Article

Cite This: ACS Nano 2019, 13, 13486−13491 www.acsnano.org

Direct Observation of Band Gap

Renormalization in Layered Indium Selenide
Zailan Zhang,†,‡ Zhesheng Chen,*,§ Meryem Bouaziz,‡ Christine Giorgetti,§,∥ Hemian Yi,‡ Jose Avila,‡
Bingbing Tian,† Abhay Shukla,⊥ Luca Perfetti,§ Dianyuan Fan,† Ying Li,*,†,#
and Azzedine Bendounan*,‡
†
International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education,
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Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen 518060, China

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‡
Société Civile Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, BP 48, Gif-sur-Yvette 91192, France
§
Laboratoire des Solides Irradiés, Ecole Polytechnique, CNRS, CEA/DRF/IRAMIS, Institut Polytechnique de Paris, Palaiseau
91128, France
∥
European Theoretical Spectroscopy Facility, Palaiseau 91128, France
⊥
Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, CNRS-UMR7590, Sorbonne Université, 4 Place Jussieu,
Paris 75252, France
#
Engineering Technology Research Center for 2D Material Information Function Devices and Systems of Guangdong Province,
Shenzhen University, Shenzhen 518060, China
*
S Supporting Information

ABSTRACT: Manipulation of intrinsic electronic struc-

tures by electron or hole doping in a controlled manner in
van der Waals layered materials is the key to control their
electrical and optical properties. Two-dimensional indium
selenide (InSe) semiconductor has attracted attention due
to its direct band gap and ultrahigh mobility as a promising
material for optoelectronic devices. In this work, we
manipulate the electronic structure of InSe by in situ
surface electron doping and obtain a significant band gap
renormalization of ∼120 meV directly observed by high-
resolution angle resolved photoemission spectroscopy.
This moderate doping level (carrier concentration of 8.1 × 1012 cm−2) can be achieved by electrical gating in field
effect transistors, demonstrating the potential to design of broad spectral response devices.
KEYWORDS: indium selenide, band gap renormalization, ARPES, electron doping

induced by electronic gating in field effect transistors

I n two-dimensional (2D) semiconductors, modulation of

the electronic structure by tuning carrier concentration in
a controlled manner has created opportunities for
advanced electronics, functional optoelectronics, and quan-
tum-logic devices.1−4 Calculations have shown that the
(FETs).10−12
Recently, the 2D III−VI semiconductor indium selenide
(InSe) has attracted a lot of attention because of its direct band
gap with the value of ∼1.3 eV in thick layers and ultrahigh
magnetic properties and phase transitions can be controlled carrier mobility.13−17 The carrier mobility in few-layer InSe is
in several 2D materials such as monolayer GaSe and InP3 by found to be as high as 103 cm2 V−1 s−1 and 104 cm2 V−1 s−1 at
tuning hole densities.5−8 Experimentally, by increasing carrier room and low temperature, respectively,18 which is of the
density, a giant band gap renormalization of ∼400 meV and order of that found in graphene and is among the highest in
indirect-to-direct band gap transitions is observed in layered 2D semiconductors. These properties make InSe an excellent
transition metal dichalcogenides (TMDs) MX2 (M = Mo, W; candidate for optoelectronic applications such as photo-
X = S, Se, Te) semiconductors.9 This is promising for detectors and solar cells.19 The band gap value and nature
multifunctional optoelectronic device application with wider determine the optical and electronic properties of the material.
spectral range from visible to infrared. Furthermore, significant
phase transitions, such as insulator−metal phase transition in Received: September 9, 2019
few-layer black phosphorus (BP) and insulator−metal−super- Accepted: October 23, 2019
conductor phase transition in few-layer MoS2, have been Published: October 23, 2019

© 2019 American Chemical Society 13486 DOI: 10.1021/acsnano.9b07144

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Figure 1. (a) Crystal structure and (b) the first Brillouin zone of ε polytype InSe. (c) Calculated band structure of InSe along out-of-plane
Γ−A direction. (d) ARPES intensity map of InSe under hν = 120 eV along K−M−Γ−K direction. (e) ARPES intensity map of InSe under hν
= 111 eV along H−A−H direction. The calculated band structures (solid curves) under kz = 0 and kz = π/c are superimposed on (d) and (e),
respectively.

Being able to change a direct band gap by a few hundred meV which are shown in Figure 1a,b. The band structure of ε-InSe
changes the optical response in a significant way. Band gap was calculated by density functional theory (DFT) with the
renormalization is a powerful technique to overcome intrinsic local density approximation (LDA) using the ABINIT code.
limits and to design novel materials properties and Due to the well-known underestimation of the band gap in
functionalities. Calculations predict that the band gap of DFT-LDA, we have added an additional rigid shift to the
bilayer InSe decreases dramatically and semiconductor to valence bands to reach the measured band gap (see the
metal phase transition is achieved by tuning carrier density, Supporting Information and Figure S1 for the details of
which can promote InSe as data storage devices.20 However, calculation). From band dispersion along Γ−A direction
the experimental engineering of InSe electronic structure with shown in Figure 1c, both the first valence band and conduction
carrier concentration has not been achieved systematically as band indicate significant kz dependence, which arises from the
yet. pz-like orbital (out-of-plane) contribution. Therefore, in order
Here, we report the direct observation of band gap to investigate the band gap modification experimentally, it is
renormalization in InSe by combining high-resolution angle- essential to project electrons from Γ−M−K plane as both
resolved photoemission spectroscopy (ARPES) with in situ CBM and VBM are located at the Γ point. ARPES experiments
surface sodium (Na) atom deposition under low temperature. can determine the in-plane (k//) of electrons in solids by the
Akin to applying a gate voltage in few-layer FETs, depositing momentum conservation of photoelectrons directly, while
alkali atom on the surface of layered semiconductors is an determining the kz requires a set of photon energy (hν)
efficient way to modulate the carrier density and the dependent ARPES measurements. Based on the nearly free
corresponding electronic structure, already achieved in several electron final state approximation with a potential parameter
2D semiconductors. With Na atom deposition, we confirm that V0, kz can be written as kz = 2m(Ek cos θ 2 + V0)/ℏ2 where θ
the band gap of InSe decreases ∼120 meV at the induced
carrier concentration of 8.1 × 1012 cm−2 as deduced from the is the emission angle and Ek is the kinetic energy of the emitted
shifts of both conduction band minimum (CBM) and valence free electrons satisfied Ek = hν − w − EB, where w is the work
band maximum (VBM). By increasing the deposition time, we function of the sample and EB is the electron binding energy.
observed a band-tail inside the gap, which might be a sign of a We performed hν dependent ARPES experiments and found
semiconductor-metal phase transition or caused by the Na V0 = 11 eV by fitting the experimental data with the kz
intercalation into the sheet of InSe. The application of electron expression (hν = 95−154 eV, see Figure S2). We further
doping reduces, in a controlled manner, the band gap of InSe, confirmed that the Γ−M−K plane can be probed by hν = 120
and therefore makes it optically active for a broad range of eV and A−H−L plane can be probed by hν = 111 eV, as
wavelengths, which can be used for near-infrared optoelec- shown in Figure 1d,e. From the ARPES result along K−M−Γ−
tronic devices and optical modulators or switches subse- K direction with hν = 120 eV shown in Figure 1d, one can
quently. clearly visualize the dispersion of valence bands, indicating the
high quality of our sample. Moreover, the experimental data
are in excellent agreement with the calculation kz = 0. From
RESULTS AND DISCUSSION our data, the energy difference from the VBM to the Fermi
van der Waals layered InSe used here belongs to ε polytype as energy is 1.27 eV. Since the band gap of pristine InSe is ∼1.28
determined by both Raman and transmission electron eV from our photoluminescence spectrum (Figure S3), we can
microscopy.16 The unit cell of ε-InSe contains two parallel deduce that our pristine sample is electron doped with the
layers obtained by a translation of one layer onto another, and chemical potential just below the CBM. The fact that our
the corresponding Brillouin zone (BZ) has hexagonal shape, pristine sample is electron doped with the chemical potential
13487 DOI: 10.1021/acsnano.9b07144
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Figure 2. Band structure evolution of InSe as a function of carrier concentration. (a) ARPES intensity map of InSe along Γ−Κ direction
under hν = 120 eV. (b−g) The zoom-in ARPES of InSe without Na deposition (b) and with Na deposition time of 3 (c), 5 (d), 11 (e), 14 (f),
and 17 min (e), respectively. (h) Comparison of EDCs at the momentum of k// = 0 ± 0.01 Å−1 in ARPES of pristine InSe and InSe with 5
min Na deposition. The dotted red curves are the calculated conduction bands of InSe and the dotted white lines indicate the Fermi levels.

Figure 3. InSe band gap renormalization as a function of electron doping. (a) EDCs of conduction band as a function of carrier
concentration. The CBM is determined as two times of peak energy related to EF of Gaussian curve fitting (dashed line). (b) EDCs of
valence band as a function of carrier concentration. The VBM is obtained by extrapolating a linear fit (dashed line) to the leading edge of the
spectra to the baseline. (c) Energy shift of CBM, VBM, core levels of In and Se, and band gap as a function of carrier concentration (or Na
deposition time).

just below the CBM is a boon for our experiment. It means the VBM and CBM are located at the Γ point, in the following,
that doped electrons will be immediately visible in the ARPES we examine the band gap of InSe by using ARPES at the
spectrum and that one can extract the band gap and further photon energy of 120 eV so as to probe the Γ−M−K plane.
study band gap modification as a function of electron doping. Electron doping by depositing alkali atom on the surface of
We now consider the appropriate energy and BZ region for sample is a stable and systematic way to precisely control
such studies. From the ARPES result along the A−H direction amount of carriers and monitor the variation of the surface
with hν = 111 eV shown in Figure 1e, the VBM is not at the A electronic structure.21−25 After the alkali atom deposition,
point but along the A−H direction, in good agreement with electrons are transferred from the alkali atom to the
the band dispersion at kz = π/c from the calculation. Since both semiconductor, which induces 2D electric dipole layers and
13488 DOI: 10.1021/acsnano.9b07144
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downward band bending at the surface. We deposited Na atom

in situ on the surface of InSe at low temperature and performed
the ARPES experiment without transferring the sample to
other environments or chambers. Figure 2 shows the ARPES
data of InSe along the Γ−K direction as a function of carrier
concentration (N) arising from Na deposition (deposition
time is from t = 0 min to t = 17 min). The carrier
concentration is approximately estimated from the area
enclosed by Fermi contours at EF based on Luttinger’s
theorem as N = ∑ kF2/2π in which the summation runs for all
the closed Fermi pockets within a single Brillouin zone. In
Figure 2a,b, before Na deposition only the valence band of
InSe is observed. This is identical to the data shown in Figure
1d taken from a different ARPES beamline. However, in Figure
2c−g, we begin to detect the bottom of the conduction band
just below the chemical potential position at the beginning of
Na deposition. This electron pocket shifts down to higher
binding energy, and one can observe it clearly when we
increase the deposition time. Figure 2h shows energy
distribution curves (EDCs) extracted at the momentum of
k// = 0 ± 0.01 Å−1 without Na deposition and with 5 min Na
deposition (N = 5.3 × 1012 cm−2). A significant peak appears at Figure 4. XPS characterization of Na 2p (a), Se 3d (b), and In 4d
EF = 0 eV in the EDC after Na deposition that corresponds to (c) core levels as a function of Na deposition time. The dotted
the signal from the conduction band. One can thus determine arrows indicate the energy shift of the peaks and the solid arrows
the band gap renormalization by extracting the energy distance indicate the formation of shoulders under long time Na
deposition. (d) Comparison of XPS of InSe as a function of Na
between the edge of the valence band (EVBM) and the edge of deposition time. Band-tails are formed and the intensities of
the peak from the conduction band (ECBM). conduction band decrease under long-time Na deposition.
In the following, we analyzed the InSe band gap
renormalization by surface electron doping. Parts a and b of
Figure 3 show the EDCs of conduction band and valence band of core levels of Na, Se, and In elements as a function of Na
extracted at the momentum of k// = 0 ± 0.01 Å−1 as a function deposition time (from 0 to 29 min). From Figure 4a−c, when
of carrier concentration, respectively. In Figure 3a, a clear the deposition time t < 24 min, the Na 2p signal appears very
downward shift of peaks from conduction band is observed by weak and broad, while the Se 3d and In 4d peaks remain sharp
increasing doping level. However, from the EDCs of the because of spin-orbit splitting. This means Na absorption at
valence band in Figure 3b, we also observe a small the surface of InSe dominates the process. Moreover, the Se 3d
nonmonotonic movement. The edge of valence band shows and In 4d peaks shift similarly to the VBM of InSe in the initial
a similar downward shift at the initial doping stage (N < 6.4 × stages of Na deposition (t < 14 min) because of surface band
1012 cm−2) and an upward shift for high doping. The shift of bending, as shown in Figure 3c. However, the Na 2p signal
both CBM and VBM and also the corresponding band gap becomes very strong and sharp and the Se 3d and In 4d peaks
renormalization as a function of electron doping are shown in show shoulders toward lower binding energy for deposition
Figure 3c. The band gap of InSe reduces ∼120 meV (from time t ≥ 24 min. This may be due to thicker Na layers
∼1.28 to 1.16 eV) for N = 8.1 × 1012 cm−2 (corresponding to a deposited on the surface of InSe and also Na intercalation into
deposition time t = 17 min). The mechanism of dynamic InSe. In addition, for long Na deposition time (t ≥ 24 min),
tuning of band gap by alkali deposition is universal as seen in strong band-tails are formed in the band gap of InSe and the
several TMDs: the surface dipole layer is formed after Na intensity of the conduction band becomes weak as shown in
deposition, and the corresponding electrical field increases with Figure 4d. This might be a sign of degeneracy and a
increasing deposition time leading to a surface Stark effect5,21 semiconductor to metal phase transition which, however,
since the VBM of InSe mainly consists of localized pz-like needs more investigation. As the ARPES, CBM, and VBM data
orbitals (vertical to the puckered plane) rather than of px and shown in Figure 2 and in Figure 3 are based on a deposition
py contributions. This means that the electronic properties of time less than 17 min, we can confirm that InSe band gap
InSe are very sensitive to electric field applied perpendicu- reduction of ∼120 meV is due to the Stark effect rather than
larly.27 In this case, the band edges of valence band and due to electronic structure modulation caused by Na
conduction band eventually move toward each other with intercalation into InSe interlayer.
increasing electric field in the surface dipole layer due to the In order to confirm these findings, we performed laser-based
spatial redistribution of their wave functions in the puckered ARPES (hν = 6.3 eV) experiments with in situ Na deposition
layer structure. It is worth noting that the carrier concentration shown in Figure 5. Similar to the data shown in Figure 2a, we
of 8.1 × 1012 cm−2 in our case can be easily achieved in FETs did not observe the signal from conduction band in pristine
by ionic liquid gating or space charge doping,4,12,26−29 which InSe (Figure 5a). After Na deposition (deposition time t < 18
could lead to tunable optoelectronics. min), the conduction band appears clearly, and the agreement
In principle, deposition of alkali atom on the surface of InSe between the measured signal and the calculation is excellent, as
may generate two processes: absorption at the surface or shown in Figure 5b−e. The corresponding EDCs in Figure 5g
intercalation into InSe interlayers.30 In Figure 4, we distinguish show the downward shift of conduction band as a function of
the two processes by using X-ray photoemission spectra (XPS) carrier concentration. However, under heavy electron doping
13489 DOI: 10.1021/acsnano.9b07144
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Figure 5. (a−f) Series of laser-based ARPES maps of InSe as a function of carrier concentration along Γ−K direction. The red dotted curves
are the first conduction band from theory calculation. (g) EDCs of conduction band as a function of carrier concentration. A sign of weak
conduction band and band-tail formation are observed under heavily electron doped InSe (deposition time t = 18 min). The dotted red
curves are the calculated conduction bands of InSe and the dotted white lines indicate the Fermi levels.

(Na deposition time of 18 min), the dispersion of conduction experiment of InSe in Figure 1 and Figure S2 was carried out at the
band gets blurry and the intensity deceases dramatically, with ANTARES beamline of synchrotron SOLEIL. The ARPES, XPS
the formation of a band-tail in the band gap shown in Figure combining with in situ Na atom deposition experiments in Figures
5f,g. The observations of conduction band shift, the carrier 2−4 were performed with hν = 120 eV at the TEMPO beamline of
synchrotron SOLEIL. In both beamlines, the photoelectrons were
concentration estimation under moderate doping, and band- collected with new generation MBS A-1 analyzers equipped with
tail formation under heavy electron doping from laser-based electrostatic lenses allowing Fermi surface mapping in order to
ARPES are consistent with the synchrotron ARPES data determine the sample orientation. The iso-energy coutours data are
shown in Figures 2−4, supporting our findings of band gap shown in the Figure S4. The laser-based ARPES and in situ Na atom
renormalization ∼120 meV and possible semiconductor to deposition experiments in Figure 5 were performed under hν = 6.3 eV
metal phase transition in the layered InSe semiconductor. at the femtoARPES platform located in synchrotron SOLEIL.32 The
sample orientation was checked by low energy electron diffraction
(LEED) before performing the laser-based ARPES experiment. The
CONCLUSIONS overall energy and momentum resolutions for all the ARPES setups
In summary, we study the electronic band structure of were better than 35 meV and 0.01 Å−1.
electron-doped InSe by means of ARPES and in situ surface Na Atom Deposition. The Na atom deposition experiments at
Na deposition. Deposition of Na atom on the surface of InSe TEMPO beamline and femtoARPES platform were performed using
donates electrons to adjacent InSe layers, and forms a dipole commercial getter sources. For the entire duration of the experiment,
layer. After moderate Na deposition, the conduction band and the sample was kept at the base temperature of 125 K and has never
been decoupled from the cryogenic manipulator.
its dispersion are clearly observed and are consistent with
calculations. We observe a band gap renormalization of ∼120
ASSOCIATED CONTENT
meV in InSe due to the strong vertical electrical field generated
by ionized Na atoms, which corresponds to a carrier *
S Supporting Information

concentration of 8.1 × 1012 cm−2 in the surface of InSe due The Supporting Information is available free of charge on the
to the Stark effect. We also find that a band-tail appears under ACS Publications website at DOI: 10.1021/acsnano.9b07144.
strong electron doping which might be a sign of semiconductor Theory calculation of InSe band structure; photon
to metal phase transition. This basic research project mimics energy dependent ARPES measurement; photolumines-
the effects of field-effect doping in InSe, which will offer cence spectrum of pristine InSe; determination of InSe
insights into the optoelectronic properties of InSe and will orientation (PDF)
potentially boost the performance of multifunctional devices.
AUTHOR INFORMATION
METHODS
Corresponding Authors
Materials and Photoluminescence Spectrum. Single crystals
of InSe in our work have been grown using the Bridgmann method.31
*E-mail: zheshengchen@gmail.com.
Photoluminescence spectrum of pristine InSe shown in Figure S3 was *E-mail: queenly@vip.sina.com.
performed on a Horiba Jobin-Yvon Xplora spectrometer in a back *E-mail: azzedine.bendounan@synchrotron-soleil.fr.
scattering geometry under ambient conduction with incident ORCID
wavelength of 638 nm. Zhesheng Chen: 0000-0001-7978-5637
X-ray-Based ARPES and Laser-Based ARPES. High-quality
single crystals of InSe were cleaved at the base pressure of 1 × 10−10 Bingbing Tian: 0000-0003-1508-6217
mbar for all ARPES experiment. The sample temperature was ∼80 K Luca Perfetti: 0000-0002-8426-557X
during experiment. The photon energy (hν) dependent ARPES Azzedine Bendounan: 0000-0001-7557-4322
13490 DOI: 10.1021/acsnano.9b07144
ACS Nano 2019, 13, 13486−13491
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Notes Photo-Detection in Atomic Layers of InSe. ACS Nano 2014, 8, 1263−

The authors declare no competing financial interest. 1272.
(16) Chen, Z.; Biscaras, J.; Shukla, A. A High Performance
Graphene/Few-Layer InSe Photo-Detector. Nanoscale 2015, 7,
ACKNOWLEDGMENTS 5981−5986.
We acknowledge A. Chevy for high-quality InSe single crystals (17) Chen, Z.; Zhang, Z.; Biscaras, J.; Shukla, A. A High
used in this work. Z.C. and L.P. acknowledge financial support Performance Self-Driven Photodetector Based on a Graphene/InSe/
from “Investissement d’Avenir” Labex PALM (ANR-10-LABX- MoS2 Vertical Heterostructure. J. Mater. Chem. C 2018, 6, 12407−
0039-PALM). B.T. and Y.L. acknowledge financial support 12412.
(18) Bandurin, D. A.; Tyurnina, A. V.; Yu, G. L.; Mishchenko, A.;
from the Science and Technology Project of Shenzhen (Grant
Zólyomi, V.; Morozov, S. V.; Kumar, R. K.; Gorbachev, R. V.;
Nos. JCYJ20180305125106329, Kudrynskyi, Z. R.; Pezzini, S.; Kovalyuk, Z. D.; Zeitler, U.; Novoselov,
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and ZDSYS201707271014468). Computer time has been Cao, Y. High Electron Mobility, Quantum Hall Effect and Anomalous
granted by GENCI (Project No. 544) and by CEA/DRF. Optical Response in Atomically Thin InSe. Nat. Nanotechnol. 2017,
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13491 DOI: 10.1021/acsnano.9b07144

ACS Nano 2019, 13, 13486−13491