Electrically driven amplified spontaneous emission from colloidal quantum dots.

Colloidal quantum dots (QDs) are attractive materials for realizing solution-processable laser diodes that could benefit from size-controlled emission wavelengths, low optical-gain thresholds and ease of integration with photonic and electronic circuits1-7. However, the implementation of such devices has been hampered by fast Auger recombination of gain-active multicarrier states1,8, poor stability of QD films at high current densities9,10 and the difficulty to obtain net optical gain in a complex device stack wherein a thin electroluminescent QD layer is combined with optically lossy charge-conducting layers11-13. Here we resolve these challenges and achieve amplified spontaneous emission (ASE) from electrically pumped colloidal QDs. The developed devices use compact, continuously graded QDs with suppressed Auger recombination incorporated into a pulsed, high-current-density charge-injection structure supplemented by a low-loss photonic waveguide. These colloidal QD ASE diodes exhibit strong, broadband optical gain and demonstrate bright edge emission with instantaneous power of up to 170 µW.

Colloidal Semiconductor Nanocrystal Lasers and Laser Diodes.

Lasers and optical amplifiers based on solution-processable materials have been long-desired devices for their compatibility with virtually any substrate, scalability, and ease of integration with on-chip photonics and electronics. These devices have been pursued across a wide range of materials including polymers, small molecules, perovskites, and chemically prepared colloidal semiconductor nanocrystals, also commonly referred to as colloidal quantum dots. The latter materials are especially attractive for implementing optical-gain media as in addition to being compatible with inexpensive and easily scalable chemical techniques, they offer multiple advantages derived from a zero-dimensional character of their electronic states. These include a size-tunable emission wavelength, low optical gain thresholds, and weak sensitivity of lasing characteristics to variations in temperature. Here we review the status of colloidal nanocrystal lasing devices, most recent advances in this field, outstanding challenges, and the ongoing progress toward technological viable devices including colloidal quantum dot laser diodes.

Spin-exchange carrier multiplication in manganese-doped colloidal quantum dots.

Carrier multiplication is a process whereby a kinetic energy of a carrier relaxes via generation of additional electron-hole pairs (excitons). This effect has been extensively studied in the context of advanced photoconversion as it could boost the yield of generated excitons. Carrier multiplication is driven by carrier-carrier interactions that lead to excitation of a valence-band electron to the conduction band. Normally, the rate of phonon-assisted relaxation exceeds that of Coulombic collisions, which limits the carrier multiplication yield. Here we show that this limitation can be overcome by exploiting not 'direct' but 'spin-exchange' Coulomb interactions in manganese-doped core/shell PbSe/CdSe quantum dots. In these structures, carrier multiplication occurs via two spin-exchange steps. First, an exciton generated in the CdSe shell is rapidly transferred to a Mn dopant. Then, the excited Mn ion undergoes spin-flip relaxation via a spin-conserving pathway, which creates two excitons in the PbSe core. Due to the extremely fast, subpicosecond timescales of spin-exchange interactions, the Mn-doped quantum dots exhibit an up-to-threefold enhancement of the multiexciton yield versus the undoped samples, which points towards the considerable potential of spin-exchange carrier multiplication in advanced photoconversion.

Continuous-wave lasing in colloidal quantum dot solids enabled by facet-selective epitaxy.

Colloidal quantum dots (CQDs) feature a low degeneracy of electronic states at the band edges compared with the corresponding bulk material, as well as a narrow emission linewidth. Unfortunately for potential laser applications, this degeneracy is incompletely lifted in the valence band, spreading the hole population among several states at room temperature. This leads to increased optical gain thresholds, demanding high photoexcitation levels to achieve population inversion (more electrons in excited states than in ground states-the condition for optical gain). This, in turn, increases Auger recombination losses, limiting the gain lifetime to sub-nanoseconds and preventing steady laser action. State degeneracy also broadens the photoluminescence linewidth at the single-particle level. Here we demonstrate a way to decrease the band-edge degeneracy and single-dot photoluminescence linewidth in CQDs by means of uniform biaxial strain. We have developed a synthetic strategy that we term facet-selective epitaxy: we first switch off, and then switch on, shell growth on the (0001) facet of wurtzite CdSe cores, producing asymmetric compressive shells that create built-in biaxial strain, while still maintaining excellent surface passivation (preventing defect formation, which otherwise would cause non-radiative recombination losses). Our synthesis spreads the excitonic fine structure uniformly and sufficiently broadly that it prevents valence-band-edge states from being thermally depopulated. We thereby reduce the optical gain threshold and demonstrate continuous-wave lasing from CQD solids, expanding the library of solution-processed materials that may be capable of continuous-wave lasing. The individual CQDs exhibit an ultra-narrow single-dot linewidth, and we successfully propagate this into the ensemble of CQDs.

Exploiting Functional Impurities for Fast and Efficient Incorporation of Manganese into Quantum Dots.

The incorporation of manganese (Mn) ions into Cd(Zn)-chalcogenide QDs activates strong spin-exchange interactions between the magnetic ions and intrinsic QD excitons that have been exploited for color conversion, sunlight harvesting, electron photoemission, and advanced imaging and sensing. The ability to take full advantage of novel functionalities enabled by Mn dopants requires accurate control of doping levels over a wide range of Mn contents. This, however, still represents a considerable challenge. Specific problems include the difficulty in obtaining high Mn contents, considerable broadening of QD size dispersion during the doping procedure, and large batch-to-batch variations in the amount of incorporated Mn. Here, we show that these problems originate from the presence of unreacted cadmium (Cd) complexes whose abundance is linked to uncontrolled impurities participating in the QD synthesis. After identifying these impurities as secondary phosphines, we modify the synthesis by introducing controlled amounts of "functional" secondary phosphine species. This allows us to realize a regime of nearly ideal QD doping when incorporation of magnetic ions occurs solely via addition of Mn-Se units without uncontrolled deposition of Cd-Se species. Using this method, we achieve very high per-dot Mn contents (>30% of all cations) and thereby realize exceptionally strong exciton-Mn exchange coupling with g-factors of ∼600.

Asymmetrically strained quantum dots with non-fluctuating single-dot emission spectra and subthermal room-temperature linewidths.

The application of colloidal semiconductor quantum dots as single-dot light sources still requires several challenges to be overcome. Recently, there has been considerable progress in suppressing intensity fluctuations (blinking) by encapsulating an emitting core in a thick protective shell. However, these nanostructures still show considerable fluctuations in both emission energy and linewidth. Here we demonstrate type-I core/shell heterostructures that overcome these deficiencies. They are made by combining wurtzite semiconductors with a large, directionally anisotropic lattice mismatch, which results in strong asymmetric compression of the emitting core. This modifies the structure of band-edge excitonic states and leads to accelerated radiative decay, reduced exciton-phonon interactions, and suppressed coupling to the fluctuating electrostatic environment. As a result, individual asymmetrically strained dots exhibit highly stable emission energy (<1 meV standard deviation) and a subthermal room-temperature linewidth (~20 meV), concurrent with nearly nonblinking behaviour, high emission quantum yields, and a widely tunable emission colour.

Dual-Emitting Dot-in-Bulk CdSe/CdS Nanocrystals with Highly Emissive Core- and Shell-Based Trions Sharing the Same Resident Electron.

Colloidal CdSe nanocrystals (NCs) overcoated with an ultrathick CdS shell, also known as dot-in-bulk (DiB) structures, can support two types of excitons, one of which is core-localized and the other, shell-localized. In the case of weak "sub-single-exciton" pumping, emission alternates between the core- and shell-related channels, which leads to two-color light. This property makes these structures uniquely suited for a variety of photonic applications as well as ideal model systems for realizing complex excitonic quasi-particles that do not occur in conventional core/shell NCs. Here, we show that the DiB design can enable an unusual regime in which the same long-lived resident electron can endow trionlike characteristics to either of the two excitons of the DiB NC (core- or shell-based). These two spectrally distinct trion states are apparent in the measured photoluminescence (PL) and spin dynamics of core and shell excitons conducted over a wide range of temperatures and applied magnetic fields. Low-temperature PL measurements indicate that core- and shell-based trions are characterized by a nearly ideal (∼100%) emission quantum yield, suggesting the strong suppression of Auger recombination for both types of excitations. Polarization-resolved PL experiments in magnetic fields of up to 60 T reveal that the core- and the shell-localized trions exhibit remarkably similar spin dynamics, which in both cases are controlled by spin-flip processes involving a heavy hole.

Optical gain in colloidal quantum dots achieved with direct-current electrical pumping.

Chemically synthesized semiconductor quantum dots (QDs) can potentially enable solution-processable laser diodes with a wide range of operational wavelengths, yet demonstrations of lasing from the QDs are still at the laboratory stage. An important challenge-realization of lasing with electrical injection-remains unresolved, largely due to fast nonradiative Auger recombination of multicarrier states that represent gain-active species in the QDs. Here we present population inversion and optical gain in colloidal nanocrystals realized with direct-current electrical pumping. Using continuously graded QDs, we achieve a considerable suppression of Auger decay such that it can be outpaced by electrical injection. Further, we apply a special current-focusing device architecture, which allows us to produce high current densities (j) up to ∼18 A cm-2 without damaging either the QDs or the injection layers. The quantitative analysis of electroluminescence and current-modulated transmission spectra indicates that with j = 3-4 A cm-2 we achieve the population inversion of the band-edge states.

Droop-Free Colloidal Quantum Dot Light-Emitting Diodes.

Colloidal semiconductor quantum dots (QDs) are a highly promising materials platform for implementing solution-processable light-emitting diodes (LEDs). They combine high photostability of traditional inorganic semiconductors with chemical flexibility of molecular systems, which makes them well-suited for large-area applications such as television screens, solid-state lighting, and outdoor signage. Additional beneficial features include size-controlled emission wavelengths, narrow bandwidths, and nearly perfect emission efficiencies. State-of-the-art QD-LEDs exhibit high internal quantum efficiencies approaching unity. However, these peak values are observed only at low current densities ( J) and correspondingly low brightnesses, whereas at higher J, the efficiency usually exhibits a quick roll-off. This efficiency droop limits achievable brightness levels and decreases device longevity due to excessive heat generation. Here, we demonstrate QD-LEDs operating with high internal efficiencies (up to 70%) virtually droop-free up to unprecedented brightness of >100,000 cd m-2 (at ∼500 mA cm-2). This exceptional performance is derived from specially engineered QDs that feature a compositionally graded interlayer and a final barrier layer. This QD design allows for improved balance between electron and hole injections combined with considerably suppressed Auger recombination, which helps mitigate efficiency losses due to charge imbalance at high currents. These results indicate a significant potential of newly developed QDs as enablers of future ultrabright, highly efficient devices for both indoor and outdoor applications.

Performance Limits of Luminescent Solar Concentrators Tested with Seed/Quantum-Well Quantum Dots in a Selective-Reflector-Based Optical Cavity.

Luminescent solar concentrators (LSCs) can serve as large-area sunlight collectors for photovoltaic devices. An important LSC characteristic is a concentration factor (C), which is defined as the ratio of the output and the input photon flux densities. This parameter can be also thought of as an effective enlargement factor of a solar cell active area. On the basis of thermodynamic considerations, the C-factor can reach extremely high values that exceed those accessible with traditional concentrating optics. In reality, however, the best reported values of C are around 30. Here we demonstrate that using a new type of high-emissivity quantum dots (QDs) incorporated into a specially designed cavity, we are able to achieve the C of ∼62 for spectrally integrated emission and ∼120 for the red portion of the photoluminescence spectrum. The key feature of these QDs is a seed/quantum-well/thick-shell design, which allows for obtaining a high emission quantum yield (>95%) simultaneously with a large LSC quality factor (QLSC of ∼100) defined as the ratio of absorption coefficients at the wavelengths of incident and reemitted light. By incorporating the QDs into a specially designed cavity equipped with a top selective reflector (a Bragg mirror or a thin silver film), we are able to effectively recycle reemitted light achieving light trapping coefficients of ∼85%. The observed performance of these devices is in remarkable agreement with analytical modeling, which allows us to project that the applied approach should allow one to boost the spectrally integrated concentration factors to more than 100 by further improving light trapping and/or increasing QLSC.

Spectroscopic and Device Aspects of Nanocrystal Quantum Dots.

The field of nanocrystal quantum dots (QDs) is already more than 30 years old, and yet continuing interest in these structures is driven by both the fascinating physics emerging from strong quantum confinement of electronic excitations, as well as a large number of prospective applications that could benefit from the tunable properties and amenability toward solution-based processing of these materials. The focus of this review is on recent advances in nanocrystal research related to applications of QD materials in lasing, light-emitting diodes (LEDs), and solar energy conversion. A specific underlying theme is innovative concepts for tuning the properties of QDs beyond what is possible via traditional size manipulation, particularly through heterostructuring. Examples of such advanced control of nanocrystal functionalities include the following: interface engineering for suppressing Auger recombination in the context of QD LEDs and lasers; Stokes-shift engineering for applications in large-area luminescent solar concentrators; and control of intraband relaxation for enhanced carrier multiplication in advanced QD photovoltaics. We examine the considerable recent progress on these multiple fronts of nanocrystal research, which has resulted in the first commercialized QD technologies. These successes explain the continuing appeal of this field to a broad community of scientists and engineers, which in turn ensures even more exciting results to come from future exploration of this fascinating class of materials.

Effect of Interfacial Alloying versus "Volume Scaling" on Auger Recombination in Compositionally Graded Semiconductor Quantum Dots.

Auger recombination is a nonradiative three-particle process wherein the electron-hole recombination energy dissipates as a kinetic energy of a third carrier. Auger decay is enhanced in quantum-dot (QD) forms of semiconductor materials compared to their bulk counterparts. Because this process is detrimental to many prospective applications of the QDs, the development of effective approaches for suppressing Auger recombination has been an important goal in the QD field. One such approach involves "smoothing" of the confinement potential, which suppresses the intraband transition involved in the dissipation of the electron-hole recombination energy. The present study evaluates the effect of increasing "smoothness" of the confinement potential on Auger decay employing a series of CdSe/CdS-based QDs wherein the core and the shell are separated by an intermediate layer of a CdSexS1-x alloy comprised of 1-5 sublayers with a radially tuned composition. As inferred from single-dot measurements, use of the five-step grading scheme allows for strong suppression of Auger decay for both biexcitons and charged excitons. Further, due to nearly identical emissivities of neutral and charged excitons, these QDs exhibit an interesting phenomenon of lifetime blinking for which random fluctuations of a photoluminescence lifetime occur for a nearly constant emission intensity.

Thick-Shell CuInS2/ZnS Quantum Dots with Suppressed "Blinking" and Narrow Single-Particle Emission Line Widths.

Quantum dots (QDs) of ternary I-III-VI2 compounds such as CuInS2 and CuInSe2 have been actively investigated as heavy-metal-free alternatives to cadmium- and lead-containing semiconductor nanomaterials. One serious limitation of these nanostructures, however, is a large photoluminescence (PL) line width (typically >300 meV), the origin of which is still not fully understood. It remains even unclear whether the observed broadening results from considerable sample heterogeneities (due, e.g., to size polydispersity) or is an unavoidable intrinsic property of individual QDs. Here, we answer this question by conducting single-particle measurements on a new type of CuInS2 (CIS) QDs with an especially thick ZnS shell. These QDs show a greatly enhanced photostability compared to core-only or thin-shell samples and, importantly, exhibit a strongly suppressed PL blinking at the single-dot level. Spectrally resolved measurements reveal that the single-dot, room-temperature PL line width is much narrower (down to ∼60 meV) than that of the ensemble samples. To explain this distinction, we invoke a model wherein PL from CIS QDs arises from radiative recombination of a delocalized band-edge electron and a localized hole residing on a Cu-related defect and also account for the effects of electron-hole Coulomb coupling. We show that random positioning of the emitting center in the QD can lead to more than 300 meV variation in the PL energy, which represents at least one of the reasons for large PL broadening of the ensemble samples. These results suggest that in addition to narrowing size dispersion, future efforts on tightening the emission spectra of these QDs might also attempt decreasing the "positional" heterogeneity of the emitting centers.

Spectro-electrochemical Probing of Intrinsic and Extrinsic Processes in Exciton Recombination in I-III-VI2 Nanocrystals.

Ternary CuInS2 nanocrystals (CIS NCs) are attracting attention as nontoxic alternatives to heavy metal-based chalcogenides for many technologically relevant applications. The photophysical processes underlying their emission mechanism are, however, still under debate. Here we address this problem by applying, for the first time, spectro-electrochemical methods to core-only CIS and core/shell CIS/ZnS NCs. The application of an electrochemical potential enables us to reversibly tune the NC Fermi energy and thereby control the occupancy of intragap defects involved in exciton decay. The results indicate that, in analogy to copper-doped II-VI NCs, emission occurs via radiative capture of a conduction-band electron by a hole localized on an intragap state likely associated with a Cu-related defect. We observe the increase in the emission efficiency under reductive electrochemical potential, which corresponds to raising the Fermi level, leading to progressive filling of intragap states with electrons. This indicates that the factor limiting the emission efficiency in these NCs is nonradiative electron trapping, while hole trapping is of lesser importance. This observation also suggests that the centers for radiative recombination are Cu2+ defects (preexisting and/or accumulated as a result of photoconversion of Cu1+ ions) as these species contain a pre-existing hole without the need for capturing a valence-band hole generated by photoexcitation. Temperature-controlled photoluminescence experiments indicate that the intrinsic limit on the emission efficiency is imposed by multiphonon nonradiative recombination of a band-edge electron and a localized hole. This process affects both shelled and unshelled CIS NCs to a similar degree, and it can be suppressed by cooling samples to below 100 K. Finally, using experimentally measured decay rates, we formulate a model that describes the electrochemical modulation of the PL efficiency in terms of the availability of intragap electron traps as well as direct injection of electrons into the NC conduction band, which activates nonradiative Auger recombination, or electrochemical conversion of the Cu2+ states into the Cu1+ species that are less emissive due to the need for their "activation" by the capture of photogenerated holes.

Single-Particle Ratiometric Pressure Sensing Based on "Double-Sensor" Colloidal Nanocrystals.

Ratiometric pressure sensitive paints (r-PSPs) are all-optical probes for monitoring oxygen flows in the vicinity of complex or miniaturized surfaces. They typically consist of a porous binder embedding mixtures of a reference and a sensor chromophore exhibiting oxygen-insensitive and oxygen-responsive luminescence, respectively. Here, we demonstrate the first example of an r-PSP based on a single two-color emitter that removes limitations of r-PSPs based on chromophore mixtures such as different temperature dependencies of the two chromophores, cross-readout between the reference and sensor signals and phase segregation. In our approach, we utilize a novel "double-sensor" r-PSP that features two spectrally separated emission bands with opposite responses to the O2 pressure, which boosts the sensitivity with respect to traditional reference-sensor pairs. Specifically, we use two-color-emitting dot-in-bulk CdSe/CdS core/shell nanocrystals, exhibiting red and green emission bands from their core and shell states, whose intensities are respectively enhanced and quenched in response to the increased oxygen partial pressure that effectively tunes the position of the nanocrystal's Fermi energy. This leads to a strong and reversible ratiometric response at the single particle level and an over 100% enhancement in the pressure sensitivity. Our proof-of-concept r-PSPs further exhibit suppressed cross-readout thanks to zero spectral overlap between the core and shell luminescence bands and a temperature-independent ratiometric response between 0 and 70 °C.

Thickness-Controlled Quasi-Two-Dimensional Colloidal PbSe Nanoplatelets.

We demonstrate controlled synthesis of discrete two-dimensional (2D) PbSe nanoplatelets (NPLs), with measurable photoluminescence, via oriented attachment directed by quantum dot (QD) surface chemistry. Halide passivation is critical to the growth of these (100) face-dominated NPLs, as corroborated by density functional theory studies. PbCl2 moieties attached to the (111) and (110) of small nanocrystals form interparticle bridges, aligning the QDs and leading to attachment. We find that a 2D bridging network is energetically favored over a 3D network, driving the formation of NPLs. Although PbI2 does not support bridging, its presence destabilizes the large (100) faces of NPLs, providing means for tuning NPL thickness. Spectroscopic analysis confirms the predicted role of thickness-dependent quantum confinement on the NPL band gap.

Phase-Transfer Ligand Exchange of Lead Chalcogenide Quantum Dots for Direct Deposition of Thick, Highly Conductive Films.

The use of semiconductor nanocrystal quantum dots (QDs) in optoelectronic devices typically requires postsynthetic chemical surface treatments to enhance electronic coupling between QDs and allow for efficient charge transport in QD films. Despite their importance in solar cells and infrared (IR) light-emitting diodes and photodetectors, advances in these chemical treatments for lead chalcogenide (PbE; E = S, Se, Te) QDs have lagged behind those of, for instance, II-VI semiconductor QDs. Here, we introduce a method for fast and effective ligand exchange for PbE QDs in solution, resulting in QDs completely passivated by a wide range of small anionic ligands. Due to electrostatic stabilization, these QDs are readily dispersible in polar solvents, in which they form highly concentrated solutions that remain stable for months. QDs of all three Pb chalcogenides retain their photoluminescence, allowing for a detailed study of the effect of the surface ionic double layer on electronic passivation of QD surfaces, which we find can be explained using the hard/soft acid-base theory. Importantly, we prepare highly conductive films of PbS, PbSe, and PbTe QDs by directly casting from solution without further chemical treatment, as determined by field-effect transistor measurements. This method allows for precise control over the surface chemistry, and therefore the transport properties of deposited films. It also permits single-step deposition of films of unprecedented thickness via continuous processing techniques, as we demonstrate by preparing a dense, smooth, 5.3-µm-thick PbSe QD film via doctor-blading. As such, it offers important advantages over laborious layer-by-layer methods for solar cells and photodetectors, while opening the door to new possibilities in ionizing-radiation detectors.

Two types of luminescence blinking revealed by spectroelectrochemistry of single quantum dots.

Photoluminescence blinking--random switching between states of high (ON) and low (OFF) emissivities--is a universal property of molecular emitters found in dyes, polymers, biological molecules and artificial nanostructures such as nanocrystal quantum dots, carbon nanotubes and nanowires. For the past 15 years, colloidal nanocrystals have been used as a model system to study this phenomenon. The occurrence of OFF periods in nanocrystal emission has been commonly attributed to the presence of an additional charge, which leads to photoluminescence quenching by non-radiative recombination (the Auger mechanism). However, this 'charging' model was recently challenged in several reports. Here we report time-resolved photoluminescence studies of individual nanocrystal quantum dots performed while electrochemically controlling the degree of their charging, with the goal of clarifying the role of charging in blinking. We find that two distinct types of blinking are possible: conventional (A-type) blinking due to charging and discharging of the nanocrystal core, in which lower photoluminescence intensities correlate with shorter photoluminescence lifetimes; and a second sort (B-type), in which large changes in the emission intensity are not accompanied by significant changes in emission dynamics. We attribute B-type blinking to charge fluctuations in the electron-accepting surface sites. When unoccupied, these sites intercept 'hot' electrons before they relax into emitting core states. Both blinking mechanisms can be electrochemically controlled and completely suppressed by application of an appropriate potential.

Spectral and Dynamical Properties of Single Excitons, Biexcitons, and Trions in Cesium-Lead-Halide Perovskite Quantum Dots.

Organic-inorganic lead-halide perovskites have been the subject of recent intense interest due to their unusually strong photovoltaic performance. A new addition to the perovskite family is all-inorganic Cs-Pb-halide perovskite nanocrystals, or quantum dots, fabricated via a moderate-temperature colloidal synthesis. While being only recently introduced to the research community, these nanomaterials have already shown promise for a range of applications from color-converting phosphors and light-emitting diodes to lasers, and even room-temperature single-photon sources. Knowledge of the optical properties of perovskite quantum dots still remains vastly incomplete. Here we apply various time-resolved spectroscopic techniques to conduct a comprehensive study of spectral and dynamical characteristics of single- and multiexciton states in CsPbX3 nanocrystals with X being either Br, I, or their mixture. Specifically, we measure exciton radiative lifetimes, absorption cross-sections, and derive the degeneracies of the band-edge electron and hole states. We also characterize the rates of intraband cooling and nonradiative Auger recombination and evaluate the strength of exciton-exciton coupling. The overall conclusion of this work is that spectroscopic properties of Cs-Pb-halide quantum dots are largely similar to those of quantum dots of more traditional semiconductors such as CdSe and PbSe. At the same time, we observe some distinctions including, for example, an appreciable effect of the halide identity on radiative lifetimes, considerably shorter biexciton Auger lifetimes, and apparent deviation of their size dependence from the "universal volume scaling" previously observed for many traditional nanocrystal systems. The high efficiency of Auger decay in perovskite quantum dots is detrimental to their prospective applications in light-emitting devices and lasers. This points toward the need for the development of approaches for effective suppression of Auger recombination in these nanomaterials, using perhaps insights gained from previous studies of II-VI nanocrystals.

Mn2+-Doped Lead Halide Perovskite Nanocrystals with Dual-Color Emission Controlled by Halide Content.

Impurity doping has been widely used to endow semiconductor nanocrystals with novel optical, electronic, and magnetic functionalities. Here, we introduce a new family of doped NCs offering unique insights into the chemical mechanism of doping, as well as into the fundamental interactions between the dopant and the semiconductor host. Specifically, by elucidating the role of relative bond strengths within the precursor and the host lattice, we develop an effective approach for incorporating manganese (Mn) ions into nanocrystals of lead-halide perovskites (CsPbX3, where X = Cl, Br, or I). In a key enabling step not possible in, for example, II-VI nanocrystals, we use gentle chemical means to finely and reversibly tune the nanocrystal band gap over a wide range of energies (1.8-3.1 eV) via postsynthetic anion exchange. We observe a dramatic effect of halide identity on relative intensities of intrinsic band-edge and Mn emission bands, which we ascribe to the influence of the energy difference between the corresponding transitions on the characteristics of energy transfer between the Mn ion and the semiconductor host.