suitable embodiment
  • n lt represents a third effective refractive index of the main body of the ATR reflection element at light of wavelength ⁇ ATR2 and at 25 ° C in vacuum
  • a l denotes the angle of incidence at the first layer boundary
  • p max is the value assigned to the lattice constant and / or the mean distance.
  • the wavelength used for the measurement ⁇ ATR2 is the wavelength 1 5 ⁇ , in particular 10 pm, preferably 5 ⁇ , particularly preferably 2 ⁇ .
  • a wavelength range of 20 pm to 2 pm fulfills the stated requirement.
  • the third effective temperature increases
  • Refractive index n lb the same value as the first effective refractive index n ta , if the value of ⁇ ATR and ⁇ ATR2 match.
  • At least one lattice constant in particular a Bravais lattice constant, preferably all lattice constants, and / or the average distance of these hollow, and / or solid first structural elements open towards the second layer boundary, fulfill in a further one
  • n lc represents a fourth effective refractive index of the main body of the A ' l ' R reflection element measured at the wavelength A A TR: ⁇ , at 25 ° C and in vacuum.
  • a 1 denotes the angle of incidence at the first visual field
  • ATm indicates the shortest wavelength used in the said ATR spectrometer for measurement.
  • p, nax is the value assigned to the lattice constant and / or the mean distance.
  • the third effective refractive index n lb assumes the same value as the fourth effective refractive index n lc when the value of ⁇ ⁇ 2 and ⁇ ATm coincide.
  • the first, third and fourth effective refractive indices of the main body only differ with regard to the wavelength used for determining the effective refractive index, the measurement in each case being
  • Vacuum is carried out at 25 ° C,
  • Subwell length structures (SWS) with respect to these wavelengths ⁇ represent ATR2 and / or ⁇ ⁇ TR3 .
  • the transmission layer can therefore also be referred to in this context as the SWS transmission layer with regard to the wavelength concerned.
  • the light source of the ATR pec trom et ers is preferably arranged so that the
  • Einstrah! vector of the light, in particular of the light beam, lies in a plane which is oriented orthogonally to the first and / or second layer boundary and / or parallel to the V-shaped grooves, or so that the light is radiated orthogonally to the second boundary layer and / or orthogonal to that.
  • Third. Surface area is emitted or orthogonal to at least one surface area of the second structural elements,
  • each second structural element in particular orthogonal to. at least one flank of each second structural element is radiated and / or radiated.
  • the transmission layer has only massive first structural elements, which are arranged in particular periodically.
  • these solid first structural elements in particular columns, are arranged on a surface which is formed by the first layer boundary becomes.
  • the transmission layer has only open hollow first structural elements, for example having holes in an otherwise continuous massive transmission layer,
  • the second structural elements are formed by solid and open hollow second structural elements in an alternating sequence, in particular in the case of grooves and the elongated elevation between the grooves.
  • the light entering the area of the SWS is preferably unable to reach the massive and hollow. Rather dissolve areas Solid and hollow portions form a transmission layer having a fifth effective refractive index ⁇ 2 at the second layer boundary at the wavelength ⁇ ATR2, in particular ⁇ ⁇ 3, at 25 ° C and in vacuo.
  • this fifth effective refractive index of the second visual boundary may also be constant over the entire layer thickness or be present only at the second layer boundary.
  • the fifth effective refractive index, n 2b is critically dependent on the refractive index of the bulk SWS and the fill factor of the SWS
  • the SWS are preferably designed and set up so that the transmission layer has a substantially constant fifth effective refractive index over its entire layer thickness. n 2b .
  • This fifth effective refractive index is in particular smaller than the first effective refractive index n la and / or the third effective refractive index
  • Refractive index n lb and / or the fourth effective refractive index n lc are Refractive index n lb and / or the fourth effective refractive index n lc .
  • a surprising advantage of using the A TR reflection element according to the invention is that the absorption signal of the sample to be measured is considerably enhanced. It is assumed that, in addition to the attenuated total reflection named for the ATR reflection elements, the electromagnetic radiation also experiences absorption in the transmission through the fluid which has penetrated into the hollow regions of the transmission layer and / or through analytes penetrated into the hollow regions. This results in a significant gain of the absorption signal over conventional ATR reflection elements.
  • This amplification of the absorption signal allows e.g. the shortening of the optical
  • the transmission layer serves as the area for
  • Called invention it is preferably in the form of the already mentioned
  • Embodiment variant of the present invention may comprise the sample receiving surface, the hollow and / or the massive second structural elements and / or the previously described to the second layer boundary open hollow and / or solid first structural elements, wherein the ATR reflection element may be designed, for example, as a triple reflective element. According to the invention, it may also be provided that a first
  • Tran m i ss s i s ch i cht represents the area for coupling the radiation, while a second transmission layer, in particular an opposite second
  • Transmittance layer that represents the sample receiving surface when properly used with the ATR reflection element. It has been shown that the so-called first
  • Embodiment of the invention in which the transmission layer forms the sample receiving surface solves the problem underlying the invention much more pronounced than the so-called second embodiment of the invention, wherein the interface region containing or formed from the hollow and / or solid second structural elements as
  • Probencarefl che acts The object underlying the invention is also achieved by an ATR spectroscopy method, wherein a beam consisting of electromagnetic waves, in particular in the infrared range, is coupled into an ATR reflection element, in particular as described above, the light beam from the ATR reflection element
  • the passage of the transmission layer is more than once, in particular wherein the light beam at least once within the
  • the method may further comprise a step of sample application, wherein a fluid, in particular containing analyte, is applied to the transmission layer and penetrates into the transmission layer. It can also be fluid to be analyzed or the analyte itself.
  • the fluid is especially with the supply of thermal energy, evaporates, with analytes remain within and optionally also on the transmission layer.
  • the electromagnetic radiation in particular radiation in the infrared range, is at the interface areas, in particular at the second interface areas, the
  • Said grating surface regions in particular the second annular surface of the main body for coupling in the electromagnetic radiation, may comprise or be formed from hollow and / or massive second structural elements.
  • the electromagnetic radiation is preferably coupled into the ATR radiation ex t on such that, at the angle a x , it is coupled with it meets the first layer boundary, where% represents a sixth effective refractive index of the fluid and / or the analytes at a used wavelength ⁇ ATR2 and measurement temperature, and wherein n 2c represents a seventh effective refractive index of the transmission layer with the fluid for the used wavelength ATR2 at the first Layer limit, where n 2c significantly depends on the refractive index of the solid areas of the SWS, the filling factor of the transmission layer and the sixth refractive index n 3 of the fluid and / or the analytes.
  • the seventh effective refractive index n 2c is thus determined in the presence of the fluid. Incidence angles that meet this condition have been found to be particularly suitable.
  • the first layer boundary is regularly prevented by adhering to the above relationships and ensures the total reflection at the second layer boundary of the transmission layer.
  • the electromagnetic radiation is at the transition from the Grandenia in the
  • Transmission layer broken.
  • the beam path in the main body and / or within the transmission layer is substantially linear.
  • the radiation through which is in the hollow are in the hollow.
  • Transmission layer located fluid and / or in the hollow areas of the Transmitted transmission layer analyte. This can lead to absorption.
  • the radiation is totally reflected. The radiation then again passes through the transmission layer.
  • the radiation is finally refracted back into the main body.
  • the radiation can then be coupled out either directly via the interface region, in particular the third interface region, for decoupling the electromagnetic radiation from the ATR reflection element, or can be guided again into the transmission layer in order to obtain the transmission total reflection. To go through the process again. The latter process can also be repeated several times.
  • the decoupled electromagnetic radiation is fed to the detector. Using appropriate data processing technology, the absorption spectrum is recorded in order to be subsequently processed and analyzed.
  • the invention furthermore relates to a process for the production of the ATR reflection element according to the invention, comprising the provision of a, in particular flat, plane-parallel substrate, in particular a silicon wafer. Furthermore, the method comprises forming a transmission layer with hollow and / or solid first structural elements open towards the second layer boundary. This is done by the
  • Layer boundary toward open hollow and / or solid first structural elements may preferably be a first etching process, a method with a metal assisted chemical etching (MACE) or a Li-off method provided.
  • the first etching process in particular dry etching, has proven to be particularly suitable. This includes the following steps:
  • MACE metal-assisted chemical etching process
  • a thin metal layer in particular noble metal layer, preferably gold layer and / or silver layer, the thickness of the metal layer preferably corresponding to the thickness of the transmission layer,
  • a lift-off method in particular comprising the following steps in this order:
  • Transparency may be lower than for the material of the body. In contrast to the main body, the transmission path is very thin.
  • the hollow and / or solid second structural elements C open to the boundary surface are now formed according to a second etching method which deviates from the first etching method.
  • a second etching method which deviates from the first etching method.
  • the second structural elements are formed by a, in particular wet-chemical, etching process, comprising the following steps in this order:
  • Etching process preferably KOH etching, of the second area, in particular of the second, third and / or fourth interface area, of the substrate.
  • the method described with steps 1), 2a) and 3a) for forming the hollow and / or solid first structural elements open towards the second layer boundary is particularly preferred.
  • the production of a transmission layer comprising hollow and / or massive first structural elements C which are open toward the second layer boundary is preferably effected by applying at least one photoresist layer to a first planar area of the substrate, Structuring of the first planar area of the substrate by means of lithography, in particular D UV lithography and at least one etching step with a first etching method, in particular a DRIE etching step.
  • the material for the substrate it is particularly suitable for silicon.
  • silicon lithography and patterning are known from semiconductor fabrication.
  • anisotropic etching in silicon hollow and / or massive second structural elements are formed, in particular with V-shaped grooves.
  • the angle of the flank formed by the anisotropic etch is determined by the crystallographic orientation of the substrate.
  • Conventional ATR reflection elements made of silicon are usually produced mechanically by cutting and polishing, without any structure! carried out. It is by Schumacher et. al., Appl Spectrosc. 2010, 64 (9), 1 022-7, also known that special silicon ATR reflective elements can be made from silicon 100 wafers.
  • the angle of the groove flanks to the planar interface region of the base body here is preferably about 55 °, in particular 54.74 °.
  • the electromagnetic radiation irradiated perpendicular to these flanks is preferably also the angle of incidence a: the
  • Refractive indices For the use according to the Invention of the ATR reflection element, however, it has surprisingly been found to be advantageous to use silicon wafers instead.
  • second structural elements are preferably etched into the interface regions for coupling and decoupling of the ATR reflection element.
  • the flank angle is only about 35 °, in particular 35.26 °.
  • Irradiation of the electromagnetic radiation along the surface normal of the flanks has a significantly smaller angle of incidence at the first layer boundary.
  • the present invention results in a significant enhancement of the absorption signal in ATR spectroscopy such as ATR infrared spectroscopy. This is an advantage especially for weakly absorbent samples or highly diluted samples.
  • the amplification of the absorption signal allows shorter optical path lengths through the ATR Reflection element than conventional ATR reflection elements with the same power.
  • the ATR-Rellexionselement invention provides in a suitable
  • Execution * form a filter effect, which divides the sample into components
  • FIG. 2 shows a schematic cross section of a further inventive device
  • Transmission layer also called measuring layer or SWS transmission layer, comprising solid and hollow areas
  • Figure 3 a) - d) are schematic cross sections of embodiments of the invention
  • ATR reflection element with different embodiments of the transmission layer according to the invention.
  • Structural elements which are formed by elevations and / or depressions, and which the massive and hollow areas of
  • FIG. 5 a) -j) schematic top views of embodiments according to the invention of the hollow and / or solid first open to the second layer boundary
  • FIG. 6 shows the schematic cross section including a possible beam path through a single reflection element according to the invention, comprising a second one
  • FIG. 7 shows a schematic cross section including the beam path through a
  • the SWS transmission layer in this embodiment forms the regions for coupling and decoupling the electromagnetic radiation and the hollow and / or solid second structural elements form the sample-receiving surface.
  • Figure 9 shows schematic cross sections through an inventive
  • Single reflection element including a further possible beam path, comprising hollow and / or massive second structural elements in the input and output region and the transmission layer formed from the
  • Figure 1 shows the schematic side view of an embodiment of the invention ATR Reiexioiiselements (1). It comprises a main body (10) with a first effective refractive index at which a first layer boundary (21) has a first layer
  • Transmission layer (2) connects.
  • the transmission layer (2) may, for example, be imaged as a porous transmission layer (the pores are not shown) and over a second layer boundary (22), which is the first one. Layer boundary (21) opposite, absorb a fluid. At the second layer boundary (22), the transmission layer (2) has a second effective refractive index which is less' than the first effective
  • Refractive index but greater than 1.
  • the second refractive index determines at what angle at the interface to the vacuum total reflection can occur.
  • FIG. 2 shows a further embodiment of the ATR reflection element according to the invention
  • the main body (10) comprises a second interface area for coupling. (1 1) and a third interface region for coupling out (12) the electromagnetic
  • the transmission layer (2) has alternating solid areas (23) and hollow areas (24), which in this example are formed by periodic elevations and depressions. These are preferably designed as hollow and massive first structural elements (25) open toward the second layer boundary. Over the second layer boundary
  • a fluid can penetrate into the hollow regions (24) of the transmission line.
  • the hollow areas are therefore open to the second layer boundary.
  • Figure 3 shows a side view of various possible embodiments of
  • Transmission layer (2) shows an embodiment in which the solid areas (23) over the hollow areas (24) of the transmission layer (2) predominate.
  • the fill factor here is more than 50%.
  • Figure b) shows an embodiment in which the hollow regions (24) over the solid areas (23) of the transmission layer (2) predominate.
  • the fill factor here is less than 50%.
  • massive areas (23) and hollow areas (24) of the transmission layer occupy the same space. In this embodiment, the fill factor is 50%.
  • An alternative embodiment forms the porous structure shown in Figure d). Size and number of hollow areas (24) designed as pores in relation to the total volume or to the total area of the cross-section of the transmission layer (2) determine the filling actuator.
  • FIG. 4 shows further possible embodiments of the surveys and / or
  • the fill factor remains constant over large parts of the thickness of the transmission layer (2). Near the first layer boundary (21) and the second layer boundary (22), the fill factor changes due to the rounded edges. While the slope of the flanks in sections in the embodiments a) and c) are 90 °, the slope of the embodiment b) is 75 °.
  • FIG. 5 shows in plan view various embodiments of the solid areas (23) and the hollow areas (24) of the transmission layer.
  • the resulting elevations (top row) and depressions (bottom row) may have different shapes.
  • Figures a) and b) show cuboid or cube-shaped elevations and depressions
  • Figures c) and d) show pyramid-shaped massive first structural elements.
  • Figures e) and f) show massive cylindrical first elements of the structure
  • Figures g) and h) show conical first structural elements.
  • the solid regions (23) and hollow regions (24) of the transmission layer may also be along one or more spatial directions parallel to the first and / or the second layer boundary
  • Figures 5 a), c), e), and g) show only massive elements of the structure. The spaces are connected continuously and form a base area.
  • Figures 5 b), d), f), and h) show only hollow structural elements. The intermediate areas are elevated and form a contiguous plateau surface.
  • Figures 5 i) and j) are both hollow structural elements as well as massive
  • FIG. 6 schematically shows the beam path of the measuring beam of a preferred embodiment
  • the electromagnetic radiation (30) passes over the second interface areas for coupling the
  • electromagnetic radiation (1 1) which are formed from flanks of solid and / or hollow second structural elements (13), in the base body (10) of the ATR reflection element (1) having a first effective refractive index.
  • Beam angle is selected in this embodiment so that the radiation in the. right angles to the flanks of the massive and / or hollow second Strakturetti meets.
  • the proportion of the electromagnetic radiation already reflected upon entry into the ATR reflection element is reduced, so that the largest possible proportion of the electromagnetic radiation for the actual absorption measurement of the analytes
  • the electromagnetic radiation (30) passes through the case body (10) of the ATR reflection element (1) and impinges on the first barrier bar (21) at an angle of incidence relative to the solder a t .
  • the transmission layer (2) consists of alternating massive solid areas (23) and hollow areas (24) formed solid and / or to the second layer boundary open hollow first structural elements (25) in
  • Exiting fluid in particular including the analytes (40), penetrates via the second layer boundary (22) into the hollow regions (24) of the transmission layer (2).
  • the fill factor over the entire thickness of the transmission layer (2) is constant.
  • the angle of incidence a 1 is selected so that no total reflection occurs at the first layer boundary (21).
  • the electromagnetic radiation (30) is broken away from the solder when entering the transmission layer (2).
  • the electromagnetic radiation (30) passes through the transmission layer (2) and also traverses the cavities filled with the fluid and / or analyte (40). Areas (24) of the transmission layer (2).
  • the electromagnetic radiation (30) strikes the second at an angle a 2 > a %
  • evanescent waves (32) penetrate into the fluid and / or into the analytes.
  • the totally reflected electromagnetic radiation (30) again passes through the transmission layer (2).
  • At the first layer boundary (21) occurs
  • FIG. 7 schematically shows an embodiment as a multiple reflection element.
  • the electromagnetic radiation (30) in the main body (10) of the ATR reflection element (1) coupled.
  • the electromagnetic radiation (30) then enters via the first layer boundary (21) in the transmission layer (2), wherein it undergoes a refraction.
  • the electromagnetic radiation (30) passes through the transmission layer (2) until it encounters the second layer boundary (22) to the fluid or to the Analytcn (40).
  • the electromagnetic radiation (30) trusts the fluid (40) which has penetrated into the hollow regions (24) of the transmission layer (2). Total reflection takes place at the second layer boundary (22), with evanescent waves (32) penetrating into the fluid.
  • the electromagnetic radiation (30) again passes through the transmission layer (2) and is refracted into the base body (10) at the first layer boundary (21).
  • the electromagnetic radiation (30) is reflected again in the direction of the transmission layer (2).
  • the electromagnetic radiation (30) again passes through the transmission layer (2) and is at the second. Layer boundary (22) totally reflected. This process can take place one or more times until the electromagnetic radiation (30) is finally decoupled from the base body (10) at the interface area for decoupling the electromagnetic radiation (12).
  • FIG. 8 shows schematically a Ausfflhrungsfonn the ATR reflection element according to the invention as a triple reflection Elemen Here forms the Transrnissionstik
  • the electromagnetic radiation (30) penetrates via the second layer boundary (22) into the transmission layer (2).
  • the transmission layer acts as an anti-reflection layer, so that the proportion of the electromagnetic radiation (30) reflected upon entering the ATR reflection element (1) is significantly reduced in comparison to radiation onto a plane boundary surface (moth eye effect).
  • the electromagnetic radiation (3) enters the main body (10) of the ATR reflection element (1) and is at the three adjacent to the fluid and / or the Analytcn (40) sides of the trapezoidal in cross section massive and / or hollow second Structural elements (13) in each case once totally reflected, wherein evanescent waves (32) in the fluid and / or in the analytes (40) penetration.
  • FIG. 9 schematically shows the beam path of the measuring beam of an embodiment of the invention
  • Flanks formed by second structural elements, in the main body of the ATR reflection element with a first effective refractive index n T occurs.
  • Cross-sectional view a) shows a cross section which is arranged orthogonal to the V-shaped grooves on the underside.
  • the cross-sectional view b) shows a 90 ° rotated cross-section of the same embodiment, this cross-section being parallel to the V-shaped grooves on the underside.
  • the transmission layer is in both
  • the Transtnissions Mrs is formed by columns (123) and the spaces (124) for receiving the fluid between the columns.
  • the light beam is irradiated orthogonally to the said layer boundaries and refracted upon entry into the base body.
  • a dashed line to the second »Schichtgreiize parallel plane is shown, wherein the light beam is arranged orthogonal to this.
  • the cross-sectional view b wherein the light beam penetrates here at an acute angle in the crystal and is broken.
  • the Einstrahlvektor of the light is thus in a plane which is oriented orthogonal to the first and / or second layer boundary and parallel to the V-shaped grooves.
  • the light is radiated along the V-shaped grooves so that the legs can be evenly illuminated.
  • the aim is to ensure a uniform angle of incidence in the cross-sectional view b). It has been shown that this is associated with improved measurement results.
  • the angle of incidence is not chosen so that the radiation at right angles to the flanks of the solid or the hollow second mentioned

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Abstract

L'invention concerne un élément de réflexion ATR, comprenant un corps de base ayant un premier indice de réfraction effectif ni, une couche de transmission, qui présente une première limite de couche et une deuxième limite de couche opposée, la couche de transmission étant orientée et aménagée pour recevoir un fluide par le biais de la deuxième limite de couche, la couche de transmission étant adjacente au corps de base, la limite entre la couche de transmission et le corps de base étant formée par la première limite de couche, la couche de transmission présentant un deuxième indice de réfraction effectif n2 au niveau de la deuxième limite de couche, le premier indice de réfraction effectif ni étant supérieur au deuxième indice de réfraction n2 et le deuxième indice de réfraction effectif n2 étant supérieur à 1, le premier indice de réfraction effectif ni et le deuxième indice de réfraction effectif n2 devant être déterminés respectivement sous vide à 25°C à la longueur d'onde IR λ ATR , λ ATR étant choisi dans le domaine de longueurs d'onde de 2 µm à 20 µm. De plus, l'invention concerne un spectromètre ATR ayant ledit élément de réflexion ATR et un procédé de spectroscopie ATR.
EP16762824.7A 2015-09-14 2016-09-08 Élément de réflexion atr et procédé de spectroscopie atr Withdrawn EP3350575A1 (fr)

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JP3770707B2 (ja) 1997-08-26 2006-04-26 松下電器産業株式会社 減衰全反射測定装置およびそれを用いた特定成分の測定方法
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US20190011364A1 (en) 2019-01-10
WO2017045998A1 (fr) 2017-03-23
US10585040B2 (en) 2020-03-10
DE102015011687B4 (de) 2023-05-11
CN108351298A (zh) 2018-07-31

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