THE LABORATORY OF CHEMISTRY AND PHYSICS OF SENSOR AND SEMICONDUCTOR MATERIALS

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Materials for sensors

Gaskov Alexander
e-mail: gaskov@inorg.chem.msu.ru
phone: +7 ( 495) 939-54-71

Nanocrystalline materials based on metal oxides for the detection of toxic and hazardous gases in the air.

For centuries, mankind has created a variety of machines to enhance its features. Created devices for spacecraft missions to other planets , submarines to swim under water , people have learned to see in the dark , consider the stars through a telescope and the smallest particles in the microscope . However, in the field of artificial olfaction progress is still quite modest . Not yet created a device which would be able to compete in their sensitivity and selectivity with the dog's nose , which domesticated still in its infancy and continues to use to this day. Meanwhile , the environment is becoming more aggressive , we live in a manmade gases emissions , the risk of leakage of natural gas , which is let down in almost every home . It should be noted that the major air pollutants , even as simple as carbon monoxide, nitrogen oxides , ammonia , hydrogen sulfide is toxic at the concentration unit in a million molecules . All this requires the creation of highly miniaturized , highly sensitive and selective " electronic noses " for early warning of the presence in the air of toxic or explosive gases .

sensorovEst material group hopes that the new materials developed at the Faculty of Chemical laboratory "Chemistry and physics of semiconductor and sensor materials " will substantially increase the artificial olfaction. The basis of such materials are semiconductor nanoparticles : tin oxide , indium or tungsten . Such a particle size between 3 and 10 nanometers are interesting because they have excellent ability to adsorb the molecules of the environment and to transmit information about the amount of adsorbed gases in the form of an electrical signal. Such properties of semiconductor surfaces have been known for a long time , but the main problem that needs to be solved is how to teach particle recognize dangerous molecules , amid a large number of substances is safe . TEM image of nanocrystalline oxide olovaChelovek this purpose uses a variety of chemical and biological receptors to identify the nature of pleasant and unpleasant odors.группа материалов для сенсоров

Our laboratory has developed a technology of chemical modification of nanoparticles of semiconductors, grafting on the surface of synthetic receptors for directional change their reactivity . These receptors can be not only well-known clusters catalysts of platinum group metals or metal oxides , but also organic receptors on the basis of new macrocyclic compounds synthesized at the Chemistry Faculty . We succeeded in synthesizing modified nanoparticles and show that the nature of the receptors determines the specificity of the material, its ability to respond selectively to one or a group of dangerous gases.

ПЭМ изображение нанокристаллического оксида олова sensing application layer microelectronic chipPonyatno that enough for practical use to synthesize a compound , it is necessary to learn to carry it on a microelectronic chip , a special substrate with electrical contact system and heater. Such microelectronic device developed by specialists of the Kurchatov Institute , they provide the desired mode for sensor and largely responsible for its performance.

A microelectronic chip , with the sensitive element on the basis of chemically modified nanoparticle is a key element of the gas detector . Several microelectronic chips based nanoparticles with different receptors that are configured for the detection of different molecules can be combined in one detector for analyzing gas mixtures. Such detectors based on 4 microelectronic chips created in cooperation with specialists from Tomsk enterprises " Senseriya " to analyze the major air pollutants and for medical purposes to analyze patients exhalation .

Sensitivity detectors based on semiconductor nanoparticles can greatly increase , if you learn how to preallocate and concentrate hazardous gases. This new direction of the laboratory , together with our colleagues from the laboratory kinetics and catalysis , which are developing special adsorbents created highly sensitive multichannel detectors , in which each channel is set to extraction, concentration andнанесение чувстивтельного слоя на микроэлектронный чип measurement of a certain group of toxic gases.

cooperation (for more info click here )

  •     Federal State Institution Russian Research Center "Kurchatov Institute ", Moscow ( Russian Research Center "Kurchatov Institute" )
  •     State Educational Institution of Higher Professional Education "Moscow Engineering Physics Institute (State University)" (MEPI )
  •     Institute of General and Inorganic Chemistry ( General and Inorganic Chemistry RAS)
  •     Research Institute of Electronic Technology ( NIIET ) , Voronezh
  •     Senseriya , Tomsk
  •     Analyzing Systems LLC , Moscow
  •     Scientific and Technical Center of Measurement gazochuvstvitelnyh sensors Lubertsy
  •     Istituto Nazionale per la Fisica della Materia Consiglio Nazionale delle Ricerche (INFM), Brescia, Italy
  •     Catalonia Institute for Energy Research (IREC), Barcelona, ​​Spain
  •     IPC University of Tuebingen (EKUT), Tubingen, Germany
  •     University of Koeln (UNIKO), Cologne, Germany
  •     EADS Deutschland GmbH - Innovation Works (EADS), Munich, Germany

projects (for more info click here)

RFBR 12 -03- 00524_a " The effect of light on the reactivity of nanocrystalline metal oxides coated with quantum dots" ( 2012 - 2014 )


  The project aims to create nanocomposites based on nanocrystalline oxide semiconductor sensitized nanocrystals (quantum dots) CdSe and study their interactions with the gas phase under irradiation with light. Fundamental objectives of the project are : (i) development of methods for the directed synthesis of sensitized materials with controlled crystallite size of 3-20 nm semiconductor matrix and CdSe nanocrystals with size 2-6 nm; (ii) the establishment of patterns of influence of irradiation with light in the visible spectrum on the electrical properties and reactivity of nanocomposites by reacting with oxygen and major air pollutants.

State . FTSTP contract № 11.519.11.1009 on " nanoheterogeneeous filamentary materials based on oxide semiconductor chemical sensors" (2012 - 2013 )


State . FTSTP contract № 11.519.11.6047 on " Create photo and gas sensing nanocomposites based on nanocrystalline oxide semiconductor sensitized A2B6 quantum dots " (2012 - 2013 )

 

Wide bandgap semiconductors nanocrystals obtained SnO2, In2O3 and ZnO and narrow-gap CdTe and CdSe, of interest to create a sensitized materials. The technique of immobilization of quantum dots and nanocomposites obtained photosensitive SnO2/CdSe and ZnO/CdSe. Such materials can be used for gas sensors operating without heating at room temperature under light conditions . The presence of a sensitizer in semiconductor oxides emission diodes allow the use of low power to achieve the following objectives : lowering the resistance of materials, initiate chemical reactions of molecules detected gas from the semiconductor surface, the desorption of the reaction products without thermal heating at room temperature.

 

State . FTSTP contract № 11.519.11.1009 on " Nanoheterogeneeous filamentary materials based on semiconducting oxides for chemical sensors " (2012 - 2013 )

 

New materials , which are whisker SnO2 and ZnO n-type conductivity , which is immobilized on the surface of clusters of CuO (PdO) p-type conductivity. Such materials have a high specific surface area, high adsorption capacity and the electrical properties depend strongly on the composition of the atmosphere. The presence of pn junctions significantly reduces the flow channel dimensions of the charge carriers in the filaments and gives hope for a high sensitivity to the presence of materials nanoheterogeneeous air gas molecules oxidants or reducing agents.

 

RFBR 12 -03- 12001_ofi_m "Creating chemically hazardous gas detectors organophosphorus and nitrogen-containing substances on the basis of selective nanocrystalline semiconductors and molecular sieve hubs " (2012 - 2013 )

 

  The project aims to develop methods of detecting hazardous products in the air based on the technology of combining semiconductor detectors with preconcentration of target molecules on molecular sieves . Methods have been developed and synthesized nanocrystalline semiconducting metal oxides , are chemically modified catalytic clusters having selectivity to organophosphorus and nitrogen - containing molecules. Synthesis of nanocrystalline oxides SnO2, In2O3, ZnO with a crystallite size controlled in the range of 3-20 nm performed by chemical vapor deposition from colloidal solutions . Catalytic clusters Au, PtO2, PdO, RuO2, CuO, NiO supported on the surface of the semiconductor matrix during synthesis or nanocrystalline oxide by an impregnation method . For selective concentration of target gases complex synthesized mesoporous aluminosilicates ( zeolite analogues ) with different pore structure with a system of controlled pore diameter from 30 A to 5.5 A. The properties of the materials of sensor measurements are carried out on the bench for a fully automated detection of H2S and NH3. As used organophosphorus desired product dimethylmethylphosphonate (DMMP), a nitrogen-containing substance used as unsymmetrical dimethylhydrazine (UDMH) .

Designed and developed by the laboratory stand , which allows to control the concentration of the target gas in the air in the range of 20 ppb - 2 ppm.

A laboratory prototype multisensor system with preconcentration of target gases , which has been tested at 100 ppb DMMP detection and 0.1mg/m3 UDMH .

 

RFBR 12 -03- and - 31446_mol " Active sites on the surface of nanocrystalline metal oxides and the specificity of their interaction with nitrogen-containing organic compounds " (2012 - 2013 )

  For the synthesis of nanocomposites based on nanocrystalline SnO2 impregnation techniques used (including wetness ) , chemical methods " prishivki " modifier covalent bond. Selected synthesis methods allow to control the composition and content of the resulting materials used modifiers (SiO2, Al2O3, Cr2O3, Nb2O5, Au). The resulting nanocomposites were characterized complex techniques - XRD, BET , TPR - H2, TPD -NH3. Composition highly sensitive materials identified by elemental analysis, - an X-ray fluorescence spectrometry for total internal reflection. Characterized by electrical and sensory properties of materials. Shown that the system SnO2-SiO2 method " prishivki " organic precursor to the surface modifier can effectively control the quantitative composition of the resulting samples. It was found that the growth of the content up to 3 % SiO2 by weight. samples simultaneously with increasing the heat treatment temperature to 700 ° C accompanied by increased sensitivity to touch SB .


RFBR 11 -03- 12111_ofi " Photoconductivity and sensory properties of nanocomposites based on hybrid semiconductor matrix sensitized with quantum dots and organometallic compounds " ( 2011 - 2012)

  The project with a wide range of modern physico-chemical methods established structure of hybrid organic -inorganic nanostructured materials . First conducted a systematic study of the influence of organic complexes of copper (II) by the amount of sensory response of tin dioxide in the gas phase . It is shown that administration of these modifiers results in an increase SnO2 sensor response with respect to H2S and ethanol vapor in air. It was shown that the formation of a semi-permeable silicone matrix structure on the surface of SnO2 significantly alters sensory characteristics of tin dioxide . Record values ​​obtained sensor response to NO2 at the maximum allowable concentrations ( <100 ppb in air) . It is shown that immobilized crown arilnaftalimidov N- derivatives on the surface of single crystals of SnO2 affords systems which are sensitive to cations Mg2+ and Ca2+ ions in solution. The technique allows to immobilize molecules fluorophores without loss of chemosensory properties.

   Coordinate projects with the framework research program EC and Russia «Surface ionization and novel concepts in nano-MOX gas sensors with increased Selectivity, Sensitivity and Stability for detection of low concentrations of toxic and explosive agents CP-FP 247768 S3 / 02.527.11.0008.» (2009 - 2012)
 
Development and testing of multi- gas detectors of new generation, including semiconductor sensors , combined with the systems of the pre-separation and concentration of molecules on the basis of new chemically modified nanocrystalline metal oxides with high selective sensitivity to toxic and explosive products in the air , including CO, NO2, H2S and NH3.We're sorry, but this page is under construction.


сенсор

Recent pubs

  • N. Vorobyeva, M. Rumyantseva, D. Filatova, E. Konstantinova, D. Grishina, A. Abakumov, S. Turner, A. Gaskov. Nanocrystalline ZnO(Ga): Paramagnetic centers, surface acidity and gas sensor properties. Sens. Actuators B, 2013, v. 182, p. 555 - 564.
  • A.A. Zhukova, M.N. Rumyantseva, V.B. Zaytsev, A.V. Zaytseva, A.M. Abakumov, A.M. Gaskov. Pd nanoparticles on SnO2(Sb) whiskers: Aggregation and reactivity in CO detection. J. Alloys and Compounds, 2013, v. 565, p. 6–10.
  • F.Shao, M.W.G. Hoffmann, J.D. Prades, R.Zamani, J. Arbiol, J.R. Morante, E. Varechkina, M. Rumyantseva, A. Gaskov, I. Giebelhaus, T. Fischer, S. Mathur, F. Hernández-Ramírez. Heterostructured p-CuO (nanoparticle)/n-SnO2 (nanowire) devices for selective H2S detection. Sens. Actuators B, 2013, v. 181, p. 130-135.
  • V. Krivetskiy, M. Rumyantseva, A. Gaskov. Design, synthesis and application of metal oxide based sensing elements: A chemical principles approach. In Metal Oxide Nanomaterials for Chemical Sensors, Integrated Analytical Systems. Springer Science+Business Media New York, 2013. p. 69-116.
  • D.D. Frolov, Y.N. Kotovshchikov, I.V. Morozov, A.I. Boltalin, A.A. Fedorova, A.V. Marikutsa, M.N. Rumyantseva, A.M. Gaskov, E.M. Sadovskaya, A.M. Abakumov. Oxygen exchange on nanocrystalline tin dioxide modified by palladium. J. Solid State Chem., 2012, v. 186, p. 1-8.
  • A. Marikutsa, V. Krivetskiy, L. Yashina, M. Rumyantseva, E. Konstantinova, A. Ponzoni, E. Comini, A. Abakumov, A. Gaskov. Catalytic impact of RuOx clusters to high ammonia sensitivity of tin dioxide. Sens. Actuators B, 2012, v. 175, p. 186–193.
  • A.V. Zaytseva, V.B. Zaytsev, M.N. Rumyantseva, A.M. Gaskov, A.A. Zhukova. SnO2 whiskers with Pd nanoparticles for gas sensor applications. J. f Nanoelectronics and Optoelectronics, 2012, v. 7(6), p. 607–613.
  • Е.А. Форш, А.В. Марикуца, М.Н. Мартышов, П.А. Форш, М.Н. Румянцева, А.М. Гаськов, П.К. Кашкаров. Исследование чувствительности нанокристаллического оксида индия с различными размерами нанокристаллов к диоксиду азота. Российские нанотехнологии, 2012, т. 7(3-4), с. 87–90.
  • V.V. Krivetsky, D.V. Petukhov, A.A. Eliseev, A.V. Smirnov, M.N. Rumyantseva, A.M. Gaskov. Acetone Sensing by Modified SnO2 Nanocrystalline Sensor Materials. In NANOTECHNOLOGICAL BASIS FOR ADVANCED SENSORS. NATO Science for Peace and Security Series B: Physics and Biophysics, 2011, Chapt. 42, p. 409-421.
  • A.A. Zhukova, M.N. Rumyantseva, V.B. Zaytsev, J. Arbiol, L. Calvo-Barrio, A.M. Gaskov. Tin Oxide Whiskers: Antimony Effect on Structure, Electrophysical, Optical and Sensor Properties. In NANOTECHNOLOGICAL BASIS FOR ADVANCED SENSORS. NATO Science for Peace and Security Series B: Physics and Biophysics, 2011, Chapt. 32, p. 287-303.
  • E.A. Konstantinova, I.S. Pentegov, A.V. Marikutsa, M.N. Rumyantseva, A.M. Gaskov, P.K. Kashkarov. EPR study of nanocrystalline tin dioxide. Physica status solidi (с), 2011, v. 8(6), p. 1957-1960.
  • A.P. Kazin, M.N. Rumyantseva, V.E. Prusakov, I.P. Suzdalev, A.M. Gaskov. Nanocrystalline ferrites NixZn1−xFe2O4: Influence of cation distribution on acidic and gas sensing properties. J. Solid State Chem., 2011, v. 184, p. 2799-2805.
  • A.V. Marikutsa, M.N. Rumyantseva, A.M. Gaskov, E.A. Konstantinova, D.A. Grishina, D.M. Deygen. CO and NH3 sensor properties and paramagnetic centers of nanocrystalline SnO2 modified by Pd and Ru. Thin Solid Films, 2011, v. 520, p. 904 – 908.
  • M.N. Martyshov, E.A. Forsh, A.V. Marikutsa, P.A. Forsh, M.N. Rumyantseva, A.M. Gaskov, P.K. Kashkarov. Influence of In2O3 nanocrystals size on the sensitivity to NO2. J. Nanoelectron. Optoelectron. 2011, v. 6(4), p. 452-455
  • С.М. Бадалян, М.Н. Румянцева, С.А. Николаев, А.В. Марикуца, В.В. Смирнов, А.С. Алиханян, А.М. Гаськов. Влияние катализаторов Au и NiO на сенсорные свойства нанокристаллического SnO2 по отношению к NO2. Неорган. материалы, 2010, т. 46(3), с. 278-283.
  • A.V. Marikutsa, M.N. Rumyantseva, L.V. Yashina, A.M. Gaskov. Role of surface hydroxyl groups in promoting room temperature CO sensing by Pd-modified nanocrystalline SnO2. J. Solid State Chem., 2010, v. 183 p. 2389–2399.
  • V. Krivetskiy, A. Ponzoni, E. Comini, S. Badalyan, M. Rumyantseva, A. Gaskov. Selectivity Modification of SnO2-Based Materials for Gas Sensor Arrays. Electroanalysis, 2010, vol. 22, No. 23, p. 2809 – 2816


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