Supporting Information:

Detection of PPB-Level H2S Concentrations

in Exhaled Breath Using Au Nanosheet
Sensors with Small Variability, High
Selectivity, and Long-Term Stability

Taro Kato,∗ Takahisa Tanaka, and Ken Uchida∗

Department of Materials Engineering, The University of Tokyo, Tokyo

E-mail: kato@ssn.t.u-tokyo.ac.jp; uchidak@material.t.u-tokyo.ac.jp

Contents

Figure S1. Comparison of influence of adhesion layers on resistivity of Au nanosheet.

Figure S2. Images of Au nanosheet surfaces at different N2 annealing temperatures.

Figure S3. Schematic of fabrication process of Au nanosheet.

Figure S4. Gas-sensing setup.

Figure S5. NBD image of Figure 2e with color inversion.

Figure S6. Temperature dependence of sensor response of Au nanosheet toward 4.0 ppm
H2 S.

Figure S7. Variability of resistances in 10 Au nanosheet sensors.

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Figure S8. Sensor response to ppb-level concentrations of H2 S.

Figure S9. Raw experimental response data to interfering gases.

Figure S10. Sensor responses of Au nanosheet sensor to the 5 different concentrations of

H2 S for creating the standard curve.

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(a) (10-7) (b) (10-8)
Cr/Au: 2/12 nm TiN/Au: 2/12 nm
Resistivity (·m) 2.5

Resistivity (·m)
6
As-deposited
2
5
1.5
As-deposited 4
1 Ti/Au: 2/12 nm
3 Bulk Au (ideally)
0.5 nm
Bulk Au TiN/Au: 2/12
2
0 100 200 300 0 100 200 300
o
Temperature ( C) Temperature (oC)
Figure S1: (a) Comparison of temperature dependence of resistivity in 12-nm-thick Au
nanosheet with different 2-nm-thick adhesion layers: Cr, Ti, and TiN. (b) Partial enlargement
of resistivity data in (a) when TiN adhesion layer is used.

S-3
 As depo. 300 ℃, 1 h 400 ℃, 1 h 500 ℃, 1 h

Figure S2: Optical microscope images of Au nanosheet surfaces at different N2 annealing

temperatures. At temperatures above 400 ◦ C, voids formed on Au nanosheets.

S-4
1. TiN/Au deposition 2. N2 annealing 3. Channel patterning 4. Au etching
(RF sputtering) (300 ℃, 1 h) (EB litho., Negative) (Ar plasma)
N2
TiN/Au=2/16 nm

SiO2 1μm SiO2 SiO2

p-Si p-Si p-Si

8. Lift-off (DMAC + 7. Electrode deposition 6. Electrode patterning 5. Resist removal

IPA, ultrasonication) (Cr/Au, EB deposition) (EB litho., Positive) (O2 plasma + SPM cleaning)

SiO2 SiO2 SiO2 SiO2

p-Si p-Si p-Si p-Si

Figure S3: Schematic of fabrication process of Au nanosheet.

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(a) Water
bubbling
(b)
MFC
Closed box
Dry air MFC

Mixer Exhaust
MFC
Sensor

H2S, H2,
MFC
etc…)
Gas outlet Heater power supply
(Exhaust) & Thermocouple

Figure S4: (a) Schematic of gas-sensing measurement setup. (b) Photographs of outside
(left) and inside (right) of measurement system.

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Figure S5: NBD image of Figure 2e with color inversion. Miller indice are assigned to all the
diffraction points. Assignment was conducted using SingleCrystal from CrystalMaker®.

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 8
4.0 ppm H2S
6 Exposure: 30 sec

Response (%)
4

0
0 50 100 150 200 250
Temperature (oC)
Figure S6: Temperature dependence of response of Au nanosheet sensor to 4.0 ppm H2 S.

S-8
 330
T: RT : 6.12  #01
325

Resistance ()
#02
#03
320
#04
315 #05
#06
310 #07
#08
305 #09
#10
300
0 2 4 6 8 10
Time (min)
Figure S7: Time characteristics of resistances in 10 Au nanosheet sensors at room temper-
ature. Standard deviation of resistance is 6.12 Ω, which is about 2% of resistance in each
sensor.

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(a) 0.8 (b) 15
27 ppb H2S peak

GC Output (mV)
0.6 H2 S T: 225 oC 10 Dry air + H2S
Response (%)

H2S: 27 ppb w/ GC
0.4 5
H2S: 5.6 ppb w/ GC
0
0.2
-5
0
0 5 10 15 -10
0 60 120 180
Time (min) Time (sec)
Figure S8: (a) Sensor response to H2 S at a concentration of 27 ppb at 225 ◦ C. (b) Outputs
from gas chromatography (GC) to the same H2S gases in (a) and Figure 3e.

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 1
NH3 CH4

Response (%)
MeOH EtOH
0.5 Acetone H2

-0.5
T: 225 oC
-1
0 5 10 15
Time (min)
Figure S9: Sensor responses of Au nanosheet sensor to different disturbing gases at 225 ◦ C:
10 ppm NH3 (red), 100 ppm CH4 (orange), 100 ppm methanol (green), 100 ppm ethanol
(blue), 100 ppm acetone (purple), and 1020 ppm H2 (pink).

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Figure S10: Sensor responses of Au nanosheet sensor to 5 different concentrations of H2 S
for creating standard curve. Base gas is air containing relative humidity (RH) of 50%. H2 S
gases contain the same humidity.

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