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Sensors and Internet of Things: the role of nanostructured semiconductors

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Future trends in materials science and nanotechnology for innovative sensing devices required within IoT.
Some visions on how IoT will impact our daily life and some materials research on novel nanostructures based enabling technologies

Published in: Technology
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Sensors and Internet of Things: the role of nanostructured semiconductors

  1. 1. SALVO MIRABELLA UNIVERSITÀ DI CATANIA CNR-IMM SENSORS AND INTERNET OF THINGS: THE ROLE OF NANOSTRUCTURED SEMICONDUCTORS
  2. 2. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 2/44 How big is Internet ? www.go-globe.com 21 August 2017
  3. 3. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 3/44 How/what does produce data ? H2H  T2H  T2T
  4. 4. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 4/44 How big is IoT ? www.weforum.org Is-this-future-of-the-internet-of-things? 27 Nov 2015 Metcalfe’s law: value of a network is proportional to the square of the number of connected users Everything that can be connected, will be connected! IoT booster for new technologies!
  5. 5. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 5/44 IoT visions
  6. 6. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 6/44 IoT visions dispensa frigo forno  …
  7. 7. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 7/44 IoT visions
  8. 8. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 8/44 IoT market value Cisco predicts the global IoT market will be $14.4T by 2022 https://www.cisco.com/web/about/ac79/docs/innov/IoE_Economy.pdf The path:
  9. 9. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 9/44 How to produce data ? Sensitivity Selectivity Speed Stability Signal to noise 5S
  10. 10. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 10/44 Sensing anything, anywhere, anytime o temperature o pressure o acc., gyro. o light o chemical o biochemical“I sensori oggi sono il driver dell’industria microelettronica” B. Vigna, Executive Vice President STM (Feb 2018)
  11. 11. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 11/44 Gas sensors (chemoresisitive) Smart cities (air pollution, ageing infrastructures, gas leaks, plume begins, GHG emission, security) Personal health (air monitoring, pregnant, children, workers)  Food (safety, spoilage, best before date)  … Adsorption enthalpy
  12. 12. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 12/44 0 100 200 300 400 500 600 WoS search: Nanostructure AND Sensor Search date: 13/03/2018 Nano & sensori ? Richard Feynman Nobel Prize 1965 1959 speech Nanotechnology advantages for sensing: - Improved speed, selectivity, sensitivity - Reduced size, power and cost - New properties (SERS, QCE, enhanced luminescence, …)
  13. 13. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 13/44 Nanostructures: advantages o sensitivity ↑ o speed ↑ o cost ↓
  14. 14. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 14/44 Nanostructured semiconductors A.Mirzaei et al. Ceramics International 42 (2016) Nanoscale, 2014, 6, 24-42
  15. 15. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 15/44 Nanostructured semiconductors Future trends (MOx gas sensors) o hollow o hierarchical o heterostructures o core/shell o metal NP decoration
  16. 16. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 16/44 Nanostructured semiconductors Hybridized Tungsten Oxide Nanostructures for Food Quality Assessment: Fabrication and Performance Evaluation Kumar et al., Scientific Reports 2018
  17. 17. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 17/44 Semi-nano Sensing for:  Air pollution  pH  Glucose  VOC  Food spoilage  UV light  Pharma-contaminants Low-cost synthesis Nanosized Semicond. Sensing application
  18. 18. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 18/44 Air pollution: nitrogen dioxide ITALIA Valori limite (DM 60/2.4.2002) NO2: 40 μg/m3  19 ppb (media annuale) 190 ppb (su 1 ora) CO: 10000 μ g/m3  8 ppm (media su 8 ore) Domanda di sensori low-cost, sensibili, selettivi
  19. 19. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 19/44 Air pollution: nitrogen dioxide E. Bruno et al., Chemosensors (2017) M. Scuderi et al., Nanotechnology (2018) Low-cost synthesis: chemical bath deposition Transmission electron microscopy
  20. 20. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 20/44 Air pollution: nitrogen dioxide 7000 7500 8000 1G 2G 3G 4G 5G 6G 7G 8G Time (s) Resistance(Ω) 5 ppmCO 5 ppmNO2 T = 350 °C 0 100 200 300 400 Temperature(°C) NO2 Oxidizing CO Reducing LOD (NO2) 50 ppb E. Bruno, et al., Chemosensors (2017)
  21. 21. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 21/44 • Al/ZnO nanoporous provides a perfect conducting/selective layer for extended gate • Al/ZnO bi-layer was connected to the gate of an LTPS TFT fabricated on flexible PI pH sensing: field effect Coll. CNR-IMM Roma & TAU Extended Gate Thin Film Transistor (polycrystalline silicon at low temperature) ZnO NW Tel Aviv University
  22. 22. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 22/44 pH sensing: field effect Basic test for further biosensors (as Enzyme FET) involving pH variation due to Enzyme-Analite reaction - Measurements were performed @ 25 °C in dark condition and after 10 min after changing pH solution - Reference electrode Ag/AgCl - IdVg performed @ Vds=0.1 V with slow ramp rate (2 s/V) - IdVds performed @ Vg=9 V - pH-sensitivity nearly 60 mV/pH, close to ideal Nernstian response (2.3 KT=60 mV/pH)) L. Maiolo, et al., Appl. Phys. Lett. (2014)
  23. 23. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 23/44 Glucose sensing NON-ENZYMATIC GLUCOSE SENSING Glucose in saliva 20-70 µM Glucose in tears 100-300 µM ENZYMATIC GLUCOSE SENSING Glucose in blood 3-8 mM Today  Tomorrow
  24. 24. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 24/44 Non-enzymatic glucose sensing e- glucosio acido gluconico OH- e- glucosio acido gluconico OH- Low-cost catalytic NiO based nanostructure
  25. 25. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 25/44 Non-enzymatic glucose sensing K. Iwu et al., Sens. and Act. B (2016)
  26. 26. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 26/44 Non-enzymatic glucose sensing M. Urso et al., Nanotechnology (2018) Tg = RT Tg = 50°C
  27. 27. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 27/44 Non-enzymatic glucose sensing S. Petralia et al., BioNanoSci. (2017) V. Strano and S. Mirabella, Nanotechnology (2018) Na(OH)  PBS pH 13  pH 11.3 Human blood test !
  28. 28. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 28/44 Food spoilage
  29. 29. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 29/44 Food spoilage Bizerba’s “OnVu” technology. It uses “intelligent” temperature-sensitive ink (bulls-eye on the label) surrounded by an outer ring serving as the standard.
  30. 30. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 30/44 Food spoilage bis(salycilaldiminato)Zn(II) Schiff Base … per gli amici: Zn-SB complex In coll. con DSC (S. DiBella, G. Maccarrone, I. Oliveri)
  31. 31. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 31/44 UV light sensing Domanda di sensori UV low-cost, sensibili, e veloci
  32. 32. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 32/44 UV sensing by ZnO microflowers Step One Growth Zinc Nitrate, HMTA and NH4F 90 °C, 5-15 min Step Two Centrifugation 3 times after washing 9000 rpm Low-cost synthesis: chemical bath deposition
  33. 33. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 33/44 0 100 200 300 400 1.0 1.2 1.4 1.6 1.8 Bias= 1 V current Light off I[nA] Time [s] Light on τon = 47 s τoff = 51 s Low-cost UV sensor fast response time Au finger Au finger ZnO MFs UV sensing by ZnO microflowers M.G. Greco, V. Strano, et al. (to be submitted)
  34. 34. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 34/44 Defects in ZnO nanorods Low-cost synthesis: chemical bath deposition - Near band edge emission: no CBMVBM transition, FX-D (Zni donor state)! - Visible band: defect states in the band gap … Above gap light PL study
  35. 35. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 35/44 Universal model E. G. Barbagiovanni, et al., Appl. Phys. Lett. (2015) E. G. Barbagiovanni, et al., RSC Adv. (2016) E. G. Barbagiovanni, et al., Nanoscale (2016) CBD VLS* HT* BGOR model works independently of the synthesis methods * grown in GREMAN (UMR-CNRS) Tours, D. Alquier group
  36. 36. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 36/44 Defects in ZnO nanorods E. G. Barbagiovanni, et al., Appl. Phys. Lett. (2015) E. G. Barbagiovanni, et al., RSC Adv. (2016) E. G. Barbagiovanni, et al., Nanoscale (2016) VZn VO Zni Oi VO
  37. 37. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 37/44 Defect-mediated UV sensing E. G. Barbagiovanni, et al., Appl. Phys. Lett. (2015) PL transient only for green line (surface O vacancy). PL transient = IV transient UV sensitive defect TOWARDS VOC’s sensing (food spoilage)
  38. 38. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 38/44 Pharma contamination 4-pAP paraminofenolo (H₂NC₆H₄OH) - Used for paracetamol synthesis - Nefrotoxic e teratogenic - Max level 50 ppm (EU, USA, China)
  39. 39. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 39/44 ZnO nanorods: pAP sensing ZnO CBD nanorods synthesis (Catania) 1.5-2 nm Au or Pt or AuPt (KULeuven) Laser ablation cluster beam deposition 1000 clusters deposition per nanorod EC testing (TelAviv Univ.) S. Cosentino, et al., JPPC (2017) G. Fiaschi, et al., JEC (2018)
  40. 40. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 40/44 ZnO nanorods: pAP sensing S. Cosentino, et al., JPPC (2017) G. Fiaschi, et al., JEC (2018)
  41. 41. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 41/44 ZnO nanorods: pAP sensing Bimetallic AuPt clusters onto ZnO NRs exhibited an enhanced sensitivity of 14.31 µA/mM cm2 and improved limit of detection of 3.6 µM. S. Cosentino, et al., JPPC (2017) G. Fiaschi, et al., JEC (2018)
  42. 42. Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 42/44 Semi-nano Sensing for:  Air pollution  pH  Glucose  VOC  Food spoilage  UV light  Pharma-contaminants Low-cost synthesis Nanosized Semicond. Sensing application
  43. 43. UniCT-DFA: F. Priolo, E. Bruno UniCT-DSC: S. Di Bella, I. Oliveri UniME-DE: G. Neri, N. Donato, G. Leonardi CNR-IMM CT: G. Franzò (Matis), TEM group CNR-IMM Roma: G. Fortunato, L. Maiolo V. Strano PhD (Mrs. ZnO !) BRIT UniCT E. Barbagiovanni post-doc (ZnO PL) CNR IMM K. O. Iwu post-doc (NiO, EC) InNano M. Urso PhD (NiO, …) ??? STM Catania Tel Aviv Univ. Columbia Univ. Tours Univ. KU Leuven
  44. 44. Grazie!

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