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Advanced Nanomaterials for Gas Sensing
Mittuniversitetet, Fakulteten för naturvetenskap, teknik och medier, Institutionen för ingenjörsvetenskap, matematik och ämnesdidaktik (2023-).ORCID-id: 0000-0003-2602-7634
2025 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
Abstract [en]

This thesis explores the development and performance of semiconducting metal oxide (SMOX)-based gas sensors prepared by different methods, specifically targeting hazardous gases like hydrogen sulfide (H₂S) and in some cases methyl mercaptan (CH₃SH). These gases pose significant risks to human health and the environment, even at low concentrations. Therefore, developing sensitive, reliable, and cost-effective sensors is crucial for industrial safety, environmental monitoring, and healthcare. 

The compact SnO₂ layers prepared by Ultrasonic Spray Pyrolysis (USP) demonstrated effective H₂S detection at an optimal operating temperature of 450°C. This method resulted in uniform, dense layers with high crystallinity and minimal impurities, ensuring a reliable sensor response. However, the sensor’s selectivity was limited by the presence of other interference gases, especially in humid environments. To enhance performance, ZnO/SnO₂ heterostructures were incorporated, fabricated by controlling precursor ratios during the USP process. These heterostructures showed improved sensor response and selectivity for detecting H₂S compared to pure SnO₂. 

The Flame Spray Pyrolysis (FSP) method successfully produced porous SnO₂ structures, which excelled in detecting low concentrations of H₂S and CH₃SH at an optimal operating temperature of 250°C. The highly porous morphology increased the surface area, yielding a remarkable gas response down to 20 ppb and enabling efficient gas diffusion, making it suitable for detecting sub-ppb levels of toxic gases.

Additionally, screen printing was employed to create ZnO/SnO₂ porous heterostructure sensors. The sensor with a 3:4 SnO₂/ZnO ratio achieved a limit of detection (LOD) of 140 ppt at an optimal operating temperature of 325°C, outperforming single-component sensors and demonstrating the effectiveness of the simple screen-printing method in producing scalable, high-performance gas sensors.

In summary, this thesis underscores the significance of material design and fabrication techniques in enhancing the performance of SMOX-based gas sensors. The findings highlight that utilizing porous structures and heterojunction engineering offers substantial advantages in sensor response and selectivity, making these sensors well-suited for real-world applications in hazardous gas detection.

sted, utgiver, år, opplag, sider
Sundsvall: Mid Sweden University , 2025. , s. 60
Serie
Mid Sweden University doctoral thesis, ISSN 1652-893X ; 417
Emneord [en]
gas sensor
HSV kategori
Identifikatorer
URN: urn:nbn:se:miun:diva-53331ISBN: 978-91-89786-88-2 (tryckt)OAI: oai:DiVA.org:miun-53331DiVA, id: diva2:1920381
Disputas
2025-01-24, C312, Holmgatan 10, Sundsvall, 08:00 (engelsk)
Opponent
Veileder
Tilgjengelig fra: 2024-12-12 Laget: 2024-12-11 Sist oppdatert: 2025-09-25bibliografisk kontrollert
Delarbeid
1. H2S gas sensing based on SnO2thin films deposited by ultrasonic spray pyrolysis on Al2O3substrate
Åpne denne publikasjonen i ny fane eller vindu >>H2S gas sensing based on SnO2thin films deposited by ultrasonic spray pyrolysis on Al2O3substrate
Vise andre…
2021 (engelsk)Inngår i: 2021 IEEE Sensors Applications Symposium (SAS), 2021Konferansepaper, Publicerat paper (Fagfellevurdert)
Abstract [en]

H2S gas is harmful for human health and environment, therefore novel gas sensors for real time and fast detection with high precision have been sought. Metal oxides are already known as promising candidate for this purpose. This article presents the performance of a gas sensor consists of a microheater and active layer formed on single alumina substrate for operating at high temperature applications. Ultrasonic spray pyrolysis deposition method was used to make both thick layer of SnO2 for microheater and thin and porous crystalline layer of SnO2 as sensing layer. The prepared sensor showed suitable dynamic response towards 10 to 50 ppm of H2S gas both in humid and dry conditions at 450 °C. In these experiments, the cross sensitivity of the sensor was also checked for other interfering gases e.g. CH4 and NO2.

Emneord
Gas sensor, H2S, Nanoporous thin film, SnO2, Ultrasonic spray pyrolysis
HSV kategori
Identifikatorer
urn:nbn:se:miun:diva-43356 (URN)10.1109/SAS51076.2021.9530172 (DOI)000755460900057 ()2-s2.0-85116142049 (Scopus ID)9781728194318 (ISBN)
Konferanse
2021 IEEE Sensors Applications Symposium, SAS 2021, 23 August 2021 through 25 August 2021
Tilgjengelig fra: 2021-10-12 Laget: 2021-10-12 Sist oppdatert: 2025-09-25bibliografisk kontrollert
2. Growing continuous zinc oxide layers with reproducible nanostructures on the seeded alumina substrates using spray pyrolysis
Åpne denne publikasjonen i ny fane eller vindu >>Growing continuous zinc oxide layers with reproducible nanostructures on the seeded alumina substrates using spray pyrolysis
2020 (engelsk)Inngår i: Ceramics International, ISSN 0272-8842, E-ISSN 1873-3956, Vol. 46, nr 7, s. 8567-8574Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

The growth of zinc oxide thin films with controlled nanostructures on the heat resistant dielectric substrates is important for the fabrication of gas sensors, transparent electric heating elements, pyroelectric electron emitters, and many other potential electronic and optoelectronic applications. The preferred substrate for many of these applications is alumina, but the production of uniform ZnO layers on alumina is hindered by the large lattice mismatch between ZnO and Al2O3 hexagonal crystal structures. Here, we systematically investigate the growth process of ZnO thin films on alumina substrates using the ultrasonic spray pyrolysis (USP) of zinc chloride solutions in ethanol and, for the first time, demonstrate the deposition of uniform layers on the alumina substrates appropriately seeded using magnetron sputtering prior to USP. On the pristine substrates, random nucleation of the isolated nanocrystallites results in uneven layers, and extending the growth process leads to the hierarchical growth of facetted ZnO nanorods and pyramids with weak physical attachments to the substrate surface. In similar conditions, USP deposition on the seeded substrates reproducibly results in continuous networks of densely packed ZnO crystallites intimately attached to the substrate surface with adjustable thickness and electrical conductance. These results are compared with those obtained for SnO2 in similar conditions. Regardless of its tetragonal crystal structure, SnO2 reproducibly forms even layers on the pristine alumina substrates. 

Emneord
Alumina substrate, Electrical conductance, Facetted micrirods, Seed layer, Spray pyrolysis, Zinc oxide
HSV kategori
Identifikatorer
urn:nbn:se:miun:diva-38230 (URN)10.1016/j.ceramint.2019.12.088 (DOI)000528340500007 ()2-s2.0-85076477283 (Scopus ID)
Tilgjengelig fra: 2020-01-15 Laget: 2020-01-15 Sist oppdatert: 2025-09-25bibliografisk kontrollert
3. Nanometer-Thick ZnO/SnO2Heterostructures Grown on Alumina for H2S Sensing
Åpne denne publikasjonen i ny fane eller vindu >>Nanometer-Thick ZnO/SnO2Heterostructures Grown on Alumina for H2S Sensing
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2022 (engelsk)Inngår i: ACS Applied Nano Materials, E-ISSN 2574-0970, Vol. 5, nr 5, s. 6954-6963Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

Designing heterostructure materials at the nanoscale is a well-known method to enhance gas sensing performance. In this study, a mixed solution of zinc chloride and tin (II) chloride dihydrate, dissolved in ethanol solvent, was used as the initial precursor for depositing the sensing layer on alumina substrates using the ultrasonic spray pyrolysis (USP) method. Several ZnO/SnO2 heterostructures were grown by applying different ratios in the initial precursors. These heterostructures were used as active materials for the sensing of H2S gas molecules. The results revealed that an increase in the zinc chloride in the USP precursor alters the H2S sensitivity of the sensor. The optimal working temperature was found to be 450 °C. The sensor, containing 5:1 (ZnCl2: SnCl2·2H2O) ratio in the USP precursor, demonstrates a higher response than the pure SnO2 (∼95 times) sample and other heterostructures. Later, the selectivity of the ZnO/SnO2 heterostructures toward 5 ppm NO2, 200 ppm methanol, and 100 ppm of CH4, acetone, and ethanol was also examined. The gas sensing mechanism of the ZnO/SnO2 was analyzed and the remarkably enhanced gas-sensing performance was mainly attributed to the heterostructure formation between ZnO and SnO2. The synthesized materials were also analyzed by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray, transmission electron microscopy, and X-ray photoelectron spectra to investigate the material distribution, grain size, and material quality of ZnO/SnO2 heterostructures. 

Emneord
gas sensors, H2S, heterostructures, ultrasonic spray pyrolysis, ZnO/SnO2
HSV kategori
Identifikatorer
urn:nbn:se:miun:diva-45084 (URN)10.1021/acsanm.2c00940 (DOI)000820253400001 ()2-s2.0-85130057633 (Scopus ID)
Tilgjengelig fra: 2022-05-31 Laget: 2022-05-31 Sist oppdatert: 2025-10-03bibliografisk kontrollert
4. Ultra-sensitive H2S and CH3SH Sensors Based on SnO2Porous Structures Utilizing Combination of Flame and Ultrasonic Spray Pyrolysis Methods
Åpne denne publikasjonen i ny fane eller vindu >>Ultra-sensitive H2S and CH3SH Sensors Based on SnO2Porous Structures Utilizing Combination of Flame and Ultrasonic Spray Pyrolysis Methods
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2024 (engelsk)Inngår i: IEEE Sensors Journal, ISSN 1530-437X, E-ISSN 1558-1748, Vol. 24, nr 22, s. 36393-36402Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

The National Institute for Occupational Safety and Health (NIOSH) has established exposure limits for sulfur-based volatile components, particularly hydrogen sulfide (H2S), at 20 ppm for an 8-hour exposure and 50 ppm for durations under 10 minutes. Detecting such toxic gases at low levels necessitates innovative sensor fabrication. This study introduces a unique sensor design, involving the direct thermophoretic deposition of SnO2 aerosol streams on one side and densely compacted SnO2 thick films via ultrasonic spray pyrolysis (UPS) on the other side, acting as a heater. Analyzing flame-made SnO2 particles using BET, XRD, and TEM techniques revealed highly crystalline particles approximately 8 nm in size. Methyl mercaptan (CH3SH) and H2S were employed as analyte gases, ranging from 20 ppb to 25 ppm and 20 ppb to 50 ppm, respectively. The results indicate that the flame-made SnO2 exhibits significant potential for developing gas sensors that are highly sensitive to CH3SH and H2S gases across a broad concentration range. The sensor demonstrates a linear increase in response at lower concentrations, saturating at concentrations exceeding 20 ppm. Consequently, highly sensitive gas sensors capable of detecting very low levels can be manufactured, suitable for machine learning applications in environmental monitoring, healthcare, and industrial safety. 

sted, utgiver, år, opplag, sider
Institute of Electrical and Electronics Engineers (IEEE), 2024
HSV kategori
Identifikatorer
urn:nbn:se:miun:diva-52918 (URN)10.1109/JSEN.2024.3467168 (DOI)001355285600139 ()2-s2.0-85205756194 (Scopus ID)
Tilgjengelig fra: 2024-10-22 Laget: 2024-10-22 Sist oppdatert: 2025-09-25bibliografisk kontrollert
5. Sub-Ppb H2S Sensing with Screen-Printed Porous ZnO/SnO2 Nanocomposite
Åpne denne publikasjonen i ny fane eller vindu >>Sub-Ppb H2S Sensing with Screen-Printed Porous ZnO/SnO2 Nanocomposite
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2024 (engelsk)Inngår i: Nanomaterials, E-ISSN 2079-4991, Vol. 14, nr 21, artikkel-id 1725Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

Hydrogen sulfide (H2S) is a highly toxic and corrosive gas commonly found in industrial emissions and natural gas processing, posing serious risks to human health and environmental safety even at low concentrations. The early detection of H2S is therefore critical for preventing accidents and ensuring compliance with safety regulations. This study presents the development of porous ZnO/SnO2-nanocomposite gas sensors tailored for the ultrasensitive detection of H2S at sub-ppb levels. Utilizing a screen-printing method, we fabricated five different sensor compositions—ranging from pure SnO2 to pure ZnO—and characterized their structural and morphological properties through X-ray diffraction (XRD) and scanning electron microscopy (SEM). Among these, the SnO2/ZnO sensor with a composition-weight ratio of 3:4 demonstrated the highest response at 325 °C, achieving a low detection limit of 0.14 ppb. The sensor was evaluated for detecting H2S concentrations ranging from 5 ppb to 500 ppb under dry, humid air and N2 conditions. The relative concentration error was carefully calculated based on analytical sensitivity, confirming the sensor’s precision in measuring gas concentrations. Our findings underscore the significant advantages of mixture nanocomposites in enhancing gas sensitivity, offering promising applications in environmental monitoring and industrial safety. This research paves the way for the advancement of highly effective gas sensors capable of operating under diverse conditions with high accuracy. 

sted, utgiver, år, opplag, sider
MDPI AG, 2024
Emneord
ZnO/SnO2 nanocomposite, gas sensor, H2S, screen printing, ultrasonic spray pyrolysis
HSV kategori
Identifikatorer
urn:nbn:se:miun:diva-53112 (URN)10.3390/nano14211725 (DOI)001352468700001 ()2-s2.0-85208437225 (Scopus ID)
Tilgjengelig fra: 2024-11-19 Laget: 2024-11-19 Sist oppdatert: 2025-09-25
6. Silicon Nanowires for Gas Sensing: A Review
Åpne denne publikasjonen i ny fane eller vindu >>Silicon Nanowires for Gas Sensing: A Review
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2020 (engelsk)Inngår i: Nanomaterials, E-ISSN 2079-4991, Vol. 10, nr 11, artikkel-id 2215Artikkel, forskningsoversikt (Fagfellevurdert) Published
Abstract [en]

The unique electronic properties of semiconductor nanowires, in particular silicon nanowires (SiNWs), are attractive for the label-free, real-time, and sensitive detection of various gases. Therefore, over the past two decades, extensive efforts have been made to study the gas sensing function of NWs. This review article presents the recent developments related to the applications of SiNWs for gas sensing. The content begins with the two basic synthesis approaches (top-down and bottom-up) whereby the advantages and disadvantages of each approach have been discussed. Afterwards, the basic sensing mechanism of SiNWs for both resistor and field effect transistor designs have been briefly described whereby the sensitivity and selectivity to gases after different functionalization methods have been further presented. In the final words, the challenges and future opportunities of SiNWs for gas sensing have been discussed.

Emneord
silicon nanowire; gas sensor; functionalization; top-down fabrication; bottom-up fabrication; heterostructures; metal oxides
HSV kategori
Identifikatorer
urn:nbn:se:miun:diva-40497 (URN)10.3390/nano10112215 (DOI)000594517400001 ()2-s2.0-85095700928 (Scopus ID)
Tilgjengelig fra: 2020-11-17 Laget: 2020-11-17 Sist oppdatert: 2025-09-25bibliografisk kontrollert
7. A Deep Learning Approach for Classification and Measurement of Hazardous Gases Using Multi-Sensor Data Fusion
Åpne denne publikasjonen i ny fane eller vindu >>A Deep Learning Approach for Classification and Measurement of Hazardous Gases Using Multi-Sensor Data Fusion
Vise andre…
2023 (engelsk)Inngår i: 2023 IEEE Sensors Applications Symposium (SAS), IEEE conference proceedings, 2023, artikkel-id 10254191Konferansepaper, Publicerat paper (Fagfellevurdert)
Abstract [en]

Significant risks to public health and the environment are posed by the release of hazardous gases from industries such as pulp and paper. In this study, the aim was to develop a multi-sensor system with a minimal number of sensors to detect and identify hazardous gases. Training and test data for two gases, hydrogen sulfide and methyl mercaptan, which are known to contribute significantly to odors, were generated in a controlled laboratory environment. The performance of two deep learning models, a 1d-CNN and a stacked LSTM, for data fusion with different sensor configurations was evaluated. The performance of these models was compared with a baseline machine learning model. It was observed that the baseline model was outperformed by the deep learning models and achieved good accuracy with a four-sensor configuration. The potential of a cost-effective multi-sensor system and deep learning models in detecting and identifying hazardous gases is demonstrated by this study, which can be used to collect data from multiple locations and help guide the development of in-situ measurement systems for real-time detection and identification of hazardous gases at industrial sites. The proposed system has important implications for reducing pollution and protecting public health.

sted, utgiver, år, opplag, sider
IEEE conference proceedings, 2023
Emneord
Gas measurement, Pulp & Paper, Multi-sensor, Data fusion, Machine learning, Deep learning, CNN, 1D-CNN, SVM, LSTM, Gas classification
HSV kategori
Identifikatorer
urn:nbn:se:miun:diva-49384 (URN)10.1109/SAS58821.2023.10254191 (DOI)001086399500100 ()2-s2.0-85174035432 (Scopus ID)
Konferanse
2023 IEEE Sensors Applications Symposium (SAS) Ottawa, ON, Canada
Tilgjengelig fra: 2023-09-26 Laget: 2023-09-26 Sist oppdatert: 2025-09-25bibliografisk kontrollert

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