Phosphorene as a superior gas sensor：

DFT coupled with NEGF study

Speaker：Meng-Chien Wang
Advisor：Prof. Ching-Ray Chang
 Gas sensor based on 2D material
• High surface to volume ratio
• Strong surface activities
 gas sensor working mechanism
1. adsorbed gas molecules may change the
electronic structure of substrate
Change in
2. charge transfer lead to change in carrier conductivity
concentration of substrate

sensor response：

𝐺 − 𝐺0
𝑆 % = × 100
𝐺0

G：conductance with gas adsorbate

G0：conductance without gas adsorbate
gas sensor performance parameter
• sensitivity：sensor response per concentration unit
of gases
• selectivity：capability of responding to a specific
group of gases or to a certain gas
• response time：time used to reach 90% of response
in the presence of gases
• recovery time ：time used to return to 90% in the
absence of gases
black phosphorus
 phosphorene
top view

𝒂𝟐
side view

𝒂𝟏

Motohiko Ezawa .Topological origin of quasi-flat edge band in

phosphorene". New Journal of Physics. 16 (11): 115004(2014)
Liangzhi Kou,Thomas Frauenheim and Changfeng Chen. Phosphorene as a
Superior Gas Sensor: Selective Adsorption and Distinct I–V Response
J. Phys. Chem. Lett., 2014, 5 (15), pp 2675–2681

Adsorption energy Ea= (Egas+Ep)–Ep+gas

Egas：energy of isolated gas molecule
Ep： energy of isolated phosphorene layer
Ep+gas：energy of the fully relaxed
phosphorene with gas adsorption
 Liangzhi Kou,Thomas Frauenheim and
Changfeng Chen. Phosphorene as a
Superior Gas Sensor: Selective Adsorption and
Distinct I–V Response
J. Phys. Chem. Lett., 2014, 5 (15), pp 2675–2681

The charge transfer Δρ=ρtot(r) –ρp(r) –ρgas(r)

ρtot(r)：charge distribution of gas-adsorbed phosphorene
ρp(r)： charge distribution of free phosphorene
ρgas(r)： charge distribution of free gas molecule
 charge transfer (positive means charge transfer from
phosphorene to gas molecule)
CO -0.03e
CO2 -0.04e
NO 0.2e
NH3 -
NO2 +

• The amount of charge transfer is correlated to the

adsorption strength (Ea)
Liangzhi Kou,Thomas Frauenheim and Changfeng Chen. Phosphorene as a
Superior Gas Sensor: Selective Adsorption and Distinct I–V Response
J. Phys. Chem. Lett., 2014, 5 (15), pp 2675–2681
calculate I-V curve using NEGF formalism
• Landauer setup

lead sample lead

fL fR
f is the Fermi-Dirac distribution function

The system consists of two portions, sample and semi infinite lead

system hamiltonian H=Hs + HL + HSL

sample lead hybridization between

sample and lead
calculate I-V curve using NEGF formalism

• the retard green function

𝕀
GR(E)=
𝐸+𝑖𝜂 𝕀− Hs −σ𝑅(𝐸)

ΣR(E)=TSL gR(E)TLS

retard green function of the lead

Define Γ(E)=i{ΣR(E)- ΣR+(E)}

calculate I-V curve using NEGF formalism

• the transmission function between lead p and lead q

+
Tpq=trace(Γp GR Γq GR)
 under bias 2.1V under bias 2.1V

phosphorene：5.26 uA phosphorene：4.41 × 10-2 uA

phosphorene+NH3：4.7 uA phosphorene+NH3：4.37 × 10-2 uA
S=10.6% S=0.9%
Liangzhi Kou,Thomas Frauenheim and Changfeng Chen. Phosphorene as a
Superior Gas Sensor: Selective Adsorption and Distinct I–V Response
J. Phys. Chem. Lett., 2014, 5 (15), pp 2675–2681
The anisotropic transport behavior

Y M

Γ . X

Jiu Pang, Qun Yang, Xiaosong Ma, Liming Wang, Chunjian Tan, Daxi
Xiong, Huaiyu Ye and Xianping Chen
DFT coupled with NEGF study of ultra-sensitive HCN and HNC gases
detection and distinct I–V response based on phosphorene.
Phys. Chem. Chem. Phys., 2017, 19, 30852-30860
 under bias 1.5V
armchair zigzag
phosphorene：1.28 uA phosphorene：4.65 × 10-3 uA
phosphorene+NO：1.42 uA (spin up) phosphorene+NO：2.59 × 10-2 uA (spin up)
phosphorene+NO：2.85 uA (spin down) phosphorene+NO：7.47 × 10-2 uA (spin down)
doping effect

N-Al covalent bond is formed

Jiu Pang, Qun Yang, Xiaosong Ma, Liming Wang,

Chunjian Tan, Daxi Xiong, Huaiyu Ye and Xianping Chen
DFT coupled with NEGF study of ultra-sensitive HCN and
HNC gases detection and distinct I–V response based on
phosphorene.
Phys. Chem. Chem. Phys., 2017, 19, 30852-30860
charge transfer modulated by electric field
Qu Yue, Zhengzheng Shao, Shengli Chang
and Jingbo Li. Adsorption of gas
molecules on monolayer MoS2 and effect of
applied electric field.
Nanoscale Research Letters 2013 8:425

If electric field is not applied,

NO adsorped on MOS2 ΔQ=0.022e
NO2 adsorped on MOS2 ΔQ=0.1e
 What can we study using NEGF?
• tight binding model
𝐻 = −𝑡 σ(Ci+ Cj+ Cj+ Ci ) +σ UiCi+Ci
i,j i

• tune the hopping parameter t and on site

energy Ui and calculate I-V curve
 What can we study using NEGF?
• qualitative study (use armchair graphene nanoribbon)
d：large small
t： large small
Uc：large small
Ug：small large
• pristine vs defective
• doping effect
Thanks for listening!