Nano Materials Science 1 (2019) 268–287

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Nano Materials Science

journal homepage: www.keaipublishing.com/cn/journals/nano-materials-science/

Band structure engineering in metal halide perovskite nanostructures for

optoelectronic applications
Qingdong Ou a, Xiaozhi Bao b, Yinan Zhang c, Huaiyu Shao b, Guichuan Xing b, Xiangping Li c,
Liyang Shao d, Qiaoliang Bao a, *
a
Department of Materials Science and Engineering, ARC Centre of Excellence in Future Low-Energy Electronics Technologies (FLEET), Monash University, Clayton,
Victoria, 3800, Australia
b
Joint Key Laboratory of the Ministry of Education, Institute of Applied Physics and Materials Engineering (IAPME), University of Macau, Macau, China
c
Guangdong Provincial Key Laboratory of Optical Fiber Sensing and Communications, Institute of Photonics Technology, Jinan University, Guangzhou, 510632, China
d
Department of Electrical and Electronic Engineering, Southern University of Science and Technology, Shenzhen, 518055, Guangdong, China

A R T I C L E I N F O A B S T R A C T

Keywords: Metal halide perovskite nanostructures have emerged as low-dimensional semiconductors of great significance in
Band structure engineering many fields such as photovoltaics, photonics, and optoelectronics. Extensive efforts on the controlled synthesis of
Perovskite nanostructures perovskite nanostructures have been made towards potential device applications. The engineering of their band
Optoelectronic applications
structures holds great promise in the rational tuning of the electronic and optical properties of perovskite
Doping
Heterostructures
nanostructures, which is one of the keys to achieving efficient and multifunctional optoelectronic devices. In this
article, we summarize recent advances in band structure engineering of perovskite nanostructures. A survey of
bandgap engineering of nanostructured perovskites is firstly presented from the aspects of dimensionality
tailoring, compositional substitution, phase segregation and transition, as well as strain and pressure stimuli. The
strategies of electronic doping are then reviewed, including defect-induced self-doping, inorganic or organic
molecules-based chemical doping, and modification by metal ions or nanostructures. Based on the bandgap en-
gineering and electronic doping, discussions on engineering energy band alignments in perovskite nanostructures
are provided for building high-performance perovskite p-n junctions and heterostructures. At last, we provide our
perspectives in engineering band structures of perovskite nanostructures towards future low-energy optoelec-
tronics technologies.

1. Introduction flexibility in choosing suitable perovskite crystals for specific optoelec-

Halide perovskites are a new generation of optoelectronic materials
with intriguing optical and electronic properties. They have been applied
in the fabrication of high-performance optoelectronic devices, ranging
from solar cells, photodetectors, and ionizing radiation detectors to light-
emitting diodes (LEDs) and lasers, as well as to memories and solar-to-
fuel conversion fields [1–8]. The wide application package reflects the
versatility and universality of the halide perovskite materials. The halide
perovskites are generally crystallized in a general chemical structure of
ABX3, where A is an organic or inorganic cation such as MA, FA, Cs, B is a
metal ion such as Pb, Sn, Bi, and X is a halide anion or halide mixture such
as I, Br, Cl, I–Br [9]. The three main components (A, B, and X), therefore,
can lead to a variety of perovskites with different properties due to the
broad tunability of composition choices, which allows us substantial
tronic applications. Recently, a type of fully organic halide perovskites
has been designed and synthesized [10], exhibiting excellent ferroelec-
tric properties, which might open a new door to the metal-free halide
perovskite field.
The halide perovskites are, in most cases, direct-bandgap semi-
conductors with a bandgap ranging across the whole visible spectrum
[11]. This is important as the charge carriers in perovskite layers can be
efficiently generated in a photovoltaic device or recombined in a light
emission device, without any assistance from phonons. The
direct-bandgap also leads to high photoluminescence quantum yield, for
example, of over 90% in surface-treated MAPbI3 perovskite thin films
[12]. The bandgap of a perovskite crystal is easily tuned simply by
changing the mixing ratio of the halides (e.g., I–Br, Br–Cl), which, in
principle, can achieve seamless tuning of the bandgap [9]. The tunability

* Corresponding author.
E-mail address: qiaoliang.bao@monash.edu (Q. Bao).

https://doi.org/10.1016/j.nanoms.2019.10.004
Received 25 July 2019; Accepted 27 August 2019
Available online 12 October 2019
2589-9651/© 2019 Chongqing University. Production and hosting by Elsevier B.V. on behalf of KeAi. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Q. Ou et al.
Fig. 1. The envelope of band structure engineering for perovskite optoelec-
tronic applications.
in bandgap allows for the creation of multicolor light emission devices of
interest and for any special device application requiring a specific
bandgap. It is reported that the luminous efficiency and external quan-
tum efficiency of perovskite light-emitting devices are now in the com-
parable level of the state-of-the-art light-emitting devices based on
quantum dots and organic materials [13–18]. which has been realized
merely in a few years.
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Nano Materials Science 1 (2019) 268–287
The light absorption property, besides the direct and tunable
bandgaps, of the perovskite also shows superiority compared with
traditional semiconductors, with an example of MAPbI3 exhibiting
higher absorption coefficient of up to ~105 cm-1 than Si and GaAs [11].
The high absorption, undoubtedly, contributes to the extremely high
photon to carrier conversion efficiency, as demonstrated in perovskite
solar cells (with high efficiency of beyond 23% in the literature
exceeding Si cells) [19]. Moreover, lead halide perovskites have chemical
elements with high atomic numbers, possessing strong attenuation
capability of high energy ionizing radiation such as X-ray, gamma-ray
[20]. Thus, efficient X-ray detectors and scintillators have been fabri-
cated using lead-based perovskites, representing another research hot-
spot of metal halide perovskites [21–25].
Although tremendous efforts have been devoted to metal-halide pe-
rovskites and their applications in optoelectronic devices such as solar
cell panels and LED displays, most of these studies are based on bulk
crystals or thin films of perovskites. Recent attention has been partly
transferred to low dimensional perovskites, including zero-dimensional
(0D), one-dimensional (1D) and two-dimensional (2D) nanomaterials.
The crystalline perovskite nanostructures with reduced dimensionality
show distinctive optoelectronic properties with quantum-confined effect
compared with their bulk counterparts [26–33]. Fundamental under-
standing of the structure-property-performance relationship of the halide
perovskite at the nanoscale is critical for high-performance optoelec-
tronic devices. Particularly, the important point to bring halide perov-
skites into semiconductor nanostructures is not only for device
miniaturization but also for studying their physical properties under
quantum confinement. Tuning of the band structures of the perovskite
nanostructures could lead to a new degree of freedom to modify the
optoelectronic characteristics of perovskites and therefore to build novel,
efficient and functional perovskite optoelectronic devices.
In this Review, we provide an overview of recent progress in band
Fig. 2. Bandgap engineering in metal halide pe-
rovskites by tailoring the dimensionality. (a)
Photoluminescence (PL) spectra of FAPbI3 nano-
crystals (NCs) with different sizes. (b) Bandgap
energies versus the edge length of FAPbI3 NCs.
Reproduced with permission from the Nature
Publishing Group [34]. (c) PL of exfoliated
monolayers for 2D layered BA2(MA)n
1PbnI3nþ1
Ruddlesden-Popper perovskites of n ¼ 1 to 4 ho-
mologues. Reproduced with permission from the
Nature Publishing Group [39]. (d) The bandgap
of PEA2A1.5Pb2.5Br8.5 (A ¼ MA and Cs) perov-
skites (see inset for atomic models) with different
numbers of layers. Reproduced with permission
from the Nature Publishing Group [40].
Q. Ou et al.
structure engineering of metal halide perovskite nanostructures for op-
toelectronic applications (Fig. 1). A survey of bandgap engineering of
perovskite nanostructures is firstly presented from the aspects of
dimensionality tailoring, compositional substitution, phase segregation
and transition, as well as strain and pressure stimuli. The strategies of
electronic doping are then reviewed including defect-induced self-
doping, inorganic or organic molecules-based chemical doping, and
modification by metal ions or nanostructures. Based on the bandgap
engineering and electronic doping, discussions on optimizing energy
band alignments in perovskite nanostructures are provided for building
high-performance perovskite p-n junctions, heterostructures and multiple
quantum wells.
2. Bandgap engineering in perovskite nanostructures
The bandgap of metal halide perovskites is widely tuneable with light
emission ranging from ultraviolet to near-infrared wavelength. This is
not only due to the intrinsic tuning of composition (e.g., the seamless
mixing ratio of halides) in a perovskite, but also a result of the ease of
controlling their dimensionality. External stimuli can also engineer the
bandgap of perovskites, including light- or electric field-induced phase
segregation (ion migration), phase transition by thermal or moisture, and
mechanical effects of strain and pressure. We will discuss these factors in
the following sections.
2.1. Dimensionality tailoring
Similar with conventional semiconductors, metal halide perovskites
can be made into low dimensions, including 0D nanocrystals (NCs) or
quantum dots (QDs), 1D nanowires (NWs) or nanorods, and 2D nano-
sheets or nanoplatelets. Owing to the quantum confinement effect, the
bandgap energy of a low-dimensional perovskite will increase compared
with its bulk counterpart. This is followed by changing the geometric size
of perovskite nanostructures that will further change the bandgap. As
shown in Fig. 2a, PL emission wavelengths were continuously tuned by
the gradual reduction in the size of FAPbI3 NCs [34]. The calculated
bandgap energy, accordingly, increased from 1.5 eV in bulk to over
1.7 eV for perovskite NCs with an edge length of ~8 nm (Fig. 2b). Re-
searchers also demonstrated that a broad tunability in the bandgap of the
typical MAPbX3 NCs can be realized [35,36]. Besides the
organic-inorganic hybrid perovskite NCs, inorganic perovskite NCs and
QDs also show such size-/diameter-dependent bandgap energies, such as
CsPbI3, and CsPbBr3 [37,38]. The high PL quantum yield and tuneable
bandgap in the visible spectrum of perovskite NCs make them promising
candidates in the realization of multicolor display or white LED lighting.
The size effect can be expected in 1D perovskite NWs. The diameter of a
perovskite NW defines the bandgap energy and emission wavelength
regardless of the length [38].
2D perovskites, recently catching a great deal of research interest,
exhibit many unique optical and electronic properties compared to both
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Nano Materials Science 1 (2019) 268–287
Fig. 3. Bandgap tuning through composition substi-
tution in the perovskite lattices. (a) The emission
wavelength of the organic-inorganic hybrid
MAPbXnY3–n perovskites tunable from 390 to 790 nm
wavelength, where X and Y refer to the halides.
Reproduced with permission from the Nature Pub-
lishing Group [9]. (b) Evolution of bandgap energy of
inorganic CsPbX3 perovskite NCs. Reproduced with
permission from the Nature Publishing Group [45].
and from the American Chemical Society [46].
perovskite bulk and other 2D materials [27,29,31,41]. The key difference
is that 2D perovskites have ionic bonds in the crystal lattice while inor-
ganic 2D materials such as TMDCs are connected by covalent bonds.
Organic molecules sandwiching 2D hybrid perovskite crystal plane also
brings additional functionality, such as tuneable quantum well structure
by adjusting the length and type of the organic chain [42–44]. Fig. 2c
shows the layer number dependent PL spectra of 2D BA2(MA)n
1PbnI3nþ1
perovskites, exhibiting a large wavelength tuning range from ~520 nm to
650 nm (~130 nm difference, that is, ~0.47 eV shift) [39]. Interestingly,
they observed the reversible surface relaxation behavior of these 2D
crystals, meaning that the excitonic energies shifted reversibly induced
by laser annealing on these 2D crystals with the encapsulation of hBN.
The similar layer-dependent trend was found in 2D perovskites with
three cations containing both organic (PEA, MA) and inorganic (Cs)
species (Fig. 2d), showing a gradual decrease of bandgap energy with
increasing layers and an energy difference between single unit-cell and
five unit-cell crystals as high as ~0.6 eV [40]. Based on the 2D perov-
skites with high energy bandgap and monodispersed phases, sky-blue
perovskite LED devices were demonstrated with high luminescence and
color stability under high driving voltages.
2.2. Compositional substitution
Compositional engineering, in addition to the quantum-confinement
engineering, is usually a very convenient and useful method to tune
the bandgap of perovskite nanostructures. Within the framework of a
perovskite crystal structure, the position of halides (X) is most tuneable in
terms of mixing with any ratio of the target. It is no doubt that the sub-
stitution of the cations (A) and metal (B) can redefine the bandgap of a
perovskite and extend the emission spectrum. Nevertheless, we focus on
anion mixing most commonly used for bandgap tuning of perovskites.
Fig. 3a shows the broad emission range across the entire visible
spectrum of the typical MAPbX3 perovskite by a selective mixture of Cl/
Br and Br/I [9]. This type of organic-inorganic hybrid perovskite nano-
structures is generally direct-bandgap semiconductor with high photo-
luminescence (PL) quantum yield and narrow bandwidth. It is
noteworthy that the emission wavelength, in principle, can be seamlessly
tuned by the fine control over the halide ratio. Similarly, continuous
spectral tunability can be realized in all-inorganic perovskite NCs
(Fig. 3b) [45–47]. Starting from CsPbBr3 NCs with a bandgap of 2.43 eV,
the halide-substituted perovskite NCs exhibited gradually increased
bandgap to 3.03 eV with maximal Cl exchange and gradually decreased
bandgap to 1.88 eV with maximal I exchange. Importantly, the anion
exchange reactions were reversible and robust. The solution-phase anion
exchange process retains both structural and optical properties of
perovskite NCs comparable to the NCs by direct synthesis. Besides the
solution exchange, vapor phase conversion was also introduced to pre-
pare mixed halide perovskites [48,49]. Therefore, both solution- and
vapor-based approaches provide effective access to tuneable bandgaps of
perovskite nanostructures in a fast, facile manner.
Q. Ou et al. Nano Materials Science 1 (2019) 268–287

Fig. 4. Halide-gradient perovskite nanowires (NWs). (a) A schematic of perovskite NWs showing a gradient distribution from the Br-rich region to the I-rich region.
(b) PL intensity images of a gradient MAPbBrxI3
x NW. Scale bar: 2 μm (c) Carrier density as a function of distance to the excitation spot for the gradient NW.
Reproduced with permission from the American Chemical Society [57]. (d) Schematic of light propagation in a composition-graded perovskite wire and gradually
changed bandgap along the long axis. (e) Darkfield PL images of a composition-graded MAPbBrxI3
x wire under local excitation. Scale bar: 5 μm. (f) PL spectra of
perovskite wires with different compositions. Reproduced with permission from the Royal Society of Chemistry [58]. (g) Schematic of a concentration-gradient
inorganic perovskite NW fabricated by stacking a CsPbCl3 microplate on a CsPbBr3 NW for solid-state ion interdiffusion. (h,i) Representative optical images in
real emission color of the Cl–Br gradient NWs formed by ion diffusion under wide-field 400 nm laser excitation. Reproduced with permission from the American
Chemical Society [59].

2.3. Phase segregation
Phase segregation is normally associated with ion migration behavior
in the perovskites. Extensively investigated factors to cause ion migration
in the perovskite crystal lattice are light illumination and electric field
[50–56]. In a mixed halide perovskite, the separation of different halide
phases leads to the reconstruction of bandgap in local regions while the
ion migration in a pure phase perovskite mostly affects defect states or
structural distortion. Fig. 4 shows three examples of halide-gradient
perovskite NWs triggered either by light illumination or by sponta-
neous diffusion. The solution-grown I–Br mixed perovskite NW in
Fig. 4a–c exhibited gradient halide distribution upon laser excitation at
one end, showing a gradual increase in carrier density away from the
laser spot that is inverse to the pure MAPbI3 perovskite [57]. Similar
profiles were observed in CVD-grown mixed perovskite NWs, in which
the emission at one end of the NW waveguide red-shifted with laser
excitation at the other terminal (Fig. 4d–f) [58]. An interesting obser-
vation is that the mixing of halide anions could be done through physical
contact between CsPbBr3 and CsPbCl3 perovskite crystals (Fig. 4g–i)
[59]. The fluorescence images clearly showed gradual emission color
change along the long direction of the wire, suggesting the gradient
bandgap of these mixed perovskite nanostructures.
Besides the gradient halide distribution in perovskite NWs, a kind of
mixed-halide perovskite nanoplatelets with gradient bandgap from 1.56
to 2.29 eV was demonstrated by thermally treating FAPbI3 nanoplatelets
with FABr vapor (Fig. 5) [60]. Except for the thin crystals (~58 nm) that
had been fully converted into FAPbBr3, the thick mixed-halide perovskite
nanoplatelets (i.e., 239 nm and 1.3 μm) exhibited strong halide segrega-
tion behavior under light illumination, which finally led to an irrevers-
ible, energetically favorable gradient halide distribution. It should be
pointed out that the PL spectra of the medium-thick crystal evolved into
Br-rich emission while the PL spectra gradually shifted to I-rich emission
for the thick crystal. It was attributed to the variation of phase stability in
different-thickness perovskite nanoplatelets, that is, stable Br-rich phase
in the medium crystal and stable I-rich phase in the thick crystal. The
energy funneling effect in such gradient bandgap structure may assist in
improving the transfer of the photogenerated carriers or the electrode
injected carriers within the gradient band structure. Therefore, the halide

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Q. Ou et al.
Fig. 5. Gradient bandgap by halide segregation in mixed-halide perovskite nanoplatelets. (a) Schematic of the gradient energy band structures. (b) Fabrication steps of
FAPb(BrxI1
x)3 nanoplatelets by Br exchange reaction in FAPbI3 nanoplatelets with different thicknesses. (c–e) Time-dependent PL spectra taken under 405 nm
continuous illumination for perovskite nanoplatelets with thicknesses of c) 58 nm, d) 239 nm, and e) 1.3 μm. Reproduced with permission from the Wiley-VCH [60].
migration-induced phase segregation is an effective way to modify the
bandgap of perovskite nanostructures.
2.4. Phase transition
Phase transition is widely studied in lead halide perovskites with its
effect on the band structures and the device performance [61–63]. It is
usually triggered by thermal effect and then the crystal lattice re-
constructs to another space group, even not in the perovskite structure.
Fig. 6a presents two phases of MAPbI3 perovskites with different octa-
hedral arrangements [64]. It is reported that individual MAPbI3 perov-
skite microplates exhibited size-dependent phase transition behavior, in
which the phase transition temperature from orthorhombic to tetragonal
phases decreases with decreasing microplate thickness [65]. This is
different from the case in bulk crystals. The thickness-dependent struc-
tural phase transition was ascribed to the difference of the surface energy
between the polymorphs. Specifically, the surface-to-volume ratio
decreased in the thicker microplate, leading to a higher phase transition
temperature. Theoretical simulations have shown the
temperature-dependent bandgap in MAPbI3 perovskite crystals (Fig. 6b),
in which two bandgaps emerged are related to the MA-ordered and
MA-disordered domains [66]. As the ordering of the MA cations would
build a strong local electric field, thus increasing the bandgap of
MA-ordered orthorhombic domains.
In addition to the thermal-induced phase transition, moisture is also a
non-negligible factor to induce phase transition in inorganic perovskites.
Fig. 6c and d show the reversible transition of crystal structures of
CsPbIBr2, where the low-temperature phase can be transitioned into the
high-temperature phase through thermal heating in ambient or inert
conditions [67]. Importantly, the metastable high-temperature phase can
be fully back-converted to low-temperature phase by moisture exposure.
It is different from the CsPbI3 perovskite that can undergo phase transi-
tion reversibly by mild heating [68]. With Br addition, the
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Nano Materials Science 1 (2019) 268–287
high-temperature phase of CsPbIBr2 is much more stable and difficult for
back-conversion. Hence, the moisture-mediated phase transition in such
perovskite crystals provides an effective route to modulate the bandgap
(e.g., optical transmission and absorption) at room temperature. This
concept was further integrated into a thermochromic solar cell with
reversible transparency and photovoltaic capability [67].
2.5. Strain modulation
The strain is an effective factor to engineer the band structure of a
semiconductor, particularly in a nanostructure form. It is important to
study the mechanical properties of perovskite nanostructures for better
understanding of the interaction between mechanical and other physical
fields for optoelectronic device applications. The in-plane mechanical
characteristics of 2D BA2MAn-1PbnX3nþ1 perovskite few layers were
investigated in grooved substrates, revealing the smaller in-plane Young's
moduli compared with covalent bonded 2D materials [69]. These 2D
perovskites showed thickness-dependent mechanical properties due to
the interlayer slippage during deformation. First-principles calculations
were also employed to theoretically estimate the effect of strain on low
dimensional perovskites, from which the bandgap of 2D MAPbI3
increased upon tensile strain and decreased upon the compressive strain
[70]. However, the band gap of 1D MAPbI3 exhibited parabolic relation
to strain, increasing upon both tensile and compressive strain.
Fig. 7a and b show the evolution of band structures and optical
bandgaps of (FAPbI3)0.85(MAPbBr3)0.15 perovskite under compressive
and tensile strain [71]. In contrast to a bandgap of 1.49 eV in strain-free
perovskite, the compressive strain (1%) resulted in a decrease to 1.44 eV
while the tensile strain (1%) induced a rise to 1.55 eV. A more detailed
picture of the strain effect on the bandgap of MAPbI3 perovskite was
calculated and shown in Fig. 7c [72]. It was found that the stretching or
compressing of Pb–I bonds under external strain roughly determined the
change in valence band maximum of MAPbI3 perovskite; the largest
Q. Ou et al. Nano Materials Science 1 (2019) 268–287

Fig. 6. Phase transition induced bandgap reconstruction. (a) Atomic models of the MAPbI3 perovskite NCs with cubic and tetragonal crystal structures. Reproduced
with permission from the IOP Publishing [64]. (b) Bandgap as a function of the pseudo-cubic lattice parameter (thermal expansion) for the MA-ordered (black
symbols) and MA-disordered (red symbols) orthorhombic systems and the tetragonal system (blue symbols). Reproduced with permission from the American As-
sociation for the Advancement of Science [66]. (c) Schematics of the low-temperature (low-T) to high-temperature (high-T) phase transition of inorganic CsPbIBr2
perovskite by heating and the high-T to low-T transition by exposure to moisture. (d) Absorption (dashed lines) and PL (solid lines) spectra of the low-T (black) and
high-T (red) CsPbIBr2 films. Reproduced with permission from the Nature Publishing Group [67].

Pb–I–Pb bond angle after strain mainly induced the shift in the conduc-
tion band minimum. Based on the possibility of strain-modulated
bandgap, we predict that the bandgap engineering of perovskite nano-
structures may provide new insight into future integrated
mechano-opto-electronic device applications.
2.6. Pressure tuning
Recently, Bandgap tuning of perovskites by external hydrostatic
pressure has become very attractive. Without changing the chemical
compositions, the high pressure can considerably modify the bond length
and bond angle in perovskite crystals, which thus results in fine-tuning of
the electronic band structures of perovskites. Several common phenom-
ena in perovskites upon pressure are bandgap narrowing or broadening,
enhancement of emission intensity, prolongation of carrier lifetime,
direct-to-indirect bandgap conversion, and phase transition. For
example, high pressure can induce intensive light emission from the
initially nonfluorescent 0D Cs4PbBr6 NCs, the emission intensity
increasing significantly with the pressure [73]. Both experimental and
theoretical studies revealed that the pressure-induced emission might be
attributed to the structural phase transition and hence the increased
binding energy of self-trapped excitons upon compression. Fig. 8a shows
an evolution of optical images of 0D Cs3Bi2I9 perovskite crystals upon
pressure [74]. Upon compression, the original bright red turns into dark
red at 4.6 GPa, gradually darkening at a higher pressure and eventually
becoming opaque black above 9.0 GPa. Interestingly, the transformation
is reversible upon decompression. The bandgap can be substantially
tuned from 2.06 eV to 1.12 eV, an impressive reduction without altering
chemical compositions. Moreover, the metallic character of this perov-
skite at 28 GPa was observed by considerable resistance decrease,
implying a semiconductor-to-conductor transition.
By contrast, organic perovskites such as MAPbI3 and MAPbBr3 exhibit
moderate bandgap tuning by pressure. An abrupt change in the bandgap
of MAPbI3 upon pressure occurs above 325 MPa due to the phase tran-
sition from a tetragonal to an orthorhombic or cubic crystal structure
(Fig. 8b) [75]. The pressure-dependent characterizations demonstrate
that besides the commonly recognized direct-bandgap characteristics, a
weakly indirect bandgap is present below the direct bandgap arising from
the Rashba-splitting of the conduction band. Similarly, MAPbBr3 un-
dergoes a phase transition upon compression (Fig. 8c) [76]. Along with
the bandgap narrowing, carrier lifetime in MAPbBr3 is prolongated up to
70% to ~100% at mild pressures of ~0.3 GPa, which may lead to the
near-bandgap photovoltage in perovskite solar cells. Recent work on 2D
hybrid perovskites shows that the metastable states of 2D hybrid pe-
rovskites induced by pressure exhibit remarkably enduring bandgap
narrowing by 8.2% compared with their 3D counterparts [77]. These
pressure-induced metastable states are ascribed to the structural
amorphization upon compression and recrystallization under decom-
pression. The transition and switching of the optoelectronic properties of
2D hybrid perovskites via compression-decompression cycles present a
promising way to manipulating the properties of the perovskite nano-
materials and devices.

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Q. Ou et al.
3. Electronic doping of perovskite nanostructures
Electronic doping is commonly used for organic semiconductor de-
vices [78–81]. In contrast to bandgap engineering, electronic doping
generally modifies the Fermi level and band levels of a semiconductor
without changing the bandgap energy. P-type doping shifts Fermi level
towards valence band; n-type doping moves Fermi level to the conduc-
tion band. Compared with organic or inorganic semiconductors, one may
expect stronger electronic interaction and doping efficiency in chemi-
cally doped perovskites, especially in hybrid perovskites that have not
only dangling bonds but also rich organic/inorganic species at the crystal
surface [82]. Therefore, various intrinsic and extrinsic doping strategies
have been introduced to electronically adjust the energy levels of
perovskite crystals as below.
3.1. Defect-induced self-doping
Intrinsically, the defects in hybrid perovskites mainly arising from
rapid crystallization induce the self-doping effect [83]. However, it is
reported the self-doping concentration can be extremely low in 2D
layered perovskites single crystals due to reduced defect formation by
large organic cations, such as PEA [84]. In most cases, the defect level of
perovskites can be intentionally controlled by thermal annealing or
precursor stoichiometry. Fig. 9 shows the examples of defect-induced
self-doping in MAPbI3 perovskite [85,86]. MAPbI3 can be tuned to
either p- or n-doped by varying the ratio of MAI and PbI2, where MAI-rich
leads to p-doped and PbI2-rich is n-doped. The deficiency may come from
the unmatched ratio of perovskite precursors or from thermal
annealing-induced organic cations removing. Without changing the
bandgap, these defects significantly modify the Fermi levels and
conductive types of perovskites at different MAI/PbI2 ratios. The
self-doped perovskites with different molar ratios were controlled by
either solution mixing (Fig. 9a) [85], or vapor co-deposition (Fig. 9b)
[86], which might be the possible cause of slight difference in
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Nano Materials Science 1 (2019) 268–287
Fig. 7. Strain modulated bandgaps. (a) Band
structures of the (FAPbI3)0.85(MAPbBr3)0.15
perovskite under biaxial tensile, zero, and
compressive strains from first-principle calcula-
tions. (b) Ultraviolet–visible absorption spectra
and PL spectra under tensile strain, strain-free,
and compressive strain conditions. Reproduced
with permission from the Nature Publishing
Group [71]. (c) The band gaps and corresponding
structures of MAPbI3 under different strains.
Reproduced with permission from the Nature
Publishing Group [72].
conductivity type in terms of the critical stoichiometry point (inversion
between p-to n-type). It should be noted that most hybrid perovskites
fabricated for solar cells could be n-doped due to the post-annealing
process, and so is the case for most perovskite nanostructures grown by
chemical vapor deposition (CVD) method.
3.2. Chemical doping
As an important extrinsic doping method, chemical doping by both
inorganic and organic molecules is mostly employed to tune the elec-
tronic properties of semiconductors due to the easy realization via sur-
face adsorption or blending and to the high charge transfer efficiency
[87].
3.2.1. Transition metal oxides
Transition metal oxides, such as MoO3, have strong p-doping capa-
bility due to their deep-lying electronic states [83,88]. Taking advantage
of the high surface-to-volume ratio of perovskite nanostructures, it is
feasible to achieve efficient doping through surface decoration. For
example, MoO3 has been widely used to modulate the energy levels and
electronic transport properties of 2D materials [88–91]. Several studies
have revealed the charge transfer between MoO3 and perovskite films
characterized by ultraviolet and X-ray photoelectron spectroscopies (UPS
and XPS) [92–94]. In this regard, researchers incorporated MoO3 as
surface dopants to tune the charge-carrier properties of 2D MAPbI3
perovskite nanosheets (Fig. 10). First-principles calculations showed that
two new chemical bonds emerged as Mo–I covalent bond and N–H…O
hydrogen bond. Together with an adsorption energy of -3.44 eV, the
strong chemical interaction between MoO3 and perovskite indicated the
efficient modulation of the electronic levels. Both spatial PL mapping and
UPS showed strong charge transfer effect while the shift of Fermi level
was extracted from XPS as ~0.49 eV. It means the Fermi level of
MoO3-doped perovskite increases to 4.97 eV towards valence band from
4.48 eV of the pristine perovskite. The example shown here is to
Q. Ou et al.
Fig. 8. Pressure tuned bandgaps. (a) Optical micrograph of Cs3Bi2I9 perovskites
in a diamond anvil cell upon compression and bandgap evolutions under high
pressure. Reproduced with permission from the Wiley-VCH [74]. (b) Change of
the direct bandgap of MAPbI3 under pressure for pressure up (blue circles) and
down (red squares) stroke. Theoretical calculations (dashed line) predict the
bandgap change before phase transition. Reproduced with permission from the
Royal Society of Chemistry [75]. (c) Bandgap narrowing in MAPbBr3 at mild
pressures, respectively. Reproduced with permission from the National Academy
of Sciences [76]. (d) Pressure-dependent bandgap evolutions of (BA)2PbI4
(n ¼ 1), (BA)2MAPb2I7 (n ¼ 2), (BA)2(MA)2Pb3I10 (n ¼ 3), (BA)2(MA)3Pb4I13
(n ¼ 4) and MAPbI3. Reproduced with permission from the National Academy of
Sciences [77].
demonstrate the possibility of doping 2D perovskites with transition
metal oxides, not limited to MoO3 and MAPbI3. We predict other 2D
perovskites with different cations such as FA, BA and halides such as Br or
I–Br mixture could be electronically modulated by oxides like MoO3,
WO3, and V2O5.
3.2.2. Small molecules
Small molecules are widely used for electronic dopants in organic
semiconductor devices. In most conditions, these small molecules such as
F4TCNQ and HATCN, are usually doped in a low concentration into
organic materials through thermal co-evaporation while they are
deposited onto 2D materials by physisorption or chemisorption [96–99].
The doping mechanism here is based on surface/interface charge transfer
doping. For perovskite nanostructures, surface charge transfer doping
could be a facile technique to modulate the electronic levels. Fig. 11
showcases several examples of small molecules-doped perovskite crystals
with modified Fermi levels. HATCN molecules in Fig. 11a were intro-
duced for 2D perovskites, suggesting that larger organic cations such as
PEA might prohibit effective charge transfer between the perovskite
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Nano Materials Science 1 (2019) 268–287
lattice and the dopant [100]. Instead, blending F4TCNQ into MAPbI3
perovskite film could cause efficient charge transfer at the grain
boundaries region, resulting in efficient hole transport between p-doped
perovskite and ITO electrode (Fig. 11b) [101]. Similar doping scheme by
F4TCNQ has been employed to electronically couple inorganic CsPbI3
perovskite NCs, showing improved hole mobility [102].
N-type surface doping by cobaltocene was realized by coating onto
MAPbI3 perovskite, with a tunable modulation of the Fermi level of
perovskite dependent on the quantity of cobaltocene (Fig. 11c) [103].
Surface molecular doping using zethrenes was examined for all-inorganic
CsPbBr3 perovskite (Fig. 11d), showing the presence of interface dipoles
and strong charge transfer from zethrenes to perovskite [104]. The near
edge X-ray absorption fine structure (NEXAFS) revealed the generally
standing-up orientation of the molecules on the surface of perovskite. This
may stimulate important future research on the influence of molecular
orientation on doping efficiency of perovskite nanostructures. The energy
levels of MAPbI3 perovskite could also be gradually tuned by mixing
zwitterionic sulfamic acid during crystal growth (Fig. 11e) [105]. We
believe this method may be used to treat the surface of perovskite nano-
structures for surface doping apart from being used as additive doping.
3.2.3. Polymers
Polymeric materials have mainly been incorporated into perovskite
films for passivating surfaces and grain boundaries or mediating the
dynamics of crystal growth [106–108]. Nonetheless, polymers can also
be considered as dopants for perovskite nanostructures. For instance, the
large-bandgap polymers (e.g., PEI, PEIE) has strong surface modification
effect on conductors (such as ITO, graphene) due to the intrinsic mo-
lecular dipole moments and the charge transfer character [109]. In recent
work, polymers with different conductive types (i.e., p-type, n-type, and
insulator) were investigated and compared in terms of doping perovskite
thin films for enhancing solar cell performance [110].
Fig. 12 shows the surface modification effect of the MAPbI3 perov-
skite by different polymers [111]. Three representative polymers were
investigated due to their different possibility of chemical interactions
with perovskites, that is, the protonated amino group in b-PEI, Lewis base
pyridine groups in PVP, and carboxylic acid groups in PAA. There
emerged new coordination bonds with different bonding strengths
because of the delocalization of the lone electron pairs at N or O atoms to
the empty orbits of Pb. The strong interactions between polymers and the
perovskite were reflected in PL spectroscopy and first-principles calcu-
lations. From the calculated DOS spectra, the electron energy level of
b-PEI modified perovskite is lower than the reference perovskite while
those of PVP and PAA modified perovskites are higher due to the reduced
density of trap states (narrow DOS distribution). Therefore, these poly-
mers are expected to effectively modulate the electronic properties of
low-dimensional perovskite crystals.
3.3. Metal-based doping
Doping by metal ions in perovskite nanostructures can be classified
into two types, alloying to partially replace the host metal frame and
inserting of transition metals in the lattice. We do not discuss here the
metal alloying, particularly for replacing toxic Pb element in perovskites,
which is widely implemented in perovskite solar cell devices [112–114].
Instead, we focus on the insertion of a small amount of transition metal
atoms into the perovskite lattice, which then causes energy transfer and
charge carrier transfer processes between these dopants and perovskite
crystals. More specific metal doping behaviors in halide perovskites have
been reviewed or discussed recently [115–117].
3.3.1. Metal ions
Fig. 13a shows representative doping of Mn2þ ions into inorganic
perovskite NCs [118]. Many reports have studied the effect of
hetero-valent doping by Mn2þ ions on the optical properties of CsPbX3
perovskite NCs, with additional emission peaks from Mn-doped domains
Q. Ou et al. Nano Materials Science 1 (2019) 268–287

Fig. 9. Defect-induced self-doping. (a) Left:

schematic conductivity type conversions in
MAPbI3 perovskites by excess MAI or PbI2 and by
elemental defects. Right: energetic levels of pe-
rovskites formed by a one-step method with
different precursor ratios. Reproduced with
permission from the AIP Publishing [85]. (b) Left:
energetic levels of the p-type and n-type MAPbI3
perovskites with different molar ratios of PbI2/-
MAI. Right: the carrier concentration and
mobility for electrons and holes in the perov-
skites. The area colors of orange and blue repre-
sent the p-type and n-type doping, respectively.
Reproduced with permission from the Nature
Publishing Group [86].

Fig. 10. Surface charge transfer doping by tran-

sition metal oxides. (a) Relaxed structure of the
MoO3-doped MAPbI3 perovskite surface. (b) PL
mapping of the partially doped perovskite nano-
sheet under 532 nm laser excitation, with the
corresponding PL spectra below. The intensity
dip at 780 nm is due to the CCD detector limit. (c)
UPS spectra evolution in the low kinetic energy
(secondary electron cut-off) with increasing
MoO3 coverage. (d) XPS core-level spectra of Mo
3d peaks during the deposition of MoO3. (e)
Schematic energy level diagram showing electron
transfer from perovskite to MoO3. Reproduced
with permission from the Wiley-VCH [95].

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Q. Ou et al. Nano Materials Science 1 (2019) 268–287

Fig. 11. Electronic doping by organic small molecules. (a) Schematic of charge transfer and energy levels between HATCN and 2D perovskites. Reproduced with
permission from the American Chemical Society [100]. (b) Schematic illustration of F4TCNQ doped perovskite crystals with favorable band bending. Reproduced with
permission from the Nature Publishing Group [101]. (c) N-type surface doping of MAPbI3 by cobaltocene. Reproduced with permission from the Wiley-VCH [103]. (d)
Surface molecular doping of CsPbBr3 using zethrenes. Reproduced with permission from the Tsinghua University Press and Springer-Verlag GmbH Germany [104]. (e)
Energy levels of MAPbI3 perovskites modified by surface sulfamic acid. Reproduced with permission from the American Chemical Society [105].

[119–122]. By comparing the difference in Mn2þ ions doping, 3D CsPbX3
and 0D Cs4PbX6 perovskite NCs were investigated, demonstrating that
the strong exciton binding energy together with the structure-induced
quantum confinement (from the isolated octahedra) in 0D Cs4PbX6
resulted in enhanced emission with high PL quantum yield compared
with 3D CsPbX3 of weak binding energy.
In addition to the hetero-valent doping by transition metal ions, rare
earth metal ions were also doped into lattices of perovskite NCs to
combine the outstanding optical properties of both perovskite NCs (high
absorption and PL quantum yield) and rare earth ions (large Strokes shift
and long lifetime) [123,124]. As displayed in Fig. 13b, Yb3þ and Ce3þ
were co-doped into CsPbCl1.5Br1.5 perovskite QDs, exhibiting efficient
down-conversion PL emission [125]. The electrons were first generated
in perovskite QDs by laser excitation, followed by relaxation to the en-
ergy level of Ce3þ ions. Then, two electrons were transferred to the level
of Yb3þ ions as the energy level of Ce3þ ions is twice that of Yb3þ ions.
This type of doping is promising in realizing multiple near-infrared
photon emissions at the absorption of one ultraviolet/visible photon.
3.3.2. Metal nanostructures
Metal nanostructures such as Au or Ag nanoparticles are commonly
used as plasmonic media to boost the enhancement of optical properties
of semiconductors [127–131]. These plasmonic nanoparticles have also
been employed to enhance light absorption and emission in perovskite
solar cells and LEDs [116,132]. It is proposed that a perovskite NC sur-
rounded by small metal nanoparticles can be an efficient plasmonic
hybrid media [133–135]. However, it is always accompanied in the
near-field enhancement by metal nanoparticles by hot electron transfer,
which would induce electronic doping effect. Recently, research has
experimentally shown a hybrid metal-semiconductor nano--
heterostructure based on inorganic CsPbBr3 perovskite NCs and Ag
nanoparticles (Fig. 13c) [126]. In this hybrid system, the efficiency of
interfacial hot excitation transfer between Ag and CsPbBr3 was greatly
improved due both to the resonant energy transfer and to the
plasmon-induced hot electron injection. According to the schematic band
diagram, hot electrons are transferred to perovskites, causing an
n-doping effect. The decoration of metal nanoparticles on perovskite
nanostructures might be an alternative approach to realize n-type doping
of perovskites besides plasmonic enhancement.
4. Band alignment engineering
Energy level alignment at semiconductor/semiconductor or semi-
conductor/metal interfaces usually plays a pivotal role in engineering the

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Fig. 12. Surface modification by polymers. (a) The chemical structure of the polymers used and a schematic of their possible interaction with MAPbI3 perovskite. (b)
PL intensity spectra of perovskites with different polymer incorporation. (c) DOS versus electron energy level in various polymer-modified perovskite devices.
Reproduced with permission from the American Association for the Advancement of Science [111].

charge transport behaviors and thus the optoelectronic performance of a
device [79,92,136,137]. It has been recognized that manipulation of the
interfacial band alignments in organic optoelectronics can effectively
optimize the electrical properties and optical performance [78,79,138].
In perovskite photovoltaics and LEDs, matching perovskite band struc-
tures with adjacent charge transport layers also facilitates the separation
and extraction of photo-generated carriers in solar cells or the injection
and recombination of charge carriers in LEDs [139,140]. Therefore, the
control over the band alignment in perovskite nanostructures and their
hybrid interfaces holds great importance in creating novel, functional
perovskite-based nanoelectronics and optoelectronics.
4.1. Perovskite p-n junctions
Semiconductor p-n junctions act as fundamental elements of a variety
of optoelectronic devices such as LEDs and photodiodes. Typically, two
factors, i.e., built-in electric field and depletion width determine the
capability of carrier manipulation of a p-n junction. Thus, various doping
approaches including ion implantation, chemical doping, electrostatic
gating, and surface charge transfer doping have been implemented to
improve the depletion characteristics in conventional bulk semi-
conductors and low dimensional materials [87,141,142], as well as in
perovskites as we discussed in Section 3. With regard to the unique
properties of halide perovskites, several attempts on constructing
perovskite p-n junctions have been made in the following sections
comprising p-n homojunctions by chemical doping, defect-induced
self-doping, and p-n heterojunctions by phase transition.
4.1.1. Doping-induced p-n homojunctions
As discussed in Section 3.2.1, MoO3 shows excellent p-type doping
effect on hybrid perovskite crystals confirmed both theoretically and
experimentally. On this basis, an in-plane p-n junction based on an in-
dividual MAPbI3 perovskite nanosheet was fabricated by spatially con-
trolling the doping of MoO3 on the surface (Fig. 14) [95]. More important
is the strong charge depletion in the 2D hybrid perovskite p-n homo-
junctions, exhibiting ultra-broad depletion region together with high
built-in potential. Surface potential profiles characterized by Kelvin
probe force microscopy showed that the depletion width in a perovskite
p-n junction with a thickness of less than 20 nm could reach beyond
10 μm under equilibrium without any external bias or illumination. A
relationship of thickness-dependent depletion width was demonstrated
for the first time in p-n junctions based on both perovskites and 2D ma-
terials, which may shed light on future research on the influence of
dimensionality on the property of a semiconductor p-n junction. Even in
the 120 nm-thick perovskite p-n junction the depletion width is still over
5 μm, which is much larger than ~0.5 μm in a Si p-n junction and

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Fig. 13. Energy level modulation

through metal ions or nanostructures.
(a) Schematic illustration of Mn2þ
doping in both 0D Cs4PbX6 (X ¼ Cl, Br/
Cl) perovskite and 3D CsPbX3 perov-
skite, with a configurational coordinate
representation of energy transfer from
host to the Mn2þ energy levels. Repro-
duced with permission from the Nature
Publishing Group [118]. (b) Schematic
diagram of energy transfer mechanism
in the Yb3þ, Ce3þ co-doped
CsPbCl1.5Br1.5 QDs. Reproduced with
permission from the Wiley-VCH [125].
(c) Schematic of the formation mecha-
nism of Ag–CsPbBr3 hybrid NCs and
energy level alignment and possible
pathways for plasmon-hot electron con-
version in this hybrid NCs. Reproduced
with permission from the Nature Pub-
lishing Group [126].

Fig. 14. Lateral perovskite p-n homojunctions formed by spatially controlled doping. (a) Schematic of the MAPbI3 perovskite nanosheet p-n junction through MoO3
surface doping and the band diagram. (b) Surface potential distribution for the lateral perovskite p-n homojunction. Scale bar: 10 μm. (c) Thickness dependence of
depletion width. (d) Schematic of the lateral perovskite p-n diode. (e) Current-voltage curves of the p-n diode in the dark and under laser illumination. (f) Short-circuit
current of the perovskite photodiode without external voltage bias. Reproduced with permission from the Wiley-VCH [95].

~0.32 μm in a monolayer WSe2–MoS2 lateral p-n junction [143]. Mean- approximately 0.5 eV, which is comparable to 0.5–0.7 eV in conventional
while, photoelectron spectroscopy characterizations revealed that the Si p-n junctions and higher than ~0.2 eV of the graphene-WS2 in-plane
energy level difference between the pristine and the doped perovskite is heterostructure [144].

279
Q. Ou et al.
The lateral p-n diode based on the 2D hybrid perovskite nanosheets
demonstrated photovoltaic power conversion with an open-circuit
voltage of ~0.5 V in good agreement with the built-in potential. At
zero bias, the p-n photodiode exhibited reliable photocurrent switching
on and off, with an EQE of 3.93% and a responsivity of 1.42 A W-1,
significantly higher than EQE <0.2% in both TMDC and BP p-n junction
devices [145–147]. The superior device performance and the excellent
depletion characteristics were ascribed to three aspects including the 2D
nanosheet morphology, the large dielectric constant, and the efficient
electronic doping. Given the different chemical doping methods pre-
sented in Section 3.2, p-n junctions based on perovskite nanostructures
can be expected and readily realized with customized depletion
properties.
The self-doping behavior induced by defects in perovskites can lead to
a p-n junction [86,148–150]. A p-type perovskite/n-type perovskite
homojunction was formed by controlling the stoichiometry of the
perovskite precursors to promote oriented transport of photo-generated
carriers inside a solar cell device [86]. The simulations showed that the
carrier recombination in the homojunction device was drastically sup-
pressed at the p-n junction interface region. The voltage bias-dependent
potential and electric field difference curves extracted from Kelvin po-
tential imaging exhibited significant potential drops and the electric field
enhancement across the p-n homojunction interface. It is anticipated that
the perovskite p-n homojunction structure holding reduced carrier
recombination loss can improve the photovoltaic conversion efficiency
beyond the current planar perovskite heterojunctions. In addition, given
the different chemical doping methods presented in Section 3.2, p-n
junctions based on perovskite nanostructures can be expected and readily
realized with customized depletion properties.
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Nano Materials Science 1 (2019) 268–287
Fig. 15. Controllable formation of p-n hetero-
junction in single CsSnI3 perovskite NW through
a localized phase transition. (a) SEM and cath-
odoluminescence (CL) characterization (715-nm
long-pass filter) of localized phase-transition
segments randomly distributed along individual
CsSnI3 NWs on flat SiO2/Si substrates. (b) Sche-
matic illustration of controllable localized phase
transition in single NW with two ends on the
bottom electrodes. (c) SEM and CL images of
CsSnI3 p-n heterojunction NW device. (d)
Current-voltage characteristics of the p-n hetero-
junction. The inset shows the energy band
alignment of Y–CsSnI3 and B–CsSnI3 under ther-
mal equilibrium. Reproduced with permission
from the National Academy of Sciences [151].
4.1.2. Phase transition-induced p-n junction
Phase transition, as we discussed in Section 2.4, can effectively
modulate the bandgap of perovskites. This concept was utilized to create
a p-n junction based on a single perovskite NW. As shown in Fig. 15,
researchers spatially controlled the occurrence of phase transition in an
individual CsSnI3 NW by localized heating [151]. The single-crystalline
CsSnI3 NW can exhibit a phase transition from a double-chain yellow
phase to an orthorhombic black phase, by means of which the p-n NW
junction can be produced with n-type yellow phase and p-type black
phase. The cathodoluminescence imaging clearly revealed the formation
of an abrupt interface between these two phases and thus the abrupt p-n
junction interface. By locally heating from the underlying electrical cir-
cuits, the p-n diode based on the single perovskite NW was fabricated,
showing evident current rectifying behavior. Thus, the unique p-n junc-
tion structure based on halide perovskite nanostructures, without the
typical chemical doping process, presents a new stage of semiconductor
p-n junctions by engineering thermal-driven phase transition.
4.2. Perovskite heterostructures
Perovskite heterostructures in parallel with perovskite p-n homo-
junctions are an emerging area of perovskite electronics and photonics
[27,31]. Heterostructuring effect always endows perovskites themselves
with exotic optical or electronic properties to achieve multiple func-
tionalities. Electronically, the perovskite heterostructures provide an
internal electric field to direct the transport behaviors of charge carriers
inside the heterostructure devices. Optically, these heterostructures
could influence the absorption or emission of photons for
high-performance perovskite optoelectronics. In the following, we
discuss two types of perovskite heterostructures, i.e.,
perovskite-perovskite heterojunctions in low dimensional forms and
Q. Ou et al. Nano Materials Science 1 (2019) 268–287

Fig. 16. Perovskite-perovskite heterostructures in different dimensionality. (a) 0D CsPbBr3/Cs4PbBr6 perovskite core/shell NCs. Reproduced with permission from the
Royal Society of Chemistry [152]. (b) Schematic representation of the possible mechanism of exciton recombination. Reproduced with permission from the Royal
Society of Chemistry [153]. (c) PL spectrum from the CsPbBr3/Cs4PbBr6 nanocomposites. Reproduced with permission from the Wiley-VCH [154]. (d) 1D multicolor
CsPbX3 perovskite NW heterojunctions. (e) Fluorescence images of the partial bromide partial chloride nanowire and 3D view of the surface potential mapping of the
heterojunction nanowire. (f) Work functions of the pure CsPbBr3 and CsPbCl3 nanowires. Reproduced with permission from the National Academy of Sciences [155].
(g) Optical images of the MAPbI3/MAPbBrxI3-x nanosheet (thin MAPbI3 sheet with a thicker MAPbBrxI3-x region at the center) (h) PL mapping. (i) PL spectra measured
from central (red trace) and peripheral (orange trace) regions of the 2D heterostructure. Reproduced with permission from the American Chemical Society [49].

perovskite-2D materials heterostructures.
4.2.1. Perovskite-perovskite heterojunctions
Perovskites, due to the ready tunability in halide substitution, as
discussed in Section 2.2, can form heterojunctions between two perov-
skite crystals with different halide compositions. These perovskite het-
erojunctions feature a low degree of lattice mismatch at the
heterojunction interface, thus having low carrier scattering cross the
junction. We select here three representative examples of perovskite-
perovskite heterojunctions, shown in Fig. 16. The first is 0D perovskite
core-shell NCs, with an exemplary schematic of CsPbBr3/Cs4PbBr6
perovskite heterostructure (Fig. 16a) [152]. The composition difference
induces different energy levels of the inorganic perovskite NCs, exhibit-
ing energy transfer-modulated light absorption and emission (Fig. 16b
and c) [153,154].
The second is 1D perovskite NW heterojunctions. In contrast to the
gradient bandgap heterostructure discussed in Section 2.3, an abrupt
CsPbCl3–CsPbBr3 heterojunction interface was realized by solution-
phase anion exchange reaction (Fig. 16d) [155,156]. The successful
formation of the perovskite NW heterojunction was revealed by the
confocal fluorescence imaging and surface potential mapping with a clear
distinguishable color contrast (Fig. 16e). A schematic diagram of the
perovskite NW heterojunction shown in Fig. 16f depicts the energy band
alignment between these two perovskites. By using the same way,
multicolor perovskite heterojunctions (CsPbCl3–CsPbBr3–CsPbI3) were
created in a single NW, which could be potentially applied as display
pixels. Complex patterns of perovskite-perovskite heterostructures are
also made possible based on nanolithography technique and halide ex-
change process.
On 2D perovskite-perovskite heterostructures, a few-layer in-plane
perovskite heterostructured nanosheet was prepared by thermally
annealing MAPbI3 nanosheets with a thicker central in MABr vapor
(Fig. 16g) [49]. As shown in PL mapping (Fig. 16h), the edge region
exhibited uniform PL emission from MAPbI3-xBrx while the central
retained PL emission from MAPbI3, with the respective spectra, plotted in
Fig. 16i. It is noted that this method can be extended into various

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Fig. 17. Heterostructures of perovskite nanostructures and 2D materials. (a) Schematic configuration of a graphene-perovskite nanoparticles phototransistor. (b) s-
SNOM infrared images showing the distribution of photo-excited carriers with an extra 405 nm laser illumination. (c) Energy level diagram showing the doping of
graphene induced by the injection of photo-excited holes and trapped electrons in perovskites. Reproduced with permission from the Wiley-VCH [163]. (d) Side view
of the perovskite NW/TMDC heterostructure interface. (e) Optical microscope image of a transferred perovskite NW network on TMDCs. (f) Band alignments of
perovskite NW/MoS2 and perovskite NW/WSe2 heterostructures. Reproduced with permission from the American Chemical Society [164]. (g) Schematic of 2D
perovskite/graphene heterostructure. Reproduced with permission from the American Chemical Society [165]. (h) SEM image of the 2D BA2PbBr4
perovskite-interdigital graphene contact device. Reproduced with permission from the American Chemical Society [166]. (i) Band energy diagram of the 2D
BA2MAn
1PbnI3nþ1 perovskite with different n. Reproduced with permission from the American Chemical Society [167].

combinations of chemical compositions simply by controlling thermal
annealing conditions. For example, one might be able to get FAPbI3--
MAPbI3 in-plane nanosheet heterostructures by treating MAPbI3 with a
thicker central in FAI vapor.
Several other perovskite-perovskite heterostructures have been
studied and applied in photodetectors and solar cells with improved
charge transport, high photon-to-electron conversion efficiency, and
even narrowband photoresponse [157–162].
4.2.2. Perovskite-2d materials heterostructures
Due to the superior optical and electronic properties of perovskite
nanostructures, extensive research has been focused on the hybridization
of these perovskite nanostructures with another star materials (2D ma-
terials, such as graphene, MoS2) [31,168]. Fig. 17 shows several repre-
sentative examples of perovskite nanostructures/2D materials
heterostructures. Graphene is a good candidate for light detection
because of its broadband absorption and high electrical conductivity
while its absorption coefficient is not high. Considering this, hybrid
perovskite nanoparticles were dispersed onto a graphene sheet to boost
the photoresponse (Fig. 17a–c) [163]. The hybrid perovskite-graphene
photodetectors yielded a responsivity in the magnitude of 105 A W-1
compared to ~ 10-2 A W-1 for pure graphene, with an impressive
enhancement factor of 107. The improvement was ascribed to the effi-
cient charge transfer between perovskite and graphene and to the
photo-induced doping effect. The advantage of using perovskite nano-
particles includes the lower recombination rate of photogenerated car-
riers compared to bulk perovskite films.
Fig. 17d shows a schematic of 1D perovskite nanowires-TMDC
monolayers heterostructures [164]. This class of 1D-2D
mixed-dimensional van der Waals heterostructures holds great promise
in constructing novel optoelectronics and generating new charge transfer
physics. Simply by transferring an inorganic perovskite nanowire
network onto monolayer TMDCs (Fig. 17e), ultrafast charge carrier
interaction occurred in the type-I CsPbBr3/MoS2 and the type-II
CsPbBr3/WSe2 heterostructures, respectively (Fig. 17f). It was revealed
that both holes and electrons were transferred from CsPbBr3 to MoS2
with a carrier transfer efficiency of 71% while merely holes from CsPbBr3
were transferred to WSe2 with an efficiency of 70% with an ultrafast

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Fig. 18. Multiple quantum wells (MQWs) based on perovskite nanostructures. (a) Atomistic model of colloidal PbS QDs in the MAPbI3 perovskite matrix. (b)
Electronic band structure of QDs and perovskite. (c) PL spectra of the QD-perovskite hybrid. Reproduced with permission from the Nature Publishing Group [169]. (d)
Multicolor heterostructures composed of 2D PEA2PbI4/PEA2MAPb2I7 perovskites. Reproduced with permission from the American Chemical Society [172]. (e)
Schematic of the energy-transfer process within perovskite MQWs. (f) Enhanced LED quantum efficiency through the dimensional tailoring of NMA2Csn
1PbnI3nþ1
perovskite MQWs. Reproduced with permission from the American Chemical Society [173].
electron transfer inversely within 7 ps.
2D perovskite can naturally form excellent interface contact with 2D
materials. Fig. 17g shows a schematic of graphene film transferred on top
of a 2D perovskite nanosheet [165]. It was found that the coverage by
graphene, besides inducing PL quenching from charge transfer, could
effectively prevent 2D MAPbI3 perovskites from degradation induced by
ambient moisture and laser illumination. Patterning graphene film on top
of 2D BA2PbBr4 perovskite flake into interdigitated electrode contacts
efficiently assisted in carrier collection, leading to a high photo-
responsivity of ~2100 A W-1 (Fig. 17h) [166]. A close look at the energy
level of both the valence band maximum and conduction band minimum
of 2D BA2MAn
1PbnI3nþ1 layered perovskite crystals (Fig. 17i), the en-
ergy band increases with respect to the decreasing layer number, which
could lead to different band bending upon contact with graphene [167].
Thus, multi-dimensional perovskite nanostructures and 2D materials
heterostructure could be created with multiple functionalities.
4.3. Multiple quantum wells (MQWs)
Perovskite MQWs are a special type of perovskite heterostructures.
They can be 0D QDs embedded into 3D perovskite lattice or 3D perov-
skite sandwiched by 2D perovskite with an energy cascade. Fig. 18a
shows a schematic of perovskite MQWs with colloidal PbS QDs in the 3D
perovskite MAPbI3 matrix [169]. From the atomic-structure model, the
PbS QD lattice matches well with the perovskite structure. An important
experimental step is that free from the traditional organic ligand capping,
the PbS QDs here were stabilized using MAI (the perovskite precursor) to
realize atomic-level coherence between PbS and MAPbI3 phase. Ener-
getically shown in Fig. 18b, the carrier transfer is favored from perovskite
to PbS QDs as the energy bands of PbS QDs are located within that of
MAPbI3. Finally, the strong luminescent efficiency of the PbS QDs has
283
Nano Materials Science 1 (2019) 268–287
been preserved along with long-range carrier transport in the perovskite
matrix. As a result, embedding PbS QDs into a high-mobility hybrid
perovskite MAPbIxBr3-x matrix could enhance radiative recombination in
the QDs by reducing the trapping losses during carrier transport [170].
Based on this composite, a record-high electroluminescence PCE of 4.9%
was achieved in the near-infrared LED. Through this QDs-in-perovskite
strategy, sensitive infrared photodetectors were realized, in which the
photocarriers were extracted via field emission, together with the sub-
sequent recirculation [171]. The hybrid photodiodes fully utilized the
superior electronic transport properties of perovskites and the
quantum-size-tuned optical absorption of the QDs, showing broadband
photoresponse from the entire visible to the short-wavelength infrared
range.
The perovskite MQWs with an energy cascade can exhibit optoelec-
tronic properties that take advantage of the best features of 2D and 3D
perovskites, although the 2D layered perovskites naturally form QW
structures. A kind of multicolor heterostructures of 2D perovskite has
been investigated (Fig. 18d), showing interlayer energy transfer from
higher energy bandgap perovskite layers to lower energy bandgap ones
on the time scale of hundreds of picoseconds due to natural type I band
alignments [172]. Benefiting from the ultrafast efficient energy transfer,
perovskite MQWs with tunable dimensionality were proposed by intro-
ducing long-chain organic cations into 3D perovskites (Fig. 18e). The
resulting improvement in crystallinity and PL quantum yield of perov-
skite MQWs led to enhanced electroluminescence efficiency in perovskite
LEDs compared with either 2D or 3D perovskite devices (Fig. 18f) [173].
Based on the concept of solution-processed perovskite MQWs, highly
efficient LEDs have been achieved [40,42,43,173–175], for example,
with an EQE of 1.5% for blue emission [40], 7.3% for red [173], and
12.7% for near-infrared [175].
Q. Ou et al.
5. Conclusions and outlook
In summary, we have comprehensively reviewed recent advances in
the band structure engineering of semiconducting perovskite nano-
structures. In addition to the current major research focus on synthesis
and morphology optimization, the tuning of band structures of these
perovskite nanostructures is of great importance in terms of realizing
efficient and functional optoelectronic devices. In particular, we dis-
cussed a range of ways to engineer the bandgap of perovskite nano-
structures from the perspective of dimensionality, composition, phase
segregation and transition, as well as external strain stimuli. Electronic
doping of perovskites as a conventionally useful technique is summarized
in aspects of defect-induced self-doping, chemical doping, and metal-
based doping, followed by a discussion on engineering band align-
ments in perovskite p-n junctions, heterostructures and multi-quantum
wells.
However, there is still plenty of room to modify the band structures of
perovskite nanostructures and thus to provide guidelines for designing
multifunctional optoelectronic nanodevices. For the bandgap tuning, the
dynamic tuning with high controllability would be very attractive for
functional perovskite devices. For example, the optical or electrical
tuning of the phase segregation might be a potential way to realize
spatial-temporal control over the bandgap of a perovskite nanostructure
(e.g., 1D nanowire or 2D nanosheet). Similarly, dynamic control of the
electronic doping level of the perovskite nanostructures is an intriguing
and important point to construct novel smart optoelectronic devices.
Chemical doping is an effective strategy to tune the optical and electronic
properties, as discussed above with transition metal oxides, small organic
molecules and polymers. Therefore, we foresee that extensive routes to
either p- or n-type doping of perovskites can be achieved using various
molecules. In this regard, the photochromic organic molecules, for
instance, could be an exceptional candidate to realize real-time reversible
switching of the doping behavior in perovskite nanostructures. For the
perovskite junctions and heterostructures, the effect of light illumination
and bias on the charge depletion characteristics still requires intensive
investigation as these two stimuli are unavoidable in an optoelectronic
device system. Therefore, we believe the review and discussion on band
structure engineering of perovskite nanostructures would provide basic
understanding and new insights to design future low-energy optoelec-
tronic devices and technologies based on this family of materials.
Acknowledgements
We acknowledge the support from Australian Research Council (ARC,
FT150100450, IH150100006 and CE170100039). Q. Ou acknowledges
the scholarship support from the MCATM and the FLEET. X. Bao ac-
knowledges the support from Shenzhen Nanshan District Pilotage Team
Program (LHTD20170006). Y. Zhang acknowledges the support from
Guangzhou Science and Technology Program (Grant No.
201804010322).
References
[1] M.A. Green, A. Ho-Baillie, H.J. Snaith, The emergence of perovskite solar cells,
Nat. Photonics 8 (2014) 506.
[2] S.D. Stranks, H.J. Snaith, Metal-halide perovskites for photovoltaic and light-
emitting devices, Nat. Nanotechnol. 10 (2015) 391.
[3] Y. Zhao, K. Zhu, Organic-inorganic hybrid lead halide perovskites for
optoelectronic and electronic applications, Chem. Soc. Rev. 45 (2015) 655.
[4] Y. Rong, Y. Hu, A. Mei, H. Tan, M.I. Saidaminov, S.I. Seok, M.D. McGehee,
E.H. Sargent, H. Han, Challenges for commercializing perovskite solar cells,
Science 361 (2018) eaat8235.
[5] J. Huang, Y. Yuan, Y. Shao, Y. Yan, Understanding the physical properties of
hybrid perovskites for photovoltaic applications, Nat. Rev. Mater. 2 (2017) 17042.
[6] H. Wang, D.H. Kim, Perovskite-based photodetectors: materials and devices,
Chem. Soc. Rev. 46 (2017) 5204.
[7] W. Zhang, G.E. Eperon, H.J. Snaith, Metal halide perovskites for energy
applications, Nat. Energy 1 (2016) 16048.
[8] W. Mao, J. Zheng, Y. Zhang, A.S. Chesman, Q. Ou, J. Hicks, F. Li, Z. Wang,
B. Graystone, T. Bell, M.U. Rothmann, N.W. Duffy, L. Spiccia, Y.-B. Cheng, Q. Bao,
284
Nano Materials Science 1 (2019) 268–287
U. Bach, Controlled growth of monocrystalline organo-lead halide perovskite and
its application in photonic devices, Angew. Chem. Int. Ed. 56 (2017) 12486.
[9] B.R. Sutherland, E.H. Sargent, Perovskite photonic sources, Nat. Photonics 10
(2016) 295.
[10] H.-Y. Ye, Y.-Y. Tang, P.-F. Li, W.-Q. Liao, J.-X. Gao, X.-N. Hua, H. Cai, P.-P. Shi, Y.-
M. You, R.-G. Xiong, Metal-free three-dimensional perovskite ferroelectrics,
Science 361 (2018) 151.
[11] T.M. Brenner, D.A. Egger, L. Kronik, G. Hodes, D. Cahen, Hybrid organic-inorganic
perovskites: low-cost semiconductors with intriguing charge-transport properties,
Nat. Rev. Mater. 1 (2016) 15007.
[12] I.L. Braly, D.W. deQuilettes, L.M. Pazos-Out
on, S. Burke, M.E. Ziffer, D.S. Ginger,
H.W. Hillhouse, Hybrid perovskite films approaching the radiative limit with over
90% photoluminescence quantum efficiency, Nat. Photonics 12 (2018) 355.
[13] B. Zhao, S. Bai, V. Kim, R. Lamboll, R. Shivanna, F. Auras, J.M. Richter,
L. Yang, L. Dai, M. Alsari, X.-J. She, L. Liang, J. Zhang, S. Lilliu, P. Gao,
H.J. Snaith, J. Wang, N.C. Greenham, R.H. Friend, D. Di, High-efficiency
perovskite-polymer bulk heterostructure light-emitting diodes, Nat. Photonics
12 (2018) 783.
[14] K. Lin, J. Xing, L.N. Quan, F.P.G. de Arquer, X. Gong, J. Lu, L. Xie, W. Zhao,
D. Zhang, C. Yan, W. Li, X. Liu, Y. Lu, J. Kirman, E.H. Sargent, Q. Xiong, Z. Wei,
Perovskite light-emitting diodes with external quantum efficiency exceeding 20
per cent, Nature 562 (2018) 245.
[15] Y. Cao, N. Wang, H. Tian, J. Guo, Y. Wei, H. Chen, Y. Miao, W. Zou, K. Pan, Y. He,
H. Cao, Y. Ke, M. Xu, Y. Wang, M. Yang, K. Du, Z. Fu, D. Kong, D. Dai, Y. Jin, G. Li,
H. Li, Q. Peng, J. Wang, W. Huang, Perovskite light-emitting diodes based on
spontaneously formed submicrometre-scale structures, Nature 562 (2018) 249.
[16] T. Chiba, Y. Hayashi, H. Ebe, K. Hoshi, J. Sato, S. Sato, Y.-J. Pu, S. Ohisa, J. Kido,
Anion-exchange red perovskite quantum dots with ammonium iodine salts for
highly efficient light-emitting devices, Nat. Photonics 12 (2018) 681.
[17] M.H. Park, J. Park, J. Lee, H.S. So, H. Kim, S.H. Jeong, T.H. Han, C. Wolf, H. Lee,
S. Yoo, T.W. Lee, Efficient perovskite light-emitting diodes using polycrystalline
core-shell-mimicked nanograins, Adv. Funct. Mater. 29 (2019), 1902017.
[18] Y. Shen, L.P. Cheng, Y.Q. Li, W. Li, J.D. Chen, S.T. Lee, J.X. Tang, High-efficiency
perovskite light-emitting diodes with synergetic outcoupling enhancement, Adv.
Mater. 31 (2019) 1901517.
[19] Q. Jiang, Y. Zhao, X. Zhang, X. Yang, Y. Chen, Z. Chu, Q. Ye, X. Li, Z. Yin, J. You,
Surface passivation of perovskite film for efficient solar cells, Nat. Photonics 13
(2019) 460.
[20] H. Wei, J. Huang, Halide lead perovskites for ionizing radiation detection, Nat.
Commun. 10 (2019) 1066.
[21] S. Yakunin, M. Sytnyk, D. Kriegner, S. Shrestha, M. Richter, G.J. Matt, H. Azimi,
C.J. Brabec, J. Stangl, M.V. Kovalenko, W. Heiss, Detection of X-ray photons by
solution-processed organic-inorganic perovskites, Nat. Photonics 9 (2015) 444.
[22] Y.C. Kim, K.H. Kim, D.Y. Son, D.N. Jeong, J.Y. Seo, Y.S. Choi, I.T. Han, S.Y. Lee,
N.G. Park, Printable organometallic perovskite enables large-area, low-dose X-ray
imaging, Nature 550 (2017) 87.
[23] W. Pan, H. Wu, J. Luo, Z. Deng, C. Ge, C. Chen, X. Jiang, W.-J. Yin, G. Niu, L. Zhu,
L. Yin, Y. Zhou, Q. Xie, X. Ke, M. Sui, J. Tang, Cs2AgBiBr6 single-crystal X-ray
detectors with a low detection limit, Nat. Photonics 11 (2017) 726.
[24] Q. Chen, J. Wu, X. Ou, B. Huang, J. Almutlaq, A.A. Zhumekenov, X. Guan, S. Han,
L. Liang, Z. Yi, J. Li, X. Xie, Y. Wang, Y. Li, D. Fan, D.B.L. Teh, A.H. All,
O.F. Mohammed, O.M. Bakr, T. Wu, M. Bettinelli, H. Yang, W. Huang, X. Liu, All-
inorganic perovskite nanocrystal scintillators, Nature 561 (2018) 88.
[25] J. Liu, B. Shabbir, C. Wang, T. Wan, Q. Ou, P. Yu, A. Tadich, X. Jiao, D. Chu, D. Qi,
D. Li, R. Kan, Y. Huang, Y. Dong, J. Jasieniak, Y. Zhang, Q. Bao, Flexible, printable
soft-X-ray detectors based on all-inorganic perovskite quantum dots, Adv. Mater.
(2019), https://doi.org/10.1002/adma.201901644.
[26] Y. Fu, H. Zhu, J. Chen, M.P. Hautzinger, X.Y. Zhu, S. Jin, Metal halide perovskite
nanostructures for optoelectronic applications and the study of physical
properties, Nat. Rev. Mater. 4 (2019) 169.
[27] E. Shi, Y. Gao, B.P. Finkenauer, A. Akriti, A.H. Coffey, L. Dou, Two-dimensional
halide perovskite nanomaterials and heterostructures, Chem. Soc. Rev. 47 (2018)
6046.
[28] L. Polavarapu, B. Nickel, J. Feldmann, A.S. Urban, Advances in quantum-confined
perovskite nanocrystals for optoelectronics, Adv. Energy Mater. 7 (2017)
1700267.
[29] C. Huo, B. Cai, Z. Yuan, B. Ma, H. Zeng, Two-dimensional metal halide
perovskites: theory, synthesis, and optoelectronics, Small Methods 1 (2017),
1600018.
[30] S.-T. Ha, R. Su, J. Xing, Q. Zhang, Q. Xiong, Metal halide perovskite
nanomaterials: synthesis and applications, Chem. Sci. 8 (2017) 2522.
[31] X. Qi, Y. Zhang, Q. Ou, S.T. Ha, C.W. Qiu, H. Zhang, Y.B. Cheng, Q. Xiong, Q. Bao,
Photonics and optoelectronics of 2D metal-halide perovskites, Small 14 (2018),
1800682.
[32] Y. Zhang, J. Liu, Z. Wang, Y. Xue, Q. Ou, L. Polavarapu, J. Zheng, X. Qi, Q. Bao,
Synthesis, properties, and optical applications of low-dimensional perovskites,
Chem. Commun. 52 (2016) 13637.
[33] X. Wen, W. Chen, J. Yang, Q. Ou, T. Yang, C. Zhou, H. Lin, Z. Wang, Y. Zhang,
G. Conibeer, Q. Bao, B. Jia, D.J. Moss, Role of surface recombination in halide
perovskite nanoplatelets, ACS Appl. Mater. Interfaces 10 (2018) 31586.
[34] M. Li, R. Begum, J. Fu, Q. Xu, T.M. Koh, S.A. Veldhuis, M. Gratzel, N. Mathews,
S. Mhaisalkar, T.C. Sum, Low threshold and efficient multiple exciton generation
in halide perovskite nanocrystals, Nat. Commun. 9 (2018) 4197.
[35] F. Zhang, H. Zhong, C. Chen, X. Wu, X. Hu, H. Huang, J. Han, B. Zou, Y. Dong,
Brightly luminescent and color-tunable colloidal CH3NH3PbX3 (X ¼ Br, I, Cl)
Q. Ou et al.
quantum dots: potential alternatives for display Technology, ACS Nano 9 (2015)
4533.
[36] H. Huang, A.S. Susha, S.V. Kershaw, T.F. Hung, A.L. Rogach, Control of emission
color of high quantum yield CH3NH3PbBr3 perovskite quantum dots by
precipitation temperature, Adv. Sci. 2 (2015) 1500194.
[37] M.C. Brennan, J.E. Herr, T.S. Nguyen-Beck, J. Zinna, S. Draguta, S. Rouvimov,
J. Parkhill, M. Kuno, Origin of the size-dependent Stokes shift in CsPbBr3
perovskite nanocrystals, J. Am. Chem. Soc. 139 (2017) 12201.
[38] P. Vashishtha, D.Z. Metin, M.E. Cryer, K. Chen, J.M. Hodgkiss, N. Gaston,
J.E. Halpert, Shape-, size-, and composition-controlled thallium lead halide
perovskite nanowires and nanocrystals with tunable band gaps, Chem. Mater. 30
(2018) 2973.
[39] K. Leng, I. Abdelwahab, I. Verzhbitskiy, M. Telychko, L. Chu, W. Fu, X. Chi,
N. Guo, Z. Chen, Z. Chen, C. Zhang, Q.H. Xu, J. Lu, M. Chhowalla, G. Eda, K.P. Loh,
Molecularly thin two-dimensional hybrid perovskites with tunable optoelectronic
properties due to reversible surface relaxation, Nat. Mater. 17 (2018) 908.
[40] J. Xing, Y. Zhao, M. Askerka, L.N. Quan, X. Gong, W. Zhao, J. Zhao, H. Tan,
G. Long, L. Gao, Z. Yang, O. Voznyy, J. Tang, Z.H. Lu, Q. Xiong, E.H. Sargent,
Color-stable highly luminescent sky-blue perovskite light-emitting diodes, Nat.
Commun. 9 (2018) 3541.
[41] L. Dou, A.B. Wong, Y. Yu, M. Lai, N. Kornienko, S.W. Eaton, A. Fu, C.G. Bischak,
J. Ma, T. Ding, Atomically thin two-dimensional organic-inorganic hybrid
perovskites, Science 349 (2015) 1518.
[42] N. Wang, L. Cheng, R. Ge, S. Zhang, Y. Miao, W. Zou, C. Yi, Y. Sun, Y. Cao,
R. Yang, Y. Wei, Q. Guo, Y. Ke, M. Yu, Y. Jin, Y. Liu, Q. Ding, D. Di, L. Yang,
G. Xing, H. Tian, C. Jin, F. Gao, R.H. Friend, J. Wang, W. Huang, Perovskite light-
emitting diodes based on solution-processed self-organized multiple quantum
wells, Nat. Photonics 10 (2016) 699.
[43] M. Yuan, L.N. Quan, R. Comin, G. Walters, R. Sabatini, O. Voznyy, S. Hoogland,
Y. Zhao, E.M. Beauregard, P. Kanjanaboos, Z. Lu, D.H. Kim, E.H. Sargent,
Perovskite energy funnels for efficient light-emitting diodes, Nat. Nanotechnol. 11
(2016) 872.
[44] J.-C. Blancon, H. Tsai, W. Nie, C.C. Stoumpos, L. Pedesseau, C. Katan,
M. Kepenekian, C.M.M. Soe, K. Appavoo, M.Y. Sfeir, Extremely efficient internal
exciton dissociation through edge states in layered 2D perovskites, Science 355
(2017) 1288.
[45] C.-Z. Ning, L. Dou, P. Yang, Bandgap engineering in semiconductor alloy
nanomaterials with widely tunable compositions, Nat. Rev. Mater. 2 (2017)
17070.
[46] Q.A. Akkerman, V. D'Innocenzo, S. Accornero, A. Scarpellini, A. Petrozza,
M. Prato, L. Manna, Tuning the optical properties of cesium lead halide perovskite
nanocrystals by anion exchange reactions, J. Am. Chem. Soc. 137 (2015) 10276.
[47] Z. Dai, Q. Ou, C. Wang, G. Si, B. Shabbir, C. Zheng, Z. Wang, Y. Zhang, Y. Huang,
Y. Dong, J.J. Jasieniak, B. Su, Q. Bao, Capillary-bridge mediated assembly of
aligned perovskite quantum dots for high-performance photodetectors, J. Mater.
Chem. C 7 (2019) 5954.
[48] S.T. Ha, X. Liu, Q. Zhang, D. Giovanni, T.C. Sum, Q. Xiong, Synthesis of organic-
inorganic lead halide perovskite nanoplatelets: towards high-performance
perovskite solar cells and optoelectronic devices, Adv. Opt. Mater. 2 (2014) 838.
[49] J. Liu, Y. Xue, Z. Wang, Z.Q. Xu, C. Zheng, B. Weber, J. Song, Y. Wang, Y. Lu,
Y. Zhang, Q. Bao, Two-dimensional CH3NH3PbI3 perovskite: synthesis and
optoelectronic application, ACS Nano 10 (2016) 3536.
[50] Z. Xiao, Y. Yuan, Y. Shao, Q. Wang, Q. Dong, C. Bi, P. Sharma, A. Gruverman,
J. Huang, Giant switchable photovoltaic effect in organometal trihalide perovskite
devices, Nat. Mater. 14 (2015) 193.
[51] C. Eames, J.M. Frost, P.R. Barnes, B.C. O'Regan, A. Walsh, M.S. Islam, Ionic
transport in hybrid lead iodide perovskite solar cells, Nat. Commun. 6 (2015)
7497.
[52] C. Zhou, G. Cao, Z. Gan, Q. Ou, W. Chen, Q. Bao, B. Jia, X. Wen, Spatially
modulating the fluorescence color of mixed-halide perovskite nanoplatelets
through direct femtosecond laser writing, ACS Appl. Mater. Interfaces 11 (2019)
26017.
[53] D.W. deQuilettes, W. Zhang, V.M. Burlakov, D.J. Graham, T. Leijtens, A. Osherov,
V. Bulovic, H.J. Snaith, D.S. Ginger, S.D. Stranks, Photo-induced halide
redistribution in organic-inorganic perovskite films, Nat. Commun. 7 (2016)
11683.
[54] S. Draguta, O. Sharia, S.J. Yoon, M.C. Brennan, Y.V. Morozov, J.M. Manser,
P.V. Kamat, W.F. Schneider, M. Kuno, Rationalizing the light-induced phase
separation of mixed halide organic-inorganic perovskites, Nat. Commun. 8 (2017)
200.
[55] Y. Zhang, Y. Wang, Z.Q. Xu, J. Liu, J. Song, Y. Xue, Z. Wang, J. Zheng, L. Jiang,
C. Zheng, F. Huang, B. Sun, Y.B. Cheng, Q. Bao, Reversible structural swell-shrink
and recoverable optical properties in hybrid inorganic-organic perovskite, ACS
Nano 10 (2016) 7031.
[56] L. Huang, Q. Gao, L.D. Sun, H. Dong, S. Shi, T. Cai, Q. Liao, C.H. Yan, Composition-
graded cesium lead halide perovskite nanowires with tunable dual-color lasing
performance, Adv. Mater. 30 (2018) e1800596.
[57] W. Tian, J. Leng, C. Zhao, S. Jin, Long-distance charge carrier funneling in
perovskite nanowires enabled by built-in halide gradient, J. Am. Chem. Soc. 139
(2017) 579.
[58] Z. Wang, J. Liu, Z.Q. Xu, Y. Xue, L. Jiang, J. Song, F. Huang, Y. Wang, Y.L. Zhong,
Y. Zhang, Y.B. Cheng, Q. Bao, Wavelength-tunable waveguides based on
polycrystalline organic-inorganic perovskite microwires, Nanoscale 8 (2016)
6258.
285
Nano Materials Science 1 (2019) 268–287
[59] D. Pan, Y. Fu, J. Chen, K.J. Czech, J.C. Wright, S. Jin, Visualization and studies of
ion-diffusion kinetics in cesium lead bromide perovskite nanowires, Nano Lett. 18
(2018) 1807.
[60] C. Zhou, Q. Ou, W. Chen, Z. Gan, J. Wang, Q. Bao, X. Wen, B. Jia, Illumination-
induced halide segregation in gradient bandgap mixed-halide perovskite
nanoplatelets, Adv. Opt. Mater. 6 (2018), 1801107.
[61] M.S. Kirschner, B.T. Diroll, P. Guo, S.M. Harvey, W. Helweh, N.C. Flanders,
A. Brumberg, N.E. Watkins, A.A. Leonard, A.M. Evans, M.R. Wasielewski,
W.R. Dichtel, X. Zhang, L.X. Chen, R.D. Schaller, Photoinduced, reversible phase
transitions in all-inorganic perovskite nanocrystals, Nat. Commun. 10 (2019) 504.
[62] P. Jain, N.S. Dalal, B.H. Toby, H.W. Kroto, A.K. Cheetham, Order-disorder
antiferroelectric phase transition in a hybrid inorganic-organic framework with
the perovskite architecture, J. Am. Chem. Soc. 130 (2008) 10450.
[63] C. Quarti, E. Mosconi, J.M. Ball, V. D'Innocenzo, C. Tao, S. Pathak, H.J. Snaith,
A. Petrozza, F. De Angelis, Structural and optical properties of methylammonium
lead iodide across the tetragonal to cubic phase transition: implications for
perovskite solar cells, Energy Environ. Sci. 9 (2016) 155.
[64] Z. Chen, H. Li, Y. Tang, X. Huang, D. Ho, C.-S. Lee, Corrigendum on ‘Shape-
controlled synthesis of organolead halide perovskite nanocrystals and their
tunable optical absorption, Mater. Res. Express 1 (2014) 015034.
[65] J. Kim, J. Kwon, M. Kim, J. Do, D. Lee, H. Han, Low-dielectric-constant polyimide
aerogel composite films with low water uptake, Nat. Commun. 48 (2016) 829.
[66] M.I. Dar, G. Jacopin, S. Meloni, A. Mattoni, N. Arora, A. Boziki, S.M. Zakeeruddin,
U. Rothlisberger, M. Gr€atzel, Origin of unusual bandgap shift and dual emission in
organic-inorganic lead halide perovskites, Sci. Adv. 2 (2016) e1601156.
[67] J. Lin, M. Lai, L. Dou, C.S. Kley, H. Chen, F. Peng, J. Sun, D. Lu, S.A. Hawks, C. Xie,
F. Cui, A.P. Alivisatos, D.T. Limmer, P. Yang, Thermochromic halide perovskite
solar cells, Nat. Mater. 17 (2018) 261.
[68] M. Lai, Q. Kong, C.G. Bischak, Y. Yu, L. Dou, S.W. Eaton, N.S. Ginsberg, P. Yang,
Structural, optical, and electrical properties of phase-controlled cesium lead iodide
nanowires, Nano Res 10 (2017) 1107.
[69] Q. Tu, I. Spanopoulos, P. Yasaei, C.C. Stoumpos, M.G. Kanatzidis, G.S. Shekhawat,
V.P. Dravid, Stretching and breaking of ultrathin 2D hybrid organic-inorganic
perovskites, ACS Nano 12 (2018) 10347.
[70] N.N. Som, P.M.W.P. Sampath, S.D. Dabhi, V. Mankad, S. Shinde, M.L.C. Attygalle,
P.K. Jha, Strain and layer modulated electronic and optical properties of low
dimensional perovskite methylammonium lead iodide: implications to solar cells,
Sol. Energy 173 (2018) 1315.
[71] C. Zhu, X. Niu, Y. Fu, N. Li, C. Hu, Y. Chen, X. He, G. Na, P. Liu, H. Zai, Y. Ge, Y. Lu,
X. Ke, Y. Bai, S. Yang, P. Chen, Y. Li, M. Sui, L. Zhang, H. Zhou, Q. Chen, Strain
engineering in perovskite solar cells and its impacts on carrier dynamics, Nat.
Commun. 10 (2019) 815.
[72] L. Zhang, W. Geng, C.J. Tong, X. Chen, T. Cao, M. Chen, Strain induced electronic
structure variation in methyl-ammonium lead iodide perovskite, Sci. Rep. 8
(2018) 7760.
[73] Z. Ma, Z. Liu, S. Lu, L. Wang, X. Feng, D. Yang, K. Wang, G. Xiao, L. Zhang,
S.A.T. Redfern, B. Zou, Pressure-induced emission of cesium lead halide perovskite
nanocrystals, Nat. Commun. 9 (2018) 4506.
[74] L. Zhang, C. Liu, L. Wang, C. Liu, K. Wang, B. Zou, Pressure-induced emission
enhancement, band-gap narrowing, and metallization of halide perovskite
Cs3Bi2I9, Angew. Chem. Int. Ed. 57 (2018) 11213.
[75] T. Wang, B. Daiber, J.M. Frost, S.A. Mann, E.C. Garnett, A. Walsh, B. Ehrler,
Indirect to direct bandgap transition in methylammonium lead halide perovskite,
Energy Environ. Sci. 10 (2017) 509.
[76] L. Kong, G. Liu, J. Gong, Q. Hu, R.D. Schaller, P. Dera, D. Zhang, Z. Liu, W. Yang,
K. Zhu, Y. Tang, C. Wang, S.H. Wei, T. Xu, H.K. Mao, Simultaneous band-gap
narrowing and carrier-lifetime prolongation of organic-inorganic trihalide
perovskites, Proc. Natl. Acad. Sci. 113 (2016) 8910.
[77] G. Liu, J. Gong, L. Kong, R.D. Schaller, Q. Hu, Z. Liu, S. Yan, W. Yang,
C.C. Stoumpos, M.G. Kanatzidis, H.K. Mao, T. Xu, Isothermal pressure-derived
metastable states in 2D hybrid perovskites showing enduring bandgap narrowing,
Proc. Natl. Acad. Sci. 115 (2018) 8076.
[78] Q.-D. Ou, C. Li, Y.-Q. Li, J.-X. Tang, Photoemission spectroscopy study on
interfacial energy level alignments in tandem organic light-emitting diodes,
J. Electron. Spectrosc. Relat. Phenom. 204 (2015) 186.
[79] Y.-Q. Li, Q.-K. Wang, Q.-D. Ou, J.-X. Tang, Interface energetics and engineering of
organic heterostructures in organic photovoltaic cells, Sci. China Chem. 59 (2016)
422.
[80] Y.-H. Deng, Y.-Q. Li, Q.-D. Ou, Q.-K. Wang, F.-Z. Sun, X.-Y. Chen, J.-X. Tang, The
doping effect of cesium-based compounds on carrier transport and operational
stability in organic light-emitting diodes, Org. Electron. 15 (2014) 1215.
[81] H.-X. Wei, Q.-D. Ou, Z. Zhang, J. Li, Y.-Q. Li, S.-T. Lee, J.-X. Tang, The role of
cesium fluoride as an n-type dopant on electron transport layer in organic light-
emitting diodes, Org. Electron. 14 (2013) 839.
[82] R. Ohmann, L.K. Ono, H.S. Kim, H. Lin, M.V. Lee, Y. Li, N.G. Park, Y. Qi, Real-
space imaging of the atomic structure of organic-inorganic perovskite, J. Am.
Chem. Soc. 137 (2015) 16049.
[83] Q.-D. Ou, C. Li, Q.-K. Wang, Y.-Q. Li, J.-X. Tang, Recent advances in energetics of
metal halide perovskite interfaces, Adv. Mater. Interfaces 4 (2017), 1600694.
[84] W. Peng, J. Yin, K.T. Ho, O. Ouellette, M. De Bastiani, B. Murali, O. El Tall,
C. Shen, X. Miao, J. Pan, E. Alarousu, J.H. He, B.S. Ooi, O.F. Mohammed,
E. Sargent, O.M. Bakr, Ultralow self-doping in two-dimensional hybrid perovskite
single crystals, Nano Lett. 17 (2017) 4759.
[85] Q. Wang, Y. Shao, H. Xie, L. Lyu, X. Liu, Y. Gao, J. Huang, Qualifying composition
dependent p and n self-doping in CH3NH3PbI3, Appl. Phys. Lett. 105 (2014)
163508.
Q. Ou et al.
[86] P. Cui, D. Wei, J. Ji, H. Huang, E. Jia, S. Dou, T. Wang, W. Wang, M. Li, Planar p-n
homojunction perovskite solar cells with efficiency exceeding 21.3%, Nat. Energy
4 (2019) 150.
[87] S. Bertolazzi, M. Gobbi, Y. Zhao, C. Backes, P. Samori, Molecular chemistry
approaches for tuning the properties of two-dimensional transition metal
dichalcogenides, Chem. Soc. Rev. 47 (2018) 6845.
[88] D. Xiang, C. Han, J. Wu, S. Zhong, Y. Liu, J. Lin, X.A. Zhang, W. Ping Hu,
B. Ozyilmaz, A.H. Neto, A.T. Wee, W. Chen, Surface transfer doping induced
effective modulation on ambipolar characteristics of few-layer black phosphorus,
Nat. Commun. 6 (2015) 6485.
[89] J. Lin, J. Zhong, S. Zhong, H. Li, H. Zhang, W. Chen, Modulating electronic
transport properties of MoS2 field effect transistor by surface overlayers, Appl.
Phys. Lett. 103 (2013) 063109.
[90] Z. Chen, I. Santoso, R. Wang, L.F. Xie, H.Y. Mao, H. Huang, Y.Z. Wang, X.Y. Gao,
Z.K. Chen, D. Ma, A.T.S. Wee, W. Chen, Surface transfer hole doping of epitaxial
graphene using MoO3 thin film, Appl. Phys. Lett. 96 (2010) 213104.
[91] M.T. Edmonds, J.T. Hellerstedt, A. Tadich, A. Schenk, K.M. O'Donnell, J. Tosado,
N.P. Butch, P. Syers, J. Paglione, M.S. Fuhrer, Air-stable electron depletion of
bi2se3 using molybdenum trioxide into the topological regime, ACS Nano 8
(2014) 6400.
[92] Q.-K. Wang, R.-B. Wang, P.-F. Shen, C. Li, Y.-Q. Li, L.-J. Liu, S. Duhm, J.-X. Tang,
Energy level offsets at lead halide perovskite/organic hybrid interfaces and their
impacts on charge separation, Adv. Mater. Interfaces 2 (2015), 1400528.
[93] P. Liu, X. Liu, L. Lyu, H. Xie, H. Zhang, D. Niu, H. Huang, C. Bi, Z. Xiao, J. Huang,
Y. Gao, Interfacial electronic structure at the CH3NH3PbI3/MoOx interface, Appl.
Phys. Lett. 106 (2015) 193903.
[94] P. Schulz, J.O. Tiepelt, J.A. Christians, I. Levine, E. Edri, E.M. Sanehira, G. Hodes,
D. Cahen, A. Kahn, High-work-function molybdenum oxide hole extraction
contacts in hybrid organic-inorganic perovskite solar cells, ACS Appl. Mater.
Interfaces 8 (2016) 31491.
[95] Q. Ou, Y. Zhang, Z. Wang, J.A. Yuwono, R. Wang, Z. Dai, W. Li, C. Zheng, Z.Q. Xu,
X. Qi, S. Duhm, N.V. Medhekar, H. Zhang, Q. Bao, Strong depletion in hybrid
perovskite p-n junctions induced by local electronic doping, Adv. Mater. 30
(2018), 1705792.
[96] S. Mouri, Y. Miyauchi, K. Matsuda, Tunable photoluminescence of monolayer
MoS(2) via chemical doping, Nano Lett. 13 (2013) 5944.
[97] W. Chen, S. Chen, D.C. Qi, X.Y. Gao, A.T.S. Wee, Surface transfer p-type doping of
epitaxial graphene, J. Am. Chem. Soc. 129 (2007) 10418.
[98] Y. He, F. Xia, Z. Shao, J. Zhao, J. Jie, Surface charge transfer doping of monolayer
phosphorene via molecular adsorption, J. Phys. Chem. Lett. 6 (2015) 4701.
[99] M.T. Edmonds, J. Hellerstedt, K.M. O'Donnell, A. Tadich, M.S. Fuhrer, Molecular
doping the topological Dirac semimetal Na3Bi across the charge neutrality point
with F4-TCNQ, ACS Appl. Mater. Interfaces 8 (2016) 16412.
[100] L. Zhao, Y.L. Lin, H. Kim, N.C. Giebink, B.P. Rand, Donor/acceptor charge-transfer
states at two-dimensional metal halide perovskite and organic semiconductor
interfaces, ACS Energy Lett 3 (2018) 2708.
[101] W.Q. Wu, Q. Wang, Y. Fang, Y. Shao, S. Tang, Y. Deng, H. Lu, Y. Liu, T. Li, Z. Yang,
A. Gruverman, J. Huang, Molecular doping enabled scalable blading of efficient
hole-transport-layer-free perovskite solar cells, Nat. Commun. 9 (2018) 1625.
[102] E.A. Gaulding, J. Hao, H.S. Kang, E.M. Miller, S.N. Habisreutinger, Q. Zhao,
A. Hazarika, P.C. Sercel, J.M. Luther, J.L. Blackburn, Conductivity tuning via
doping with electron donating and withdrawing molecules in perovskite CsPbI3
nanocrystal films, Adv. Mater. (2019) e1902250.
[103] E.E. Perry, J.G. Labram, N.R. Venkatesan, H. Nakayama, M.L. Chabinyc, N-type
surface doping of MAPbI3 via charge transfer from small molecules, Adv. Electron.
Mater. 4 (2018), 1800087.
[104] H. Pan Arramel, A. Xie, S. Hou, X. Yin, C.S. Tang, N.T. Hoa, M.D. Birowosuto,
H. Wang, C. Dang, A. Rusydi, A.T.S. Wee, J. Wu, Surface molecular doping of all-
inorganic perovskite using zethrenes molecules, Nano Res 12 (2018) 77.
[105] Y. Guo, W. Sato, K. Shoyama, E. Nakamura, Sulfamic acid-catalyzed lead
perovskite formation for solar cell fabrication on glass or plastic substrates, J. Am.
Chem. Soc. 138 (2016) 5410.
[106] T.H. Han, J.W. Lee, C. Choi, S. Tan, C. Lee, Y. Zhao, Z. Dai, N. De Marco, S.J. Lee,
S.H. Bae, Y. Yuan, H.M. Lee, Y. Huang, Y. Yang, Perovskite-polymer composite
cross-linker approach for highly-stable and efficient perovskite solar cells, Nat.
Commun. 10 (2019) 520.
[107] J. Yang, S. Xiong, T. Qu, Y. Zhang, X. He, X. Guo, Q. Zhao, S. Braun, J. Chen, J. Xu,
Y. Li, X. Liu, C. Duan, J. Tang, M. Fahlman, Q. Bao, Extremely low-cost and green
cellulose passivating perovskites for stable and high-performance solar cells, ACS
Appl. Mater. Interfaces 11 (2019) 13491.
[108] V.M. Arivunithi, S.S. Reddy, V.G. Sree, H.-Y. Park, J. Park, Y.-C. Kang, E.-S. Shin,
Y.-Y. Noh, M. Song, S.-H. Jin, Efficiency exceeding 20% in perovskite solar cells
with side-chain liquid crystalline polymer-doped perovskite absorbers, Adv.
Energy Mater. 8 (2018), 1801637.
[109] Y. Zhou, C. Fuentes-Hernandez, J. Shim, J. Meyer, A.J. Giordano, H. Li, P. Winget,
T. Papadopoulos, H. Cheun, J. Kim, A universal method to produce low-work
function electrodes for organic electronics, Science 336 (2012) 327.
[110] J. Jiang, Q. Wang, Z. Jin, X. Zhang, J. Lei, H. Bin, Z.-G. Zhang, Y. Li, S.F. Liu,
Polymer doping for high-efficiency perovskite solar cells with improved moisture
stability, Adv. Energy Mater. 8 (2018), 1701757.
[111] L. Zuo, H. Guo, S. Jariwala, N. De Marco, S. Dong, R. DeBlock, D.S. Ginger,
B. Dunn, M. Wang, Y. Yang, Polymer-modified halide perovskite films for efficient
and stable planar heterojunction solar cells, Sci. Adv. 3 (2017), e1700106.
[112] J.T.-W. Wang, Z. Wang, S. Pathak, W. Zhang, D.W. deQuilettes, F. Wisnivesky-
Rocca-Rivarola, J. Huang, P.K. Nayak, J.B. Patel, H.A. Mohd Yusof, Y. Vaynzof,
R. Zhu, I. Ramirez, J. Zhang, C. Ducati, C. Grovenor, M.B. Johnston, D.S. Ginger,
286
Nano Materials Science 1 (2019) 268–287
R.J. Nicholas, H.J. Snaith, Efficient perovskite solar cells by metal ion doping,
Energy Environ. Sci. 9 (2016) 2892.
[113] Z.K. Wang, M. Li, Y.G. Yang, Y. Hu, H. Ma, X.Y. Gao, L.S. Liao, High efficiency Pb-
in binary metal perovskite solar cells, Adv. Mater. 28 (2016) 6695.
[114] Z. Shi, J. Guo, Y. Chen, Q. Li, Y. Pan, H. Zhang, Y. Xia, W. Huang, Lead-free
organic-inorganic hybrid perovskites for photovoltaic applications: recent
advances and perspectives, Adv. Mater. 29 (2017), 1605005.
[115] Y. Zhou, J. Chen, O.M. Bakr, H.-T. Sun, Metal-doped lead halide perovskites:
synthesis, properties, and optoelectronic applications, Chem. Mater. 30 (2018)
6589.
[116] G. Kakavelakis, K. Petridis, E. Kymakis, Recent advances in plasmonic metal and
rare-earth-element upconversion nanoparticle doped perovskite solar cells,
J. Mater. Chem. A 5 (2017) 21604.
[117] X. Zhang, L. Li, Z. Sun, J. Luo, Rational chemical doping of metal halide
perovskites, Chem. Soc. Rev. 48 (2018) 517.
[118] P. Arunkumar, H.B. Cho, K.H. Gil, S. Unithrattil, Y.H. Kim, W. Bin Im, Probing
molecule-like isolated octahedra via-phase stabilization of zero-dimensional
cesium lead halide nanocrystals, Nat. Commun. 9 (2018) 4691.
[119] D. Parobek, B.J. Roman, Y. Dong, H. Jin, E. Lee, M. Sheldon, D.H. Son, Exciton-to-
Dopant energy transfer in Mn-doped cesium lead halide perovskite nanocrystals,
Nano Lett. 16 (2016) 7376.
[120] F. Li, Z. Xia, Y. Gong, L. Gu, Q. Liu, Optical properties of Mn2þ doped cesium lead
halide perovskite nanocrystals via a cation-anion co-substitution exchange
reaction, J. Mater. Chem. C 5 (2017) 9281.
[121] W. Xu, F. Li, F. Lin, Y. Chen, Z. Cai, Y. Wang, X. Chen, Synthesis of CsPbCl3-Mn
nanocrystals via cation exchange, Adv. Opt. Mater. 5 (2017) 1700520.
[122] F. Meinardi, Q.A. Akkerman, F. Bruni, S. Park, M. Mauri, Z. Dang, L. Manna,
S. Brovelli, Doped halide perovskite nanocrystals for reabsorption-free
luminescent solar concentrators, ACS Energy Lett 2 (2017) 2368.
[123] G. Pan, X. Bai, D. Yang, X. Chen, P. Jing, S. Qu, L. Zhang, D. Zhou, J. Zhu, W. Xu,
B. Dong, H. Song, Doping lanthanide into perovskite nanocrystals: highly
improved and expanded optical properties, Nano Lett. 17 (2017) 8005.
[124] Q. Hu, Z. Li, Z. Tan, H. Song, C. Ge, G. Niu, J. Han, J. Tang, Rare earth ion-doped
CsPbBr3 nanocrystals, Adv. Opt. Mater. 6 (2018) 1700864.
[125] D. Zhou, D. Liu, G. Pan, X. Chen, D. Li, W. Xu, X. Bai, H. Song, Cerium and
ytterbium codoped halide perovskite quantum dots: a novel and efficient
downconverter for improving the performance of silicon solar cells, Adv. Mater.
29 (2017), 1704149.
[126] X. Huang, H. Li, C. Zhang, S. Tan, Z. Chen, L. Chen, Z. Lu, X. Wang, M. Xiao,
Efficient plasmon-hot electron conversion in Ag-CsPbBr3 hybrid nanocrystals, Nat.
Commun. 10 (2019) 1163.
[127] Q.-D. Ou, Y.-Q. Li, J.-X. Tang, Light manipulation in organic photovoltaics, Adv.
Sci. 3 (2016) 1600123.
[128] D.-D. Zhang, R. Wang, Y.-Y. Ma, H.-X. Wei, Q.-D. Ou, Q.-K. Wang, L. Zhou, S.-
T. Lee, Y.-Q. Li, J.-X. Tang, Realizing both improved luminance and stability in
organic light-emitting devices based on a solution-processed inter-layer composed
of MoOX and Au nanoparticles mixture, Org. Electron. 15 (2014) 961.
[129] L. Zhou, H.Y. Xiang, Y.F. Zhu, Q.D. Ou, Q.K. Wang, J. Du, R. Hu, X.B. Huang,
J.X. Tang, Multifunctional silver nanoparticle interlayer-modified ZnO as the
electron-injection layer for efficient inverted organic light-emitting diodes, ACS
Appl. Mater. Interfaces 11 (2019) 9251.
[130] Q.-D. Ou, L. Zhou, Y.-Q. Li, J.-D. Chen, C. Li, S. Shen, J.-X. Tang, Simultaneously
enhancing color spatial uniformity and operational stability with deterministic
quasi-periodic nanocone arrays for tandem organic light-emitting diodes, Adv.
Opt. Mater. 3 (2015) 87.
[131] Q.-D. Ou, H.-J. Xie, J.-D. Chen, L. Zhou, Y.-Q. Li, J.-X. Tang, Enhanced light
harvesting in flexible polymer solar cells: synergistic simulation of a plasmonic
meta-mirror and a transparent silver mesowire electrode, J. Mater. Chem. A 4
(2016) 18952.
[132] Y. Zhang, C.-K. Lim, Z. Dai, G. Yu, J.W. Haus, H. Zhang, P.N. Prasad, Photonics and
optoelectronics using nano-structured hybrid perovskite media and their optical
cavities, Phys. Rep. 795 (2019) 1.
[133] S. Ye, M. Yu, W. Yan, J. Song, J. Qu, Enhanced photoluminescence of CsPbBr3@Ag
hybrid perovskite quantum dots, J. Mater. Chem. C 5 (2017) 8187.
[134] S. Chen, D. Lyu, T. Ling, W. Guo, Reversible modulation of CsPbBr3 perovskite
nanocrystal/gold nanoparticle heterostructures, Chem. Commun. 54 (2018) 4605.
[135] S.K. Balakrishnan, P.V. Kamat, Au-CsPbBr3 hybrid architecture: anchoring gold
nanoparticles on cubic perovskite nanocrystals, ACS Energy Lett 2 (2017) 88.
[136] X. Bao, Q. Ou, Z.-Q. Xu, Y. Zhang, Q. Bao, H. Zhang, Band structure engineering in
2D materials for optoelectronic applications, Adv. Mater. Technol. 3 (2018),
1800072.
[137] J.M. Yang, Y. Luo, Q. Bao, Y.Q. Li, J.X. Tang, Recent advances in energetics and
stability of metal halide perovskites for optoelectronic applications, Adv. Mater.
Interfaces 6 (2018), 1801351.
[138] M. Oehzelt, K. Akaike, N. Koch, G. Heimel, Energy-level alignment at organic
heterointerfaces, Sci. Adv. 1 (2015), e1501127.
[139] H. Zhou, Q. Chen, G. Li, S. Luo, T.B. Song, H.S. Duan, Z. Hong, J. You, Y. Liu,
Y. Yang, Interface engineering of highly efficient perovskite solar cells, Science
345 (2014) 542.
[140] H. Cho, S.-H. Jeong, M.-H. Park, Y.-H. Kim, C. Wolf, C.-L. Lee, J.H. Heo,
A. Sadhanala, N. Myoung, S. Yoo, S.H. Im, R.H. Friend, T.-W. Lee, Overcoming the
electroluminescence efficiency limitations of perovskite light-emitting diodes,
Science 350 (2015) 1222.
[141] X. Zhang, Z. Shao, X. Zhang, Y. He, J. Jie, Surface charge transfer doping of low-
dimensional nanostructures toward high-performance nanodevices, Adv. Mater.
28 (2016) 10409.
Q. Ou et al.
[142] B. Lüssem, M. Riede, K. Leo, Doping of organic semiconductors, Phys. Status Solidi
A 210 (2013) 9.
[143] M.-Y. Li, Y. Shi, C.-C. Cheng, L.-S. Lu, Y.-C. Lin, H.-L. Tang, M.-L. Tsai, C.-W. Chu,
K.-H. Wei, J.-H. He, W.-H. Chang, K. Suenaga, L.-J. Li, Epitaxial growth of a
monolayer WSe2-MoS2 lateral p-n junction with an atomically sharp interface,
Science 349 (2015) 524.
[144] C. Zheng, Q. Zhang, B. Weber, H. Ilatikhameneh, F. Chen, H. Sahasrabudhe,
R. Rahman, S. Li, Z. Chen, J. Hellerstedt, Y. Zhang, W.H. Duan, Q. Bao,
M.S. Fuhrer, Direct observation of 2D electrostatics and ohmic contacts in
template-grown graphene/WS2 heterostructures, ACS Nano 11 (2017) 2785.
[145] B.W. Baugher, H.O. Churchill, Y. Yang, P. Jarillo-Herrero, Optoelectronic devices
based on electrically tunable p-n diodes in a monolayer dichalcogenide, Nat.
Nanotechnol. 9 (2014) 262.
[146] A. Pospischil, M.M. Furchi, T. Mueller, Solar-energy conversion and light emission
in an atomic monolayer p-n diode, Nat. Nanotechnol. 9 (2014) 257.
[147] M. Buscema, D.J. Groenendijk, G.A. Steele, H.S. van der Zant, A. Castellanos-
Gomez, Photovoltaic effect in few-layer black phosphorus PN junctions defined by
local electrostatic gating, Nat. Commun. 5 (2014) 4651.
[148] B. Danekamp, C. Muller, M. Sendner, P.P. Boix, M. Sessolo, R. Lovrincic,
H.J. Bolink, Perovskite-perovskite homojunctions via compositional doping,
J. Phys. Chem. Lett. 9 (2018) 2770.
[149] M.C. Kim, B.J. Kim, D.Y. Son, N.G. Park, H.S. Jung, M. Choi, Observation of
enhanced hole extraction in Br concentration gradient perovskite materials, Nano
Lett. 16 (2016) 5756.
[150] F. Fu, S. Pisoni, T.P. Weiss, T. Feurer, A. Wackerlin, P. Fuchs, S. Nishiwaki,
L. Zortea, A.N. Tiwari, S. Buecheler, Compositionally graded absorber for efficient
and stable near-infrared-transparent perovskite solar cells, Adv. Sci. 5 (2018)
1700675.
[151] Q. Kong, W. Lee, M. Lai, C.G. Bischak, G. Gao, A.B. Wong, T. Lei, Y. Yu, L.W. Wang,
N.S. Ginsberg, P. Yang, Phase-transition-induced p-n junction in single halide
perovskite nanowire, Proc. Natl. Acad. Sci. 115 (2018) 8889.
[152] C. Jia, H. Li, X. Meng, H. Li, CsPbX3/Cs4PbX6 core/shell perovskite nanocrystals,
Chem. Commun. 54 (2018) 6300.
[153] T. Xuan, S. Lou, J. Huang, L. Cao, X. Yang, H. Li, J. Wang, Monodisperse and
brightly luminescent CsPbBr3/Cs4PbBr6 perovskite composite nanocrystals,
Nanoscale 10 (2018) 9840.
[154] Y. Wang, D. Yu, Z. Wang, X. Li, X. Chen, V. Nalla, H. Zeng, H. Sun, Solution-grown
CsPbBr3/Cs4PbBr6 perovskite nanocomposites: toward temperature-insensitive
optical gain, Small 13 (2017), 1701587.
[155] L. Dou, M. Lai, C.S. Kley, Y. Yang, C.G. Bischak, D. Zhang, S.W. Eaton,
N.S. Ginsberg, P. Yang, Spatially resolved multicolor CsPbX3 nanowire
heterojunctions via anion exchange, Proc. Natl. Acad. Sci. 114 (2017) 7216.
[156] M. Lai, A. Obliger, D. Lu, C.S. Kley, C.G. Bischak, Q. Kong, T. Lei, L. Dou,
N.S. Ginsberg, D.T. Limmer, P. Yang, Intrinsic anion diffusivity in lead halide
perovskites is facilitated by a soft lattice, Proc. Natl. Acad. Sci. 115 (2018) 11929.
[157] B. Hwang, J.S. Lee, 2D perovskite-based self-aligned lateral heterostructure
photodetectors utilizing vapor deposition, Adv. Opt. Mater. 7 (2019) 1801356.
[158] M. Spina, L. Mihaly, K. Holczer, B. Nafradi, A. Pisoni, L. Forro, E. Horvath,
Photodiode response in a CH3NH3PbI3/CH3NH3SnI3 heterojunction, ACS Appl.
Mater. Interfaces 9 (2017) 10198.
[159] B. Li, Y. Zhang, L. Zhang, L. Yin, Graded heterojunction engineering for hole-
conductor-free perovskite solar cells with high hole extraction efficiency and
conductivity, Adv. Mater. 29 (2017) 1701221.
287
Nano Materials Science 1 (2019) 268–287
[160] H.W. Qiao, S. Yang, Y. Wang, X. Chen, T.Y. Wen, L.J. Tang, Q. Cheng, Y. Hou,
H. Zhao, H.G. Yang, A gradient heterostructure based on tolerance factor in high-
performance perovskite solar cells with 0.84 fill factor, Adv. Mater. 31 (2019),
1804217.
[161] K.T. Cho, S. Paek, G. Grancini, C. Rold
an-Carmona, P. Gao, Y. Lee,
M.K. Nazeeruddin, Highly efficient perovskite solar cells with a compositionally
engineered perovskite/hole transporting material interface, Energy Environ. Sci.
10 (2017) 621.
[162] J. Wang, J. Li, S. Lan, C. Fang, H. Shen, Q. Xiong, D. Li, Controllable growth of
centimeter-sized 2D perovskite heterostructures for highly narrow dual-band
photodetectors, ACS Nano 13 (2019) 5473.
[163] Y. Wang, Y. Zhang, Y. Lu, W. Xu, H. Mu, C. Chen, H. Qiao, J. Song, S. Li, B. Sun, Y.-
B. Cheng, Q. Bao, Hybrid graphene-perovskite phototransistors with ultrahigh
responsivity and gain, Adv. Opt. Mater. 3 (2015) 1389.
[164] Q. Fang, Q. Shang, L. Zhao, R. Wang, Z. Zhang, P. Yang, X. Sui, X. Qiu, X. Liu,
Q. Zhang, Y. Zhang, Ultrafast charge transfer in perovskite nanowire/2d transition
metal dichalcogenide heterostructures, J. Phys. Chem. Lett. 9 (2018) 1655.
[165] Z. Wang, Q. Ou, Y. Zhang, Q. Zhang, H.Y. Hoh, Q. Bao, Degradation of two-
dimensional CH3NH3PbI3 perovskite and CH3NH3PbI3/graphene heterostructure,
ACS Appl. Mater. Interfaces 10 (2018) 24258.
[166] Z. Tan, Y. Wu, H. Hong, J. Yin, J. Zhang, L. Lin, M. Wang, X. Sun, L. Sun, Y. Huang,
K. Liu, Z. Liu, H. Peng, Two-dimensional (C4H9NH3)2PbBr4 perovskite crystals for
high-performance photodetector, J. Am. Chem. Soc. 138 (2016) 16612.
[167] Y. Shao, Y. Liu, X. Chen, C. Chen, I. Sarpkaya, Z. Chen, Y. Fang, J. Kong,
K. Watanabe, T. Taniguchi, A. Taylor, J. Huang, F. Xia, Stable graphene-two-
dimensional multiphase perovskite heterostructure phototransistors with high
gain, Nano Lett. 17 (2017) 7330.
[168] S. Chen, G. Shi, Two-dimensional materials for halide perovskite-based
optoelectronic devices, Adv. Mater. 29 (2017), 1605448.
[169] Z. Ning, X. Gong, R. Comin, G. Walters, F. Fan, O. Voznyy, E. Yassitepe, A. Buin,
S. Hoogland, E.H. Sargent, Quantum-dot-in-perovskite solids, Nature 523 (2015)
324.
[170] X. Gong, Z. Yang, G. Walters, R. Comin, Z. Ning, E. Beauregard, V. Adinolfi,
O. Voznyy, E.H. Sargent, Highly efficient quantum dot near-infrared light-emitting
diodes, Nat. Photonics 10 (2016) 253.
[171] F.P. Garcia de Arquer, X. Gong, R.P. Sabatini, M. Liu, G.H. Kim, B.R. Sutherland,
O. Voznyy, J. Xu, Y. Pang, S. Hoogland, D. Sinton, E. Sargent, Field-emission from
quantum-dot-in-perovskite solids, Nat. Commun. 8 (2017) 14757.
[172] Y. Fu, W. Zheng, X. Wang, M.P. Hautzinger, D. Pan, L. Dang, J.C. Wright, A. Pan,
S. Jin, Multicolor heterostructures of two-dimensional layered halide perovskites
that show interlayer energy transfer, J. Am. Chem. Soc. 140 (2018) 15675.
[173] J. Chang, S. Zhang, N. Wang, Y. Sun, Y. Wei, R. Li, C. Yi, J. Wang, W. Huang,
Enhanced performance of red perovskite light-emitting diodes through the
dimensional tailoring of perovskite multiple quantum wells, J. Phys. Chem. Lett. 9
(2018) 881.
[174] S. Zhang, C. Yi, N. Wang, Y. Sun, W. Zou, Y. Wei, Y. Cao, Y. Miao, R. Li, Y. Yin,
N. Zhao, J. Wang, W. Huang, Efficient red perovskite light-emitting diodes based
on solution-processed multiple quantum wells, Adv. Mater. (2017).
[175] W. Zou, R. Li, S. Zhang, Y. Liu, N. Wang, Y. Cao, Y. Miao, M. Xu, Q. Guo, D. Di,
L. Zhang, C. Yi, F. Gao, R.H. Friend, J. Wang, W. Huang, Minimising efficiency roll-
off in high-brightness perovskite light-emitting diodes, Nat. Commun. 9 (2018)
608.