First Seminar1

1
DEVELOPMENT AND CHARACTERIZATION OF GAS AND

HUMIDITY SENSORS USING METAL SULPHIDE
NANOSTRUCTURES
Muhammad Faheem Afsar1,2
Supervisor: Dr. Muhammad Aftab Rafiq1
Co-Supervisor: Dr. Muhammad Masood ul Hasan1
1Micro and Nano Devices Group

Department of Metallurgy and Materials Engineering
2Department of Physics and Applied Mathematics PIEAS,
Nilore, Islamabad Pakistan
2
NANOSTRUCTURES
Layout
 Introduction
a) Metal sulphide
b) Metal sulphide nanostructure materials properties
c) Metal sulphide nanostructure materials applications
d) Literature survey
e) Copper sulphide (CuS) , Lead sulphide (PbS) and CdS
f) Solid state reaction method
 Experimental
a) Synthesis of CuS , PbS and CdS nanostructure
 Characterization Techniques
 Device Fabrication
 Facilities required and availability
 Expected outcomes
 Work plan 3
HUMIDITY SENSORS USING METAL SULPHIDE NANO
STRUCTURES
a) Metal sulphides
 Composition of metals (Zn, Pb, Cu, Cd, Bi, Sn, Mo, Fe etc) with sulfur
b) Properties of metal sulphide nanostructures

 Melting point above those of oxides
 Salt-like or hard-metal like
 Generally hydrolyzed by water
 Oxidize in moist air at ambient temp or in dry air at elevated temp
 Some possess semi-metallic character and have electronic properties
 Excellent mechanical and thermal properties
 Excellent resistance against corrosion and chemical erosion
4
STRUCTURES
Applications of Metal sulphide nanostructures
 Development of highly sensitive gas and humidity sensors
 Fabrication of electronic and photonic devices
 Lubricants for optical and sensitive instruments
 Batteries
 Phosphor Ingredients
 Pigments
 Ceramic coatings
 Semiconductor and automobile industry
 Infrared filters
5
STRUCTURES
Chemical methods to prepare nanostructured materials
Processing Mechanical methods Nanocrystalline
route materials
 Solid-state Mechanical Milling powder
 Liquid Sol-gel powder/film
Sonochemistry powder
Hydrothermal powder
Electrodeposition powder/film
Gas Atomization powder
Laser Beam melting film
Melt Spinning continuous
ribbon
6
STRUCTURES
Processing Mechanical methods Nanocrystalline

route materials
 Vapor Chemical Vapor Deposition powder/film
Physical Vapor Deposition powder/film
Aerosol Processes powder/film
Flame-Assisted Deposition powder
7
STRUCTURES
Metal sulphides literature survey
1. Ahmad, Mushtaq, et al. “Charge conduction and relaxation in MoS2 nanoflakes
synthesized by simple solid state reacation.” Journal of Applied Physics, 114.4
(2013): 043710.
2. Ahmad, Mushtaq, M. A. Rafiq, and M. M. Hasan. “Transport characteristics and
colossal dielectric response of cadmium sulphide nanoparticles.” Journal of
Applied Physics, 114.13 (2013): 133702.
3. Ahmad, Mushtaq, et al. “ Structural and Electrical properties of Zinc Sulphide
Nanoparticles.” Electronics, Communications and Photonics Conference
(SIECPC), 2011 Saudi International. IEEE, 2011.
4. Ahmad, Mushtaq, et al. “Dielectric and transport properties of bismuth sulphide
prepared by solid state reaction method.” Journal of Applied Physics, 113.4
(2013): 043704.
8
STRUCTURES
5. Sagade, Abhay A., and Ramphal Sharma. “Copper sulphide (Cux
S) as an amonia gas sensor working at room temperature.” Sensors and
Actuators B: Chemical, 133.3 (2008): 135-143.
6. Bo, Xiangjie, et al. “In situ growth of copper sulphide nano particles on ordered
mesoporous carbon and their application as nonenzymaytic amperometric”
sensor of hydrogen peroxide.” Talanta 81.1 (2010): 339-345.
7. Yamazoe, Noboru, and Yasuhiro Shimizu. “ Humidity sensors: principles and
application.” Sensors and Actuators 10.3 (1986): 379-398.
8. Fu, Tiexiang. “ Research on gas-sensing properties of lead sulphide-based
sensor for detection of NO 2 and NH 3 at room
temperature.” Sensors and Actuators B: Chemical, 140.1 (2009): 116-121.
STRUCTURES
Metal sulphides literature survey

 Synthesis of CuS, PbS and CdS nanostructures through solid
state reaction method at low temperature and ambient
pressure for electrical, Ferroelectric, humidity and gas sensing
properties are not reported yet (Literature gap)
 We plan to synthesize CuS, PbS and CdS nanostructures

through solid state reaction method at low temperature and
ambient pressure and study their electrical, Ferro electrical
humidity and gas sensing properties.
10
STRUCTURES
 Solid state reaction method
 Stoichiometric reaction of powders (elements, binary
compounds, ternary compounds, etc) at required
temperture in air, under vacuum, or in inert or reactive
gases
A B C G
 A top to bottom approach

 Simple and no use of solvent
 Facilitates the diffusion of atoms or ions
11
STRUCTURES
 Metal sulphide nanostructures in literature
 𝐵𝑖2 𝑆3
 𝑁𝑖𝑆
 𝑍𝑛𝑆
 𝑀𝑜𝑆2
 𝑊𝑆2 , etc………
12
STRUCTURES
 Synthesis steps
Metal Acetate Thiourea
Mixing and grinding
Heating
Grinding
XRD, SEM, TEM
Characterization etc
Device Fabrication Electrical,

Humidity and 13
Device Testing gas sensing
STRUCTURES
 Synthesis of CuS Nanostructure
 Stoichiometric amounts of copper acetate and thiourea in the
ratio 1:1 were mixed and grinded in Piston Morten
 The resulting gel like compound was then put in a crucible
and annealed at 200℃ for 5h
 Decomposition of thiourea occurs at 150℃ producing 𝐻2 𝑆
gas as 𝑆𝐶(𝑁𝐻2 )2 → 𝑁𝐻2 𝐶𝑁 + 𝐻2 𝑆
 𝐻2 𝑆 gas reacts with 𝐶𝑢+ salt from copper acetate to prepare
blackish colored CuS as 𝐶𝑢+ + 𝐻2 𝑆 → 𝐶𝑢𝑆 + 2𝐻+
 The required compound from crucible grinded in Piston
Morten to obtain the powder form of material
 This powder material is used for XRD, SEM, etc
characterization
14
STRUCTURES
 Xrd Spectrum
70000
040
60000
50000
Intensity (a.u)
40000
151
122
002
111
232
30000
081
061
021
110 120
270 162
20000
250
101
131
210 141
211
042
113
10000
080
251
133
0
0 10 20 30 40 50 60 70 80 90

15
PDF card number 00-033-1375
STRUCTURES
 Transmission electron microscopy
16
STRUCTURES
 CuS nanocrystallites
 Prepared CuS powder was comprised of nanocrystals

 The average crystallite size was ~ 16.337nm
 I-VI semiconductor (p-type)
 Crystalizes with hexagonal symmetry
17
STRUCTURES
 Transport properties of CuS nanocrystallites

 Final device structure
CuS Nano crystals Copper pad
Composite substrate
18
STRUCTURES
 Copper pads were photolithographically defined on composite

substrate.
 The separation between copper lines is 350μm.
 CuS nanocrystals were deposited on the substrate by screen
printing method.
19
STRUCTURES
 DC measurement
 DC measurements were carried out on Keithley
2400 Source-meter.
 Material Development Corporation (MDC) probe

station was used for IV characteristics
measurements and the software used was provided
by MDC
20
STRUCTURES
Agilent E4980 meter
Keithley 2400 Source meter
Temperature Controller
21
STRUCTURES
 I-V Characteristics CuS Nanocrystellites
0.0001
405K
305K
Current(A)
0.0000
305K
405K
-0.0001
-5 0 5
Voltage(V)
22
STRUCTURES
 DC measurement
-6
-5
-4
Z(K)
310K
-3 320K
330K
340K
-2
350K
360K
-1 370K
fit data
0
0 5 10 15 20 25 30 35
Z (K
23
STRUCTURES
310K 310K
320K 320K
0.4 330K 330K
340k -4
6.0x10 340K
350K 350K
360K 360K
370K 370K
 (Sm 

M"
0.2
-4
3.0x10
0.0
0.0
0 1 2 0 1x10
6 6
2x10
f(M Hz) f (Hz)
24
STRUCTURES
3
4
4.0x10 -7x10
310K
3
310K -6x10 320K
320K 330K
330K 3 340K
340K -5x10 350K
4
350K 360k
2.0x10 360K
3
-4x10 370K
370k
Z
Z
3
-3x10
3
-2x10
0.0
3
-1x10
0
0 1x10
6
2x10
6
0 1x10
6 6
2x10
f (Hz) f (Hz)
25
STRUCTURES
Volatage dependent P-E Loop for CuS
Voltage dependent P-E Loop for CuS

30
0V
5V
20 10V
15V
10
P(C/cm2)
-10
-20
-30
-80 -60 -40 -20 0 20 40 60 80
E(V/cm) 26
STRUCTURES
Pr Ec
-Pr 60 -Ec
20 Ps Es
-Ps -Es
P(C/cm )
2
E(V/cm)
0 0
-20 -60
0 7 14
0 7 14
Voltage(V)
Voltage(V)
27
STRUCTURES
Temperature dependent P-E Loop for CuS
Temp dependent P-E Loop for CuS
6 0
25 C
0
75 C
4 0
125 C
0
175 C
2
P(C/cm2)
-2
-4
-6
-8
-30 -20 -10 0 10 20 30
E(V/cm) 28
STRUCTURES
Pr Ec
4 -Pr 20 -Ec
Ps Es
-Ps -Es
P(C/cm2)
E(v/cm)
0 0
-4 -20
60 120 180 60 120 180

0 0
T C) T C)
29
STRUCTURES
Gas sensing properties of CuS
-4
8.0x10
air b
6.0x10
-4 1min
2min
4.0x10
-4 3min
air a
-4
2.0x10
Current(A)
0.0
-4
-2.0x10
-4
-4.0x10
-4
-6.0x10
-4
-8.0x10
-1.0 -0.5 0.0 0.5 1.0
Voltage(V)
30
STRUCTURES
Gas sensing properties of CuS
31
STRUCTURES
 Synthesis of PbS Nanostructure
 Stoichiometric amounts of lead acetate and thiourea in the
 The resulting gel like compound was then put in a crucible
and annealed at 200℃ for 5h
 Decomposition of thiourea occurs at 150℃ producing 𝐻2 𝑆
gas as 𝑆𝐶(𝑁𝐻2 )2 → 𝑁𝐻2 𝐶𝑁 + 𝐻2 𝑆
 𝐻2 𝑆 gas reacts with 𝑃𝑏 + salt from copper acetate to prepare
blackish colored PbS as 𝑃𝑏 + + 𝐻2 𝑆 → 𝑃𝑏𝑆 + 2𝐻+
 The required compound from crucible grinded in Piston
Morten to obtain the powder form of material
characterization
32
STRUCTURES
 X-ray diffraction 1000
200
(PbS)
800
111
Intensity (a.u)
600 220
400 311
200 222
331
400
0
20 30 40 50 60 70
2
 Peaks were indexed to cubic PbS
 JCPDS card number 01-078-0876
 The cell parameters a, b and c are 3.7960, 3.7960 and 16.3820𝑨°
respectively
 The average crystallite size was ~ 16.337nm
33
STRUCTURES
 Scanning electron microscopy
34
STRUCTURES
 CuS nanocrystallites
 Prepared PbS powder was comprised of nanocrystals

 The average crystallite size was ~ 16.337nm
 I-VI semiconductor (p-type)
 Crystalizes with cubic symmetry
35
STRUCTURES
 Transport properties of PbS nanocrystallites
 Final device structure
PbS Nano crystals Copper pad
Composite substrate
36
STRUCTURES
 Copper pads were photolithographically defined on
composite substrate.
 The separation between copper lines is 350μm.
 PbS nanocrystals were deposited on the substrate by

screen printing method.
37
STRUCTURES
 I-V Characteristics CuS Nanocrystellites
0.0001
380K
300K
Current (A)
0.0000
300K
380K
-0.0001
-5 0 5
Voltage(V) 38
STRUCTURES
Voltage dependent P-E Loop for PbS
Voltage dependent P-E L for PbS
10
0V
8 5V (c)
10V
6 15V
4 20V
2
P(C/cm )
2
0
-2
-4
-6
-8
-10
-80 -60 -40 -20 0 20 40 60 80
E(v/cm)
39
STRUCTURES
9 80
8 70 Ec (e)
7 Pr (d)
Ps
60 Es
6 50 -Ec
5 -Pr
40 -Es
4 -Ps
3 30
2 20
E(KV/cm)
1 10
P(C/cm )
2
0 0
-1 -10
-2 -20
-3 -30
-4 -40
-5
-6 -50
-7 -60
-8 -70
-9 -80
0 5 10 15 20 0 5 10 15 20
Voltage(V) Voltage(V)
40
STRUCTURES
Temperature dependent P-E Loop for PbS
Temp dependent P-E Loop for PbS

20 22C (f)
50C
15 60C
100C
10 150C
200C
5
P(C/cm )
2
0
-5
-10
-15
-20
-80 -60 -40 -20 0 20 40 60 80
E(v/cm)
41
STRUCTURES
90
20 Pr (g) 80
Ps 70
15 -Pr 60
-Ps 50 (h)
10 40
30
5 20 Ec
P(C/cm2)
10
E(v/cm)
Es
0 0 -Ec
-10
-5 -20 -Es
-30
-10 -40
-50
-15 -60
-70
-20 -80
-90
0 20 40 60 80 100 120 140 160 180 200 220 0 20 40 60 80 100 120 140 160 180 200 220
0 0
T C) T C)
42
DEVELOPMENT AND CHARACTERIZATION OF
GAS AND HUMIDITY SENSORS USING METAL
SULPHIDE NANO STRUCTURES
Gas sensing properties of PbS
-6
4.0x10
air b
-6
3.0x10 2min
4min
-6
2.0x10 8min
16min
-6 air a
1.0x10
Current(A)
0.0
-6
-1.0x10
-6
-2.0x10
-6
-3.0x10
-6
-4.0x10
-1.0 -0.5 0.0 0.5 1.0
Voltage(V) 43
44
 Synthesis of CdS Nanostructure
 Stoichiometric amounts of Cadmium acetate and thiourea in the
 The resulting gel like compound was then put in a crucible and
annealed at 200℃ for 5h
 Decomposition of thiourea occurs at 150℃ producing 𝐻2 𝑆 gas
as 𝑆𝐶(𝑁𝐻2 )2 → 𝑁𝐻2 𝐶𝑁 + 𝐻2 𝑆
 𝐻2 𝑆 gas reacts with 𝑃𝑏 + salt from copper acetate to prepare
yellowish colored CdS as 𝐶𝑑 2+ + 𝐻2 𝑆 → 𝐶𝑑𝑆 + 2𝐻+
 The required compound from crucible grinded in Piston Morten
to obtain the powder form of material
characterization
45
(002)
 X-ray diffraction CdS
(101)
120
(100)
Intensity (a.u)
(110)
(112)
60
(103)
(102)
(203)
(114)
(211)
(105)
0
20 40 60 80
2
 Peaks were indexed to hexagonal CdS
 JCPDS card number 41-1049
 The cell parameters a, b and c are 4.11, 4.11 and 6.68𝑨°
respectively
 The average crystallite size was ~ 17nm 46
STRUCTURES
Scanning electron microscopy
47
STRUCTURES
48
STRUCTURES
49
STRUCTURES
Voltage dependent P-E Loop for CdS
Voltage dependent P-E Loop for CdS
0V
30 5V
10V
20 15V
20V
10
P(C/cm2)
-10
-20
-30
-150 -100 -50 0 50 100 150

E(V/cm)
50
STRUCTURES
Ec
Pr
-Ec
-Pr 80
20 Es
Ps
-Es
-Ps
P(C/cm )
E(V/cm)
2
0 0
-20 -80
0 10 20 0 10 20
Voltage(V) Voltage(V)
51
STRUCTURES
Temperature dependent P-E Loop for CdS
Temp dependent P-E Loop for CdS
20 0
25 C
0
15 50 C
0
75 C
10
5
P(C/cm2)
-5
-10
-15
-20
-80 -60 -40 -20 0 20 40 60 80
E(V/cm)
52
STRUCTURES
80
20
60 Ec
Pr -Ec
-Pr 40 Es
10 Ps -Es
-Ps 20
P(C/cm2)
E(v/cm)
0 0
-20
-10
-40
-20 -60
-80
20 40 60 80 20 30 40 50 60 70 80
0
T C) 0
T C)
53
STRUCTURES
Gas sensing properties of CdS
air b
-3
1.0x10 1min
2min
3min
-4 4min
5.0x10
air a
Current(A)
0.0
-4
-5.0x10
-3
-1.0x10
-1.0 -0.5 0.0 0.5 1.0

Voltage(V) 54
NANOSTRUCTURES
𝑅𝑔𝑎𝑠
𝐺𝑎𝑠 𝑅𝑒𝑠𝑝𝑜𝑛𝑠𝑒 = 1 −
𝑅𝑎𝑖𝑟
From graph: 𝑅𝑎𝑖𝑟 = 77𝑀𝜴 𝑎𝑛𝑑 𝑅𝑔𝑎𝑠 = 13𝑀𝜴
𝐺𝑎𝑠 𝑅𝑒𝑠𝑝𝑜𝑛𝑠𝑒 = 83%
55
STRUCTURES
Facilities required and availability
 Electrospinning setup and high temperature furnace
 Available in Micro and Nano Devices group (DMME,
PIEAS)
 UV spectrometer
 Available in PIEAS
 FTIR, TGA, BET surface area analyzer and X-Ray
diffractrometer
 Available in PIEAS
 Scanning electron microscope (occasional use)
 Available in PIEAS/NUST
 Probe station, Parameter analyzer and LCR meter
major equipment required for this purpose
 Available in Micro and Nano Devices Group (DMME,
PIEAS) 56
STRUCTURES
Expected out comes
 Understanding transport properties of metal sulphide
nanostructures by fabricating two terminal and three
terminal devices.
 To exploit understanding of transport properties of metal

sulphide nanostructures to fabricate sensors and
demonstrate their operation.
 Publication of results in international peer reviewed

journals.
57
STRUCTURES
WORK PLAN
Sub Tasks Time Frame
C 01 Year 02Year 03 Year 04 Year
O
U Approval of study Plan
R
S
E Completion of course work
W
O
1st Qualifying Exam
R
K
Literature survey
R Synopsis Approval
E
S
E Experimental work
A
R
C
Characterization
H
2nd Qualifying Exam
W Analysis of Results and publications

O
R
K
Thesis writing
We are here till 26-05-2015
58
ACKNOWLEDGEMENTS
PIEAS
 DPAM
 DMME
 HEC ( for IRSIP)
60

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1

DEVELOPMENT AND CHARACTERIZATION OF GAS AND

Muhammad Faheem Afsar1,2

Supervisor: Dr. Muhammad Aftab Rafiq1

Co-Supervisor: Dr. Muhammad Masood ul Hasan1

1Micro and Nano Devices Group

b) Metal sulphide nanostructure materials properties

c) Metal sulphide nanostructure materials applications

e) Copper sulphide (CuS) , Lead sulphide (PbS) and CdS

f) Solid state reaction method

a) Synthesis of CuS , PbS and CdS nanostructure

 Facilities required and availability

b) Properties of metal sulphide nanostructures

 Salt-like or hard-metal like

 Generally hydrolyzed by water

 Oxidize in moist air at ambient temp or in dry air at elevated temp

 Some possess semi-metallic character and have electronic properties

 Excellent mechanical and thermal properties

 Excellent resistance against corrosion and chemical erosion

 Lubricants for optical and sensitive instruments

 Semiconductor and automobile industry

Processing Mechanical methods Nanocrystalline

Metal sulphides literature survey

 We plan to synthesize CuS, PbS and CdS nanostructures

 A top to bottom approach

Metal Acetate Thiourea

Mixing and grinding

Device Fabrication Electrical,

 Prepared CuS powder was comprised of nanocrystals

 Transport properties of CuS nanocrystallites

CuS Nano crystals Copper pad

 Copper pads were photolithographically defined on composite

 Material Development Corporation (MDC) probe

Keithley 2400 Source meter

Voltage dependent P-E Loop for CuS

60 120 180 60 120 180

 Prepared PbS powder was comprised of nanocrystals

PbS Nano crystals Copper pad

 PbS nanocrystals were deposited on the substrate by

Temp dependent P-E Loop for PbS

-150 -100 -50 0 50 100 150

-1.0 -0.5 0.0 0.5 1.0

From graph: 𝑅𝑎𝑖𝑟 = 77𝑀𝜴 𝑎𝑛𝑑 𝑅𝑔𝑎𝑠 = 13𝑀𝜴

𝐺𝑎𝑠 𝑅𝑒𝑠𝑝𝑜𝑛𝑠𝑒 = 83%

 To exploit understanding of transport properties of metal

 Publication of results in international peer reviewed

W Analysis of Results and publications

We are here till 26-05-2015

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