WO2014180716A1 - Capteur de gaz et procédé de détection d'au moins un composant gazeux - Google Patents

Capteur de gaz et procédé de détection d'au moins un composant gazeux Download PDF

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Publication number
WO2014180716A1
WO2014180716A1 PCT/EP2014/058726 EP2014058726W WO2014180716A1 WO 2014180716 A1 WO2014180716 A1 WO 2014180716A1 EP 2014058726 W EP2014058726 W EP 2014058726W WO 2014180716 A1 WO2014180716 A1 WO 2014180716A1
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WIPO (PCT)
Prior art keywords
photonic crystal
resonator
gas sensor
gas
electromagnetic radiation
Prior art date
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PCT/EP2014/058726
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German (de)
English (en)
Inventor
Jonathan Finley
Harry Hedler
Christian KRAEH
Alexandru POPESCU
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Siemens Aktiengesellschaft
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Publication of WO2014180716A1 publication Critical patent/WO2014180716A1/fr

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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
    • G01N21/25—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
    • G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
    • 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
    • G01J3/02—Details
    • G01J3/10—Arrangements of light sources specially adapted for spectrometry or colorimetry
    • G01J3/108—Arrangements of light sources specially adapted for spectrometry or colorimetry for measurement in the infrared range
    • 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
    • G01J3/28—Investigating the spectrum
    • G01J3/42—Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry
    • 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
    • G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J5/02—Constructional details
    • G01J5/08—Optical arrangements
    • G01J5/0801—Means for wavelength selection or discrimination
    • G01J5/0802—Optical filters
    • 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
    • G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J5/02—Constructional details
    • G01J5/08—Optical arrangements
    • G01J5/0853—Optical arrangements having infrared absorbers other than the usual absorber layers deposited on infrared detectors like bolometers, wherein the heat propagation between the absorber and the detecting element occurs within a solid
    • 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
    • G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J5/10—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
    • G01J5/12—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using thermoelectric elements, e.g. thermocouples
    • 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
    • G01N21/031—Multipass arrangements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • 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
    • G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J5/10—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
    • G01J5/12—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using thermoelectric elements, e.g. thermocouples
    • G01J2005/123—Thermoelectric array

Definitions

  • the invention relates to a gas sensor for detecting at least one gas component.
  • the gas sensor comprises a photonic crystal which has a plurality of structural elements arranged periodically in at least one spatial direction. Furthermore, the photonic crystal has at least one impurity, by which at least one resonator for electromagnetic radiation of a wavelength which is absorbable by the at least one gas component is formed.
  • the invention also relates to a method for detecting at least one gas component.
  • gas sensors can be gases in the environment detektie ⁇ ren. This allows, for example, the detection of Ga ⁇ sen as CO, CO 2, H 2 O and methane, in particular when determining development of their concentration to make statements about the air quality.
  • gas sensors can be used to monitor the concentration of hazardous and toxic gases. Especially in combination with automatic ventilation systems, the air quality in closed rooms can be monitored and controlled.
  • a gas sensor is made as compact as possible, has a low energy consumption and if it makes it possible to detect the concentration of the individual gas components or gas species unaffected by other present gas species.
  • Gas sensors are an established technology, which can be based on a variety of measurement principles.
  • the measuring principles differ in the way in which chemical information is converted into a (mostly electronic) signal, which is then further processed.
  • Principles for gas detection include resistive, capacitive, potentiometric, amperometric, thermal, gravimetric and optical methods.
  • Optical measurement, especially infrared gas spectroscopy, is of particular importance in the detection of gas components. Infrared gas spectroscopy is based on the excitation of energy states in gas molecules by infrared light. This occurs with each gas species at one or more characteristic gas absorption frequencies or wavelengths, which are also referred to as absorption lines.
  • infrared spectrometer infrared light from a source, which may be, for example, a La ⁇ serdiode, emitted in a gas volume. Subsequently ⁇ d the attenuation of the light by means of a Detek ⁇ tors is evaluated. It is important here that the light source radiates electromagnetic radiation with sufficient intensity in the infrared range and that the attenuation can subsequently be detected in a wavelength-specific manner. By measuring the absorption lines of different gas components separately, the concentration of individual gas species can be determined independently of each other.
  • 7,352,466 B2 describes a gas sensor with a photonic crystal which has a plurality of periodically arranged structural elements.
  • a light-emitting diode, light generated in this case is passed through the pho ⁇ tonic crystal.
  • the light interacts with the gas component in the cavity.
  • a part of the energy of the light irradiated in the photonic crystal is absorbed. Accordingly, light of reduced intensity emerges again from the photonic crystal, which is detected by means of a photodiode.
  • the DE 10 2010 034 428 B3 describes a gas sensor ⁇ with a photonic crystal, wherein said periodically arranged, free-standing columns of a metal or a metal alloy are provided.
  • Defects in the photonic crystal form resonators whose resonant frequencies lie in a frequency range in which gas components to be detected absorb light. The light is generated by heating columns of the photonic crystal.
  • columns are arranged in the resonator, which unlike the other columns of the photonic crystal are not heated.
  • the energy transfer from the resonator to the neutral, not actively heated columns then allows conclusions about the concentration of the gas component to be detected. In this case, a high temperature detected by the detector indicates that only a small amount of radiation was absorbed in the resonator.
  • the gas component to be detected is only present in a low concentration.
  • Object of the present invention is to provide a gas sensor and a method of the type mentioned, by means of which gas components can be detected particularly reliable.
  • the gas sensor according to the invention comprises a detector wel ⁇ cher as different from the photonic crystal Bauele ⁇ ment is formed.
  • the detector is designed to detect electromagnetic radiation emitted by the at least one resonator.
  • the detector is located in the spatial vicinity of the photonic crystal with the at least one resonator, and thus allows to detect the radiation emitted by the we ⁇ antes a resonator without the resonator itself is disrupted here.
  • the gas sensor is particularly reliable in terms of the detection of the at least one gas component.
  • Molecules of the gas component in the at least one resonator reduce by absorption the energy of the electromagnetic radiation emitted by the resonator when the resonator is designed to retain electromagnetic radiation of the wavelength absorbable by the gas component and to release it to the detector after some time.
  • no electromagnetic radiation absorbing see gas component is located in the resonator, the output from the resonator electromagnetic ⁇ cal radiation passes without attenuation to the detector. Because of this to ⁇ sammenhangs to statements about the gas component or gas species and their concentration can be made.
  • the gas sensor is based on the use of the photonic crystal.
  • a photonic crystal has a regelbau ⁇ ssige arrangement of structural elements, ie an array of microstructures, which form a photonic structure having a band gap.
  • the periodically arranged structural elements of the photonic crystal affect the Ausbrei ⁇ processing of electromagnetic waves in many ways.
  • the periodicity of the arrangement of the structural ⁇ turetti corresponds almost equals the wavelength of the light influenced.
  • the propagation of the light takes place in the spatial direction in which the periodicity of the structural elements is given, in energy bands, which are also known as fashions. Since the structural elements in the photonic crystal alternate with regions which are occupied by the air containing the gas component to be detected, a high contrast of the respective refractive indices is usually present in the photonic crystal. This high refractive index contrast ensures that electromagnetic ⁇ cal radiation of certain wavelengths or frequencies in the photonic crystal can not spread. This phenomenon of prohibiting the propagation of electromagnetic radiation in the photonic crystal is also referred to as the occurrence of a photonic band gap.
  • Electromagnetic radiation in particular light, which fulfills this band gap condition, ie has a wavelength or frequency which can not propagate in the photonic crystal, can thus be confined in the defect for a specific time.
  • the impurities serve so ⁇ as a resonator for the electromagnetic radiation of this wavelength.
  • Resonators for corresponding gas components can thus be generated by targeted introduction of defects or impurities in the structure of the photonic crystal.
  • light which fulfills the resonance conditions of the respective resonator can then be held for a certain time, in this case interacting with the gas component to be detected and then emerge from the resonator in a form weakened by absorption.
  • the energy radiated by the at least one resonator can be detected particularly well.
  • the energy of the electromagnetic radiation emitted by the photonic crystal in areas free from impurity can be used as a reference.
  • the photonic crystal By using the photonic crystal can also be realized a particularly small size of the gas sensor.
  • absorption by gas components to be detected takes place mainly in the infrared range and especially in the near infrared range.
  • These wavelengths lying in the range of micrometers also correspond approximately to the sizes of the structural elements of the photonic crystal, for example their diameters and distances from one another.
  • the resonators may also have the order of microns. As a result, hundreds or thousands of resonators can already be realized in a very small photonic crystal, depending on the geometry of the structural elements.
  • the determination of the presence or concentration of the gas components is particularly reliable due to the perception of the changes in the electromagnetic radiation emitted by the resonator.
  • a particularly suitable structure of the photonic crystal can provide when the structural elements are formed as anchored in a substrate rods according to an advantageous embodiment of the invention, wherein the Wenig ⁇ least one resonator by the absence of at least one rod to a according to the periodicity for the rod is formed.
  • the resonator is created by deliberately omitting one or more rods. Between the rods there is air or a gas mixture containing the gas components to be detected, so that gas-open resonators are created by the omission of rods. Then, namely, the electromagnetic radiation in the resonator can interact particularly well with the gas components contained in the air.
  • the volume of the resonator in this case contains the gas mixture or the air with the gas components to be detected.
  • the electromagnetic waves trapped in such a resonator are then mainly concentrated in the air, and they can then interact well with gas molecules in the resonator.
  • the impurity may be formed as a point defect, ie as a cavity, which is formed by omitting a single rod or as a line defect or waveguide, which is generated by the omission of a plurality of adjacent bars.
  • the at least one resonator adjacent to ⁇ structural elements to be ⁇ neighboring structural elements have a distance which is smaller or greater than a distance corresponding to the periodicity of the structure elements from one another.
  • the resonator can be tuned to the frequency of the detected gas component particularly good, so to that wavelength at which the gas component absorbs the electromagnetic radiation ⁇ diagram.
  • the structural elements have a distance from one another corresponding to a first periodicity and / or a first shape and in a second region a distance from one another corresponding to a second periodicity and / or a second shape.
  • This is based on the recognition that changes in the geometry of the photonic crystal are accompanied by changes in the energy bands and thus also in the band gaps. This also leads to shifts in the resonator frequencies or resonator modes. If, for example, one changes the distance between the structural elements, the modes shift to higher or lower frequencies. Thus, a large bandwidth of resonator frequencies can be provided in a photonic crystal.
  • Structural elements also leads to a shift of the energy bands and the band gaps.
  • ligen resonator frequencies are provided. This makes it possible to detect a multitude of different gas components. Namely, a plurality of wavelength-tuned resonator modes can be provided. It can be particularly well ensured that at least one of these ⁇ resonator or resonator frequencies is very close to the gas absorption line of the gas to be detected component.
  • the change in the shape of the structural elements can in particular in the change of a diameter of the same best ⁇ hen, since structural elements with different diameters ⁇ sern can be produced particularly easily.
  • a Tempe ⁇ temperature of the photonic crystal is set such that a frequency of the electromagnetic radiation reflected in at least one resonator corresponds to that which is absorbable by the at least one gas component.
  • the operating frequency of the resonator that is to say the desired resonator frequency
  • the operating frequency of the resonator can be adjusted by a specific change in the temperature of the photonic crystal. Due to a temperature change, namely the refractive index of the material of the structural elements of the photonic Kris ⁇ talls changes, and it is depending on the temperature to different thermal expansions of the structural elements.
  • the temperature-dependent different refractive indices and thermal expansions can be used particularly well to tune the frequencies of the resonators to the desired, that is absorbed by the gas component frequencies.
  • the gas sensor comprises heating means, which is adapted to generate electromagnetic radiation in the photo ⁇ photonic crystal. Then, no external light source for providing the electromagnetic radiation needs to be provided, so that the gas sensor is particularly simple. In addition, there is a very low energy consumption of the gas sensor, since very little energy is needed to heat the photonic crystal for the purpose of generating the electromagnetic radiation.
  • the heating device may comprise an electrical conductor which is arranged on a substrate of the photonic crystal carrying the structural elements. By heating the substrate, it is thus possible to heat the substrate particularly homogeneously
  • Structural elements of the photonic crystal can be achieved.
  • it is particularly easy to adjust changes in the temperature of the photonic crystal. This applies in particular if the electrical conductor is arranged in a meandering manner on the substrate.
  • the photonic crystal is the outer circumferential side at least be rich ⁇ partially surrounded by a wall which has a high reflectivity for itself in the photonic crystal propagating electromagnetic Strah ⁇ lung. It is therefore preferably more than half of the incident on the wall electromagnetic radiation reflected by this. This will work lost particularly little electromagnetic radiation, which is beneficial to the energy consumption of the gas sensor ⁇ acts.
  • the at least one wall has a low tendency to generate electromagnetic radiation. By providing such a wall with a low intrinsic radiation, there is no undesirable interaction with the electromagnetic radiation propagating in the photonic crystal, so that the latter need only have a comparatively low intensity. This also has an advantageous effect on the Energyver ⁇ consumption of the gas sensor.
  • the detector is designed as a thermo-electric energy converter, which has substantially parallel aligned columns, the columns are electrically connected in pairs to each other to ⁇ construction of a thermoelectric voltage.
  • the columns have a very high aspect Behaves ⁇ nis, thus a high ratio of length to diameter up, not only high sensitivities, but also very small pixels, for example 10 microns to 10 microns can be achieved. Moreover, such a detector allows a particularly simple evaluation of the thermally generated ⁇ tured voltage.
  • end regions of the pillars face respective end regions of the structural elements of the photonic crystal, whereby pillars of the photonic crystal are arranged in at least a portion thereof in which the at least one resonator is formed in the opposite photonic crystal.
  • At least one filter which is permeable to the electromagnetic radiation emitted by the at least one resonator, is arranged between the detector and the photonic crystal. This ensures that only a particularly small amount of energy actually leaves the photonic crystal. This is the low energy consumption of the gas sensor zuträg ⁇ Lich.
  • At least one cover element which has a passage opening in the region of the at least one resonator, can be arranged between the detector and the photonic crystal. It can thus be ensured that only a small amount of energy in the form of the electromagnetic radiation emitted by the resonators leaves the photonic crystal.
  • the cover member may propagating electro-magnetic radiation ⁇ are designed to be reflective on its side facing the photonic crystal side of the photonic crystal. This can be achieved, for example, by the provision of a reflective coating on the cover element.
  • an area occupied by the detector area is equal to at least Wesentli ⁇ chen an area occupied by the photonic crystal surface. Then, with an especially good spatial resolution, the electromagnetic radiation emitted by the photonic crystal can be assigned to the resonators.
  • an electromagnetic radiation is introduced ⁇ is in a photonic crystal having a plurality of periodically arranged in at least one spatial direction structural elements.
  • the photonic crystal has at least one interference ⁇ spot, through which a resonator for elekt ⁇ romagnetician radiation of a wavelength is at least formed, which is absorbed by the at least one gas component.
  • electromagnetic radiation emitted by the at least one resonator, which emerges from the photonic crystal enters a detector of the gas sensor, and it is detected by means of the detector.
  • the detector is embodied as different from the photonic crystal construction ⁇ element.
  • the gas sensor can be detected particularly reliable in operation, the gas component.
  • the advantages and preferred embodiments described for the gas sensor according to the invention also apply to the method according to the invention and vice versa.
  • the description above mentioned features and combinations of features as well as mentioned below in the Figurenbe ⁇ letters and / or alone shown in the figures features and combinations of features can be used not only in the respectively specified combination but also in other combinations or in isolation, without the To leave frame of the invention.
  • Figure 1 is a perspective view showing a photonic Kris ⁇ tall as FIG 16 is used in a gas sensor according to the application;
  • FIG. 2 shows energy bands and a band gap for frequencies of electromagnetic radiation which are given in the photonic crystal according to FIG. 1;
  • FIG 3 is a perspective view of a photonic Kris ⁇ talls, wherein ge ⁇ create by omitting a single rod, an impurity in the form of a cavity;
  • FIG. 4 shows a perspective view of a photonic Kris ⁇ talls, wherein by omitting three neighboring rods an impurity in the form of a cavity is created;
  • FIG 5 is a perspective view of a photonic Kris ⁇ talls, wherein by omitting nine neighboring rods an impurity in the form of a cavity is created; the resonance frequencies and the band structure of the photonic crystal according to FIG 3 and the elekt ⁇ generic component of the electromagnetic field in the resonant frequencies of the resonators of the see photonic crystal; Variations in the size of cavities formed as cavities in the photonic crystal and the associated wavelengths in which the cavities act as resonators; the respective refractive index of silicon used for the rods of the photonic crystal as a function of the wavelength for different temperatures; the wavelength of an energy band of a photonic crystal ⁇ rule as a function of temperature; a graph in which lines indicate different geometries of resonators, and the wavelengths associated with these geometries, in which the respective resonators are designed to trap electromagnetic radiation and an absorption line of a gas component; continuously changing the temperature of the photonic crystal and the concomitant change in the wavelength at which the defect
  • FIG. 13 shows the dependence of the electromagnetic radiation emitted by a black body on its temperature
  • FIG. 14 schematically shows the photonic crystal of the gas sensor according to FIG 16, wherein the photonic crystal is disposed between walls with high reflectivity, and wherein a heating device for heating the photonic crystal is provided;
  • FIG. 15 shows a perspective view of a detector of the gas sensor according to FIG. 16;
  • thermopile Detek- tors according to FIG 15 the rods of the photonic Kris ⁇ talls are arranged opposite;
  • FIG. 17 shows the gas sensor according to FIG. 16, wherein a filter and a cover with openings are arranged between the detector and the photonic crystal.
  • FIG. 1 shows a photonic structure in the form of a photonic crystal ⁇ rule 1, wherein a plurality of Strukturele ⁇ elements in the form of free-standing bars 2 are arranged at a present in jewei- celled spatial directions regularity.
  • the distances of the bars 2 from each other ⁇ in one in Figure 1 indicated by an arrow 3 first spatial direction the same size.
  • the distances of the bars 2 from each other in a direction perpendicular thereto spatial direction which is illustrated in Figure 1 by a further arrow 4, each equal.
  • the photonic crystal 1 shown in FIG. 1 is thus a photonic structure with two-dimensionally periodically arranged structural elements in the form of the pillars 2, between which there is air with gas components whose concentration is to be measured. Accordingly, the photonic crystal 1 is used in a gas sensor 5 shown in FIG.
  • a gas sensor 5 shown in FIG.
  • photonic crystals 1 which has only structural elements arranged periodically in a spatial direction.
  • photonic crystals 1 can come to a ⁇ set, having in three spatial directions periodically arranged structural elements. This may be seen as pre- ⁇ that varies periodically in Hochrich- processing in the example shown in FIG 1 photonic crystal 1, the diameter of each rod.
  • Such one-dimensional or three-dimensional saudi ⁇ -dimensional photonic crystals 1 wei ⁇ sen properties which takes advantage in the gas sensor. 5
  • the photonic crystal 1 influences the propagation of electromagnetic radiation, for example light with wavelengths in the infrared region in the direction of the periodicity of the photonic crystal 1, in the present case in the spatial directions indicated by the arrows 3, 4 in energy bands.
  • a band structure 6 of the photonic crystal 1 according to FIG. 1 is shown in FIG.
  • ⁇ be attached on an ordinate 7, the normalized frequency of the light.
  • An abscissa 8 indicates the directions of propagation of the light in the photonic crystal 1.
  • the edges of the graph shown in FIG 2 are perpendicular to each other ste ⁇ Henden spatial directions describe the center of a respective individual cell of the photonic crystal 1. therebetween.
  • First and second types of curves 9, 10 indicated in the graph illustrate the energy bands or modes in which there is a possibility of propagation of the light in the photonic crystal 1.
  • the first curves 9 illustrate the bands or modes of the transversely magnetically polarized light
  • the second curves 10 illustrate the modes of transversely electrically polarized light.
  • the rods 2, which form the periodic arrangement in the form of an array of microstructures are preferably made of silicon.
  • a substrate 24, in which the rods 2 are anchored, in the present case also preferably consists of silicon.
  • Such photonic band gaps 11 in the photonic crystal 1 makes it possible to introduce into the photonic crystal 1 targeted impurities or defects, which act as resonators.
  • Such resonators can be made available, for example, by individual ones of the bars 2 ⁇ omitted.
  • FIG. 3 shows a first example of such resonators 12 produced by the omission of individual bars 2.
  • the resonators 12 are in this case formed as cavities or gaps in the form of point defects between the individual bars 2.
  • the light temporarily confined in the resonator 12 can interact with the gas molecules in the resonator 12. In this case, an absorption of light of the wavelength can occur, which corresponds to the resonant frequency of the resonator 12.
  • the photonic crystal 1 is shown, in which by omitting more than one rod 2 an impurity in Shape of a line defect is created.
  • an impurity in Shape of a line defect is created.
  • 2 5 shows the photonic crystal 1, in which
  • a further resonator 14 is generated.
  • the resonators 12, 13, 14 can be formed in particular in one and the same photonic crystal 1. Then the probability is quite high that different resonator frequencies are available for absorbing the wavelengths of the gas components to be detected.
  • the resonators 12, 13, 14 shown in FIG. 3, FIG. 4 and FIG. 5 are gas-open resonators 12, 13, 14.
  • the air whose gas components are to be detected can thus penetrate into the corresponding cavities.
  • FIG. 6 illustrates three resonance frequencies 15, 16, 17 of the resonator 12, which were obtained by omitting a single rod 2 in the rod array according to FIG.
  • a band structure 18 of the photonic crystal 1 shown in FIG 3 is shown.
  • This band structure 18 refers to the transverse magnetic polarized light, which in the photonic crystal 1 entspre ⁇ accordingly can spread the available energy bands.
  • the corresponding energy bands provide a respective continuum 19 at states between which - in the present case three - band gaps 20 are located.
  • the second band gap 20 has the first resonant frequency 15 of the resonator 12.
  • the third band gap 20 are the second Resonanzfre ⁇ frequency 16 and the third resonant frequency 17 of the resonator 12th
  • the electrical components of the respective electromagnetic field and their spatial position relative to the resonator 12 are illustrated by respective regions 21, 22, 23.
  • the electrical component is illustrated by the area 21, almost exclusively a concentration of the electromagnetic field in the resonator that are available in the air 12 shows.
  • the resonance frequency 15, 16, 17 of the resonator 12, 13, 14 or the resonance wavelength is endeavored to bring the wavelength in accordance, in which the gas to be detected sublingually component light ⁇ biert.
  • the resonant frequencies 15, 16, 17 of the resonator 12, 13, 14 in the photonic crystal 1 depend on factors such as
  • the material used for the rods 2 can changed ⁇ changed or be selected accordingly.
  • the band gaps 11, 20 occur is a great contrast as possible of the respective refractive index of the material of the bars 2 and adjacent to the bars 2 provided air.
  • the material selected for the bars 2 also influences the position of the band gaps 11, 20 and also the position of the resonant frequencies 15, 16, 17 or resonator modes which may be present in the band gaps 11, 20.
  • a graph 25 in FIG 7 is a graph 26, the re sonanzwellenin constitute the resonator 12, so that Reso ⁇ nanzwellenide which is established in a cubic array of the photonic crystal 1 formed from silicon rods, when the resonator 12 by omitting a single rod 2, ie by a point defect in the grid was generated.
  • Another curve 27 in the graph 25 corresponds to the resonance wavelength in a ⁇ resonator 28, which was obtained by omission of two adjacent rods.
  • the size of the distance of the approach was in this case a fraction of a distance a, which corresponds to the distance between the centers of two adjacent bars 2 in areas of the photonic crystal 1 remote from the resonator 12.
  • This distance a is also called a grid pitch. If the size of the defect of a resonator 12 formed by omitting a rod 2 is denoted by LI, then the size of the resonator 12 of size LI + 0.1a increased by one-tenth of the distance a corresponds to this.
  • the band structure 6 shown in FIG 2 has accordingly for a specific Ver ⁇ ratio of the radius of the rods 2 to the distance a of the bars 2 from each other ⁇ valid. Furthermore, the band structure 6, 18 depends on the type of grid which form the bars 2. In the two-dimensional photonic crystal 1 shown here, a cubic lattice is selected, but other lattice types such as hexagonal, trigonal or tetragonal lattices may be used.
  • the resonance frequencies 15, 16, 17 of the resonators 12, 13, 14, 28 influence.
  • the optical properties of the photonic crystal 1 are temperature-dependent.
  • the resonant frequencies 15, 16, 17 of the resonator 12 can be adjusted through targeted Tempe ⁇ raturation Sung.
  • the change of the temperature affects the optical properties of the photonic crystal 1, for example, due to the change in the refractive index of the material used for the bars 2 of the photonic crystal 1 with the temperature. This should be with reference to FIG ⁇ anschaulicht 8 ver.
  • the refractive index is a temperature-dependent quantity, and the exact relationship between the temperature and the refractive index can vary greatly depending on the material. For example, there are big differences between the Temperature dependencies of the respective refractive index of metals, semiconductors and insulators.
  • the change in refractive index for example, the tempera ⁇ tur Scheme of 293 Kelvin to 1600 Kelvin and a shaft is described length range of 1.2 micrometers to 14 micrometers by a model.
  • FIG. 8 shows a family of curves 30, each of which describes the refractive index of silicon as a function of the wavelength for different temperatures. In this case, the refractive index is indicated on an ordinate 31 and the wavelength in micrometers on an abscissa 32.
  • the temperature dependence of a mode in the photonic crystal 1 can be represented as a function of the temperature. Accordingly, in FIG 9, a curve 33 is shown which illustrates the temperature dependent ⁇ ness of the wavelength of the second mode of a rod 2 of Sili ⁇ zium of the photonic crystal 1 at the center of the individual ⁇ cells as a function of temperature. This center is also called the ⁇ point.
  • a corresponding point 34 which illustrates the position of this second mode in the band structure 6 according to FIG. 2, is also shown in FIG. 9 for explanation.
  • the curve 33 shown in FIG. 9 applies to a distance a of the centers of the bars 2 from each other, which is 2.1 micrometers, and to a radius of the bars 2 of 618 nm.
  • the wavelength in FIG. 9 is plotted on an ordinate 35 and the temperature on an abscissa 36.
  • the change in temperature can change the geometry of the photonic crystal 1 due to thermal expansion effects. Depending on the geometry and material of the photonic crystal 1, this effect may have different effects on the optical properties of the photonic crystal 1.
  • This can be realized once by providing a plurality of resonators 12, 13, 14, 28 of different sizes. This ensures that a multiplicity of wavelength-offset resonant frequencies 15, 16, 17 are available. At least one of these resonance frequencies 15, 16, 17 is then at least very close to a gas absorption line.
  • ⁇ vorzugt varying geometries, so varying shapes of the structural elements, in particular varying By ⁇ diameter of the bars 2 as well as varying distances a between the rods 2 has This means that resonance frequencies of 15, 16, 17 the resonators 12, 13, 14, 28 can be brought at least close to a gas ⁇ absorption line, in particular overlap with a gas absorption line.
  • wavelengths are applied at wel ⁇ cher on an abscissa and lines 38, 39, 40, 41, 42, with the different geometries of the resonators 12, 13, 14, 28 and / or Illustrate the different arrangements and / or shapes of the bars 2 resonant wavelengths.
  • the resonance wavelength of one of the resonators 12, 13, 14, 28 illustrated by the line 40 is very close to a gas absorption line 43.
  • FIG 11 is illustrated, as may be made to overlap by kontinuier ⁇ Liche variations of the temperature of the photonic crystal 1, a resonant wavelength of a resonator 12, 13, 14, 28 with said gas absorption line 43rd Again, the abscissa 37, the wavelength is plotted, while a line 44 illustrates that wavelength at which at a lower temperature certain resonator 12, 13, 14, 28 satisfies the resonance conditions and so the light is held for a certain time in the resonator 12, 13, 14, 28.
  • An arrow 45 in FIG. 11 illustrates the continuous one
  • the continuous increase of the temperature ge ⁇ Häss the arrow 45 is given as a function of time, which is plotted on an abscissa 46, while the temperature is indicated on an ordinate 47th
  • a line 48 indicates the temperature at which the line 44 and the gas absorption line 43 are in overlap.
  • a plurality of resonators 12, 13, 14, 28 can be generated, so that the detection of a plurality of gas species or gas components is possible.
  • the photonic crystal 1 can be divided into regions with different geometries.
  • the resonators 12, 13, 14, 28 in the respective area are then preferably designed for the detection of a specific gas component. This can, for example, thereby allowing the ⁇ that in each region a plurality of resonators 12,
  • the electromagnetic radiation which collects in the respective resonator 12, 13, 14, 28 is generated by heating at least part of the photonic crystal 1, ie the rods 2 and / or the substrate 24. The goal here is to bring the photonic crystal 1 to a temperature which is greater than the temperature of its surroundings.
  • Each structural element of the photonic crystal 1 and also the substrate 24 radiates electromagnetic
  • the thermal radiation in the photonic crystal 1 is influenced by the optical properties of the photonic crystal 1.
  • a defect-free photonic crystal 1 in which therefore no acting as resonators 12, 13, 14, 28 impurities are provided, the radiation of the rods 2 in the direction of the periodicity in the frequency range of the band gaps 11, 20 is suppressed. This can be explained by the prohibition of light propagation in the frequency range of the band gaps 11, 20.
  • the photonic crystal 1 which has cavities approximately in the form of the resonators 12, 13, 14, 28, however, this can increase the accumulation of the electromagnetic radiation, which has one of the resonance frequencies 15, 16, 17, in the resonators 12, 13, 14 , 28 result.
  • the reason for this is that the bars 2 adjacent to the respective cavity do not have any electromagnetic radiation in the region of the band gaps 11, 20.
  • Table radiation in the direction of the periodicity of the photonic crystal 1 in the photonic crystal 1 may submit. Namely, there are no modes or energy bands for receiving this electromagnetic radiation. However, the bars 2 can partially emit this electromagnetic radiation into the resonator 12, 13, 14, 28.
  • the resonator 12, 13, 14, 28 supplies resonant modes or resonant frequencies 15, 16, 17 in the region of the respective band gap 11, 20 for this purpose.
  • the Purcell effect leads to an increased emission of electromagnetic radiation in the resonant frequency 15, 16, 17 of the cavities.
  • the Purcell effect states that the probability of emission increases when the source of the emission is in a resonator
  • FIG 14 shows schematically a first component 51 of the gas sensor shown in FIG 16 5.
  • the component 51 comprises the pho ⁇ tonic crystal 1 to the bars 2 and the defects or cavities, through which the resonators are formed 12, 13, 14, 28, only the resonator 12 being shown for the sake of simplicity.
  • the electrical conductor 52 may in particular be made of platinum.
  • the photonic crystal 1 is arranged between walls 53, of which the photonic crystal 1 see crystal 1 facing and in particular with respect to the substrate 24 inclined surfaces 54 have a high reflectivity.
  • the walls 53 of the component 51 are characterized by a low self-emission.
  • a further component of the gas sensor 5 is a detector 55 shown in perspective in FIG. 15, which is designed as a component that is different from the photonic crystal 1.
  • This detector 55 is preferably formed as an infrared detector array and includes, for example, a plurality of columns 56, 57, which are each electrically connected in pairs with each other ⁇ .
  • the respective columns 56, 57 form legs of a thermocouple, wherein the legs of Materia ⁇ lien with different thermo-force exist, so have different Seebeck coefficients.
  • Upon application of heat to the columns 56, 57 a thermal voltage forms accordingly. This electrical signal is then detected.
  • the ends of the columns 56, 57 facing the free ends of the rods 2 of the photonic crystal 1 in the gas sensor 5 are preferably covered with an absorber layer 58, which is designed to absorb infrared radiation.
  • the electromagnetic radiation via absorption in the columns 56 is received 57, which are also referred to as thermopiles, and Conver ⁇ advantage in a detectable signal.
  • Dimensions of the detector 55, in particular a through ⁇ diameter and a pitch of the columns 56, 57 in particular can be adapted to the geometry of the photonic crystal. 1
  • the layout of a function of the absorption of infra ⁇ red radiation a respective voltage emitting units of the detector 55, which are also referred to as a pixel, can be designed so that both the intensity of the 28 of the photonic from the resonators 12, 13, 14, Crystal 1 emitted electromagnetic radiation and the intensity of in undisturbed areas of the photonic crystal 1 off given electromagnetic radiation can be detected separately from each other.
  • thermoelectric detector 55 Such a three-dimensional thermoelectric detector 55, as shown schematically in FIG.
  • the degree of coverage may be 80 to 90%.
  • the detector 55 is a very high sensitivity on which is due to the high aspect ratio of kla ⁇ len 56, 57, ie by a large value of the holding Ver ⁇ isses their length to their diameter.
  • the aspect ratio can be up to about 100: 1.
  • the Sensitive ⁇ ness of the detector 55 can be more than 1,000 volts per watt recorded by the detector 55 thermal power.
  • the columns 56, 57 projecting from a substrate 59 in the present case perpendicularly out, which can be det gebil ⁇ for example, silicon.
  • the individual columns 56, 57 or thermosets can in particular each consist of p-doped and n-doped silicon.
  • an evaluation circuit such as a CMOS-evaluation circuit, can be arranged so that it is inte grated in the detector ⁇ 55th
  • individual column pairs 60 are arranged in the gas sensor 5 via the cavities forming the resonators 12. These pairs of columns 60 so absorb the com plete ⁇ emitted from the resonators 12 electromagnetic radiation.
  • Other column pairs 61 of the detector 55 are arranged demge ⁇ genüber over areas of the photonic crystal 1, which are free of impurities in the form of the resonators 12, 13, 14, 28.
  • a filter 62 and / or a partially transparent cover 63 can be provided between the photonic crystal 1 and the detector 55 may be arranged.
  • the corresponding, the filter 62 and the cover 62 aufwei ⁇ send gas sensor 5 is shown schematically in FIG 17.
  • the fil ter 62 is in this case adapted to electromagnetic Strah ⁇ averaging that frequency pass to the detector 55 which the resonant frequency 15, 16, 17 of the resonators 12, 13,
  • the filter 62 can each have suitable filter properties in respective regions arranged above corresponding resonators 12, 13, 14, 28.
  • the filter 62 ensures that comparatively little electromagnetic radiation is emitted from the photonic crystal 1 towards the detector 55. This is the low energy consumption of the photonic crystal 1 having component 51 of the gas sensor 5 beneficial.
  • cover 63 By means of the cover 63, too, it is possible to prevent electromagnetic radiation which is emitted by the rods 2 of the photonic crystal 1 from reaching the detector 55.
  • cover 63 corresponding holes are bezie ⁇ tion openings 64 provided, which upper half of the resonators 12, 13, 14, 28 of the photonic crystal 1 are arranged. This ensures that the single ⁇ Lich arranged above the resonators 12, 13, 14, 28 of the photonic crystal 1 pairs of columns 60 detect the output from the resonators 12, 13, 14, 28 of electromagnetic radiation.
  • the cover 63 may be mirror-coated on its side facing the photonic crystal 1 to additionally prevent too much electromagnetic radiation from leaving the photonic crystal 1.
  • the resonators 12, 13, 14, 28 of the photonic crystal 1 can therefore hold light with the resonance frequency 15, 16, 17 for a certain time in the photonic crystal 1. If this resonant frequency 15, 16, 17 coincides with the gas absorption line 43 of the gas to be detected, absorption of electromagnetic radiation in the resonator 12, 13, 14, 28 occurs. This leads to a reduction in the intensity of the resonator 12, 13, 14, 28 emitted electromagnetic radiation. The reduction in the intensity of the electromagnetic radiation can be detected by means of the detector 55.
  • the resonance frequencies 15, 16, 17 of the resonators 12, 13, 14, 28 of the photonic crystal 1 are known, it is also possible to deduce the gas component to be detected.
  • the concentration of this gas component can then be deduced from the degree of attenuation of the electromagnetic radiation emitted by the resonator 12, 13, 14, 28.
  • the Sensi tivity of the gas sensor 5 with respect to the gas component to be detected in this case depends largely on the quality of the Re ⁇ sonatoren 12, 13, 14, 28 from, in which the absorption of the light takes place. This quality can be by means of the so-called Q-factor ⁇ indicate which expresses how long the Electromagnetic radiation in the resonator 12, 13, 14, 28 is retained.
  • the gas sensor 5 described here thus uses optical properties of the photonic crystal 1, which consists of a regular array of structural elements or microstructures in the form of the bars 2 with deliberately introduced defects.
  • the band structure 6, 18 of the photonic crystal 1 has band gaps 11, 20.
  • the detector 55 is preferably in the form of the infrared radiation-sensitive and shown in FIG 15 detector array, which of the resonators 12, 13, 14, 28 emitted electromagnetic radiation detected. Since gas molecules in the resonators 12, 13, 14, 28 can reduce the intensity of the electromagnetic radiation emitted by the resonators 12, 13, 14, 28 due to absorption, the gas component and its concentration can be deduced from this reduction. In addition, by adjusting the layout and, in particular, continuously changing the temperature of the photonic crystal 1, different gas components can be simultaneously detected.
  • the concept of the gas sensor 5 described herein including ⁇ thus constitutes the use of gas open (micro) resonators 12, 13, 14, 28 in the photonic crystal 1, which - be ⁇ vorzugt groups - at defined, different wavelengths are in resonance.
  • the excitation and control of the corresponding resonance frequencies 15, 16, 17 of the resonators 12, 13, 14, 28 takes place by heating the photonic crystal 1 and due to the radiation resulting therefrom.
  • the detection of the radiated energy is effected by the sensitive to infrared radiation micro-detector elements in the form of columns 56, 57 of the detector 55, which are opposed to the respective Re ⁇ sonatoren 12, 13, 14, 28 associated.
  • the radiated energy of the undisturbed photonic crystal 1 can be determined for reference purposes.
  • the determination of the gas components is effected by the perception of the change in the detected intensity of the electromagnetic radiation emitted by the respective resonators 12, 13, 14, 28.
  • the size of the surface of the detector 55 facing the photonic crystal 1 preferably corresponds at least substantially to the size of the surface of the photonic crystal 1 facing the detector 55.
  • the very low energy consumption of the component 51 of the gas sensor 5 results inter alia from the fact that the infrared radiation emitted by the photonic crystal 1 is generated by thermal pumping. If infrared radiation in the single-digit micrometer range is used, temperatures ranging from 150 ° C. to 300 ° C. are sufficient to set the resonance frequencies 15, 16, 17 in the photonic crystal 1 in the region of the resonators 12, 13, 14, 28.
  • the detector 55 may be manufactured ⁇ det in particular as a passive, uncooled system, as so for the signal acquisition by means of the detector 55 no additional energy needs to be provided.
  • the detector 55 is coupled to a - particularly application-specific - integrated circuit (ASIC) for signal evaluation, it needs a certain amount of electrical energy for the supply.
  • ASIC application-specific - integrated circuit

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Abstract

L'invention concerne un capteur de gaz (5) pour la détection d'au moins un composant gazeux. Le capteur de gaz (5) comprend un cristal photonique (1) qui présente une multiplicité d'éléments structuraux (2) disposés périodiquement dans au moins une direction spatiale. Le cristal photonique (1) présente en outre au moins une imperfection, par laquelle au moins un résonateur (12) est formé pour le rayonnement électromagnétique d'une longueur d'ondes qui peut être absorbé par au moins un composant gazeux. Le capteur de gaz (5) comprend un détecteur (55), qui est constitué comme un élément constitutif différent du cristal photonique (1) et est réalisé pour détecter un rayonnement électromagnétique émis de l'au moins un résonateur (12). En outre, l'invention concerne un procédé de détection d'au moins un composant gazeux.
PCT/EP2014/058726 2013-05-10 2014-04-29 Capteur de gaz et procédé de détection d'au moins un composant gazeux WO2014180716A1 (fr)

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DE102013208603.2A DE102013208603A1 (de) 2013-05-10 2013-05-10 Gassensor und Verfahren zum Detektieren wenigstens einer Gaskomponente
DE102013208603.2 2013-05-10

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JP6355857B2 (ja) * 2015-03-09 2018-07-11 カリフォルニア・インスティテュート・オブ・テクノロジーＣａｌｉｆｏｒｎｉａ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｔｅｃｈｎｏｌｏｇｙ 中赤外ハイパースペクトル分光システム及び方法
RU2725011C1 (ru) * 2019-12-24 2020-06-29 Самсунг Электроникс Ко., Лтд. Сенсорное устройство для распознавания смесей летучих соединений и способ его изготовления

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DE102005008077A1 (de) * 2005-02-22 2006-08-31 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Strahler, sowie Vorrichtung und Verfahren zur Analyse der qualitativen und/oder quantitativen Zusammensetzung von Fluiden mit einem solchen Strahler
US7352466B2 (en) 2005-06-17 2008-04-01 Canon Kabushiki Kaisha Gas detection and photonic crystal devices design using predicted spectral responses
US20080252890A1 (en) * 2004-03-24 2008-10-16 Susumu Noda Target Substance Sensor and Method Thereof Using a Photonic Crystal
US7582910B2 (en) 2005-02-28 2009-09-01 The Regents Of The University Of California High efficiency light emitting diode (LED) with optimized photonic crystal extractor
DE102009043413B3 (de) * 2009-09-29 2011-06-01 Siemens Aktiengesellschaft Thermo-elektrischer Energiewandler mit dreidimensionaler Mikro-Struktur, Verfahren zum Herstellen des Energiewandlers und Verwendung des Energiewandlers
DE102010034428B3 (de) 2010-08-16 2011-12-15 Siemens Aktiengesellschaft Vorrichtung und System zur selektiven Detektion von Gaskomponenten oder von Konzentrationen von Gaskomponente in einem zu untersuchendem Gas und Verfahren zum Betrieb einer derartigen Vorrichtung

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JP4533044B2 (ja) * 2003-08-27 2010-08-25 キヤノン株式会社 センサ
ATE387624T1 (de) * 2004-09-27 2008-03-15 Hewlett Packard Development Co Photonisches kristallinterferometer
CN101458210B (zh) * 2007-12-12 2012-09-19 清华大学 折射率传感器

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WO2002086469A1 (fr) * 2001-04-21 2002-10-31 Universität Konstanz Detecteur de fluide et procede de detection d'un fluide
US20080252890A1 (en) * 2004-03-24 2008-10-16 Susumu Noda Target Substance Sensor and Method Thereof Using a Photonic Crystal
DE102005008077A1 (de) * 2005-02-22 2006-08-31 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Strahler, sowie Vorrichtung und Verfahren zur Analyse der qualitativen und/oder quantitativen Zusammensetzung von Fluiden mit einem solchen Strahler
US7582910B2 (en) 2005-02-28 2009-09-01 The Regents Of The University Of California High efficiency light emitting diode (LED) with optimized photonic crystal extractor
US7352466B2 (en) 2005-06-17 2008-04-01 Canon Kabushiki Kaisha Gas detection and photonic crystal devices design using predicted spectral responses
DE102009043413B3 (de) * 2009-09-29 2011-06-01 Siemens Aktiengesellschaft Thermo-elektrischer Energiewandler mit dreidimensionaler Mikro-Struktur, Verfahren zum Herstellen des Energiewandlers und Verwendung des Energiewandlers
DE102010034428B3 (de) 2010-08-16 2011-12-15 Siemens Aktiengesellschaft Vorrichtung und System zur selektiven Detektion von Gaskomponenten oder von Konzentrationen von Gaskomponente in einem zu untersuchendem Gas und Verfahren zum Betrieb einer derartigen Vorrichtung

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