Received: 16 August 2021 Revised: 14 October 2021 Accepted: 24 October 2021

DOI: 10.1002/inf2.12290

REVIEW ARTICLE

Interfacial charge and energy transfer in van der Waals

heterojunctions

Zehua Hu1 | Xue Liu2 |
ndez-Martínez3

Pedro Ludwig Herna |
4 5 6 7
Shishu Zhang | Peng Gu | Wei Du | Weigao Xu |
Hilmi Volkan Demir3,8 | Haiyun Liu5 | Qihua Xiong4,5,9
1
Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore
2
Institutes of Physical Science and Information Technology, Anhui University, Hefei, P.R. China
3
LUMINOUS! Center of Excellence for Semiconductor Lighting and Display, School of Electrical and Electronics Engineering, Nanyang
Technological University, Singapore, Singapore
4
State Key Laboratory of Low-Dimensional Quantum Physics, Department of Physics, Tsinghua University, Beijing, P.R. China
5
Beijing Academy of Quantum Information Sciences, Beijing, P.R. China
6
Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, Suzhou, P.R. China
7
Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, P.R. China
8
Department of Physics, Department of Electrical and Electronics Engineering, UNAM-National Nanotechnology Research Center and Institute of
Materials Science and Nanotechnology, Bilkent University, Ankara, Turkey
9
Beijing Innovation Center for Future Chips, Tsinghua University, Beijing, P.R. China

Correspondence
Qihua Xiong, State Key Laboratory of
Abstract
Low-Dimensional Quantum Physics, Van der Waals heterojunctions are fast-emerging quantum structures fabricated
Department of Physics, Tsinghua
by the controlled stacking of two-dimensional (2D) materials. Owing to the
University, Beijing 100084, P.R. China.
Email: qihua_xiong@[Link] atomically thin thickness, their carrier properties are not only determined by
Zehua Hu, Division of Physics and the host material itself, but also defined by the interlayer interactions, includ-
Applied Physics, School of Physical and ing dielectric environment, charge trapping centers, and stacking angles. The
Mathematical Sciences, Nanyang
abundant constituents without the limitation of lattice constant matching
Technological University, Singapore
637371, Singapore. enable fascinating electrical, optical, and magnetic properties in van der Waals
Email: [Link]@[Link] heterojunctions toward next-generation devices in photonics, optoelectronics,
Haiyun Liu, Beijing Academy of Quantum and information sciences. This review focuses on the charge and energy trans-
Information Sciences, Beijing 100193,
P.R. China.
fer processes and their dynamics in transition metal dichalcogenides (TMDCs),
Email: liuhy@[Link] a family of quantum materials with strong excitonic effects and unique valley
properties, and other related 2D materials such as graphene and hexagonal-
Funding information
Agency for Science, Technology and
boron nitride. In the first part, we summarize the ultrafast charge transfer pro-
Research, Grant/Award Number: 152 cesses in van der Waals heterojunctions, including its experimental evidence
73 00025; Central University Basic and theoretical understanding, the interlayer excitons at the TMDC interfaces,
Research Fund of China, Grant/Award
Numbers: 020514380231, 021014380177; and the hot carrier injection at the graphene/TMDCs interface. In the second

Zehua Hu, Xue Liu, and Pedro Ludwig Hern
andez-Martínez contributed equally to this work.

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2022 The Authors. InfoMat published by UESTC and John Wiley & Sons Australia, Ltd.

InfoMat. 2022;4:e12290. [Link]/journal/infomat 1 of 21

[Link]
2 of 21 HU ET AL.

National Natural Science Foundation of

China, Grant/Award Numbers: 12104006, part, the energy transfer, including both Förster and Dexter types, are reviewed
21873048, 92056204; National Research from both experimental and theoretical perspectives. Finally, we highlight the
Foundation, Grant/Award Number: NRF-
NRFI2016-08; Natural Science Foundation
typical charge and energy transfer applications in photodetectors and summa-
of Jiangsu Province, Grant/Award rize the challenges and opportunities for future development in this field.
Number: BK20180319; Start up fundations
from Anhui University; Tsinghua KEYWORDS
University; State Key Laboratory of Low- 2-dimensional semiconductors, carrier dynamics, charge and energy transfer, optical
Dimensional Quantum Physics
spectroscopy, optoelectronics

1 | INTRODUCTION fascinating physical properties such as largely enhanced

proximity effect and valley-polarized interlayer exciton.
Traditional bulk semiconducting heterojunctions such as Moreover, the physical properties of the vdWs hetero-
those containing gallium arsenide (GaAs) quantum wells junctions are tunable due to the susceptibility to the stacking
(QWs) are mainly prepared by molecular beam epitaxy, order, crystal orientation alignments, electric/magnetic/opti-
which is expensive and requires lattice-constant matching cal field, strain, and temperature.7–11
at the interface. In recent years, two-dimensional (2D) The rise of vdWs heterojunction has ignited broad
material has been discovered to possess weak van der research interests into interfacial carrier dynamics as they
Waals (vdWs) interlayer interaction, thereby readily scales are the bedrock of fundamental physics and optoelec-
down to a few-layer or even monolayer limit.1 Today, tre- tronic applications. Interfacial carrier dynamics, includ-
mendous 2D materials have been extensively studied, with ing charge transfer (CT) and energy transfer (ET), are
various physical properties including metallic, semicon- ubiquitous phenomena and essential processes that gov-
ducting, and insulating aspects.2 More interestingly, owing ern the interfacial properties of the vdWs hetero-
to their dangling-bond-free surfaces, they can be stacked junctions. Although the interfacial carrier dynamics have
together to form vdWs heterojunctions (Figure 1A), there- been widely explored for several decades in various
fore having richer and much more tunable material donor-acceptor systems such as organic semiconductor
properties.4–6 Since the carrier wavefunction is delocalized interface and biological molecules,12,13 vdWs hetero-
and penetrates into adjacent layers, the carriers in the dif- junction is a brand new platform in the quantum limit
ferent layers could interact with each other, creating with strong quantum confinement and coherence effect.

F I G U R E 1 Typical 2D materials and the band alignment. (A) Typical 2D materials used for the building blocks of van der Waals
heterojunctions. (B) Schematic of type-I and type-II band alignments and the allowed charge transfer (CT) directions, respectively. (B)
Reproduced with permission from Reference 3. Copyright 2017, Royal Society of Chemistry
HU ET AL. 3 of 21

The carriers also feature the valley degree of freedom due type-I band alignment is formed,3 while they are sepa-
to the spin-valley locking effect in transition metal rated in different layers for a type-II band alignment.21 A
dichalcogenides (TMDC) systems, thus expanding the type-III band alignment requires a much larger energy
carrier dynamics of electrons/holes into valley-dependent offset, that is, the conduction band minimum (CBM) in
and setting the foundation for valleytronics.14 one layer is below the valence band maximum (VBM),22
This review mainly discusses the carrier dynamics in which is also possible in the 2D semiconductor family but
TMDC vdWs heterojunctions as they are semiconductors is not the focus in this review. In the following, we
with a sizable bandgap and strong excitonic effect.15,16 describe experimental findings regarding the CT processes
Their individual physical properties have been exten- in 2D heterojunctions, including demonstrations, charac-
sively investigated theoretically and experimentally, terizations, and manipulations. Also, we briefly survey
which sets the foundation for heterojunction investiga- recent theoretical efforts on understanding the physical
tion. In the first part, we start by discussing the experi- mechanisms of the ultrafast dynamics. Then, we highlight
mental evidence of ultrafast interfacial CT and the the exotic properties in TMDC/TMDC and TMDC/
related theoretical understanding. Subsequently, the graphene heterojunctions due to the interlayer CT.
interlayer exciton that forms as a direct consequence of
CT is summarized. The interlayer exciton attracts broad
interest because it inherits the spin-valley locking effect 2.1 | Quantum coherence induced
from monolayer TMDC and has a much longer lifetime ultrafast CT
than intralayer exciton, showing great potential in val-
leytronics and exciton transistors. This part ends with a The energy offset between CBM or VBM provides the driv-
summary on CT at the graphene/TMDC interface, which ing force to enable CT at 2D heterogeneous interfaces.
exhibits rich physics because the hot carriers and Followed by this prerequisite, several experimental studies
plasmons in graphene are susceptible to the pump wave- explored the CT processes in vertically stacked hetero-
length. In the second part on ET, both Förster and Dexter structures, as shown in Figure 2A,B. Since the CT offers
types are discussed. We first provide a comprehensive an additional relaxation channel between individual
theoretical understanding of Förster resonance energy layers, the steady-state photoluminescence (PL) quenching
transfer (FRET) in vdWs heterojunctions and then of the constituent monolayers is typical.23,27 Besides, the
focus on experimental progress. Notably, the spin-orbit- Raman scattering of graphene and TMDC monolayers
coupling-induced valence band splitting and high exhibit specific dependence on their charge carrier density
intrinsic doping make the individual exciton state quite via electron–phonon coupling, that is, the G-mode of
complicated (such as B and C exciton, trion, and graphene upshifts or downshifts under the electron or hole
biexciton), so as the FRET dynamics. For Dexter-type doping, respectively28–30; the A1g mode of TMDC mono-
energy transfer (DET), we emphasize the modulation of layer is more sensitive to its doping level than other extrin-
band alignment and the DET dynamics via an external sic factors such as strain, stress, and temperature.31–35
electric field. In the subsequent part, we introduce a typi- Thus, a combination of PL and Raman scattering spectros-
cal device application, that is, interlayer CT and ET copies and their corresponding 2D spatial mappings are
enhanced photodetector. Finally, a summary and outlook useful tools to systematically study the interlayer CT
are given toward the future development of CT and ET in between graphene, hexagonal-boron nitride (h-BN), and
vdWs heterojunctions. TMDC monolayers.
For example, Guillaume et al. reported a photoin-
duced electron transfer from MoSe2 to graphene and a
2 | CT IN 2D MATERIAL hole accumulation in MoSe2.24 Their comprehensive
HETEROJUNCTIONS analysis of the graphene and MoSe2 Raman modes rev-
ealed that the graphene gets continually n-doped under
Thanks to the weak interlayer coupling between the the increasing incident photon flux and the Fermi energy
interfaces, researchers usually consider the electronic of the graphene is saturated at ~290 meV above the Dirac
states of 2D materials to approximately localize within point (Figure 2E–H). A detailed summary of the ultrafast
individual layers, which is a similar treatment for inter- carrier dynamics between graphene and TMDC will be
faces between bulk materials and quantum wells.17 In given in Section 2.3. In addition, the transport properties
this case, one can effectively evaluate the band alignment of graphene, that is, the charge-neutral point determined
according to the band edge energy of different layers.18–20 by the resistance gate dependence, were used as a probe
As shown in Figure 1B, when the lowest occupied energy of the photoinduced CT between graphene and h-BN
levels of electrons and holes reside in the same layer, a defect states due to its high sensivity to the doping
4 of 21 HU ET AL.

F I G U R E 2 Interlayer charge transfer (CT) probed by static optical spectroscopies. (A–D) The schematic (A), optical image (B), PL
mapping (C), and PL spectrum of a MoS2/WS2 heterostructure (D). (E–H) The optical image (E), PL mapping (F), graphene Raman G-mode
frequency mapping (G), and G-mode width mapping (H) in a MoSe2/graphene heterostructure. (I,J) Photoinduced doping effect in
graphene/h-BN heterojunction in the schematic diagram (I), and demonstrated by the charge neutrality point shifting (J). The red trace is
from the pristine sample, while the other traces are obtained after photodoping. (K,L) Manipulation of the CT between h-BN defect levels
and graphene. (K) The optical image of the heterostructure containing WS2/hBN/graphene and hBN/graphene regions. (L) Evolution of the
Raman G-mode upon increasing photon flux in different regions. (A–D) Reproduced with permission from Reference 23. Copyright 2014,
Nature Publishing group. (E–H) Reproduced with permission from Reference 24. Copyright 2018, American Physical Society. (I,J)
Reproduced with permission from Reference 25. Copyright 2014, Nature Publishing group. (K,L) Reproduced with permission from
Reference 26. Copyright 2020, American Physical Society

level.25,36 From their observations, the donor-like defects compensates the electron transfer and keeps graphene
in h-BN provide excited electrons in CB under optical charge-neutral.26 In contrast, on a weakly coupled WS2/
excitation. These mobile electrons continuously transfer MoSe2 heterojunction, the limited overlap of electronic
into the graphene with positively charged localized wavefunctions across the heterojunctions (and the lack
defects left in h-BN, introducing a screening effect to of interlayer phonon vibrations) promotes the interfacial
the back gate until graphene becomes charge-neutral quantum fluctuations, resulting in an exciting PL
(Figure 2I,J).25 Moreover, in a sandwiched hetero- blinking phenomenon.37 The PL intensities (and decay
structure, the manipulation of the CT between graphene dynamics) of the two adjacent layers are always
and adjacent h-BN defect levels by adding or removing a inversely correlated, that is, as one falls, another rises.
top WS2 layer was demonstrated (Figure 2K,L).26 The These studies provide a comprehensive demonstration,
donor-like defects in h-BN are utilized to provide defect understanding, and manipulation of CT between 2D
excited states and ground states under optical excitation. systems.
Without a top WS2 layer, the graphene was gradually n- Time-resolved pump-probe measurement is a powerful
doped until reaching a saturation Fermi energy of technique to elucidate the CT dynamics with femtosecond
~220 meV. However, by adding a top WS2 layer, the timescale resolution. Hong et al. first demonstrated a hole
doping level of graphene is no longer changed since a transfer from photoexcited 1L-MoS2 to 1L-WS2 using a
hole transfer from WS2 to graphene also happens by the combined PL mapping and ultrafast pump-probe spectros-
assistance of defect ground states in h-BN, which copy method.23 At the MoS2/WS2 overlapping region, the
HU ET AL. 5 of 21

F I G U R E 3 Interlayer charge transfer (CT) probed by pump-probe spectroscopies. (A) Schematic of the CT between MoS2 and WS2
monolayers. (B) Energy-resolved transient absorption spectra of a MoS2/WS2 heterostructure and pure MoS2 monolayer, excited by an
optical pulse near the lower-energy MoS2 A exciton energy. (C) Schematic of the CT between MoS2 and MoSe2 monolayers under 395 nm
excitation. Blue and purple dots are differential reflection signals from 1L-MoS2 and MoS2/MoSe2 heterostructure, respectively. (D) Coherent
CT in MoS2/WS2/MoSe2 trilayer heterostructure. (E) Twist angle dependence of the CT time and recombination lifetime. (A,B) Reproduced
with permission from Reference 23. Copyright 2014, Nature Publishing group. (C) Reproduced with permission from Reference 38.
Copyright 2014, American Chemical Society. (D) Reproduced with permission from Reference 39. Copyright 2017, American Chemical
Society. (E) Reproduced with permission from Reference 40. Copyright 2017, American Chemical Society

authors only pumped the small bandgap MoS2 and processes show a pronounced difference at various twist
observed a photo-bleach signal of the large bandgap WS2 angles, as featured by different signal decay times (Figure
that appears almost at the same time with the pump beam, 3E).40 Surprisingly, the electron–hole recombination life-
corresponding to the ultrafast hole transfer process time varies by almost three orders of magnitude from sam-
(an upper limit of 50 fs, Figure 3A,B).23 It suggests that the ple to sample (Figure 3E), but without a clear correlation
CT happens in a much shorter time scale than the intra- with their twist angles. The charge recombination kinetics
layer exciton lifetime (~few to tens of picoseconds).41,42 are independent of the excitation density or charge density,
Following the initial research study, several research indicating defect-assisted electron–hole recombination as
groups made an effort to understand the mechanism fur- the dominant mechanism. From these experimental
ther.38,39,43 The study from Ceballos et al. identified elec- results, despite the significant interlayer momentum mis-
tron (hole) transfer from MoSe2 to MoS2 (from MoS2 to match and the weak interlayer coupling, the CT at the 2D
MoSe2) at different exciting energies (Figure 3C).38 interface is ultrafast and happens at a time scale of 100 fs.
The same group reported picosecond electron transfer in In addition, minimizing the trap densities at the TMDC
a trilayer heterostructure of MoSe2/WS2/MoS2, indica- heterojunctions is also crucial to probe the intrinsic physics
ting the coherent nature of the rapid CT processes (Figure of momentum conservation in radiative interlayer exciton
3D).39 Moreover, a few more groups examined the rise and emission, which remains challenging for the community.
decay time of the transient transmission signal depending Photo-excited electron–hole pairs must dissociate into
on the angle alignment between the two stacking crystal free carriers before efficient CT at vdWs interfaces. How-
lattices.40,44,45 From their observations based on hetero- ever, suppose one only considers the band edge offsets
structures formed by either mechanically exfoliated or between CBM or VBM. In that case, the CT driving force
CVD synthesized monolayers, the ultrafast CT rate charac- is usually insufficient to overcome the exciton binding
terized by the rise time shows robustness against interlayer energies (~300 meV).21,23,46,47 Although the CT directions
stacking configurations and thus momentum mis- are well-expected according to the band alignment pre-
match.40,44 In contrast, the electron–hole recombination dictions, the ultrafast dynamics is not easily understood
6 of 21 HU ET AL.

using traditional noncoherent CT picture.48,49 In the per- indirect emission, suggesting the formation of interlayer
spective of Zhu and coauthors,50 the difference between excitons.58 Dr. Rivera and coauthors first reported the
the molecular donor/acceptor interface and TMDC direct observation through PL and PL excitation (PLE)
heterostructure interface is emphasized, that is, the delo- spectroscopies, featured as a reduced energy peak distinct
calization in real space can dictate the charge separation from constituent monolayers in the PL spectrum associ-
at the molecular interfaces, but it may play the opposite ated with a much longer lifetime ~1.8 ns (Figure 4A).27
role at 2D semiconductor heterostructures. In the follow- Due to its out-of-plane dipole orientation, the vertical
ing part, we briefly summarize some of the theoretical electric field is able to control the exciton properties, such
understanding of the mechanisms. as emission energy, luminescence intensity, diffusion
Several researchers have performed numerical calcu- length, and lifetime.27,60–62 Although the CT process
lations using time-dependent density-functional theory seems independent of the lattice orientation between
(TD-DFT) and proposed a coherent CT mechanism.51–54 constituent monolayers as aforementioned, the PL inten-
Wang et al. revealed an enhanced coupling between ini- sity of interlayer excitons displays a strong dependence
tial and final hole states in MoS2 and WS2 layer and con- on the twist angle, with the PL intensity reaching a maxi-
cluded that the charged dipole layer is responsible for the mum near 0
(60
) and gradually vanishing between 10

unexpected rapid transfer of holes.51 Long et al. proposed and 50
. This observation suggests that the formation of
a slightly different picture, where the delocalization of bright interlayer excitons requires finite interlayer hop-
the photo-excited states between the donor and acceptor ping and kinetic energy, as expected by a theoretical sim-
materials assists in overcoming the electron–hole pair ulation.63 Then, a few following research works reported
attraction and leads to efficient charge separation.52 detailed temporal, excitation, and temperature depen-
Besides, Li et al. compared the electron and hole transfer dence of the emission properties and analyzed the fine
and electron–hole recombination across a MoS2/WS2 structure of the interlayer excitons to resolve momentum
heterostructure and concluded that a longer quantum direct and indirect species.64,65
coherence favored faster CT, while the electron–hole Another important feature making interlayer excitons
recombination is much slower due to the strongly local- more exciting is that they inherit the valley-contrasting
ized initial and final states within different layers.53 property from monolayers (Figure 4B,C). Polarization-
Moreover, in the report from Wang et al., the coupling dependent PL measurements confirmed the presence of
strengths for ±K, Γv , and Qc valleys have been carefully valley-polarized interlayer excitons, that is, ~30% valley-
compared, suggesting the strong layer mixing of Γv and polarized interlayer exciton emission with circularly
Qc valleys can mediate the twist angle-insensitive ultra- polarized excitation (Figure 4D). More importantly, the
fast interlayer CT.54 valley polarization lifetime can prolong by several orders
of magnitudes under an external electric field (up to
microsecond, Figure 4E).59,66 Such a long lifetime allows
2.2 | The rising of interlayer excitons for the visualization of a long lateral drift and diffusion
carrying the valley polarization information over several
Interlayer excitons, that is, bound electron–hole pair micrometers.59 Such generation and transport of valley-
located separately in the adjacent materials, have been polarized excitons in heterojunctions stimulate further
first pursued in GaAs coupled quantum wells55 and control and manipulation. For example, Unuchek et al.
widely studied for exciton Bose–Einstein condensation reported that the diffusion of valley-polarized excitons
phenomena.56 In type-II TMDC heterostructures, the could be controlled and switched by an external electric
ultrafast CT and the poorly screened Coulomb interac- field.60,67 Ciarrocchi et al. have resolved two separate nar-
tion give rise to interlayer excitons. Moreover, suitable row interlayer transitions with opposite helicities, thus
bandgaps and extraordinary high binding energy for exci- realizing a polarization switching device through electri-
tons in TMDC monolayers enable direct optical observa- cal control.68 These results make solid cases for their
tions of the interlayer excitons at elevated temperatures, promising applications in next-generation photonic and
which initiates enormous research activities on this spe- valleytronic devices.
cific topic. In this part, we summarize contemporary A twist and/or a difference in lattice constant
research progresses of the interlayer excitons. between two stacking layers can give rise to a Moiré pat-
The interlayer excitons in semiconducting hetero- tern with a superlattice potential.69 This approach was
structures with type-II band alignment were predicted as applied to achieve unconventional superconducting in
a direct resultant from interlayer CT.57 Fang et al. have bilayer graphene70,71 and led to the direct observation of
demonstrated a strong interlayer coupling between 2D Moiré excitons in WSe2/WS2,72 MoSe2/WSe2,73,74 and
interfaces, causing a spatially direct absorption but MoS2/WS275 heterojunctions with small twist angles, as
HU ET AL. 7 of 21

F I G U R E 4 Interlayer exciton properties. (A) Observation of the interlayer exciton in WSe2/MoSe2 heterostructure. (B,C) Schematic of
the valley polarization of the interlayer excitons. (D,E) Gate tuning of the valley polarization and lifetimes for the interlayer excitons. Black
and red dots correspond to the same and opposite circular polarization between excitation and collection directions. Blue dots represent the
degree of circular polarization. (A) Reproduced with permission from Reference 27. Copyright 2015, Nature Publishing group. (B–E)
Reproduced with permission from Reference 59. Copyright 2016, American Association for the Advancement of Science

evidenced by the multiple emergent peaks either in the level anticrossing and oscillator strength redistribution,
absorption or emission spectra. Besides, the Moiré- indicating the realization of a strong coupling regime.78
trapped interlayer excitons inherit the same valley- Bai et al. reported the transfer of Moiré potentials from
contrasting physics but with linewidths over 100 times quantum-dot-like zero-dimensional traps into parallel stri-
narrower.72 The technical details of these studies indicate pes like 1D quantum wires by external strain, resulting in
that the twist angle and the stacking configuration are linearly polarized excitons in the 1D Moiré potentials.79 So
the key parameters. Weston et al. used atomic-resolution far, the study of Moiré physics under extreme conditions
transmission electron microscopy to reveal the lattice such as high magnetic field and high pressure is still lac-
reconstruction in heterojunction under different twist king. Such experiments could provide useful information
angles, reflecting the strikingly different structures in about the spin-valley dynamics in this new platform,
morphology and electronic properties.76,77 The twist which requires further exploration.
angles and the presence of Moiré potentials also show
substantial modifications to the dynamics and diffusion
of the interlayer excitons. It is worth noting that the 2.3 | CT in TMDC/graphene
impact of such Moiré potentials on both intralayer and heterostructure
interlayer excitons was suppressed at higher exciton den-
sity due to the shallow depth of the potential in the 2D Ultrafast CT can also happen at the interface between the
landscape. However, this feature may benefit the success- TMDC monolayer and the graphene, which typically
ful engineering of the Moiré superlattices, which may occurs on the timescale of ~1 ps and motivates the appli-
open up a new area for exploring the novel quantum phe- cations in ultrafast photodetectors and all-optical
nomenon. For example, Tang et al. tuned the Moiré modulators.80–83 The preferred CT direction, from TMDC
excitons by a vertical electric field with the exciton energy- to graphene or vice versa, depends on the pumping
8 of 21 HU ET AL.

F I G U R E 5 Ultrafast charge transfer (CT) at the transition metal dichalcogenide (TMDC)/graphene interface. (A) Schematic of the CT
from the TMDC monolayer to graphene using the high-energy pump and low-energy probe. (B) Transient absorption spectra measured from
bare graphene and MoS2/graphene heterostructure with pump energy of 2.33 eV and probe energy of 0.8–1.4 eV. Compared to bare
graphene, the heterostructure shows decelerated graphene hot carrier cooling dynamics due to the CT from MoS2 to graphene.
(C) Modulation of graphene plasmon via ultrafast CT from MoS2 to graphene. (D) Schematic of the CT from graphene to TMDC via hot
carrier injection using the low-energy pump and high-energy probe. (E) Quantum yield (QY) of hot electron injection in WS2/graphene
heterostructure measured as a function of the pump energy. (F) Photocarrier generation in WS2/graphene heterostructure in the longer
timescale (>100 ps) via acoustic phonon recycling. (B) Reproduced with permission from Reference 84. Copyright 2020, American Chemical
Society. (C) Reproduced with permission from Reference 83. Copyright 2020, John Wiley and Sons. (E) Reproduced with permission from
Reference 85. Copyright 2019, American Association for the Advancement of Science. (F) Reproduced with permission from Reference 86.
Copyright 2020, Nature Publishing group

energy. As shown in Figure 5A, when the excitation modulator based on the same heterostructure and CT
energy is higher than the optical bandgap of the TMDC direction.83 Graphene plasmons is excited with an infrared
monolayer, the electrons in the TMDC monolayer can be beam, while another visible light tune graphene plasmon
efficiently pumped from the ground state to the excited in situ based on the ultrafast interfacial charge injection
state. Simultaneously, photoexcited carriers can also be from photoexcited monolayer MoS2, which efficiently
generated in graphene but with limited carrier density due modifies the doping level of graphene. Figure 5C clearly
to its relatively low absorption. By integrating a MoS2 shows the modulation of graphene plasmon amplitude
monolayer with graphene to form the heterostructure, and and frequency by changing the visible laser power.
monitoring the carrier relaxation in graphene using a low- Benefitting from the ultrahigh photosensitivity of TMDC
energy probe, Lee et al. reported the deceleration of hot monolayer, the heterostructure modulator features low
carrier cooling (by four times) in graphene induced by the energy consumption. Plasmonic modulation of 44 cm1
nondissipative excited-state CT from the MoS2 monolayer was achieved with a visible light illumination intensity of
to the neighboring graphene (Figure 5B).84 Such a CT only 0.15 mW cm2.
direction leads to an increased photoexcited carrier popu- On the other hand, when the excitation energy is not
lation in graphene, slowing down the carrier cooling due high enough to pump the TMDC directly (Figure 5D),
to the enhanced hot optical phonon bottleneck effect. The the initial main excited state population will be hot car-
slowed hot carrier cooling strategy has been widely riers in graphene, which can quickly transfer to the
adopted for boosting the maximum power conversion effi- TMDC side. The CT efficiency and dynamics can be con-
ciency of photodetectors and solar cells. Dai et al. have veniently probed in the high-energy range by monitoring
recently demonstrated an efficient all-optical plasmonic the ground state bleaching signal at the TMDC exciton
HU ET AL. 9 of 21

resonance frequency. Hot carrier injection has been well reabsorption processes, thus maintaining high-energy
investigated in metallic plasmonic-TMDC hetero- conversion efficiency. According to the different interac-
structures.87,88 For example, Wen et al. reported plasmonic tion mechanisms, the ET processes can be divided into
hot carrier injection from gold nanorod into a WSe2 Förster and Dexter types, where the former relies on
bilayer. The injected hot carriers break the bilayer WSe2's dipole–dipole coupling and interacts in a relatively long
inversion symmetry and induce the second harmonic gen- distance (<10 nm); and the latter establishes on charge
eration.87,89–91 Compared to a noble-metal-based exchange interaction and only works in the atomic prox-
plasmonic system where the hot carrier excitation is effi- imity (≤1 nm). In this part, we review the state-of-art
cient only around the plasmon resonance frequency, hot understanding of these two mechanisms at the 2D semi-
carriers in graphene can be excited efficiently with a wide conductor heterojunctions.
range of pump energies due to its broad absorption range.
The quantum yield (QY) of hot carrier injection from
graphene into TMDC depends on the pump energy. For 3.1 | Förster-resonance ET
example, in the WS2/graphene heterostructure, experi-
mentally extracted QY increases from 0% to 60% when the FRET, a process of transferring the excitons from an
pump energy increases from 0.4 to 1.6 eV, as shown in Fig- excited donor to an unexcited acceptor by nonradiative
ure 5E.85 This QY enhancement stems from the thermal- dipole–dipole interactions, is the underlying mechanism
ized hot carrier distribution, which depends on the pump of numerous applications, including color tuning, bio-
energy and has a long tail toward higher energy due to sensing, light-harvesting, and light generation. The FRET
electron–electron scattering. The hot carrier injection to rate strongly depends on (1) the center-to-center separa-
the monolayer WS2 is only allowed when the hot carrier tion between the donor and acceptor pair and (2) the För-
energy overcomes the injection barrier determined by the ster radius. Efficient FRET is limited typically to a length
energy alignment between graphene and the monolayer scale of approximate 10 nm due to the strong distance
WS2. In addition to the directly transferred graphene hot dependence of the process. This strong distance depen-
carrier, which gives rise to the bleaching signal at the A dency can be modified by changing the acceptor geome-
exciton resonance of the monolayer WS2 in the timescale try, for example, from a quantum dot (QD) (k FRET / d6 )
of shorter than 5 ps, Jiang et al. further observed a delayed to a quantum well (kFRET / d4 ) (see Table 1).92 It is
bleaching signal in the timescale of longer than 100 ps worth mentioning that the FRET rate depends on the
(Figure 5F).86 They attributed the delayed bleaching to the geometry and dimensionality of the acceptor and the
acoustic phonon recycling effect, which converts the effective dielectric constant of the donor (Table 2).92 In
photogenerated heat in graphene back into the carrier dis- the following, we briefly review the basics of FRET the-
tribution in the monolayer WS2 and enhances the overall ory and focus on the 2D confinement case.
photocarrier generation efficiency. The FRET mechanism is illustrated by the band/
energy level diagrams in Figure 6 schematically. This
model only considers single donor-acceptor pair with a
3 | ET IN 2D MATERIAL ground state j0⟩ and an excited state jexc⟩. FRET requires
HETEROJUNCTIONS the donor in the excited state. For example, absorbing a
photon in the donor excites the electron into the higher
ET is a physical process where the donor's excited state excited states. Then, the hot electron relaxes into the low-
ETs to the acceptor's ground state. It is a nonradiative est excited state by phonon scattering and bonds with the
interaction that avoids the photon emission and hole to form an exciton (typically in ps or sub-ps

T A B L E 1 Generic distance dependence of the FRET rate given the acceptor's geometry (Adapted with permission from Reference 92,
American Chemical Society)

Quantum dot (QD, 0D Nanowire (NW,1D Quantum well (QW, 2D

Acceptor/Donor confinement) confinement) confinement)
QD QD ! QD QD ! NW QD ! QW
NW NW ! QD NW ! NW NW ! QW
QW QW ! QD QW ! NW QW ! QW
Acceptor distance k FRET,QD / d16 k FRET,NW / d15 k FRET,QW / d14
dependence
10 of 21 HU ET AL.

TABLE 2 Effective dielectrics summary

α-direction Spherical (e.g., QD) Cylindrical (e.g., NW) Rectangular (e.g., QW)
X εeff D ¼ εQD þ2ε
3
M
εeff D ¼ εNW2þεM εeff ¼ εM

Y εeff D ¼ εQD þ2ε

3
M εeff ¼ εM εeff ¼ εM

Z εeff D ¼
εQD þ2εM
3
εeff D ¼ εNW2þεM εeff ¼ εM

Note: The effective dielectric constants for QD, NW, and QW are expressed in the long-distance approximation. In this table, the main axis of the cylinder is
considered to be along the y-direction. Adapted with permission from Reference 92, American Chemical Society.


where U b int ¼ ⟨0exc bV int jiexc ⟩ is the potential energy cre-
ated by the exciton. With this approximation, Fermi's
Golden Rule can be simplified using the fluctuation-
dissipation theorem (FDT)93,94

2
kFRET ¼  Im½dV ρðrÞΦint ðrÞ  ð3Þ
ℏ

Using the QD formalism developed in References 95 and

96, the final expression for the transfer rate is given by
F I G U R E 6 Schematic diagram of Förster resonance energy
   
transfer (FRET). An electron is excited to a higher state (blue line) and 2 εA ðωÞ
relaxes to its lower excited state (red line). Green lines represent k FRET ¼ Im dV Ein ðrÞ  Ein ðrÞ ð4Þ
ℏ 4π
radiative recombination. Black dashed lines represent the nonradiative
deexcitation (at the donor) and excitation (at the acceptor) via FRET
where the integration is taken over the acceptor volume,
εA ðωÞ is the dielectric function of the acceptor, and Ein ðrÞ
timescale). The formed exciton could transfer into the includes the effective electric field created by an exciton
nearby acceptor nonradiatively via dipole–dipole cou- at the donor site. The electric field is calculated with
pling. The ET ratio is determined by the relative rate EðrÞ ¼ rΦðrÞ and the electric potential ΦðrÞ, in CGS
between the FRET and recombination. units, can be obtained by97
The FRET rate can be calculated using Fermi's Golden
 
Rule, which gives the probability of an exciton to be trans- edexc ðr  r0 Þ  α b
Φα ðrÞ ¼ ð5Þ
ferred from a donor to an acceptor, as expressed by εeff D j r  r0 j 3

( )
2 X   2 
 
k FRET ¼ ⟨f exc ; 0exc bV int jiexc ;0exc ⟩ δ ℏωexc  ℏωf where edexc is the dipole moment of the exciton and εeff D
ℏ f
is the effective dielectric constant of the donor, which
ð1Þ depends on the geometry and the exciton dipole orienta-
tion, α ¼ x, y, z (Table 2). The overall FRET rate is calcu-
where jiexc ; 0exc ⟩ is the initial state with an exciton in the lated as
donor and zero excitons in the acceptor; jf exc ; 0exc ⟩ is the
final state with an exciton in the acceptor and zero exci- k x,FRET þ k y,FRET þ k z,FRET
b int is the exciton Coulomb interaction k FRET ¼ ð6Þ
tons in the donor; V 3
operator; ℏωexc and ℏωf is the exciton's photon energy of
the donor and acceptor, respectively. In a simplified where kα,FRET is the FRET transfer rate for the α-exciton
model, the initial and final states can be written as ðα ¼ x, y, zÞ.
jiexc ; 0exc ⟩ ¼ jiexc ⟩j0exc ⟩ and jf exc ; 0exc ⟩ ¼ jf exc ⟩j0exc ⟩, respec- For a 2D acceptor (QWs and 2D semiconductors) with
tively, and Fermi's Golden Rule can be approximated by thickness Lw embedded between two barriers with dielec-
tric constant ε2D . Two barriers have finite thickness Ll
( )
2 X  

2 

b int j0exc ⟩ δ ℏωexc  ℏωf
 and semi-infinite thickness, respectively. Under the
k FRET ≈ ⟨f exc U ð2Þ Lw < < Ll limit, the electric potential can be written
ℏ f
as92,98
HU ET AL. 11 of 21

 
2εM the scaling factor is proportional to kFRET / 1=d4 in the
Φ2D ðrÞ ¼ Φα ðrÞ ð7Þ
ε2D þ εM 2D limit rather than k FRET / 1=d6 in 3D confinement (see
Table 1), thus theoretically enabling a stronger interac-
Combining Equations (7) and (4), the FRET rate tion and more pronounced long-range characteristics.
reduces to92 The FRET process in two donor-acceptor material
systems, that is, 0D/2D material and 2D/2D material,
     
2  2εM 2 ε2D ðωÞ 
have been widely studied. In most of the 0D/2D hetero-
k α,FRET ¼  Im 2D dS E α ðr Þ  E α ðr Þ
ℏ ε2D þ εM  4π junctions, 0D QDs, also known as nanocrystals, act as the
ð8Þ donor due to their high optical absorption and QY, while
2D material is typically the acceptor.99–103 In a pioneering
work, Chen et al. studied the interaction between CdSe/
Here the integration is over the surface of the 2D accep- ZnS QD and graphene.104 The PL intensity of QD
tor. Assuming that the 2D acceptor thickness is much strongly quenches on graphene compared to quartz sub-
smaller than the separation distance (d) between them, strate (Figure 7A). Due to the screening effect of the insu-
the FRET rate can be further simplified as92,98 lating ligand shell, photoinduced CT is relatively slow
and has a negligible effect.105 However, the QD blinking
   
2 edexc 2 1  2εM 2 effect resulting from the electron trapping between nano-
k α,FRET ¼ bα Im½εQW ðωexc Þ ð9Þ
ℏ εeff D d4 εQW þ εM  crystal and substrate vanishes on graphene, suggesting
that the quenching rate is significantly faster than the
where bα ¼ 16 , 16 , 8 for α ¼ x, y, z, respectively; and εM is
3 3 3 charge trapping rate. Thereby, the QD quenching is
the medium dielectric constant. It is worth noting that attributed to FRET, as further confirmed by the graphene

F I G U R E 7 Energy transfer between quantum dot (QD) and 2D material. (A) PL image of individual CdSe/ZnS nanocrystals on 1L-
graphene (SLG) and quartz. (B) Evolution of the PL quenching factor with the number of graphene layers. The black dots and red curve are
experimentally obtained and theoretically calculated data, respectively. (C) Optical image of a mechanically exfoliated MoS2 flake with
indicated layer numbers. (D) QD PL lifetime mapping of the flakes shown in (C). (E) kFRET as a function of the number of MoS2 layers. The
dashed line represents the ET rate to bulk-like MoS2. Blue circles and solid curves are experimentally obtained and theoretically calculated
data, respectively. (F) Normalized kFRET from QDs to graphene and MoS2 as a function of the layer thickness. The kFRET on the respective
bulk crystals uses for the normalization. Inset: Absolute rates of PL decay. (G) Numerical simulations of the electric field of a QD dipole
inside the acceptor layers. The electric field in graphene is reduced by a factor of 2 for better comparison with MoS2. (A, B) Reproduced with
permission from Reference 104. Copyright 2010, American Chemical Society. (C–E) Reproduced with permission from Reference 103.
Copyright 2014, American Chemical Society. (F,G) Reproduced with permission from Reference 102. Copyright 2016, American Chemical
Society
12 of 21 HU ET AL.

thickness-dependent experiments and theoretical simula- blocking CT and maintaining a high-efficiency ET level
tions (Figure 7B). Similarly, Prins et al. studied the inter- simultaneously. Unlike the typical down-conversion, in
action between CdSe/CdZnS QD and MoS2, as shown in which ETs from the large bandgap material to the small
Figure 7C,D.103 The PL lifetime mapping shows that the one, the B exciton in MoS2 (quasiparticle gap ~2.2 eV)
QD lifetime is much shorter on thin MoS2 than the sub- enables the ET into WS2 (quasiparticle gap ~2.4 eV) A
strate. According to the formula ηET ¼ 1  τDA =τD , in exciton.110,111 This counterintuitive ET direction reveals
which ηET is the FRET efficiency, τD and τDA is the life- the complicated ET dynamics in 2D/2D system due
time of the donor on the bare substrate and in the hetero- to the band splitting induced multiple exciton states.
junction, respectively, ηET is ~80% on few-layer MoS2 and With the reduced Coulomb screening effect and high
enhances to 98% on a monolayer MoS2 (Figure 7E). Such intrinsic doping, the practical circumstances become
high FRET efficiency stems from the reduced dielectric even more complicated due to the formation of trion,
screening effect at the monolayer limit, making QD a spin-forbidden dark exciton, indirect exciton, and biexciton,
perfect light absorption layer for 2D semiconductors. It is especially at low temperatures.112
worth noting that the FRET rate (kFRET) monotonically We systematically investigated the ET dynamics in
increases with the increasing graphene thickness and WS2/h-BN/MoSe2 heterojunction to address the above con-
decreases with the increasing MoS2 thickness (Figure cern. ~6 layers h-BN (~3 nm) is chosen as the spacer to
7F). Raja et al. systematically investigated this counterin- block the CT and maintain the ET simultaneously.107 In
tuitive phenomenon and attributed it to the competition 1L-WS2/h-BN/1L-MoSe2 heterojunction, the MoSe2 exciton
between screening and absorption of the QD dipole's emission doubles, while WS2 trion emission quenches, indi-
electric field inside the acceptor layer.102 To be specific, cating the ET donor is the trion in WS2 rather than the
monolayer MoS2 and bilayer graphene share similar exciton (Figure 8B). The PL lifetime measurements verify
thickness and absorption (imaginary part of the dielec- that WS2 exciton lifetime is too short (<14 ps) to induce ET
tric function), but the screening effect (real part of the (~38 ps); while its trion lifetime is much longer (~57 ps)
dielectric function) in MoS2 is much higher than due to the difficulty for the electron dissociated from the
graphene, leading to a much faster kFRET on graphene trion to find an empty state in the conduction band during
than MoS2 (Figure 7G). When the thickness increases, recombination.113 The trion-mediated three-step FRET pro-
the screening of the electric field in MoS2 is so strong cess is schematically drawn in Figure 8E, with (I) the for-
that it induces the net decrease of kFRET, while the mation of trions in WS2 within 2 ps after optical
screening of the electric field is much weaker in excitation113; (II) ~40% trions recombining radiatively in
graphene than its absorption that induces a net increase WS2 in ~57 ps; and (III) the other ~60% electron–hole pairs
of kFRET. Based on the theoretical calculations, the from the dissociated trions transferring into MoSe2 in
authors established a model that can predict the kFRET ~38 ps. Meanwhile, the electrons dissociated from the tri-
evolution with the acceptor layer thickness according to ons accumulate at the WS2/h-BN interface to induce the
the material's dielectric function. optical gating effect, leading to the p-doping of MoSe2 and
Due to the reduced dimension and the strong confine- the quenching of the trions (Figure 8B–E).107
ment induced in-plane dipole orientation in 2D semicon- Not limited to 2D TMDC heterojunction, Zhang
ductors, the 2D/2D material system possesses a high et al. explored the FRET dynamics in 2D perovskite/2D
geometry factor к, and the dipole–dipole coupling TMDC.114 The enhancement factor (EF) is defined as
strength is proportional to 1=d4 rather than 1=d6 in the EF ¼ I DA =I A , where IDA and IA are the PL intensity of the
molecular system (Equation 7), enabling a pronounced acceptor in the heterojunction and on the bare substrate,
long-distance interaction. Kozawa et al. demonstrated an respectively. In (C6H5C2H4NH3)2PbI4/WS2 heterojunction,
efficient FRET in a tightly contacted WS2/MoSe2 hetero- the WS2 EF reaches up to ~8, which results from a collec-
junction.106 Despite the type-II band alignment induced tive contribution from both the closely contacted interface
ultrafast charge separation and PL quenching, PLE spec- and the long-distance bulk states. Interestingly, the defect
troscopy shows that the MoSe2 (acceptor) A exciton emis- states at the interface between WS2 and organic moiety
sion is enhanced when pumping energy is in resonance offer another low-energy state to accept the energy trans-
with WS2 (donor) A and B exciton states (Figure 8A). The ferred from both the bulk state in the perovskite and WS2.
estimated ET rate is ~1 ps at low temperature, one of the
fastest ET rates among all the donor-acceptor material
systems. In the following work, Xu et al. systematically 3.2 | Dexter-type energy transfer
studied the effect of h-BN thickness on the CT/ET
dynamics in WS2/h-BN/MoS2 heterojunction and found DET,115 also known as electron exchange ET, is a process
that ~4 layers are the optimal h-BN thickness for within which two adjacent molecules exchange their
HU ET AL. 13 of 21

F I G U R E 8 Energy transfer (ET) in 2D material heterojunctions. (A) PLE spectra for monolayer and heterojunction (WS2/MoSe2) at
MoSe2 A exciton (top panel) and WS2 A exciton (bottom panel) emission energies at 1.61 and 1.98 eV, respectively. (B) PL spectra at WS2/h-
BN/MoSe2, h-BN/MoSe2, and WS2/h-BN, respectively. (C,D) WS2 trion lifetime at WS2/h-BN and WS2/h-BN/MoSe2, respectively.
(E) Schematic band diagrams and the dynamic processes in WS2/h-BN/MoSe2. The dashed line indicates the Fermi level. (F–I) Transient
reflectance spectra of WSe2-MoTe2 heterostructures. Transient reflectance spectra for 1L-WSe2 (F) and 1L-WSe2/1L-MoTe2 (G). (H,I)
Comparison of A exciton bleach dynamics in 1L- (H) and 2L-WSe2 (I) with their corresponding heterostructures. (J) The enhancement factor
versus the gate voltage in the three different regions. Schematics of the heterojunction and the Fermi level are also shown. (A) Reproduced
with permission from Reference 106. Copyright 2016, American Chemical Society. (B–E) Reproduced with permission from Reference 107.
Copyright 2020, American Chemical Society. (F–I) Reproduced with from Reference 108. Copyright 2019, American Chemical Society.
(J) Reproduced with permission from Reference 109. Copyright 2020, Nature Publishing Group

electrons based on the overlap of their wavefunctions normalized spectral overlap integral, K is an experimen-
(i.e., electron cloud), requiring the two emitters to be tal constant, d is the distance between donor and accep-
closely contacted (≤1 nm). In the vdWs heterojunction tor, and L is the sum of vdWs radius of the donor and
with type-I band alignment (Figure 1B), the electron and acceptor. Unlike the dipole–dipole coupling in FRET,
hole could transfer from the donor to the acceptor simul- which only allows the transfer of bright excitons, the
taneously after optical excitation and relaxation. DET can mechanism of DET enables the transfer of both bright
also occur between nonemissive electronic states of the and dark excitons, thus offering a promising strategy to
materials, such as spin-forbidden triplet states. This brighten the dark exciton in few-layer TMDCs toward
exchange mechanism is based on the Wigner spin conser- high-efficiency ET. However, the DET results in TMDC
vation rule, which includes: (1) singlet-singlet ET: heterojunctions have been rarely reported due to the
k DET
(1 D  þ1 A ! 1 D þ 1 A); and (2) triplet-triplet ET: difficulty to find a suitable type-I band alignment
k DET
(3 D  þ1 A ! 1 D þ 3 A). Thetransfer
 116 rate of DET (k DET ) heterostructure. In a smartly designed WSe2/MoTe2 het-
is given by k DET ¼ KJexp 2d L , where J is the erojunction with the type-I band alignment by Yamaoka
14 of 21 HU ET AL.

et al. and Wu et al., PLE spectra confirm that WSe2 crystal LaF3 as the substrate to impose a strong gating
(donor) and MoTe2 (acceptor) exciton emission intensi- effect, thus shifting the Fermi level in WS2/MoSe2 hetero-
ties are quenched and enhanced with the above bandgap junction into WS2's conduction band.109 As a result, it
excitation in the heterojunction, supporting ET's exis- blocks the electron transfer from MoSe2 to WS2 while
tence.108,117 In the transient reflectance spectra, the preserves hole transfer from WS2 to MoSe2, leading to the
WSe2 exciton bleaching signal in 1L-WSe2 and 1L-WSe2/1 sharp increase of EF from 0.6 to 1.8 (Figure 8J, point C).
L-MoTe2 recovers at ~50 ps and ~180 fs, respectively, Furthermore, upon resonant excitation with WS2 A exci-
from which the calculated ηET is ~99% (Figure 8F–H). ton (~2 eV), the EF enhances to ~4 folds, revealing a
2L-WSe2/1L-MoTe2 exhibits similar transient reflectance highly efficient DET process (or the authors called exci-
results, as shown in Figure 8I. Since excitons in bilayer or ton funneling effect in the original article).
thicker TMDCs are momentum-dark and forbid the
FRET, the similar dynamic results between 1L- and
2L-WSe2/MoTe2 confirm the ET mechanism to be DET. 4 | CT/ET I MPROVED
WSe2/black phosphorus (BP) heterojunction expands the PHOTODETECTOR
DET dynamics into the mid-infrared regime (~450 meV).
Notably, the BP PL in the heterojunction preserves the The integration of 2D materials into heterojunctions is
linear anisotropy due to the intrinsic anisotropic exciton not restricted by the lattice constant matching at the
emission.118–120 A similar idea applies to organic semi- interface, thus enabling high degrees of device design
conductor/TMDC heterojunction, in which pentacene and fabrication freedom. Since 2D materials belong to a
(donor)/MoSe2 (acceptor) heterojunction forms type-I specific type of “interface” materials, the optoelectronic
band alignment. Zhang et al. demonstrated a ~86 times performance of the heterojunctions is primarily deter-
higher level of pump efficiency in the heterojunction mined by the carrier dynamics at the interface. This
than a single monolayer MoSe2,121 resulting from the section uses the most widely studied device, that is, pho-
high QY in pentacene and the ultrafast ET rate. Mean- todetector, to show the effect of interfacial CT/ET on the
while, the pentacene's low dielectric constant reduces the device performance optimization.126–128
screening effect in MoSe2, thus increasing the trion bind- The first strategy uses interfacial CT to tune the elec-
ing energy from 23.4 (on SiO2) to 28.3 meV. trical and optical properties of the channel 2D semicon-
Bellis et al. expanded the interfacial carrier dynamics ductor to improve the device performance. Lin et al. used
from the vertically stacked to a laterally grown TMDC Cs2CO3, a strong n-dopant, to functionalize the MoS2
heterojunction composed of MoS2 and MoSe2 with a field-effect transistor (FET), leading to the enhanced elec-
type-I band alignment.122 By performing transient reflec- tron concentration and mobility. Such anomalous
tance spectroscopy with both spatial and temporal resolu- enhancement in mobility is attributed to the screening of
tion, the authors deduced the transfer velocity of both defect scattering centers by injecting electrons.129–131
electrons and holes of ~104 m s1.122 However, in the ver- Meanwhile, the carrier lifetime is enhanced with the for-
tical heterojunction composed of the same materials, the mation of trions, which induces a high optical gain, thus
same research group had reported ultrafast CT with the enhancing the photodetector responsivity by ~5 times.
formation of indirect excitons.38 The contradiction Similarly, the responsivity of Cs2CO3 decorated WSe2
between the two cases may result from the different elec- FET dramatically enhances by almost three orders of
tronic band structures between the mechanically stacked magnitudes.132 Apart from the contributions mentioned
and epitaxial grown heterostructure. To fully address the above, the reduced effective Schottky barrier height
CT/ET dynamics in 2D heterostructures, advanced exper- between the metal contacts and WSe2 also facilitates the
imental techniques such as micro-angle-resolved photo- effective collection of photogenerated electrons.
emission spectroscopy that can resolve the interface band The second strategy to obtain a high-performance pho-
alignment are highly needed. todetector is to efficiently dissociate the photogenerated
Since only a limited number of 2D heterojunction electron–hole pair using the built-in field at the junction.
form type-I band alignment and exhibit efficient DET, In a typical junction design, electrodes on different mate-
many critical problems, for example, the transfer dynam- rials harvest the electrons and holes, respectively. In an
ics of spin-forbidden dark excitons and valley-polarized upgraded photodetector configuration, Shin et al. designed
excitons, remain unexplored. Thereby, it is essential to a MoS2/WSe2 heterojunction, where electrodes both posi-
engineer the band structure to enrich the donor-acceptor tion on the MoS2 channel layer that completely covers the
material components. The band structure of 2D materials underlying WSe2 layer (Figure 9A).133 As plotted in Figure
can be tuned through either chemical or physical 9B, the type-II band alignment leads to the accumulation
methods, as reported.123–125 Meng et al. used a 3D ionic of photogenerated electrons and holes in the MoS2 and
HU ET AL. 15 of 21

F I G U R E 9 Charge/energy transfer improved photodetectors. (A–C) The schematic device structure (A), band alignment (B), and
transfer characteristic (C) of the MoS2/WSe2 photodetector. (D–F) The schematic drawing (D), absorption spectrum (E), and I–V curve under
4.7 μm illumination (F) of the HfS2/WS2 interlayer exciton photodetector. (G–I) Transfer characteristic in the dark and under 595 nm
illumination (G), Wavelength-dependent photoresponsivity (H), and the spacer thickness dependent ET efficiency (I) of the TDBC/MoS2
device. (A–C) Reproduced with permission from Reference 133. Copyright 2020, American Chemical Society. (D–F) Reproduced with
permission from Reference 134. Copyright 2020, Nature Publishing Group. (G–I) Reproduced with permission from Reference 135.
Copyright 2018, American Chemical Society

WSe2 layer, respectively. Thus, it only harvests the elec- heterojunction, which forms interlayer exciton with a
trons in the MoS2 channel layer. The accumulated holes large oscillation strength comparable to intralayer exci-
in the WSe2 layer induce the optical gating effect, which ton.134 Thus, the interlayer exciton state could directly
further enhances photogenerated electron concentration absorb the photons with much smaller energy than the
and lifetime, as evidenced by the successive negative constituent semiconductors' bandgaps, expanding the
shift of the transfer curve's threshold voltage with the operation wavelength to ~0.2 eV (mid-infrared) and
increasing laser power (Figure 9C). Thus, the photode- could be further reduced to ~0.06 eV under gate voltage
tector performance is vastly enhanced under illumina- (Figure 9D,E). Besides, photogenerated electrons and
tion, achieving a high photoconductive gain of 106, a holes accumulate rather than depleted at the interface,
high photoresponsivity of 2700 A W1, a specific requiring external voltage to extract the free carriers. As
detectivity of 5  1011 Jones, and a moderate response shown in Figure 9F, under 4.7 μm illumination, a nega-
time of 17 ms.133 Not limited to higher device perfor- tive bias could increase the charge extraction with an
mance, CT has been utilized to expand the response enhanced photocurrent, while positive bias enhances
wavelength in TMDC heterojunction using interlayer the confinement of interlayer exciton and fewer extract-
exciton as the absorber. Lukman et al. built a HfS2/WS2 able carriers. This prototype device shows superior
16 of 21 HU ET AL.

detectivity than other commercially available infrared intrinsic doping lead to various excitonic states with
photodetectors, especially at room or elevated different lifetimes, which must be carefully treated in
temperatures. dealing with the dynamics. Recently, both weak and
ET could also improve photodetector performance. strong coupling regimes have been achieved between
Cheng et al. fabricated a heterojunction composed of a TMDC's exciton state and optical cavity mode.138 Since
j-aggregate thin film of organic dye (5,6-dichloro-2[3-[5,6- the optical cavity mode can also manipulate FRET, it
dichloro-1-ethyl-3-(3-sulfopropyl)-2(3H)-benzimidazolidene]- may achieve long-distance ET with ultra-high effi-
1-propenyl]-1-ethyl-3-(3-sulfopropyl) benzimidazolium ciency.139 Various heterojunctions with type-I band
hydroxide) (TDBC) and a 1L-MoS2.135 Both the dark alignment have been found to facilitate DET process.
and photo-conductivity improve with the deposition of The ability to transfer and brighten the dark exciton
j-aggregate, indicating efficient n-doping and ET (Fig- makes it ideal for probing the dark states. However,
ure 9G). The EF from ET is extracted from the current results are still limited to the momentum-dark
wavelength-dependent photoresponsivity measure- excitons, whereas the spin-forbidden dark state
ment, which has a maximum value of 93 ± 5% at remains unexplored. Finally, both CT and ET play
600 nm as a result of the near-perfect spectral overlap important roles in optimizing the responsivity, speed,
(Figure 9H). Furthermore, the experimentally deduced and operation wavelength of photodetectors.
ET efficiency fits well with FRET theory by tuning the In conclusion, the CT and ET in 2D material hetero-
h-BN spacer thickness (Figure 9I), confirming that junctions are determined by the band edge alignment
dipole–dipole coupling dominates the ET process. and primarily affected by the band structure, relative
Since the ET timescale ranges from picoseconds to tens dielectric function, stacking order, crystal orientation
of picoseconds, it avoids any charge trapping processes alignments, and the external electric/magnetic/optical/
at the interface, thus a promising strategy to achieve strain field. A clever design is critical to achieve the pro-
high responsivity and ultrafast response speed simulta- posed functionality and study the underlying carrier
neously (the highest reported response speed is 3 ps for dynamics. For example, inserting a thin insulating layer
MoS2 photodetector136). between two TMDC layers could block the CT, and keep
the FRET almost intact. Interfacial CT and ET in vdWs
heterojunctions set the foundation to explore the funda-
5 | C ONCLUSIONS A ND OUTLOOK mental carrier dynamics and pave the way for practical
device applications in ultrafast and high-performance
The recent progress on the understanding of charge and optoelectronics.
ET dynamics in vdWs heterojunction has been reviewed.
The CT at vdWs heterojunctions is ultrafast due to the ACKNOWLEDGMENTS
strong quantum coherence effect, showing great potential Qihua Xiong gratefully acknowledges strong support
for ultrafast optical modulators. When two TMD layers from the State Key Laboratory of Low-Dimensional
are carefully aligned, the formed interlayer exciton with Quantum Physics and start-up grant from Tsinghua
valley degree-of-freedom has innovated significant devel- University. Haiyun Liu gratefully acknowledges funding
opment in fundamental physics, including long-distance support from the National Natural Science Foundation
diffusion, Bose-Einstein condensates, and Moiré-excitons. of China (Grant No. 92056204). Hilmi Volkan Demir
However, most of the current works focus on the inter- and Pedro Ludwig Hern
andez-Martínez gratefully
layer exciton between WS2, MoS2, MoSe2, and WSe2, for- acknowledge support from the National Research Foun-
ming between the K valleys in the Brillouin zone, thus dation, Prime Minister's Office, Singapore under its
strongly dependent on the stacking angle with weak Investigatorship Program (NRF-NRFI2016-08) and the
oscillation strength. From a more practical point of Singapore Agency for Science, Technology and Research
view, interlayer exciton that forms at Γ point features (A*STAR) SERC Pharos Program under Grant
high oscillation strength and is immune to the twist No. 152 73 00025. Hilmi Volkan Demir also acknowl-
angle, thus expanding the optical absorption into the edges TUBA. Xue Liu acknowledges the financial sup-
mid-infrared region.134,137 The second part on ET has port from the National Natural Science Foundation of
reviewed both the Förster and Dexter types. A compre- China (12104006) and the start up fundations from
hensive theoretical understanding of both mechanisms Anhui University. Weigao Xu thanks the Fundamental
is given. One crucial parameter in the FRET dynamics Research Funds for the Central Universities in China
is the dielectric function's real and imaginary parts, (020514380231; 021014380177), the National Natural
that is, screening and absorption of the electric field. Science Foundation of China (21873048), the Natural
Moreover, the quantum confinement effect and high Science Foundation of Jiangsu Province (BK20180319).
HU ET AL. 17 of 21

CONFLICT OF INTEREST 18. Terrones H, L
opez-Urías F, Terrones M. Novel hetero-layered

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ORCID
Cho K. Band alignment of two-dimensional transition
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functionalization. Adv Mater. 2018;30(43):e1801931. AUTHOR BIOGRAPHIES
121. Zhang L, Sharma A, Zhu Y, et al. Efficient and layer-
dependent exciton pumping across atomically thin organic- Zehua Hu received his
inorganic type-I heterostructures. Adv Mater. 2018;30(40):
Bachelor's degree in Phys-
e1803986.
122. Bellus MZ, Mahjouri-Samani M, Lane SD, et al. Photocarrier
ics from Nanjing Univer-
transfer across monolayer MoS2-MoSe2 lateral hetero- sity in 2014, and PhD
junctions. ACS Nano. 2018;12(7):7086-7092. degree in physics from the
123. Han C, Hu Z, Gomes LC, et al. Surface functionalization of National University of
black phosphorus via potassium toward high-performance Singapore in 2018. He is
complementary devices. Nano Lett. 2017;17(7):4122-4129. currently a research fellow
124. Wang Y, Xiao J, Zhu H, et al. Structural phase transition in
in Nanyang Technological
monolayer MoTe2 driven by electrostatic doping. Nature.
University. His research
2017;550(7677):487-491.
125. Klein J, Wierzbowski J, Regler A, et al. Stark effect spectroscopy interests include optical
of mono- and few-layer MoS2. Nano Lett. 2016;16(3):1554-1559. spectroscopy and optoelectronics in low-dimensional
126. Wang J, Hu W. Recent progress on integrating two- semiconducting materials, especially the ultrafast car-
dimensional materials with ferroelectrics for memory devices rier dynamics in the heterojunctions.
and photodetectors. Chin Phys B. 2017;26(3):037106.
127. Bai G, Lyu Y, Wu Z, Xu S, Hao J. Lanthanide near-infrared Xue Liu received his PhD
emission and energy transfer in layered WS2/MoS2 in Physics from Tulane Uni-
heterostructure. Sci China Mater. 2019;63(4):575-581. versity in 2017. From 2017
128. Wei X, Yan F-G, Shen C, Lv Q-S, Wang K-Y. Photodetectors to 2020, he worked as a
based on junctions of two-dimensional transition metal postdoctoral research fellow
dichalcogenides. Chin Phys B. 2017;26(3):038504. at Nanyang Technological
129. Yang Q, Xue Y, Chen H, Dou X, Sun B. Photo-induced doping
University, Singapore. He is
effect and dynamic process in monolayer MoSe2. J Semicond.
2020;41(8):082004.
currently a full professor in
130. Lin JD, Han C, Wang F, et al. Electron-doping-enhanced trion the Institutes of Physical
formation in monolayer molybdenum disulfide functionalized Science and Information
with cesium carbonate. ACS Nano. 2014;8(5):5323-5329. Technology at Anhui Uni-
131. Wu Z, Luo Z, Shen Y, et al. Defects as a factor limiting carrier versity. His research inter-
mobility in WSe2: a spectroscopic investigation. Nano Res. ests include electric and optoelectronic properties of low
2016;9(12):3622-3631.
HU ET AL. 21 of 21

dimensional materials and heterostructures, and their investigations of light-matter interactions in low-
applications in next generation functional devices. dimensional quantum matter. He currently serves as
Associate Editor for Nano Letters, Journal of Semicon-
Qihua Xiong is a Profes-
ductors and Chinese Physics B, and international advi-
sor of Physics at Tsinghua
sory board or editorial board for many prestigious
University, Fellow of
journals, such as ACS Photonics, Nano Research, Sci-
American Physical Society
ence China Materials, eSciences, and so on.
and Optical Society of
America. He received his
PhD from Penn State Uni-
versity in 2006, and then
How to cite this article: Hu Z, Liu X,
conducted postdoctoral
Hern
andez-Martínez PL, et al. Interfacial charge
research at Harvard Uni-
and energy transfer in van der Waals
versity. From 2009 to
heterojunctions. InfoMat. 2022;4(3):e12290.
2020, he worked at Nanyang Technological University.
doi:10.1002/inf2.12290
His group is specialized in optical spectroscopy
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