New approaches to airborne particle monitoring Lloyd Spetz, 1,2 J. Huotari 2 , C. Bur 1,3 , M. Sobocinski 2

1. New approaches to airborne particle monitoring • Lloyd Spetz,1,2 • J. Huotari2, C. Bur1,3, M. Sobocinski2 • R. Bjorklund1, J. Juuti2, J. Lappalainen2, • H. Jantunen2, A. Schütze3, M. Andersson1 • 1Div Applied Sensor Science, Dept. Physics, Chemistry and Biology, Linköping University, SE-581 83 Linköping, Sweden, • 2Microelectronics and Material Physics Laboratories, University of Oulu • FIN 900 14 Oulu, Finland • 3Laboratory for Measurement Technology, Saarland University, Campus A5 1 • D-66123 Saarbrücken, Germany

2. New approaches to airborne particle monitoring • SiC-FET improved sensor devices • New design, improved function • Applications • Monitoringofparticles by • Impedancespectroscopy • Heating and detectionof emissions • Futuretechnology

3. SiC-FET sensors, wafer and mounting SiC-FET sensor system 4” SiCwafer, ~2000 chip Processing on 4” SiC wafers using standard methods

4. H2O CO2 O2 C3H6 NH3 H2 SiC-FET transistor as gas sensor Strong OH dipoles charge the gate Three phase boundary: gas - metal - oxide H H O O Metal Insulator Semiconductor H H H Si O Si O Si O Porous film Pt, Ir, Pd, … SiO2 SiC/Si I/V characteristics SiC-FET: presenceof gas – a shift in the I/V-curve Mike Andersson

5. Silicon Carbide Sensors Combustioncontrol in small power plants Gas sensors • Control ofprimary and secondary air by • 2 SiC-FET gas sensors • (different operation temperatures) • 1 temperature sensor • Increasedefficiency • and lower emissions Mike Andersson Temperature sensor

6. SenSiC AB: Silicon Carbide SensorsCombustioncontrol in small power plants Emissions, uncontrolledcombustion Emissions from controlledcombustion The sensors measurethe ratiobetween CO and oxygen in the fluegases Mike Andersson

7. SenSiC AB: SiC-FET sensor system combustioncontrol in small and medium sizedpower plants www.sensic.se New application: Control of urea injectionwhenusing SCR by ammoniasensors in power plants and stationary diesel engines

8. Control of urea injection in power plants SNCR – Selective Non-CatalyticReductionof NO/ NO2 by NH3 through urea injection in the flue gas Control of urea injection by an NH3 sensor SCR-SelectivCatalyticReductionof NO/NO2 in a catalyticconverter by NH3

9. Portable nanoparticle sensor • Nanoparticles show adversehealtheffect accordingto • Size • Shape • Content • Concentration • Nanoparticles damage cells • Toxiceffect on cells CHEMPACK project (2011-2014) FiDiPro position University ofOulu i Finland Welding nanoparticles (courtesy of Pam Drake, National Institute for Occupational Safety and Health NIOSH). Asbestos fibers (courtesy of the US Geological Survey).

10. Soot sensor surface Thermos Soot sensor based on Thermophoresis Thermophoresis: A force acting on particles in a temperature gradient → Soot is deposited on the coldest surface Thermos packaging to decrease temperature on the sensor surface

11. Exhaustpipe Sootmeasurement in diesel engine Soot sensor Robert Bjorklund, Linköing University and Ann Grant, Volvo Technology

12. MW,°C 0 100 200 300 t(min) Sootmeasurementsduring6 World HarmonizedTransientCycles Heater on, 600°C Exhaust gas 200°C Sensor 160°C 30 min/cycle, 18 min response time, 1370 mg/cycle, 40 mg/kWh) Robert Bjorklund and Ann Grant

13. Particle generator Joni Huotari Peter Möller Mike Andersson Robert Bjorklund • PALAS RGB 1000 dryparticlegenerator • Pegasornanoparticlesensor as reference • Flowthroughchamber for testing of sensors (SiC-FETs) • A measurementchamber with probeconnectionswillbebuilt for measurementsfrom DC to GHzrange

14. Impedance spectroscopy of particles Airbornesteelplant particles Opticalspectra Deposited CNT particles SEM SEM: CNT (89 µg/ml) CNT (8.9 µg/ml) Joni Houtari Impedancespectra, potential for size, concentration and kind ofparticles and possible for on-line measurements

15. Detectionofparticlecontent Waste Flow controller 1 100ml/min Sensor chamber N2 Gas mixing program Flow controller 2 100ml/min Heater with particles Data acquisition LabView O2 Electronics Const. I control T-control Heatingofparticles and detectionof emissions with gas sensors Christian Bur SiC- FET sensor

16. Detectionofparticlecontent Ammoniacontainingfly ashParticlesheatedto 430°C. DetectionbySiC-FETs and environmental massspectrometer. Gas flow: 25ml/ min Massspectrometer signal SiC-FET signal. Pt gate, T=220oC, IS-G = 55 µA Christian Bur

17. Future: Envisaged packaging ideas Detectionofemittedgases by sensor array Maciej Soboskinski Mike Anderson Jari Juuti One alternative co-fired LTCC modules

18. Conclusions • Toxicgasesand airbornenanoparticlesneedto be monitored for environmental control • The new generation SiC-FETsprovide a powerful sensor platform for detectionofgases (and eventuallyparticles) • The contentofnanoparticlesis importanttomeasure: Impedancespectroscopy or heatingparticles and subsequentdetectionof the emissions by gas sensors

19. Acknowledgements Microelectronics and Material Science Laboratories, University ofOulu Prof. Heli Jantunen Prof. Jyrki Lappalainen Prof. Anita Lloyd Spetz Ass. Prof. Jari Juuti Dr Mike Andersson Joni Huotari, PhD student Maciej Soboskinskij, PhD student Laboratory for Measurement Technology, Saarland University Prof. Andreas Schütze Christian Bur, PhD student Applied Sensor Science at Linköping University Prof. Anita Lloyd Spetz Dr. Mike Andersson Dr. Robert Bjorklund Dr. Jens Eriksson, post doc ZhafiraDarmastuti, PhD student Christian Bur, PhD student Hossein Fashandi, PhD student Peter Möller, research engineer Grant support is acknowledged from: The VINN Excellence Center in Research & Innovation on FunctionalNanostructured Materials(FunMat) The Swedish Agency for Innovation Systems (VINNOVA), The Swedish Research Council andTEKES in Finland COST Action EuNetAir TD 1105 EuropeanNetwork on Air Pollution Control

20. Clean environmentthroughair qualitycontrol by sensor systems A cleanenvironmentshouldbelongto human rights. Sensor systems areneeded for emission monitoring and control. Toxicsubstancesinclude: NOx, SO2, CO, O3, PAH, PM10, PM2.5, PM1 The vulcano St. Helena Swedish Lucia performance (1963) Sourcesof emissions: e.g. industry, vehicles, volcanousand candles (soot)

21. SiC-FET transducer platform for gas sensors Presenceof gas Absenceof gas Cross sectionofdepletionSiC-FET Gate sensinglayer: porouscatalyticmetal, Pt, Ir I/V characteristics SiC-FET: presence (red dashed line) of a gas - internal voltage drop at the gate metal/ insulator interface – a shift in the I/V-curve Mike Andersson

22. Impedance spectra of particles from steel plant and CNTs Impedancespectra, potential for on-line measurements CNT Steel plant particles SEM: CNTs deposited on IDEs Joni Huotari Optical image, airborne particles from steel plant

23. NH3 detectionusing new SiC-FET sensor design NH3 CO Sensor signalsettoalarmlevelof15-20ppm ammonia.Detectionof NH3 in lowoxygenand high CO concentrationfunctions Mike Andersson

24. Steel plant particles CNTs Impedance spectra of particles from steel plant and CNTs Joni Huotari Impedance spectra for detection of concentration, size, content with potential for on-line measurements

25. On Road US On Road EU On Road Japan PM (g/kWh) 0.15 EU-II 95/96 US’04 0.10 EU-III 00/01 0.05 Japan NLT 05 EU-IV 05/06 US’07 2.0 3.5 5.0 EU-VI 13/14 ~ EU-V 08/09 NOx (g/kWh) US’10 Market legislations for heavyduty trucks 0.02 7.0 From 2015: 0.4g/kW-hr for NOx, 0.02 g/kW-hr for PM

26. Silicon Carbide Sensors Combustioncontrol in small power plants Mike Andersson

27. SCR, SelectiveCatalyticReduction, system NH2CONH2 + H2O 2 NH3 + CO2 Catalyst Urea injection NH NOx 3 Urea 4NO +4NH3 + O2 4N2 + 6H2O 2NO2 +4NH3 + O2 3N2 + 6H2O Engine Tank Engine Control model Algorithms Catalyst model • NH3 sensor requirements: • Operation T > 400C • (700C short periods oftime) • Detection limit <10 ppm SCR now in trucks by both Volvo and Scania OBD (On Board Diagnostics) expected

28. NH3 Lab measurements Mike Andersson SiC-FET sensor signal to ammoniafor two SiC FETs. Detection limit < 5 ppm in 10% O2 / N2.

29. Particles spread by volcanos The eruption plume of St. Helen volcano, in 1980 courtesy of NASA. Aggressive African-endemic Kaposi’s sarcoma of the foot Podoconiosis Volcanic iron oxide rich soil in Rwanda (courtesy Biomed Central.) Buzea et al. Biointerphases, 2, 4 (2007) MR17-MR71

30. The SiC-FET ammonia sensor • Diesel enginemeasurement • SCR system • TwoMISiCFET sensors and opticalreference instrument H. Svenningstorp, H. Wingbrant

31. 31 Presentcommercialparticledetectors DEKATI ELPI (Electrical Low Pressure Impactor (6 nm – 10 µm) Nano-ID™ NPS500 based on DMA (Differential Mobility Analyzer) technology, portable particle measurement device (5-500nm)

32. NH3 sensor mountingfor urea control in boilers Värmeforskprojects: A08-828 and P08-823 Partners: SenSiC AB, Alstom Sweden AB, Tekniska Verken, Vattenfall Two position sensor mounting ~ 40 cm apart Robert Bjorklund

33. Gobi desert dust storm spread Buzea et al. Biointerphases, 2, 4 (2007) MR17-MR71 Ten major sources of dust in the world Hitchhiker in Luxemburg, 1977 Bacteria, hitch hiking by African dust, was found in North America.

34. Healthy particles Pale blue swirls in Lake Michigan, probably caused by calcium carbonate chalk from the lake’s limestone floor (credit: NASA/GSFC) Sea spray from ocean waves (courtesy NASA). TEM image of mineral dust mixture with sea salt collected from the marine troposphere Buzea et al. Biointerphases, 2, 4 (2007) MR17-MR71

35. Fires produce (nano)particles Distribution of active fires detected by Terra’s MODIS sensor across the planet on 10-19 July 2006 Buzea et al. Biointerphases, 2, 4 (2007) MR17-MR71

36. Detectionofparticlecontent First results, detectionofammoniacontainingfly ash particles. Particlesareheatedrepeatedlyto ~ 800°C. A small gas flowbringsemissionsfromheatertoSiC-FET sensors. Workplace and Indoor Aerosol conference in Lund: Detection of Pd in particles by the catalytic CO conversion efficiency Christian Bur

38. Future development Particles are charged, SiC- FET device a possibility Source and drain contacts need protection by over glass, but also bond wires must be protected Additional functionality by smart packaging, LTCC packaging (Docent Jari Juuti): Collection of particles by thermophoresis (cold sensor surface), applied voltage, magnetic field Detection of content of particles by heating at a hot spot and detection of emissions by a sensor array, smart operation and data evaluation

39. Tailoring of SiC based field effect sensors for CO2 monitoring SiC based CO2 sensor Li2CO3-BaCO3 sensing layer MgO prevents response to hydrogen containing gases H. Inoue, M. Andersson, M. Yuasa, T. Kida, A. Lloyd Spetz, and K. Shimanoe: CO2 sensor combining an MISiC capacitor and a binary carbonate, Electrochemical and Solid-State Letters, 14 (1) (2011) J4-J7.

40. Tailoring of SiC based field effect sensors for O2 monitoring Response to oxygen No response to hydrogen containing gases M. Andersson, A. Lloyd Spetz, Tailoring of SiC based field effect gas sensors for improved selectivity to non-hydrogen containing species, IMCS13, Perth, Australia, July 12-14, 2010, 369.

41. Sensor system for control of small and medium sized power plants www.sensic.se Mike Andersson and Magnus Palm: installation of a sensor system for control of a domestic boiler) at Ariterm Sweden AB (key partner)

42. 42 Present commercial particle detectors • NANOSIGHT • - optical method to measure size • laser light source • typical range 10 nm - 1000 nm • BECKMAN COULTER • particle size of fluid with nanoparticles • laser light • - for size analysis: electrophoretic light scattering (ELS) • LIGHTHOUSE WORLDWIDE SOLUTIONS • - handheld and portable particle counters • - minimum sensitivity: 200 nm • AIRMODUS • - condensation to grow 1 nm diameter nanoparticles to optically detectable sizes • KANOMAX • condensation to grow 15 nm diameter nanoparticles to optically detectable sizes • PEGASOR • Portable real time measuring instrument • Detection of total surface area, mass, number of particles BECKMAN COULTER AIRMODUS NANOSIGHT LM10 LIGHTHOUSE HANDHELD 2016 KANOMAX MODEL 3800

43. Envisaged packaging ideas Material combinations and process development to enable wafer level integration of functional packages by cost effective means.