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WO2008151349A1 - Détecteur pour détection de gaz - Google Patents

Détecteur pour détection de gaz Download PDF

Info

Publication number
WO2008151349A1
WO2008151349A1 PCT/AT2008/000216 AT2008000216W WO2008151349A1 WO 2008151349 A1 WO2008151349 A1 WO 2008151349A1 AT 2008000216 W AT2008000216 W AT 2008000216W WO 2008151349 A1 WO2008151349 A1 WO 2008151349A1
Authority
WO
WIPO (PCT)
Prior art keywords
sensor
organic
oxygen
layer
sensor according
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.)
Ceased
Application number
PCT/AT2008/000216
Other languages
German (de)
English (en)
Inventor
Georg Jakopic
Elke Kraker
Bernhard Lamprecht
Anja Haase
Christian Konrad
Stefan Köstler
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.)
Joanneum Research Forschungs GmbH
Original Assignee
Joanneum Research Forschungs GmbH
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 Joanneum Research Forschungs GmbH filed Critical Joanneum Research Forschungs GmbH
Publication of WO2008151349A1 publication Critical patent/WO2008151349A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/783—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour for analysing gases
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • 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
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7786—Fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/06—Illumination; Optics
    • G01N2201/062—LED's
    • G01N2201/0628—Organic LED [OLED]

Definitions

  • the invention is based on a sensor for detecting gases, in particular oxygen.
  • oxygen sensors that detect the partial pressure of oxygen in different environmental conditions and in different areas (e.g., heating systems, internal combustion engines, medical technology).
  • Fig. 1 shows the principle of an oxygen sensor operating by means of a zirconia probe.
  • the ceramic material zirconium oxide is a solid electrolyte and is suitable as an oxygen ion conductor. Within a certain temperature range, which depends on the doping of the zirconium oxide, it has the ability to incorporate oxygen ions in vacancies of the crystal lattice.
  • the oxygen ions are formed on a conductive contact layer, which is usually made of platinum.
  • the concentration of oxygen in a sample gas is thus crucial for the level of oxygen activity or the number of oxygen ions.
  • the basic structure of a sensor provides a solid electrolyte, which is contacted on both sides. One side of the electrolyte is filled with a reference gas, e.g.
  • Air operated the other side with sample gas.
  • the mechanical design of the sensor separates both gas sides from each other, so that a mixing of the gases is prevented.
  • heated or unheated sensors are used.
  • the oxygen partial pressure is measured by the voltage (electromotive force) tapped at the electrodes.
  • oxygen sensors are known which are based on the principle of a galvanic fuel cell for measuring the oxygen partial pressure.
  • the ambient atmosphere or the measurement gas diffuses through a synthetic membrane to a thin electrolyte layer to the cathode of the sensor.
  • the electrolyte, the cathode material and the composition of the anode, which consists mainly of lead, are designed so that oxygen that diffuses to the cathode is electrochemically reduced.
  • the anode material is oxidized. Since the cathode and anode of such sensors are electrically contacted, an ion current flows through the sensor. The corresponding electrical current corresponds to the oxygen partial pressure and can be measured in series by a resistor.
  • Oxygen sensors based on optical principles are also known.
  • laser light is reflected back and forth with the help of mirrors until it has traveled a total distance of about 1 meter.
  • the laser source used is a vertical cavity surface emitting laser (VSEL).
  • VSEL vertical cavity surface emitting laser
  • the VCSELs used emit light at a wavelength of 760 nm. At this wavelength oxygen absorbs and thus the molecule can be detected very sensitively.
  • fiber optic oxygen sensor are known.
  • the basic principle of the fiber optic oxygen sensor is a fluorescent probe with a thin film at the tip and a blue LED as the excitation source.
  • the sensor measures the absolute oxygen concentration via fluorescence measurement technology.
  • the light of the blue LED is brought to the thin film on the probe tip.
  • the excited fluorescence is reflected back and returned to the spectrometer via optical fibers.
  • a 550nm edge filter is incorporated. If oxygen diffuses into the gas to be measured or into the liquid, then the fluorescence goes out and the degree of extinction correlates directly with the oxygen concentration.
  • a disadvantage of conventional optically operating oxygen sensors is mainly that the light source, the detector (s) and the optical elements are discrete, comparatively large components which are assembled and held by mechanical or adhesive bonds. This means that such sensors can reach a considerable size and their production can be carried out only to a limited cost.
  • the object of the invention is thus to provide an integrated sensor which is small, lightweight and inexpensive.
  • a sensor which comprises an organic light emitting diode, a first polarizing filter, an organic fluorescent or phosphorescent layer, a second polarizing filter, and at least one organic photodiode.
  • the main advantage of using the polarization filter is the complete independence of the wavelength difference between excitation light and fluorescent light.
  • the difference may also be zero nanometers.
  • fluorescent dyes that have only a very small Stokes shift, but good detection properties, and their emission via conventional thin-film filter can not be separated sufficiently from the excitation, are used.
  • FIG. 1 is a schematic view of an oxygen sensor according to the prior art
  • FIG. 2 shows a schematic overall view of a sensor arrangement for use with an organic oxygen sensor designed according to the invention
  • FIG. 3 shows a schematic view of the arrangement of the polarization filters of an oxygen sensor according to the invention
  • 5 is a schematic representation of an organic light emitting diode for use with an inventively designed organic oxygen sensor
  • 6 shows a schematic representation of an organic photodiode for use with an organic oxygen sensor designed according to the invention
  • FIG. 7 shows a graphic illustration of a functional verification of an oxygen sensor designed according to the invention.
  • FIG. 8 shows a graphic illustration of the suppression of the excitation light in an oxygen sensor designed according to the invention.
  • a general arrangement of an inventively designed organic oxygen sensor 1 is shown schematically in Fig. 2.
  • a sensor, in particular an oxygen sensor 1 according to the subject invention basically comprises the following elements:
  • an organic light-emitting diode (oLED) 2 which supplies the light for the generation of the luminescence of the organic oxygen-sensitive dye, a wavelength separator 7, and
  • the wavelength separator 7 comprises the following subelements:
  • a polarization filter 3 which linearly polarizes the light emitted by the oLED 2
  • an organic fluorescent or phosphorescent layer 4 on which the lifetime of the luminescence depends on the partial pressure of oxygen to which the layer is exposed, and whose emitted luminescent light has a certain degree of depolarization, and a further polarization filter 5, the direction of which is crossed to the the first is and suppresses the linearly polarized excitation light light.
  • the organic light-emitting diode 2 is excited with a sinusoidally modulated voltage whose modulation frequency is adapted to the lifetime of the luminescence, as indicated on the left in FIG. 2.
  • a sinusoidal photocurrent or a sinusoidal photovoltage is also supplied by the organic photodiode 6, which has a phase shift ⁇ to the excitation voltage, as shown in Fig. 2 right.
  • the size of this phase shift ⁇ is essentially dependent on the luminescence lifetime of the organic dye in the layer 4 and thus on the oxygen partial pressure to be determined.
  • the oxygen sensor 1 can be coupled with a reading device, not shown further, which also takes over the power supply for the light-emitting diode 2.
  • the coupling of the oxygen sensor 1 to the reading device can be carried out inductively via electrical contacts or via a built-in oxygen sensor 1 high-frequency transmission part.
  • Fig. 3 the operating principle of the suppression of the excitation light by a suitable arrangement of polarizers 3, 5 in the wavelength separator 7 is shown schematically.
  • FIGS. 4A to 4D show highly schematically preferred embodiments of organic oxygen sensors designed according to the invention. In each case, a section through the layer structure of the oxygen sensor is shown.
  • a first embodiment of the subject invention according to FIG. 4A consists of an organic light-emitting diode 2, a substrate 8, a first polarizer 3, a first spacer 9, an active sensor layer 4, possibly a second spacer 10, a second polarizer 5, whose self-direction 90 ° with that of the first includes, and an organic photodiode 6, which detects the luminescence emitted by the active sensor layer 4 luminescent light.
  • a second embodiment of the subject invention according to FIG. 4B consists of an organic light-emitting diode 2, a substrate 8, a first polarizer 3, a first spacer 9, an active sensor layer 4, a second spacer 10, an edge filter 11 for suppressing the excitation light second polarizer 5, whose self-direction includes 90 ° with that of the first, and an organic photodiode 6, which detects the luminescence emitted from the active layer 4 luminescent light.
  • 4C consists of an organic light emitting diode 2, a substrate 8, a first polarizer 3, a first spacer 9, an active sensor layer 4, possibly a second spacer 10, a first organic photodiode 12 for detecting the Excitation light with a certain transparency for the emitted luminescent light, a second polarizer 5, whose self-direction includes 90 ° with that of the first, and a second organic photodiode 6, which detects the luminescence emitted from the active layer 4 luminescence.
  • a fourth embodiment of the subject invention according to FIG. 4D consists of an organic light-emitting diode 2, a substrate 8, a first polarizer 3, a first spacer 9, an active sensor layer 4, possibly a second spacer 10, a first organic photodiode 12 for detecting the Excitation light with a certain transparency for the emitted luminescent light, an edge filter 11 for suppressing the excitation light, a second polarizer 5 whose self-direction includes 90 ° with that of the first, and a second organic photodiode 6, which detects the luminescence emitted from the active layer luminescence.
  • the spacer (s) 9, 10 according to FIGS. 4A to 4D can cover all or part of the surface of the substrate 8. If the lateral possibility for lateral diffusion is sufficient, the spacers 9, 10 can also be dispensed with.
  • each of the layers described may completely or partially cover the cross-section.
  • the invention contains as light source an organic light-emitting diode 2, which is shown by way of example in FIG.
  • the organic light-emitting diode 2 is manufactured in sandwich structure.
  • One or more organic thin films are contacted by two electrically conductive electrodes 13, 14.
  • the organic light emitting diode 2 typically consists of a hole and an electron transport layer (HTL and ETL).
  • HTL and ETL electron transport layer
  • para-hexaphenyl can be used as the emitter material and N, N-diphenyl-N, N '- (3-methylphenyl) -1,1'-biphenyl-4 as a hole transport layer , 4'-diamines are used.
  • the invention contains an organic luminescent layer 4, which is applied by suitable methods (eg spin coating, dip coating, knife coating, curtain coating or vapor deposition) and the luminescence lifetime is a sufficiently strong function of the oxygen partial pressure, the Layer 4 is exposed for detection.
  • suitable methods eg spin coating, dip coating, knife coating, curtain coating or vapor deposition
  • the invention includes at least one organic photodiode 6, 12 for detecting the emitted fluorescent light or the excitation light, which is shown schematically in Fig. 6.
  • the organic photodiode 6, 12 is manufactured in sandwich structure.
  • One or more organic thin films are contacted by two electrically conductive electrodes 15, 16.
  • the starting point for the fabrication of the photodiode 6, 12 is, for example, a glass substrate 17.
  • various structuring methods such as photolithography, electron beam lithography, FIB (focused ion beam) or lift-off technique can be used.
  • the application of the organic and metallic thin films 18 takes place e.g. by vacuum sublimation in corresponding evaporator systems or by spincoats or inkjet printers of polymer materials.
  • FIG. 6 shows a possible embodiment which contains silver or gold as electrode materials and as organic thin films 18 the semiconductors 3,4,9,10-perylenetetracarboxylic bis-benzimidazoles and copper phthalocyanine.
  • the maximum of the spectral sensitivity of this cell is about 615 nm.
  • Other possible active materials are as p-type semiconductors: ZnPc, CuPc, pentacene, PTCDA, TPD and as n-type semiconductors: perylene derivatives (PTCBI, MPP), FCuPc.
  • the organic semiconductors are chosen so that the maximum of the photocurrent sensitivity coincides with the maximum of the intensity of the light to be detected.
  • the invention includes one or more polarizers 3, 5, embodied either as film polarizers to which the adjacent elements are suitably connected (eg by lamination or gluing with optical glue), or to the neighboring elements as Dünn harshpolarisatoren be applied, using any technique that ensures both the desired polarization properties and the elements to which the polarizers 3, 5 are applied, not damaged, can be used.
  • the invention may include one or more spacers 9, 10 unless lateral diffusion into the organic luminescent layer is sufficient.
  • the spacers 9, 10 are designed or structured in such a way that they allow the oxygen to enter and exit the organic luminescence layer without impairing the optical function of the oxygen sensor 1.
  • Tab. 1 shows the exact values for the voltage at the organic photodiode 6 (oPD) and the phase shift between the excitation voltage of the organic light-emitting diode (SD) 2 and the photovoltage:
  • the light source used was an organic light-emitting diode 2 with a maximum of the emission wavelength at 400 nm. The maximum lower two curves reflect the emission in air, the maximum upper curves when flushing the sensor layer 4 with carbon dioxide.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pathology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Molecular Biology (AREA)
  • Optics & Photonics (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Polarising Elements (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

Détecteur (1), en particulier détecteur d'oxygène, pour la détection d'oxygène gazeux ou dissous, caractérisé en ce qu'il comprend une diode électroluminescente organique (2), un premier filtre de polarisation (3), une couche fluorescente ou phosphorescente organique (4), un second filtre de polarisation (5), et au moins une photodiode organique (6, 12).
PCT/AT2008/000216 2007-06-14 2008-06-13 Détecteur pour détection de gaz Ceased WO2008151349A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT9262007A AT505337B1 (de) 2007-06-14 2007-06-14 Sensor zur detektion von gasen
ATA926/2007 2007-06-14

Publications (1)

Publication Number Publication Date
WO2008151349A1 true WO2008151349A1 (fr) 2008-12-18

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ID=39943013

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT2008/000216 Ceased WO2008151349A1 (fr) 2007-06-14 2008-06-13 Détecteur pour détection de gaz

Country Status (2)

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AT (1) AT505337B1 (fr)
WO (1) WO2008151349A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5157262A (en) * 1986-04-23 1992-10-20 Avl Medical Instruments Ag Sensor element for determination of concentration of substances
US6107083A (en) * 1998-08-21 2000-08-22 Bayer Corporation Optical oxidative enzyme-based sensors
WO2001038857A1 (fr) * 1999-11-24 2001-05-31 Iowa State University Research Foundation, Inc. Capteurs optiques et groupements de capteurs optiques contenant des dispositifs electroluminescents en couche mince
US20020042174A1 (en) * 1999-01-05 2002-04-11 Yoshihito Kunugi Vapochromic LED
US20020173040A1 (en) * 2001-04-04 2002-11-21 Potyrailo Radislav Alexandrovich Chemically-resistant sensor devices, and systems and methods for using same
US20030023181A1 (en) * 2001-07-26 2003-01-30 Mault James R. Gas analyzer of the fluorescent-film type particularly useful for respiratory analysis
WO2005015173A1 (fr) * 2003-06-17 2005-02-17 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Capteurs comprenant des composants en polymere

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5157262A (en) * 1986-04-23 1992-10-20 Avl Medical Instruments Ag Sensor element for determination of concentration of substances
US6107083A (en) * 1998-08-21 2000-08-22 Bayer Corporation Optical oxidative enzyme-based sensors
US20020042174A1 (en) * 1999-01-05 2002-04-11 Yoshihito Kunugi Vapochromic LED
WO2001038857A1 (fr) * 1999-11-24 2001-05-31 Iowa State University Research Foundation, Inc. Capteurs optiques et groupements de capteurs optiques contenant des dispositifs electroluminescents en couche mince
US20020173040A1 (en) * 2001-04-04 2002-11-21 Potyrailo Radislav Alexandrovich Chemically-resistant sensor devices, and systems and methods for using same
US20030023181A1 (en) * 2001-07-26 2003-01-30 Mault James R. Gas analyzer of the fluorescent-film type particularly useful for respiratory analysis
WO2005015173A1 (fr) * 2003-06-17 2005-02-17 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Capteurs comprenant des composants en polymere

Also Published As

Publication number Publication date
AT505337A1 (de) 2008-12-15
AT505337B1 (de) 2009-08-15

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