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Thin films for indoor air monitoring: Measurements of Volatile Organic Compounds
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Physics.
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Volatile organic compounds (VOCs) in the indoor air have adverse effects on the dwellers residing in a building or a vehicle. One of these effects is called sick building syndrome (SBS). SBS refers to situations in which the users of a building develop acute health effects and discomfort depending on the time they spend inside some buildings without having any specific illness. Furthermore, monitoring volatile organic compounds could lead to early diagnosis of specific illnesses through breath analysis. Among those VOCs formaldehyde, acetaldehyde can be listed.

In this thesis, VOC detecting thin film sensors have been investigated. Such sensors have been manufactured using semiconducting metal oxides, ligand activated gold nanoparticles and Graphene/TiO2 mixtures. Advanced gas deposition unit, have been used to produce NiO thin films and Au nanoparticles. DC magnetron sputtering has been used to produce InSnO and VO2 thin film sensors. Graphene/TiO2 sensors have been manufactured using doctor-blading.

While presenting the results, first, material characterization details are presented for each sensor, then, gas sensing results are presented. Morphologies, crystalline structures and chemical properties have been analyzed using scanning electron microscopy, X-ray diffraction and X-ray photo electron spectroscopy. Furthermore, more detailed analyses have been performed on NiO samples using extended X-ray absorption fine structure method and N2 adsorption measurements. Gas sensing measurements were focused on monitoring formaldehyde and acetaldehyde. However, responses ethanol and methane were measured in some cases to monitor selectivity. Graphene/TiO2 samples were used to monitor NO2 and NH3. For NiO thin film sensors and Au nano particles, fluctuation enhanced gas sensing is also presented in addition to conductometric measurements. 

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2016. , 78 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1422
Keyword [en]
gas sensor, thin film, adcanced gas depostion, sputter deposition, nickel oxide, gold nanoparticles, indium tin oxide, acetaldehyde, formaldehyde
National Category
Nano Technology
Identifiers
URN: urn:nbn:se:uu:diva-302558ISBN: 978-91-554-9683-8 (print)OAI: oai:DiVA.org:uu-302558DiVA: diva2:958138
Public defence
2016-10-21, Room Å2001, Ångströmlaboratoriet, Lägerhyddsv 1, 13:15 (English)
Opponent
Supervisors
Funder
EU, FP7, Seventh Framework Programme, 267234
Available from: 2016-09-28 Created: 2016-09-06 Last updated: 2016-10-14Bibliographically approved
List of papers
1. Porous Nickel Oxide Film Sensor for Formaldehyde
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2014 (English)In: INERA Workshop: Transition Metal Oxides as Functional Layers in Smart windows and Water Splitting Devices / Parallel session of the 18th International School on Condensed Matter Physics, 2014, UNSP 012012- p.Conference paper, Published paper (Refereed)
Abstract [en]

Formaldehyde is a volatile organic compound and a harmful indoor pollutant contributing to the "sick building syndrome". We used advanced gas deposition to fabricate highly porous nickel oxide (NiO) thin films for formaldehyde sensing. The films were deposited on Al2O3 substrates with prefabricated comb-structured electrodes and a resistive heater at the opposite face. The morphology and structure of the films were investigated with scanning electron microscopy and X-ray diffraction. Porosity was determined by nitrogen adsorption isotherms with the Brunauer-Emmett-Teller method. Gas sensing measurements were performed to demonstrate the resistive response of the sensors with respect to different concentrations of formaldehyde at 150 degrees C.

Series
Journal of Physics Conference Series, ISSN 1742-6588 ; 559
National Category
Engineering and Technology
Identifiers
urn:nbn:se:uu:diva-237084 (URN)10.1088/1742-6596/559/1/012012 (DOI)000346420600012 ()
Conference
INERA Workshop on Transition Metal Oxides as Functional Layers in Smart windows and Water Splitting Devices / Parallel session of the 18th International School on Condensed Matter Physics, sep 4-6, 2014, Varna, Bulgaria
Available from: 2014-11-26 Created: 2014-11-26 Last updated: 2016-10-14Bibliographically approved
2. Nickel oxide thin film sensor for fluctuation-enhanced gas sensing of formaldehyde
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2015 (English)In: 2015 IEEE Sensors, 2015Conference paper, Published paper (Refereed)
Abstract [en]

Nanocrystalline nickel-oxide-based thin films were prepared by advanced reactive gas deposition, and the response of these films to formaldehyde was studied by fluctuation-enhanced sensing. Morphological and structural analyses showed porous deposits of nickel oxide particles with face-centered cubic structure. Resistance fluctuations were measured upon exposure to ethanol, formaldehyde and methane at 200 degrees C. Power density spectra were used to quantify the response. The response to formaldehyde was higher than to ethanol at 200 degrees C, and no significant response was observed for methane thus demonstrating some gas-species selectivity.

Keyword
nickel oxide; formaldehyde; gas sensor; fluctuation-enhanced sensing; gas evaporation
National Category
Materials Engineering
Identifiers
urn:nbn:se:uu:diva-268295 (URN)10.1109/ICSENS.2015.7370408 (DOI)000380440800240 ()9781479982035 (ISBN)
Conference
IEEE Sensors Conference, Busan, Korea, November 1-4
Available from: 2015-12-03 Created: 2015-12-03 Last updated: 2016-12-07Bibliographically approved
3. Characterization of porous Nickel Oxide Films produced with Advanced Reactive Gas Deposition
Open this publication in new window or tab >>Characterization of porous Nickel Oxide Films produced with Advanced Reactive Gas Deposition
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(English)Manuscript (preprint) (Other academic)
National Category
Engineering and Technology
Identifiers
urn:nbn:se:uu:diva-302552 (URN)
External cooperation:
Available from: 2016-09-06 Created: 2016-09-06 Last updated: 2016-09-20
4. Fluctuation-enhanced and conductometric gas sensing with nanocrystalline NiO thin films: A comparison
Open this publication in new window or tab >>Fluctuation-enhanced and conductometric gas sensing with nanocrystalline NiO thin films: A comparison
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(English)Article in journal (Refereed) Submitted
National Category
Engineering and Technology
Identifiers
urn:nbn:se:uu:diva-302553 (URN)
External cooperation:
Available from: 2016-09-06 Created: 2016-09-06 Last updated: 2016-09-20
5. Sputter-Deposited Indium-Tin Oxide Thin Films for Acetaldehyde Gas Sensing
Open this publication in new window or tab >>Sputter-Deposited Indium-Tin Oxide Thin Films for Acetaldehyde Gas Sensing
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2016 (English)In: Coatings, ISSN 2079-6412, Vol. 6, no 2, 19Article in journal (Refereed) Published
Abstract [en]

Reactive dual-target DC magnetron sputtering was used to prepare In-Sn oxide thin films with a wide range of compositions. The films were subjected to annealing post-treatment at 400 degrees C or 500 degrees C for different periods of time. Compositional and structural characterizations were performed by X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, Rutherford backscattering and scanning electron microscopy. Films were investigated for gas sensing at 200 degrees C by measuring their resistance response upon exposure to acetaldehyde mixed with synthetic air. We found that the relative indium-to-tin content was very important and that measurable sensor responses could be recorded at acetaldehyde concentrations down to 200 ppb, with small resistance drift between repeated exposures, for both crystalline SnO2-like films and for amorphous films consisting of about equal amounts of In and Sn. We also demonstrated that it is not possible to prepare crystalline sensors with intermediate indium-to-tin compositions by sputter deposition and post-annealing up to 500 degrees C.

Keyword
indium tin oxide, magnetron sputtering, gas sensor, acetaldehyde
National Category
Materials Engineering
Identifiers
urn:nbn:se:uu:diva-299731 (URN)10.3390/coatings6020019 (DOI)000378428700006 ()
Funder
EU, FP7, Seventh Framework Programme, 267234
Available from: 2016-07-26 Created: 2016-07-26 Last updated: 2017-11-28Bibliographically approved
6. Fabrication of ultra-pure gold nanoparticles capped with dodecanethiol for Schottky-diode chemical gas sensing devices
Open this publication in new window or tab >>Fabrication of ultra-pure gold nanoparticles capped with dodecanethiol for Schottky-diode chemical gas sensing devices
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2017 (English)In: Sensors and actuators. B, Chemical, ISSN 0925-4005, E-ISSN 1873-3077, Vol. 239, 455-461 p.Article in journal (Refereed) Published
Abstract [en]

Ultra-pure monolayer-capped gold nanoparticles for chemical gas sensing devices were prepared by a novel two-step process: a physical vapour deposition technique was first employed to make dispersed ultra-pure size-controlled gold nanoparticles, and this step was followed by a coating process for functionalization of the gold nanoparticles with an organic ligand, specifically dodecanethiol. X-ray photoelectron spectroscopy proved that the nano-assemblies had high purity. Chemical sensing devices based on these nano-assemblies showed Schottky-diode behaviour. We believe this is the first observation of Schottky-diodes fabricated from nanomaterials based on metallic nanoparticles. Gas sensing experiments demonstrated that these devices were suitable for detecting volatile organic compounds.

National Category
Engineering and Technology Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-302548 (URN)10.1016/j.snb.2016.07.182 (DOI)000388951300056 ()
Funder
EU, FP7, Seventh Framework Programme, 267234
Available from: 2016-09-06 Created: 2016-09-06 Last updated: 2017-09-28Bibliographically approved
7. Fluctuation-enhanced sensing with organically functionalized gold nanoparticle gas sensors targeting biomedical applications
Open this publication in new window or tab >>Fluctuation-enhanced sensing with organically functionalized gold nanoparticle gas sensors targeting biomedical applications
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2016 (English)In: Talanta: The International Journal of Pure and Applied Analytical Chemistry, ISSN 0039-9140, E-ISSN 1873-3573, Vol. 160, 9-14 p.Article in journal (Refereed) Published
Abstract [en]

Detection of volatile organic compounds is a useful approach to non-invasive diagnosis of diseases through breath analysis. Our experimental study presents a newly developed prototype gas sensor, based on organically-functionalized gold nanoparticles, and results on formaldehyde detection using fluctuation-enhanced gas sensing. Formaldehyde was easily detected via intense fluctuations of the gas sensor's resistance, while the cross-influence of ethanol vapor (a confounding factor in exhaled breath, related to alcohol consumption) was negligible.

Keyword
Organically-functionalized gold nanoparticles; Formaldehyde detection; Fluctuation enhanced sensing; Flicker noise
National Category
Chemical Engineering
Identifiers
urn:nbn:se:uu:diva-302550 (URN)10.1016/j.talanta.2016.06.063 (DOI)000383524400002 ()27591581 (PubMedID)
Funder
EU, European Research Council, 267234
Available from: 2016-09-06 Created: 2016-09-06 Last updated: 2017-11-21Bibliographically approved
8. Resistive gas sensors – Perspectives on selectivity and sensitivity improvement
Open this publication in new window or tab >>Resistive gas sensors – Perspectives on selectivity and sensitivity improvement
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2016 (English)Conference paper, Published paper (Refereed)
National Category
Engineering and Technology
Identifiers
urn:nbn:se:uu:diva-302554 (URN)
Conference
NANOfIM 2016
Available from: 2016-09-06 Created: 2016-09-06 Last updated: 2016-10-18Bibliographically approved

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Cindemir, Umut

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