Sensors and Internet of Things: the role of nanostructured semiconductors

SALVO MIRABELLA
UNIVERSITÀ DI CATANIA
CNR-IMM
SENSORS AND INTERNET OF THINGS:
THE ROLE OF NANOSTRUCTURED SEMICONDUCTORS

Science Colloquia, DFA 21 Marzo 2018 mirabella@ct.infn.it 2/44
How big is Internet ?
www.go-globe.com
21 August 2017

How/what does produce data ?
H2H  T2H  T2T

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!

IoT visions

IoT visions
dispensa
frigo
forno
 …

IoT visions

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:

How to produce data ?
Sensitivity
Selectivity
Speed
Stability
Signal to noise
5S

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)

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

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, …)

Nanostructures: advantages
o sensitivity ↑
o speed ↑
o cost ↓

Nanostructured semiconductors
A.Mirzaei et al. Ceramics International 42 (2016)
Nanoscale, 2014, 6, 24-42

Future trends (MOx gas sensors)
o hollow
o hierarchical
o heterostructures
o core/shell
o metal NP decoration

Hybridized Tungsten Oxide
Nanostructures for Food Quality
Assessment: Fabrication and
Performance Evaluation
Kumar et al., Scientific Reports 2018

Semi-nano
Sensing for:
 Air pollution
 pH
 Glucose
 VOC
 Food spoilage
 UV light
 Pharma-contaminants
Low-cost
synthesis
Nanosized
Semicond.
Sensing
application

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

E. Bruno et al., Chemosensors (2017)
M. Scuderi et al., Nanotechnology (2018)
Low-cost synthesis: chemical bath deposition
Transmission electron microscopy

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)

• 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

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)

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

Non-enzymatic glucose sensing
e-
glucosio acido gluconico
OH-
e-
glucosio acido gluconico
OH-
Low-cost catalytic NiO based nanostructure

K. Iwu et al., Sens. and Act. B (2016)

M. Urso et al., Nanotechnology (2018)
Tg = RT Tg = 50°C

S. Petralia et al., BioNanoSci. (2017)
V. Strano and S. Mirabella, Nanotechnology (2018)
Na(OH)  PBS
pH 13  pH 11.3
Human blood test !

Food spoilage

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.

Food spoilage
bis(salycilaldiminato)Zn(II) Schiff Base
… per gli amici: Zn-SB complex
In coll. con DSC (S. DiBella,
G. Maccarrone, I. Oliveri)

UV light sensing
Domanda di sensori UV
low-cost, sensibili, e
veloci

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

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)

Defects in ZnO nanorods
- 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

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

Defects in ZnO nanorods
E. G. Barbagiovanni, et al., RSC Adv. (2016)
E. G. Barbagiovanni, et al., Nanoscale (2016)
VZn
VO
Zni
Oi
VO

Defect-mediated UV sensing
PL transient only for green line
(surface O vacancy).
PL transient = IV transient
UV sensitive defect
TOWARDS VOC’s
sensing (food spoilage)

Pharma contamination
4-pAP paraminofenolo (H₂NC₆H₄OH)
- Used for paracetamol synthesis
- Nefrotoxic e teratogenic
- Max level 50 ppm (EU, USA, China)

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)

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.

Semi-nano
Sensing for:
 Air pollution
 pH
 Glucose
 VOC
 Food spoilage
 UV light
 Pharma-contaminants
Low-cost
synthesis
Nanosized
Semicond.
Sensing
application

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

Sensors and Internet of Things: the role of nanostructured semiconductors

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