Using steric hindrance to manipulate and stabilize metal halide perovskites for optoelectronics

The chemical instability of metal halide perovskite materials can be ascribed to their unique properties of softness, in which the chemical bonding between metal halide octahedral frameworks and cations is the weak ionic and hydrogen bonding as in most perovskite structures. Therefore, various strategies have been developed to stabilize the cations and metal halide frameworks, which include incorporating additives, developing two-dimensional perovskites and perovskite nanocrystals, etc. Recently, the important role of utilizing steric hindrance for stabilizing and passivating perovskites has been demonstrated. In this perspective, we summarize the applications of steric hindrance in manipulating and stabilizing perovskites. We will also discuss how steric hindrance influences the fundamental kinetics of perovskite crystallization and film formation processes. The similarities and differences of the steric hindrance between perovskite solar cells and perovskite light emission diodes are also discussed. In all, utilizing steric hindrance is a promising strategy to manipulate and stabilize metal halide perovskites for optoelectronics.

Manipulation on steric hindrance can influence the fundamental kinetics of perovskite crystallization and film formation, therefore stabilizing and passivating perovskite structures, and promoting the commercialization of stable perovskite devices.     

Low-Dimensional Phase Regulation to Restrain Non-Radiative Recombination for Sky-Blue Perovskite LEDs with EQE Exceeding 15 %

Achieving efficient blue electroluminescence (EL) remains the fundamental challenge that impedes perovskite light-emitting diodes (PeLEDs) towards commercial applications. The bottleneck accounting for the inefficient blue PeLEDs is broadly attributed to the poor-emissive blue perovskite emitters based on either mixed halide engineering or reduced-dimensional strategy. Herein, we report the high-performing sky-blue PeLEDs (490 nm) with the maximum EQE exceeding 15 % by incorporating a molecular modifier, namely 4,4′-Difluorophenone, for significantly suppressing the non-radiative recombination and tuning of the low-dimensional phase distribution of quasi-2D blue perovskites, which represents a remarkable paradigm for developing the new generation of blue lighting sources.     

Manipulating Local Lattice Distortion for Spectrally Stable and Efficient Mixed-halide Blue Perovskite LEDs

Mixed-halide perovskites are considered the most straightforward candidate to realize blue perovskite light-emitting diodes (PeLEDs). However, they suffer severe halide migration, leading to spectral instability, which is particularly exaggerated in high chloride alloying perovskites. Here, we demonstrate energy barrier of halide migration can be tuned by manipulating the degree of local lattice distortion (LLD). Enlarging the LLD degree to a suitable level can increase the halide migration energy barrier. We herein report an “A-site” cation engineering to tune the LLD degree to an optimal level. DFT simulation and experimental data confirm that LLD manipulation suppresses the halide migration in perovskites. Conclusively, mixed-halide blue PeLEDs with a champion EQE of 14.2 % at 475 nm have been achieved. Moreover, the devices exhibit excellent operational spectral stability (T₅₀ of 72 min), representing one of the most efficient and stable pure-blue PeLEDs reported yet.     

Self-trapped exciton emission and piezochromism in conventional 3D lead bromide perovskite nanocrystals under high pressure

Developing single-component materials with bright-white emission is required for energy-saving applications. Self-trapped exciton (STE) emission is regarded as a robust way to generate intrinsic white light in halide perovskites. However, STE emission usually occurs in low-dimensional perovskites whereby a lower level of structural connectivity reduces the conductivity. Enabling conventional three-dimensional (3D) perovskites to produce STEs to elicit competitive white emission is challenging. Here, we first achieved STEs-related emission of white light with outstanding chromaticity coordinates of (0.330, 0.325) in typical 3D perovskites, Mn-doped CsPbBr₃ nanocrystals (NCs), through pressure processing. Remarkable piezochromism from red to blue was also realized in compressed Mn-doped CsPbBr₃ NCs. Doping engineering by size-mismatched Mn dopants could give rise to the formation of localized carriers. Hence, high pressure could further induce octahedra distortion to accommodate the STEs, which has never occurred in pure 3D perovskites. Our study not only offers deep insights into the photophysical nature of perovskites, it also provides a promising strategy towards high-quality, stable white-light emission.

We first achieved self-trapped exciton emission with outstanding white-light chromaticity coordinates of (0.330, 0.325) in conventional 3D halide perovskite nanocrystals through pressure engineering.     

Suppressing thermal quenching of lead halide perovskite nanocrystals by constructing a wide-bandgap surface layer for achieving thermally stable white light-emitting diodes

Lead halide perovskite nanocrystals as promising ultrapure emitters are outstanding candidates for next-generation light-emitting diodes (LEDs) and display applications, but the thermal quenching behavior of light emission has severely hampered their real-world applications. Here, we report an anion passivation strategy to suppress the emission thermal quenching behavior of CsPbBr₃ perovskite nanocrystals. By treating with specific anions (such as SO₄²⁻, OH⁻, and F⁻ ions), the corresponding wide-bandgap passivation layers, PbSO₄, Pb(OH)₂, and PbF₂, were obtained. They not only repair the surface defects of CsPbBr₃ nanocrystals but also stabilize the phase structure of the inner CsPbBr₃ core by constructing a core–shell like structure. The photoluminescence thermal resistance experiments show that the treated sample could preserve 79% of its original emission intensity up to 373 K, far superior to that (17%) of pristine CsPbBr₃. Based on the thermally stable CsPbBr₃ nanocrystals, we achieved temperature-stable white LED devices with a stable electroluminescence spectrum, color gamut and color coordinates in thermal stress tests (up to 373 K).

Highly thermotolerant CsPbBr₃ perovskite nanocrystals with anti-thermal quenching performance were obtained by constructing wide-bandgap passivation layers coated strongly on the perovskite surface.     

Mixed lead–tin perovskite films with >7 μs charge carrier lifetimes realized by maltol post-treatment

Mixed lead–tin (Pb–Sn) halide perovskites with optimum band gaps near 1.3 eV are promising candidates for next-generation solar cells. However, the performance of solar cells fabricated with Pb–Sn perovskites is restricted by the facile oxidation of Sn(ii) to Sn(iv), which induces self-doping. Maltol, a naturally occurring flavor enhancer and strong metal binding agent, was found to effectively suppress Sn(iv) formation and passivate defects in mixed Pb–Sn perovskite films. When used in combination with Sn(iv) scavenging, the maltol surface treatment led to high-quality perovskite films which showed enhanced photoluminescence intensities and charge carrier lifetimes in excess of 7 μs. The scavenging and surface treatments resulted in highly reproducible solar cell devices, with photoconversion efficiencies of up to 21.4% under AM1.5G illumination.

Maltol, a metal binding agent, effectively passivates defects on the surface of mixed lead–tin perovskite films. The carrier lifetimes of the resultant perovskite films are over 7 μs. The solar cell devices exhibit efficiencies of up to 21.4%.     

Alloying a single and a double perovskite: a Cu+/2+ mixed-valence layered halide perovskite with strong optical absorption

Introducing heterovalent cations at the octahedral sites of halide perovskites can substantially change their optoelectronic properties. Yet, in most cases, only small amounts of such metals can be incorporated as impurities into the three-dimensional lattice. Here, we exploit the greater structural flexibility of the two-dimensional (2D) perovskite framework to place three distinct stoichiometric cations in the octahedral sites. The new layered perovskites A^I₄[Cu^II(Cu^IIn^III)_0.5Cl₈] (1, A = organic cation) may be derived from a Cu^I–In^III double perovskite by replacing half of the octahedral metal sites with Cu²⁺. Electron paramagnetic resonance and X-ray absorption spectroscopy confirm the presence of Cu²⁺ in 1. Crystallographic studies demonstrate that 1 represents an averaging of the Cu^I–In^III double perovskite and Cu^II single perovskite structures. However, whereas the highly insulating Cu^I–In^III and Cu^II perovskites are colorless and yellow, respectively, 1 is black, with substantially higher electronic conductivity than that of either endmember. We trace these emergent properties in 1 to intervalence charge transfer between the mixed-valence Cu centers. We further propose a tiling model to describe how the Cu⁺, Cu²⁺, and In³⁺ coordination spheres can pack most favorably into a 2D perovskite lattice, which explains the unusual 1 : 2 : 1 ratio of these cations found in 1. Magnetic susceptibility data of 1 further corroborate this packing model. The emergence of enhanced visible light absorption and electronic conductivity in 1 demonstrates the importance of devising strategies for increasing the compositional complexity of halide perovskites.

A novel 2D halide perovskite with stoichiometric quantities of Cu⁺, Cu²⁺, and In³⁺ in the inorganic slabs shows emergent properties not seen in Cu^II or Cu^I–In^III perovskites, including enhanced visible-light absorption and electronic conductivity.     

The atomic-level structure of bandgap engineered double perovskite alloys Cs2AgIn1−xFexCl6

Although lead-free halide double perovskites are considered as promising alternatives to lead halide perovskites for optoelectronic applications, state-of-the-art double perovskites are limited by their large bandgap. The doping/alloying strategy, key to bandgap engineering in traditional semiconductors, has also been employed to tune the bandgap of halide double perovskites. However, this strategy has yet to generate new double perovskites with suitable bandgaps for practical applications, partially due to the lack of fundamental understanding of how the doping/alloying affects the atomic-level structure. Here, we take the benchmark double perovskite Cs₂AgInCl₆ as an example to reveal the atomic-level structure of double perovskite alloys (DPAs) Cs₂AgIn_1−xFe_xCl₆ (x = 0–1) by employing solid-state nuclear magnetic resonance (ssNMR). The presence of paramagnetic alloying ions (e.g. Fe³⁺ in this case) in double perovskites makes it possible to investigate the nuclear relaxation times, providing a straightforward approach to understand the distribution of paramagnetic alloying ions. Our results indicate that paramagnetic Fe³⁺ replaces diamagnetic In³⁺ in the Cs₂AgInCl₆ lattice with the formation of [FeCl₆]³⁻·[AgCl₆]⁵⁻ domains, which show different sizes and distribution modes in different alloying ratios. This work provides new insights into the atomic-level structure of bandgap engineered DPAs, which is of critical significance in developing efficient optoelectronic/spintronic devices.

Through Fe³⁺-alloying, the bandgap of benchmark double perovskite Cs₂AgInCl₆ can be tuned from 2.8 eV to 1.6 eV. The atomic-level structure of Cs₂AgIn_1−xFe_xCl₆ was revealed by solid-state nuclear magnetic resonance (ssNMR).     

Improved Performance of All-Inorganic Perovskite Light-emitting Diodes via Nanostructured Stamp Imprinting

Halide perovskites are emerging emitters with excellent optoelectronic properties. Contrary to the large grain fabrication goal in perovskite solar cells, perovskite light-emitting diodes (PeLEDs) based on small grain enable efficient radiative recombination because of relatively higher charge carrier densities due to spatial confinement. However, achieving small-sized grain growth with superior crystal quality and film morphology remains a challenge. In this work, we demonstrated a nanostructured stamp thermal imprinting strategy to boost the surface coverage and improve the crystalline quality of CsPbBr₃ film, particularly confine the grain size, leading to the improvement of luminance and efficiency of PeLEDs. We improved the thermal imprinting process utilizing the nanostructured stamp to selectively manipulate the nucleation and growth in the nanoscale region and acquire small-sized grain accompanied by improved crystal quality and surface morphology of the film. By optimizing the imprinting pressure and the period of the nanostructures, appropriate grain size, high surface coverage, small surface roughness and improved crystallization could be achieved synchronously. Finally, the maximum luminance and efficiency of PeLEDs achieved by nanostructured stamp imprinting with a period of 320 nm are 67600 cd/m² and 16.36 cd/A, respectively. This corresponds to improvements of 123 % in luminance and 100 % in efficiency, compared to that of PeLEDs without the imprinting.     

Chemical regulation of metal halide perovskite nanomaterials for efficient light-emitting diodes

Metal halide perovskite nanomaterials emerged as attractive emitting materials for light-emitting diodes (LEDs) devices due to their high photoluminescence quantum yield (PLQY), narrow bandwidth, high charge-carrier mobility, bandgap tunability, and facile synthesis. In the past few years, it has been witnessed an unprecedented advance in the field of metal halide perovskite nanomaterials based LEDs (PeLEDs) with a rapid external quantum efficiency (EQE) increase from 0.1% to 14.36%. From the viewpoint of material chemistry, the chemical regulation of metal halide perovskite nanomaterials made a great contribution to the efficiency improvement of PeLEDs. In this review, we categorize the strategies of chemical regulation as A-site cation engineering, B-site ion doping, X-site ion exchange, dimensional confinement, ligand exchange, surface passivation and interface optimization of transport layers for improving the EQEs of PeLEDs. We also show the potentials of chemical regulation strategies to enhance the stability of PeLEDs. Finally, we present insight toward future research directions and an outlook to further improve EQEs and stabilities of PeLEDs aiming to practical applications.     

Influence of hidden halogen mobility on local structure of CsSn(Cl1−xBrx)3 mixed-halide perovskites by solid-state NMR

Tin halide perovskites are promising candidates for lead-free photovoltaic and optoelectronic materials, but not all of them have been well characterized. It is essential to determine how the bulk photophysical properties are correlated with their structures at both short and long ranges. Although CsSnCl₃ is normally stable in the cubic perovskite structure only above 379 K, it was prepared as a metastable phase at room temperature. The transition from the cubic to the monoclinic phase, which is the stable form at room temperature, was tracked by solid-state ¹³³Cs NMR spectroscopy and shown to take place through a first-order kinetics process. The complete solid solution CsSn(Cl_1−xBr_x)₃ (0 ≤ x ≤ 1) was successfully prepared, exhibiting cubic perovskite structures extending between the metastable CsSnCl₃ and stable CsSnBr₃ end-members. The NMR spectra of CsSnBr₃ samples obtained by three routes (high-temperature, mechanochemical, and solvent-assisted reactions) show distinct chemical shift ranges, spin-lattice relaxation parameters and peak widths, indicative of differences in local structure, defects and degree of crystallinity within these samples. Variable-temperature ¹¹⁹Sn spin-lattice relaxation measurements reveal spontaneous mobility of Br atoms in CsSnBr₃. The degradation of CsSnBr₃, exposed to an ambient atmosphere for nearly a year, was monitored by NMR spectroscopy and powder X-ray diffraction, as well as by optical absorption spectroscopy.

Unravelling the atomic-level chemical structure, slow phase conversion or degradation pathways and rapid halogen hopping of cesium tin(ii) halide perovskites using solid-state ¹¹⁹Sn and ¹³³Cs NMR spectroscopy.     

Foldable semi-ladder polymers: novel aggregation behavior and high-performance solution-processed organic light-emitting transistors

A critical issue in developing high-performance organic light-emitting transistors (OLETs) is to balance the trade-off between charge transport and light emission in a semiconducting material. Although traditional materials for organic light-emitting diodes (OLEDs) or organic field-effect transistors (OFETs) have shown modest performance in OLET devices, design strategies towards high-performance OLET materials and the crucial structure–performance relationship remain unclear. Our research effort in developing cross-conjugated weak acceptor-weak donor copolymers for luminescent properties lead us to an unintentional discovery that these copolymers form coiled foldamers with intramolecular H-aggregation, leading to their exceptional OLET properties. An impressive external quantum efficiency (EQE) of 6.9% in solution-processed multi-layer OLET devices was achieved.

Coiled foldamers with intramolecular H-aggregation in semi-ladder copolymers lead towards the highest EQE of 6.9% in solution-processed multi-layer OLETs.     

Ligand Engineering Enables Efficient Pure Red Tin-Based Perovskite Light-Emitting Diodes

With increasing ecological and environmental concerns, tin (Sn)-based perovskite light-emitting diodes (PeLEDs) are competitive candidates for future displays because of their environmental friendliness, excellent photoelectric properties, and low-cost solution-processed fabrication. Nonetheless, their electroluminescence (EL) performance still lags behind that of lead (Pb)-based PeLEDs due to the fast crystallization rate of Sn-based perovskite films and undesired oxidation from Sn²⁺ to Sn⁴⁺, leading to poor film morphology and coverage, as well as high density defects. Here, we propose a ligand engineering strategy to construct high-quality phenethylammonium tin iodide (PEA₂SnI₄) perovskite films by using L-glutathione reduced (GSH) as surface ligands toward efficient pure red PEA₂SnI₄-based PeLEDs. We show that the hydrogen-bond and coordinate interactions between GSH and PEA₂SnI₄ effectively reduce the crystallization rate of the perovskites and suppress the oxidation of Sn²⁺ and formation of defects. The improved pure red perovskite films not only show excellent uniformity, density, and coverage but also exhibit enhanced optical properties and stability. Finally, state-of-the-art pure red PeLEDs achieve a record external quantum efficiency of 9.32 % in the field of PEA₂SnI₄-based devices. This work demonstrates that ligand engineering represents a feasible route to enhance the EL performance of Sn-based PeLEDs.     

Defect mitigation using d-penicillamine for efficient methylammonium-free perovskite solar cells with high operational stability

Trap-dominated non-radiative charge recombination is one of the key factors that limit the performance of perovskite solar cells (PSCs), which was widely studied in methylammonium (MA) containing PSCs. However, there is a need to elucidate the defect chemistry of thermally stable, MA-free, cesium/formamidinium (Cs/FA)-based perovskites. Herein, we show that d-penicillamine (PA), an edible antidote for treating heavy metal ions, not only effectively passivates the iodine vacancies (Pb²⁺ defects) through coordination with the –SH and –COOH groups in PA, but also finely tunes the crystallinity of Cs/FA-based perovskite film. Benefiting from these merits, a reduction of non-radiative recombination and an increase in photoluminescence lifetime have been achieved. As a result, the champion MA-free device exhibits an impressive power conversion efficiency (PCE) of 22.4%, an open-circuit voltage of 1.163 V, a notable fill factor of 82%, and excellent long-term operational stability. Moreover, the defect passivation strategy can be further extended to a mini module (substrate: 4 × 4 cm², active area: 7.2 cm²) as well as a wide-bandgap (∼1.73 eV) Cs/FA perovskite system by delivering PCEs of 16.3% and 20.2%, respectively, demonstrating its universality in defect passivation for efficient PSCs.

Iodine vacancy defects in MA-free perovskite are effectively passivated through the interaction between Pb²⁺ and the functional groups in d-penicillamine, resulting in an impressive efficiency of 22.4% along with excellent operational stability.     

Ultrastable Perovskite–Zeolite Composite Enabled by Encapsulation and In Situ Passivation

Metal halide perovskites have been widely applied in optoelectronic fields, but their poor stability hinders their actual applications. A perovskite–zeolite composite was synthesized via in situ growth in air from aluminophosphate AlPO-5 zeolite crystals and perovskite nanocrystals. The zeolite matrix provides quantum confinement for perovskite nanocrystals, achieving efficient green emission, and it passivates the defects of perovskite by H-bonding interaction, which leads to a longer lifetime compared to bulk perovskite film. Furthermore, the AlPO-5 zeolite also acts as a protection shield and enables ultrahigh stability of perovskite nanocrystals under 150 °C heat stress, under a 15-month long-term ambient exposure, and even in water for more than 2 weeks, respectively. The strategy of in situ passivation and encapsulation for the perovskite@AlPO-5 composite was amenable to a range of perovskites, from MA- to Cs-based perovskites. Benefiting from high stability and photoluminescence performance, the composite exhibits great potential to be virtually applied in light-emitting diodes (LEDs) and backlight displays.     

Weaving host matrices with intermolecular hydrogen bonds for high-efficiency white thermally activated delayed fluorescence

A thermally activated delayed fluorescence (TADF) white organic light-emitting diode (WOLED) holds great promise for low-cost, large-scale lighting applications. Nevertheless, manipulating exciton allocation in a white TADF single layer is still a challenge. Herein, we demonstrate that the exciton kinetic process of dually doped white TADF films is strongly dependent on the grid regularity of the host matrix. Intermolecular hydrogen bonds (IHBs) are used to weave the matrices of two host molecules DPEQPO and DPSQPO featuring four phosphine oxide (PO) groups and different IHB orientations. The DPSQPO matrix forms regular grids to uniformly disperse and separate dopants, while DPEQPO exhibits chaotic IHBs, in turn inducing a heterogeneous dopant distribution. As a consequence, in both photoluminescence and electroluminescence processes, in contrast to DPEQPO hosted systems with comparable singlet Förster resonance energy transfer and triplet Dexter energy transfer, DPSQPO provides a FRET-predominant exciton allocation between blue and yellow dopants, which markedly suppresses triplet quenching and improves the white color purity, resulting in a state-of-the-art external quantum efficiency up to 24.2% of its single-emissive-layer pure-white TADF diode, in contrast to 16.0% for DPEQPO based analogs. These results indicate the significance of host engineering for exciton kinetics and suggest the feasibility of host grid design for developing high-performance TADF lighting.

A thermally activated delayed fluorescence (TADF) white organic light-emitting diode (WOLED) holds great promise for low-cost, large-scale lighting applications.     

Evolution of pure hydrocarbon hosts: simpler structure,higher performance and universal application in RGB phosphorescent organic light-emitting diodes

In the field of phosphorescent organic light-emitting diodes (PhOLEDs), designing high-efficiency universal host materials for red, green and blue (RGB) phosphors has been quite a challenge. To date, most of the high-efficiency universal hosts reported incorporate heteroatoms, which have a crucial role in the device performance. However, the introduction of different kinds of heterocycles increases the design complexity and cost of the target material and also creates potential instability in the device performance. In this work, we show that pure aromatic hydrocarbon hosts designed with the 9,9′-spirobifluorene scaffold are high-efficiency and versatile hosts for PhOLEDs. With external quantum efficiencies of 27.3%, 26.0% and 27.1% for RGB PhOLEDs respectively, this work not only reports the first examples of high-efficiency pure hydrocarbon materials used as hosts in RGB PhOLEDs but also the highest performance reported to date for a universal host (including heteroatom-based hosts). This work shows that the PHC design strategy is promising for the future development of the OLED industry as a high-performance and low-cost option.

In this work, we propose pure hydrocarbon materials as universal hosts for high-efficiency red, green and blue phosphorescent organic light-emitting diodes.     

High-efficiency hyperfluorescent white light-emitting diodes based on high-concentration-doped TADF sensitizer matrices via spatial and energy gap effects

Despite the success of monochromatic hyperfluorescent (HF) organic light-emitting diodes (OLEDs), high-efficiency HF white OLEDs (WOLEDs) are still a big challenge. Herein, we demonstrate HF WOLEDs with state-of-the-art efficiencies, featuring a quasi-bilayer emissive layer (EML) composed of an ultrathin (0.1 nm) blue fluorescence (FL) emitter (TBPe) layer and a layer of thermally activated delayed fluorescence (TADF) sensitizer matrix heavily doped with a yellow FL emitter (TBRb, 3%). Based on an asymmetric high-energy-gap TADF sensitizer host (PhCzSPOTz), such an “ultrathin blue emitting layer (UTBL)” strategy endowed the HF WOLEDs with a record power efficiency of ∼80 lm W⁻¹, approaching the level of fluorescent tubes. Transient photoluminescence (PL) and electroluminescence (EL) kinetics demonstrate that the spatial separation of TBPe from the TADF sensitizer and TBRb, and the large energy gap between the latter two effectively suppress triplet leakage, in addition to suppressing triplet diffusion in the PhCzSPOTz matrix with anisotropic intermolecular interactions. These results provide a new insight into the exciton allocation process in HF white light-emitting systems.

A thermally activated delayed fluorescence host was developed to realize high-efficiency fluorescence white organic light-emitting diodes (WOLED) through spatial and energy gap effects.     

Room-temperature ferroelectric and ferroelastic orders coexisting in a new tetrafluoroborate-based perovskite

The coexistence of multiferroic orders has attracted increasing attention for its potential applications in multiple-state memory, switches, and computing, but it is still challenging to design single-phase crystalline materials hosting multiferroic orders at above room temperature. By utilizing versatile ABX₃-type perovskites as a structural model, we judiciously introduced a polar organic cation with easily changeable conformations into a tetrafluoroborate-based perovskite system, and successfully obtained an unprecedented molecular perovskite, (homopiperazine-1,4-diium)[K(BF₄)₃], hosting both ferroelectricity and ferroelasticity at above room temperature. By using the combined techniques of variable-temperature single-crystal X-ray structural analyses, differential scanning calorimetry, and dielectric, second harmonic generation, and piezoresponse force microscopy measurements, we demonstrated the domain structures for ferroelectric and ferroelastic orders, and furthermore disclosed how the delicate interplay between stepwise changed dynamics of organic cations and cooperative deformation of the inorganic framework induces ferroelectric and ferroelastic phase transitions at 311 K and 455 K, respectively. This instance, together with the underlying mechanism of ferroic transitions, provides important clues for designing advanced multiferroic materials based on organic–inorganic hybrid crystals.

An unprecedented tetrafluoroborate-based perovskite reveals the coexistence of ferroelastic and ferroelectric transitions arising from delicate interplay between stepwise frozen organic cations and cooperative deformation of the framework.     

A time-domain view of charge carriers in semiconductor nanocrystal solids

The movement of charge carriers within semiconductor nanocrystal solids is fundamental to the operation of nanocrystal devices, including solar cells, LEDs, lasers, photodetectors, and thermoelectric modules. In this perspective, we explain how recent advances in the measurement and simulation of charge carrier dynamics in nanocrystal solids have led to a more complete picture of mesoscale interactions. Specifically, we show how time-resolved optical spectroscopy and transient photocurrent techniques can be used to track both equilibrium and non-equilibrium dynamics in nanocrystal solids. We discuss the central role of energetic disorder, the impact of trap states, and how these critical parameters are influenced by chemical modification of the nanocrystal surface. Finally, we close with a forward-looking assessment of emerging nanocrystal systems, including anisotropic nanocrystals, such as nanoplatelets, and colloidal lead halide perovskites.

Time-domain spectroscopy and transient photocurrent techniques have revealed new understanding of mesoscale carrier dynamics in nanocrystal solids, including the role of energetic disorder, interactions with trap states, and nonequilibrium dynamics