Hanoi University of Science and Technology

School of Materials Science and Engineering

Syntheses and Gas Sensing Properties

of SnO and Cu2O Nanomaterials

Vu Xuan Hien
I INTRODUCTION TO GAS SENSOR

SYNTHESIS OF Cu2O SUBMICRON-STRUCTURES USING RF

II MAGNETRON SPUTTERING AND THEIR H2S SENSING
PROPERTIES

III NH3 SENSING PROPERTIES OF SnO THIN FILM BY RF

MAGNETRON SPUTTERING

IV VISIBLE LIGHT INDUCED GAS SENSING PROPERTIES OF

SnO THIN FILM

V CONCLUSIONS

VI PAPER & CONFERENCE LIST

 I.1. History of Gas Sensor
Canary in a cage
• Canaries are more susceptible than
humans to low oxygen, methane gas, or
CO gas.
• A passed out canary means a dangerous
gas situation.
Flame Safety Lamp (Davey’s Lamp)
• Invented by Sir Humphry Davey (of
England) in 1815
• Oil flame adjusted to specific height in
fresh air

John Bardeen, William Shockley, Walter Brattain Taguchi

➢ Brattain and Bardeen first reported gas sensitive effects on Ge in 1953.

➢ Heiland, Bielanski and Seiyama found gas sensing effects on metal oxides.
➢ Taguchi finally brought metal oxide gas sensor to an industrial product focused of explosive gases.
Field effect Surface acoustic wave Metal oxide Optical Electrochemical
gas sensor (SAW) gas sensor gas sensor gas sensor gas sensor

Sensor Structure Sensing Material (n-type, p-type)

 Depletion zone

Accumulation
zone

n-type semiconductor p-type semiconductor

KNU 2015/05/21
• Cuprous oxide is a p-type semiconductor with a direct bandgap of ~2.17 eV.
• Cu2O has been applied in many fields, like catalysis, lithium-ion battery-anode materials,
photo-electrodes, low-cost solar cells and sensors.
• Cu2O thin film can be deposited by sputtering.
• Tailoring the morphology of Cu2O by sputtering is a big issue.

Synthesis of Cu2O Multi-morphology

by Sputtering

?
Apply For Gas Sensing Applications
SnO applications Rutile structure Litharge structure
SnO2 applications
a=0.473nm, c=0.318nm, c/a=0.67 a=0.38nm, c=0.48nm, c/a=1.27
Ruby glass Gas sensor

Touchscreen
Sn
Coating layer

Ce2O3 + SnO Electrode layer

β-SnO α-SnO
(Eg = 2.5 ~ 3.0 eV) SnO2 (Eg = 2.5 ~ 3.0 eV)
Vis UV
(Eg = 3.6 eV)

Precursor & Reducing agent Pigment

0.38nm

SnO2 (101) SnO (001)

Based on those reasons, I propose a study entitle:

SYNTHESES AND GAS SENSING PROPERTIES OF

SnO AND Cu2O NANOMATERIALS
SYNTHESIS OF Cu2O SUBMICRON-STRUCTURES
USING RF MAGNETRON SPUTTERING AND
THEIR H2S SENSING PROPERTIES
PART 1
 Target Material Metallic Cu
O2/(Ar+O2) 3, 4, 6 %

RF-magnetron Sputtering Power 30 W

Working Pressure 5 mTorr

Growth Temperature 550 oC
Base Pressure 3×10-6 Torr

Target-Substrate Distance 80 mm

Deposit Time 30 min

Separating electrode

Mount electrode on TO-Header

(Use silver paste)

Connect electrode to the pins

by silver wires
(use silver paste)

Dry in oven at 90oC for 40 minutes

 Intensity (a.u.)

28
Cu2O (110) Cu2O (110) Cu2O (110)

32
CuO (110)

36
Cu2O (111) Cu2O (111) Cu2O (111)
Au (111) Au (111) Au (111)

40
Cu2O (200) Cu2O (200)
Cu2O (200) Cu (111) Cu (111)

44
Au (200) Au (200) Au (200)

48
Cu (200) Cu (200)

52
56
(c) Cu2O thin-film sensor

60
2 (degree, CuK)
Cu2O (220) Cu2O (220) Cu2O (220)
(b) Cu2O submicron-rod sensor
(a) Cu2O submicron-tree sensor

64
Au (220) Au (220) Au (220)

68
72

Cu2O (311) Cu2O (311) Cu2O (311)

76

Cu2O (222) Cu2O (222) Cu2O (222)

Au (311) Au (311) Au (311)
(b)
(a)

(c)
80
• TMelt-Cu = 1085 oC
• TMelt-Cu nanoparticles with
oxide shells (10–70 nm in
diameter, oxide thickness >2
o
nm) ~ 274 C
• Growth mechanism:
VLS (vapor-liquid-solid)
VSS (vapor-solid-solid)
VQS (vapor-quasiliquid-solid)
• Growth rate of Cu2O
nanorods: 50 nm/s

➢ Possible growth
mechanism:

VLS + VQS
 (a)
Transportation (e) (f)
Route Oxide Layers
1 µm

2 nm
(b)
Growth
Zone
20 nm Ripple Oxide
20 nm Layers (e) 5 nm
100 nm
(c) (d) (g) (h)
50 nm
Random
Growth (020)
0.21 nm
(110)
Transition (200)
Location
22 00 nn m
m

(220)
Axial
Growth 22 nn m
m 2 nm 5 1/nm
1 0 0 nm
 2048 2048
T = 300oC 10 ppm H2S
1024 (a) 10 ppm H2S 1024 v = 200 sccm

512 Cu2O submicron-trees 512 Cu2O submicron-trees

256 Cu2O submicron-rods 256 Cu2O submicron-rods
Response (S = Ra/Rg)

Response (S = Ra/Rg)
Cu2O thin film Cu2O thin film
128 128
64 T = 200oC 64 10 ppm H2S
v = 200 sccm
32 H2S off 32
16 10 ppm H2S 16 H2S off
8 8
10 ppm H2S
4 4
H2S on H2S on
2 2
10 ppm H2S
1 1 (b)
0 5 10 15 20 25 30 35 40 45 50 55 60 0 5 10 15 20 25 30 35 40 45 50 55 60
Time (min) Time (min)
16384
65536
Dry air
Dry air 32768 T = 300oC
8192 T = 300oC Target
Target 10 ppm NO2 v = 200 sccm gas on 10 ppm NO2 v = 200 sccm
16384
gas on 100 ppm NH3
4096 100 ppm NH3 8192
Resistance (ohm)

1000 ppm CO2

Resistance (ohm)
1000 ppm CO2
4096
2048 8000 ppm CH4 8000 ppm CH4
2048
8000 ppm C3H8 8000 ppm C3H8
1024 1024
10 ppm H2S 5 ppm H2S
0 10 20 30
Response (S = Ra/Rg)
40 50 512 10 ppm H2S
512
Target 256 0 200 400 600 800 1000
gas off Response (S = Ra/Rg)
256 128 Target
(c) (d) gas off
64
128
-5 0 5 10 15 20 25 30 35 40 45 50 55 60 65 0 5 10 15 20 25 30 35 40 45 50 55 60
Time (min) Time (min)
2H 2 S ( g ) + 3O2n − (ads) → 2H 2O( g ) + 2SO2 ( g ) + 3ne−
2SO2 + O2n − (ads) → 2SO3 + ne−
CuO + H 2 S → CuS + H 2O
2CuS + 3O2 → 2CuO + 2SO2
✓ Cuprous oxide thin films, submicron-sized rods and submicron
trees were synthesized by RF-magnetron sputtering.

✓ The morphologies of Cu2O were easily tailored by modulating

the ratio of Ar/O2 during the sputtering process.

✓ The sensor based on Cu2O submicron-trees showed the best H2S

sensing property at 200 oC among the three different
morphologies investigated.

✓ Both the submicron-sized tree and rod sensors were selective

toward H2S.

✓ The sensing mechanism of all samples involved a phase

transformation from Cu2O to CuS.
NH3 SENSING PROPERTIES OF SnO
THIN FILM BY RF MAGNETRON
SPUTTERING
PART 2
 SnO (101)
Pristine thin film
Thin film treated from RT to 300oC
Target Material Sn
O2/(Ar+O2) 3%

RF-magnetron Sputtering Power 50 W

Intensity (a.u.)

Working Pressure 10 mTorr

Growth Temperature 200oC
SnO (002)

SnO (112)
Base Pressure 3×10-6 Torr

Target-Substrate Distance 70 mm

Deposit Time 160 s (1.6 nm/s)

Thickness 100 nm

29.8◦ 37.1◦ 50.7◦

10 20 30 40 50 60 70 80 90
2*theta (degree)

➢ Index to tetragonal structure of SnO (JCPDS: 01-072-1012)

 Approx. thickness (nm)
0 20 40 60 80 100

100 (a) 19 sputtering cycles

(nearly 19 min in total)
80
Rate of 5.26 nm/min
Atomic Concentration (%)

60 C1s
O1s
Sn3d5
40

20

0 5 10 15 20 25 30 35
Sputtering time (minute)
 Approx. thickness (nm)
0 20 40 60 80 100

100 (a)
80
Atomic Concentration (%)

60 C1s
O1s
Sn3d5
40

20

0 5 10 15 20 25 30 35
Sputtering time (minute)
 954

952

950

948 200ppm

Resistance (ohm)
NH3
946
Air

944

942 100ppm
NH3
940

938 50ppm
NH3
936
0 10 20 30 40 50
Time (minute)
1.02
150oC
1.01
200oC

1.00

Relative Resistance 0.99

0.98

0.97
NH3 (200ppm) + Air Air
0.96
0 10 20 30 40 50 60 70 80 90
Time (minute)
 1 1 1 1
= + + ⋯+
𝑅𝑠𝑒𝑛𝑠𝑜𝑟 𝑅𝑆𝑛𝑂2 𝑅𝑆𝑛𝑂1 𝑅𝑆𝑛𝑂𝑛

2𝑁𝐻3 𝑔𝑎𝑠 + 3𝑂2− → 𝑁2 𝑔𝑎𝑠 + 3𝐻2 𝑂 𝑔𝑎𝑠 + 6𝑒 −

2𝑁𝐻3 𝑔𝑎𝑠 + 3𝑂2− → 𝑁2 𝑔𝑎𝑠 + 3𝐻2 𝑂 𝑔𝑎𝑠 − 6ℎ+
✓ SnO thin films, 100 nm thickness, were deposited by RF
magnetron sputtering.

✓ The extremely thin layers of SnO2 (less than 6 nm) was found on
the surface of the thin film.

✓ For the NH3 sensing test, the sensor exhibited a p-type

semiconducting sensing characteristics at working temperature
below 200 oC.

✓ The sensor was sensitive to 50 ppm NH3 at 200 oC with a good

repeatability.

✓ The sensing behavior of the SnO sensor was explained in detail

using equivalent circuit.
VISIBLE LIGHT INDUCED GAS SENSING
PROPERTIES OF SnO THIN FILM
PART 3
 Laser
- Power: 65 mW
- Blue (λ = 405 nm)
- Green (λ = 510 nm)
- Red (λ = 658 nm)

Chamber
Stainless steel
Temperature: RT
Humidity: ~25%

Hot Plate
Temperature: 25 oC
 (a) (b)
(002)
Intensity(a.u.)
(001)

(004)
(211)

20 25 30 35 40 45 50 55 60 65 70 75 80
2 (degree, CuK)
 6,2E-08
6,0E-08 100 oC 150 oC 200 oC
5,8E-08
5,6E-08
5,4E-08
(β)
5,2E-08
5,0E-08
(δ)
4,8E-08
4,6E-08
(γ) (δ)
Current (A)

3,7E-08
3,6E-08
3,5E-08
(α) (β)
3,5E-08
3,4E-08
3,4E-08
3,3E-08
1,1E-08
(α) (γ)
1,1E-08

1,0E-08 20 ppm H2S Air

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

Time (min)
 6E-08

On On On On
S1 R
5E-08
S2
Photo Current (A)

4E-08

3E-08

2E-08

1E-08
20 ppm H2S Dry air

-400 0 400 800 1200 1600 2000 2400 2800

Time (s)
 5.2E-08 5.2E-08
Dry Dry Dry air Dry air
air air
5.0E-08
5.0E-08 1 ppm
H2S
4.8E-08
4.8E-08
Current (A)

Current (A)
4.6E-08 ppm
H2S
4.6E-08
4.4E-08 10
ppm
4.4E-08 H2S
4.2E-08 15
(a) ppm (b)
H2S
4.2E-08 4.0E-08
20
H2S Dry H2S Dry H2S Dry H2S Dry H2S Dry H2S Dry ppm
on air on air on air on air on air on air H2S
3.8E-08
4.0E-08
0 20 40 60 80 100 120 140 160 180 200 220 240 260 0 30 60 90 120 150 180 210
Time (min) Time (min)

➢ After first 2 circles, the sensing signal was completely stable.

➢ The minimum H2S concentration which the sensor can detect is 5 ppm.
 5.2E-08
5.0E-08 (a)
4.8E-08
4.6E-08
4.4E-08
4.2E-08
Current (A)

4.0E-08 (b)
3.8E-08

1.2E-08
(c)
1.0E-08
[Blue] SO 2 NO2 H2 S NH3
8.0E-09
[H2S] Green Red Dark

6.0E-09 Target Gas In Dry air (d)

0 200 400 600 800 1000 1200 1400 1600 1800

Time (s)
✓ Single crystal SnO thin film with the film thickness of 10 nm was
deposited by RF magnetron sputtering
✓ By temperature induction, a transformation of the H2S sensing
behavior from p-type SnO to n-type SnO2 was recorded when the
operating temperature was equal and above 150 oC.
✓ Under illumination by blue or green light at 25 oC, only p-type
semiconducting gas sensing properties of the SnO thin film with
good response and high stability was received.
✓ The sensor is mostly selective with H2S under different testing
condition in which 2-step response in the response-recovery
curve was found for this gas.
✓ A possible gas sensing mechanism of p-type semiconductor under
visible light was proposed and discussed in detail.
✓ Cu2O rod-like and tree-like submicron-scale were first introduced
by RF magnetron sputtering which provide strong evidence for
the existence of VQS mechanism.
✓ Sensors based Cu2O submicron-rods/trees were 100 % selective
toward 10 ppm H2S at 200-300 oC.
✓ For the first time, p-type semiconducting gas sensing properties
of SnO thin film was recorded below 200 oC.
✓ Negative effect of SnO2 layer on the SnO surface was completely
removed under visible-light illumination at RT.
✓ Blue-light induced gas sensing properties of SnO thin film shows
excellent stability and sensitivity at RT.
✓ Sensing mechanism of all devices were proposed and discussed in
detail in visual models.