Red-Emitting CsPbI3/ZnSe Colloidal Nanoheterostructures with Enhanced Optical Properties and Stability.

Producing heterostructures of cesium lead halide perovskites and metal-chalcogenides in the form of colloidal nanocrystals can improve their optical features and stability, and also govern the recombination of charge carriers. Herein, the synthesis of red-emitting CsPbI3/ZnSe nanoheterostructures is reported via an in situ hot injection method, which provides the crystallization conditions for both components, subsequently leading to heteroepitaxial growth. Steady-state absorption and photoluminescence studies alongside X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy analysis evidence on a type-I band alignment for CsPbI3/ZnSe nanoheterostructures, which exhibit photoluminescence quantum yield of 96% due to the effective passivation of surface defects, and an enhancement in carrier lifetime. Furthermore, the heterostructure growth of ZnSe domains leads to significant improvement in the stability of the CsPbI3 nanocrystals under ambient conditions and against thermal and UV irradiation stress.

Fine-Tuning Crystal Structures of Lead Bromide Perovskite Nanocrystals through Trace Cadmium(II) Doping for Efficient Color-Saturated Green LEDs.

Decreasing perovskite nanocrystal size increases radiative recombination due to the quantum confinement effect, but also increases the Auger recombination rate which leads to carrier imbalance in the emitting layers of electroluminescent devices. Here, we overcome this trade-off by increasing the exciton effective mass without affecting the size, which is realized through the trace Cd2+ doping of formamidinium lead bromide perovskite nanocrystals. We observe an ~2.7 times increase in the exciton binding energy benefiting from a slight distortion of the [BX6]4- octahedra caused by doping in the case of that the Auger recombination rate is almost unchanged. As a result, bright color-saturated green emitting perovskite nanocrystals with a photoluminescence quantum yield of 96 % are obtained. Cd2+ doping also shifts up the energy levels of the nanocrystals, relative to the Fermi level so that heavily n-doped emitters convert into only slightly n-doped ones; this boosts the charge injection efficiency of the corresponding light-emitting diodes. The light-emitting devices based on those nanocrystals reached a high external quantum efficiency of 29.4 % corresponding to a current efficiency of 123 cd A-1, and showed dramatically improved device lifetime, with a narrow bandwidth of 22 nm and Commission Internationale de I'Eclairage coordinates of (0.20, 0.76) for color-saturated green emission for the electroluminescence peak centered at 534 nm, thus being fully compliant with the latest standard for wide color gamut displays.

Temperature Dependence of Charge Transport Properties of Quasi-2D Chiral Perovskite Thin-Film Field-Effect Transistors.

Chiral halide perovskite materials promise both superior light response and the capability to distinguish circularly polarized emissions, which are especially common in the fluorescence spectra of organic chiral materials. Herein, thin-film field-effect transistors (FETs) based on chiral quasi-two-dimensional perovskites are explored, and the temperature dependence of the charge carrier transport mechanism over the broad temperature range (80-300 K) is revealed. A typical p-type charge transport behavior is observed for both left-handed (S-C6H5(CN2)2NH3)2(CH3NH3)n-1PbnI3n+1 and right-handed (R-C6H5(CN2)2NH3)2(CH3NH3)n-1PbnI3n+1 chiral perovskites, with maximum carrier mobilities of 1.7 × 10-5 cm2 V-1 s-1 and 2.5 × 10-5 cm2 V-1 s-1 at around 280 K, respectively. The shallow traps with smaller activation energy (0.03 eV) hinder the carrier transport over the lower temperature regime (80-180 K), while deep traps with 1 order of magnitude larger activation energy than the shallow traps moderate the charge carrier transport in the temperature range of 180-300 K. From the charge carrier mechanism point of view, impurity scattering is established as the dominant factor from 80 K until around 280 K, while phonon scattering becomes predominant up to room temperature. Responsivities of 0.15 A W-1 and 0.14 A W-1 for left-handed and right-handed chiral perovskite FET devices are obtained.

Ultraviolet Circularly Polarized Luminescence in Chiral Perovskite Nanoplatelet-Molecular Hybrids: Direct Binding Versus Efficient Triplet Energy Transfer.

The development of ultraviolet circularly polarized light (UVCPL) sources has the potential to benefit plenty of practical applications but remains a challenge due to limitations in available material systems and a limited understanding of the excited state chirality transfer. Herein, by constructing hybrid structures of the chiral perovskite CsPbBr3 nanoplatelets and organic molecules, excited state chirality transfer is achieved, either via direct binding or triplet energy transfer, leading to efficient UVCPL emission. The underlying photophysical mechanisms of these two scenarios are clarified by comprehensive optical studies. Intriguingly, UVCPL realized via the triple energy transfer, followed by the triplet-triplet annihilation upconversion processes, demonstrates a 50-fold enhanced dissymmetry factor glum. Furthermore, stereoselective photopolymerization of diacetylene monomer is demonstrated by using such efficient UVCPL. This study provides both novel insights and a practical approach for realizing UVCPL, which can also be extended to other material systems and spectral regions, such as visible and near-infrared.

Obviating Ligand Exchange Preserves the Intact Surface of HgTe Colloidal Quantum Dots and Enhances Performance of Short Wavelength Infrared Photodetectors.

A large volume, scalable synthesis procedure of HgTe quantum dots (QDs) capped initially with short-chain conductive ligands ensures ligand exchange-free and simple device fabrication. An effective n- or p-type self-doping of HgTe QDs is achieved by varying cation-anion ratio, as well as shifting the Fermi level position by introducing single- or double-cyclic thiol ligands, that is, 2-furanmethanethiol (FMT) or 2,5-dimercapto-3,4-thiadiasole (DMTD) in the synthesis. This allows for preserving the intact surface of the HgTe QDs, thus ensuring a one order of magnitude reduced surface trap density compared with HgTe subjected to solid-state ligand exchange. The charge carrier diffusion length can be extended from 50 to 90 nm when the device active area consists of a bi-layer of cation-rich HgTe QDs capped with DMTD and FMT, respectively. As a result, the responsivity under 1340 nm illumination is boosted to 1 AW-1 at zero bias and up to 40 AW-1 under -1 V bias at room temperature. Due to high noise current density, the specific detectivity of these photodetectors reaches up to 1010 Jones at room temperature and under an inert atmosphere. Meanwhile, high photoconductive gain ensures a rise in the external quantum efficiency of up to 1000% under reverse bias.

Metal Halide Perovskite Photo-Field-Effect Transistors with Chiral Selectivity.

Organic-inorganic (hybrid) metal halide perovskites (MHPs) incorporating chiral organic ligand molecules are naturally sensitive to left- and right-handed circular polarized light, potentially enabling selective circular polarized photodetection. Here, the photoresponses in chiral MHP polycrystalline thin films made of ((S)-(-)-α-methyl benzylamine)2PbI4 and ((R)-(+)-α-methyl benzylamine)2PbI4, denoted as (S-MBA)2 PbI4 and (R-MBA)2PbI4, respectively, are investigated by employing a thin-film field-effect transistor (FET) configuration. The left-hand-sensitive films made of (S-MBA)2PbI4 perovskite show higher photocurrent under left-handed circularly polarized (LCP) light than under right-handed circularly polarized (RCP) illumination under otherwise identical conditions. Conversely, the right-hand-sensitive films made of (R-MBA)2PbI4 are more sensitive to RCP than LCP illumination over a wide temperature range of 77-300 K. Furthermore, based on FET measurements, we found evidence of two different carrier transport mechanisms with two distinct activation energies in the 77-260 and 280-300 K temperature ranges, respectively. In the former temperature range, shallow traps are dominant in the perovskite film, which are filled by thermally activated carriers with increasing temperature; in the latter temperature range, deep traps with one order of magnitude larger activation energy dominate. Both types of chiral MHPs show intrinsic p-type carrier transport behavior regardless of the handedness (S or R) of these materials. The optimal carrier mobility for both handedness of material is around (2.7 ± 0.2) × 10-7 cm2 V-1 s-1 at 270-280 K, which is two magnitudes larger than those reported in nonchiral perovskite MAPbI3 polycrystalline thin films. These findings suggest that chiral MHPs can be an excellent candidate for selective circular polarized photodetection applications, without additional polarizing optical components, enabling simplified construction of detection systems.

Highly Stable and Efficient Light-Emitting Diodes Based on Orthorhombic γ-CsPbI3 Nanocrystals.

Orthorhombic γ-CsPbI3 possesses the highest structural stability among the optically active (light-emissive) CsPbI3 perovskites. Here, we make use of a seed-assisted heteroepitaxial growth to fabricate seed/core/shell CaIx/γ-CsPbI3/CaI2 nanocrystals. Ultrasmall CaIx nanoparticles serve as seeds to template the Pb-centered octahedral arrangement which enables the formation of the γ-CsPbI3 phase and at the same time inhibit lattice strain by blocking the force transfer that otherwise leads to an octahedral twist and so improve the structural stability of the resulting nanocrystals. An outer shell composed from the same material, CaI2, isolates the formed γ-CsPbI3 nanocrystals from the environment, which also significantly improves their stability under ambient conditions. Optical and electrical studies indicate that the seed/core/shell CaIx/γ-CsPbI3/CaI2 structure possesses a shallower set of trap states as compared to cubic α-CsPbI3 nanocrystals. Light-emitting diodes utilizing these γ-CsPbI3 nanocrystals show a record high external quantum efficiency of 25.3%, high brightness of over 13600 cd/m2, and an operational lifetime of ∼14 h before reaching 50% of their initial luminance. These devices can repeatedly be illuminated over 650 times at ∼500 cd/m2 with no decline of brightness, which indicates their great commercial potential.

Mercury chalcogenide colloidal quantum dots for infrared photodetection: from synthesis to device applications.

Commercial infrared (IR) photodetectors based on epitaxial growth inorganic semiconductors, e.g. InGaAs and HgCdTe, suffer from high fabrication cost, poor compatibility with silicon integrated circuits, rigid substrates and bulky cooling systems, which leaves a large development window for the emerging solution-processable semiconductor-based photo-sensing devices. Among the solution-processable semiconductors, mercury (Hg) chalcogenide colloidal quantum dots (QDs) exhibit unique ultra-broad and tuneable photo-responses in the short-wave infrared to far-wave infrared range, and have demonstrated photo-sensing abilities comparable to the commercial products, especially with advances in high operation temperature. Here, we provide a focused review on photodetectors employing Hg chalcogenide colloidal QDs, with a comprehensive summary of the essential progress in the areas of synthesis methods of QDs, property control, device engineering, focus plane array integration, etc. Besides imaging demonstrations, a series of Hg chalcogenide QD photodetector based flexible, integrated, multi-functional applications are also summarized. This review shows prospects for the next-generation low-cost highly-sensitive and compact IR photodetectors based on solution-processable Hg chalcogenide colloidal QDs.

Co-doping of tellurium with bismuth enhances stability and photoluminescence quantum yield of Cs2AgInCl6 double perovskite nanocrystals.

The co-doping of double perovskites is a useful approach in terms of improving their stability and photoluminescence quantum yield. Herein, Bi3+ and Te4+ cations have been co-doped into Cs2AgInCl6 nanocrystals. Doping with Te4+ cations promotes radiative recombination of self-trapped excitons due to increased defect formation energies of silver and indium vacancies, according to experimental and theoretical results. When used in excess, the TeO2 precursor would generate residual TeO2, Te2O3Cl2, R2TeO, or all three of them, which confined undesired chlorine ions on oxygen vacancies to counteract the pull from the Cs2AgInCl6 host, resulting in improved coordination with surface oleic acid ligands. As a result, 1% Bi and 8% Te co-doped Cs2AgInCl6 nanocrystals reach a high photoluminescence quantum yield of 34% and show an improved stability, maintaining over 70% of their original emission intensity after storage for more than 1 month. These findings are important in the context of producing high-performance properly doped double perovskite nanocrystals for optoelectronic applications.

Amine-Terminated Carbon Dots Linking Hole Transport Layer and Vertically Oriented Quasi-2D Perovskites through Hydrogen Bonds Enable Efficient LEDs.

Close attention to the interfaces of solution-processed metal halide perovskite-based light-emitting devices (LEDs) is crucial for their optimal performance. Solution processing of these devices typically leads to the formation of van der Waals interfaces with a weak connection between different functional layers, leaving great room for improvement in charge transport through strengthening of the interlayer interaction. Here, we have realized a hydrogen-bond-assisted interface that makes use of ultrasmall amine-terminated carbon dots to enhance the interaction between the hole transport layer made of PEDOT:PSS and the hybrid lead bromide perovskite emitting layer, which not only promotes the hole injection efficiency but also orients the quasi-2D perovskite crystals penetrating the vertical direction of the device without any, or very few, horizontal grain boundaries, which has a profound effect on the photophysical and transport properties of the emitting layer. As a result, LEDs based on quasi-2D perovskites show up to 24.5% external quantum efficiency, 80 000 cd m-2 brightness, and over 5-fold extended longevity.

Bright, Magnetic NIR-II Quantum Dot Probe for Sensitive Dual-Modality Imaging and Intensive Combination Therapy of Cancer.

Improving the effectiveness of cancer therapy will require tools that enable more specific cancer targeting and improved tumor visualization. Theranostics have the potential for improving cancer care because of their ability to serve as both diagnostics and therapeutics; however, their diagnostic potential is often limited by tissue-associated light absorption and scattering. Herein, we develop CuInSe2@ZnS:Mn quantum dots (QDs) with intrinsic multifunctionality that both enable the accurate localization of small metastases and act as potent tumor ablation agents. By leveraging the growth kinetics of a ZnS shell on a biocompatible CuInSe2 core, Mn doping, and folic acid functionalization, we produce biocompatible QDs with high near-infrared (NIR)-II fluorescence efficiency up to 31.2%, high contrast on magnetic resonance imaging (MRI), and preferential distribution in 4T1 breast cancer tumors. MRI-enabled contrast of these nanoprobes is sufficient to timely identify small metastases in the lungs, which is critically important for preventing cancer spreading and recurrence. Further, exciting tumor-resident QDs with NIR light produces both fluorescence for tumor visualization through radiative recombination pathways as well as heat and radicals through nonradiative recombination pathways that kill cancer cells and initiate an anticancer immune response, which eliminates tumor and prevents tumor regrowth in 80% of mice.

Co-Doping of Cerium and Bismuth into Lead-Free Double Perovskite Cs2AgInCl6 Nanocrystals Results in Improved Photoluminescence Efficiency.

Lead-free double cation metal halide perovskites have recently attracted considerable attention, with continuing research efforts focusing on the improvement of their stability and photoluminescence quantum yield (PL QY). In this study, Ce3+ has been co-doped together with Bi3+ into lead-free double perovskite Cs2AgInCl6 nanocrystals (NCs) in order to improve their crystallinity and PL QY. Both uncoordinated chloride ions and silver vacancies could be eliminated using this co-doping strategy, and the resulting Ce3+,Bi3+-co-doped Cs2AgInCl6 NCs showed adjustable PL emission peaks in the range of 589 to 577 nm by varying the doping amount of Ce3+ with a fixed feeding ratio of bismuth precursor set at 1%. Cs2AgInCl6 NCs doped with 1% Bi alone reached a PL QY of 10% for the PL peak centered at 591 nm, while those co-doped with 1% Bi and 2% Ce together achieved the highest PL QY of 26% for the PL peak centered at 580 nm. The use of Ce3+ as a dopant promoted the localization of self-trapped excitons to prevent PL quenching, although the ion's 5d excited state may potentially provide an energetically favorable indirect route for the radiative relaxation process. This also resulted in a blue shift of the PL maximum and increased the exciton binding energy, thus promoting the radiative recombination of self-trapped excitons.

A Near-Infrared Absorbing and Emissive Quadruple Helicene Enabled by the Scholl Reaction of Perylene.

Herein, we report the synthesis, structural analysis, optical and chiroptical properties of a novel quadruple helicene, which has two [6] and two [7]helicene moieties fused in a contorted framework of 92 sp2 carbon atoms. It was synthesized by the Scholl reaction of a perylene-containing substrate with the formation of eight carbon-carbon bonds on the perylene unit in a single synthetic operation. Chemical oxidation of the quadruple helicene with tris(4-bromophenyl)ammoniumyl hexachloroantimonate resulted in an air-stable dication, which exhibits the same helicity in its four helicene moieties as unambiguously identified by single-crystal X-ray crystallography. The quadruple helicene exhibits unusual near-infrared absorption and emission with absorption and emission maxima at 848 nm and 977 nm, respectively, and its isolated enantiomers exhibit electronic circular dichroism in the near-infrared and visible-light regions.

Room Temperature Fabrication of Stable, Strongly Luminescent Dion-Jacobson Tin Bromide Perovskite Microcrystals Achieved through Use of Primary Alcohols.

Lead-free two-dimensional metal halide perovskites have recently emerged as promising light-emitting materials due to their improved stability and attractive optical properties. Herein, a facile room temperature wet milling method has been developed to make Dion-Jacobson (DJ) phase ODASnBr4 perovskite microcrystals, whose crystallization was accomplished via the aid of introduced primary alcohols: ethanol, butanol, pentanol, and hexanol. Due to the strong intermolecular hydrogen bonding, the use of ethanol promoted the formation of non-doped ODASnBr4 microcrystals, with an emission peaked at 599 nm and a high photoluminescence quantum yield (PL QY) of 81%. By introducing other primary alcohols with weaker intermolecular hydrogen bonding such as butanol, pentanol, and hexanol, [SnBr6]4- octahedral slabs of the DJ perovskite microcrystals experienced various degrees of expansion while forming O-H…Br hydrogen bonds. This resulted in the emission spectra of these alcohol-doped microcrystals to be adjusted in the range from 572 to 601 nm, while keeping the PL QY high, at around 89%. Our synthetic strategy provides a viable pathway towards strongly emitting lead-free DJ perovskite microcrystals with an improved stability.

Continuous Flow Synthesis of Persistent Luminescent Chromium-Doped Zinc Gallate Nanoparticles.

Near-infrared persistent luminescent (or afterglow) nanoparticles with the biologically appropriate size are promising materials for background-free imaging applications, while the conventional batch synthesis hardly allows for reproducibility in controlling particle size because of the random variations of reaction parameters. Here, highly efficient chemistry was matched with an automated continuous flow approach for directly synthesizing differently sized ZnGa2O4:Cr3+ (ZGC) nanoparticles exhibiting long persistent luminescence. The key flow factors responsible for regulating the particle formation process, especially the high pressure-temperature and varied residence time, were investigated to be able to tune the particle size from 2 to 6 nm and to improve the persistent luminescence. Upon silica shell encapsulation of the nanoparticles accompanied by an annealing process, the persistent luminescence of the resulting particles was remarkably enhanced. High-fidelity automated flow chemistry demonstrated here offers an alternative for producing ZGC nanoparticles and will be helpful for other compositionally complex metal oxide nanoparticles.

Carbon Dots Detect Water-to-Ice Phase Transition and Act as Alcohol Sensors via Fluorescence Turn-Off/On Mechanism.

Highly fluorescent carbon nanoparticles called carbon dots (CDs) have been the focus of intense research due to their simple chemical synthesis, nontoxic nature, and broad application potential including optoelectronics, photocatalysis, biomedicine, and energy-related technologies. Although a detailed elucidation of the mechanism of their photoluminescence (PL) remains an unmet challenge, the CDs exhibit robust, reproducible, and environment-sensitive PL signals, enabling us to monitor selected chemical phenomena including phase transitions or detection of ultralow concentrations of molecular species in solution. Herein, we report the PL turn-off/on behavior of aqueous CDs allowing the reversible monitoring of the water-ice phase transition. The bright PL attributable to molecular fluorophores present on the CD surface was quenched by changing the liquid aqueous environment to solid phase (ice). Based on light-induced electron paramagnetic resonance (LEPR) measurements and density functional theory (DFT) calculations, the proposed kinetic model assuming the presence of charge-separated trap states rationalized the observed sensitivity of PL lifetimes to the environment. Importantly, the PL quenching induced by freezing could be suppressed by adding a small amount of alcohols. This was attributed to a high tendency of alcohol to increase its concentration at the CD/solvent interface, as revealed by all-atom molecular dynamics simulations. Based on this behavior, a fluorescence "turn-on" alcohol sensor for exhaled breath condensate (EBC) analysis has been developed. This provided an easy method to detect alcohols among other common interferents in EBC with a low detection limit (100 ppm), which has a potential to become an inexpensive and noninvasive clinically useful diagnostic tool for early stage lung cancer screening.

Smoothing the energy transfer pathway in quasi-2D perovskite films using methanesulfonate leads to highly efficient light-emitting devices.

Quasi-two-dimensional (quasi-2D) Ruddlesden-Popper (RP) perovskites such as BA2Csn-1PbnBr3n+1 (BA = butylammonium, n > 1) are promising emitters, but their electroluminescence performance is limited by a severe non-radiative recombination during the energy transfer process. Here, we make use of methanesulfonate (MeS) that can interact with the spacer BA cations via strong hydrogen bonding interaction to reconstruct the quasi-2D perovskite structure, which increases the energy acceptor-to-donor ratio and enhances the energy transfer in perovskite films, thus improving the light emission efficiency. MeS additives also lower the defect density in RP perovskites, which is due to the elimination of uncoordinated Pb2+ by the electron-rich Lewis base MeS and the weakened adsorbate blocking effect. As a result, green light-emitting diodes fabricated using these quasi-2D RP perovskite films reach current efficiency of 63 cd A-1 and 20.5% external quantum efficiency, which are the best reported performance for devices based on quasi-2D perovskites so far.

Two-Dimensional and Subnanometer-Thin Quasi-Copper-Sulfide Semiconductor Formed upon Copper-Copper Bonding.

Ultrathin two-dimensional (2D) semiconductors exhibit outstanding properties, but it remains challenging to obtain monolayer-structured inorganic semiconductors naturally occurring as nonlayered crystals. Copper sulfides are a class of widely studied nonlayered metal chalcogenide semiconductors. Although 2D copper sulfides can provide extraordinary physical and chemical applications, investigations of 2D copper sulfides in the extreme quantum limit are constrained by the difficulty in preparing monolayered copper sulfides. Here, we report a subnanometer-thin quasi-copper-sulfide (q-CS) semiconductor formed upon self-assembly of copper(I)-dodecanethiol complexes. Extended X-ray absorption fine structure analysis revealed that the existence of Cu-Cu bonding endowed the layer-structured q-CS with semiconductor properties, such as appreciable interband photoluminescence. Theoretical studies on the band structure demonstrated that the optical properties of copper-dodecanethiol assemblies were dominated by the q-CS layer and the photoluminescence originated from exciton radiative recombination across an indirect band gap, borne out by experimental observation at higher temperatures, but with the onset of a direct emission process at cryogenic temperatures. The following studies revealed that the metal-metal bonding occurred not only in copper-alkanethiolate complex assemblies with variable alkyl chain length but also in silver-alkanethiolate and cadmium-alkanethiolate assemblies. Therefore, the current studies may herald a class of 2D semiconductors with extremely thin thickness out of nonlayered metal sulfides to bridge the gap between conventional inorganic semiconductors and organic semiconductors.

Morphology Control of Luminescent Carbon Nanomaterials: From Dots to Rolls and Belts.

In this work, we report a successful extension of the family of light-emitting colloidal carbon nanostructures to a number of different shapes and morphologies, namely, carbon nanorolls (CNRs) and carbon nanobelts (CNBs). Near infrared (NIR)-emissive CNRs were synthesized via a solvothermal fusion of carbon dots (CDs) triggered by a dehydration process of their surface functional groups. They appear in a form of short cylinders, with diameters ranging from 20 to 40 nm and cylinder lengths ranging from 7 to 20 nm. In ethanol solution, CNRs have a maximum absorption peak at 665 nm and a NIR emission band extending from 650 to 800 nm, with a photoluminescence quantum yield of 9.2%. Intriguingly, the rolled structure of CNRs can be uncoiled under 655 nm laser irradiation (power density 1 W·cm-2) of their solution in ethanol, forming CNBs with a width of 7-20 nm and lengths reaching several hundreds of nanometers, which is accompanied by a considerably decreased absorption band at 665 nm and a decreased NIR emission. This unfolding is ascribed to the decrease of the strength of interlayer hydrogen bonding, owing to the photothermally induced dehydration and further carbonization of the CNRs. Alongside the decreased NIR emission, CNBs exhibit enhanced green and red emissions under UV and green light excitation, respectively, which allows us to demonstrate multiple-level luminescence encryptions on a paper stamped with CNR- and CNB-inks.

Phase-Controlled Growth of CuInS2 Shells to Realize Colloidal CuInSe2/CuInS2 Core/Shell Nanostructures.

Synthetic routes to deposit CuInS2 (CIS) shells with either a cubic chalcopyrite (CP) or a hexagonal wurtzite (WZ) phase on trigonal pyramidal-shaped CuInSe2 (CISe) core nanocrystals (NCs) with a cubic CP crystal structure have been developed and governed by tuning the amount of the sulfur precursor tert-dodecanethiol. During the synthesis of CP-CIS/CP-CISe core/shell NCs, the CP-CIS shell initially starts to grow epitaxially in a uniform way, while the further addition of the CIS precursor induces islandlike growth, and finally a branched CIS shell is formed. In a stark contrast, when a WZ-CIS shell is deposited, it initially grows on a portion of each of the facets of the trigonal pyramidal-shaped CISe cores to form a monolayer, which then continues to increase in thickness and forms a multilayered WZ-CIS shell. Both CP-CISe/CP-CIS core/shell NCs and CP-CISe/WZ-CISe core/shell NCs exhibit rather low photoluminescence quantum yields (<10%), even with a smaller-sized CISe core, which calls for further refinements of the shell growth methods. Synthetic methods for the growth of CIS shells as described here allow for direct deposition of cadmium-free ternary compounds as shell materials and provide important insights into the different modes of growth of heterostructured NCs, ranging from epitaxial to island- and branched-like, as well to the facet-specific multilayer deposition.