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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Enhanced Emission from Bright Excitons in Asymmetrically Strained Colloidal CdSe/Cd x Zn 1– x Se Quantum Dots

Colloidal CdSe quantum dots (QDs) designed with a high degree of asymmetric internal strain have recently been shown to host a number of desirable optical properties including subthermal room-temperature line widths, suppressed spectral diffusion, and high photoluminescence (PL) quantum yields. It remains an open question, however, whether they are well-suited for applications requiring emission of identical single photons. Here we measure the low-temperature PL dynamics and the polarization-resolved fluorescence line narrowing spectra from ensembles of these strained QDs. Our spectroscopy reveals the radiative recombination rates of bright and dark excitons, the relaxation rate between the two, and the energy spectra of the quantized acoustic phonons in the QDs that can contribute to relaxation processes. In comparison to conventional colloidal CdSe/ZnS core/shell QDs, we find that in asymmetrically strained CdSe QDs over six times more light is emitted directly by the bright exciton. Furthermore, these results are therefore encouraging for the prospects of chemically synthesized colloidal QDs as emitters of single indistinguishable photons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Synthetic Ligand Selection Affects Stoichiometry, Carrier Dynamics, and Trapping in CuInSe 2 Nanocrystals

CuInSe 2 nanocrystals exhibit tunable near-infrared bandgaps that bolster utility in photovoltaic applications as well as offer potential as substitutes for more-toxic Cd- and Pb-based semiconductor compositions. However, they can present a variety of defect states as well as unusual photophysics. In this work, we examine the effects of ligand composition (oleylamine, diphenylphosphine, and tributylphosphine) on carrier dynamics in these materials. Via spectroscopic measurements such as photoluminescence and transient absorption, we find that ligands present during the synthesis of CuInSe 2 nanocrystals impart non-radiative electronic states which compete with radiative recombination and give rise to low photoluminescence quantum yields. We characterize the nature of these defect states (hole vs. electron traps) and investigate whether they exist at the surface or interior of the nanocrystals. Carrier lifetimes are highly dependent on ligand identity where oleylamine-capped nanocrystals exhibit rapid trapping (< 20 ps) followed by diphenylphosphine (< 500 ps) and finally tributylphosphine (> 2 ns). A majority of carrier population localizes at indium copper antisites (electrons), copper vacancies (holes), or surface traps (electrons and/or holes), all of which are non-emissive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Lateral Integration of SnS and GeSe van der Waals Semiconductors: Interface Formation, Electronic Structure, and Nanoscale Optoelectronics

The emergence of atomically thin crystals has allowed extending materials integration to lateral heterostructures where different 2D materials are covalently connected in the plane. The concept of lateral heterostructures can be generalized to thicker layered crystals, provided that a suitably faceted seed crystal presents edges to which a compatible second van der Waals material can be attached layer by layer. Here, we examine the possibility of integrating multilayer crystals of the group IV monochalcogenides SnS and GeSe, which have the same crystal structure, small lattice mismatch, and similar bandgaps. In a two-step growth process, lateral epitaxy of GeSe on the sidewalls of multilayer SnS flakes (obtained by vapor transport of a SnS 2 precursor on graphite) yields heterostructures of laterally stitched crystalline GeSe and SnS without any detectable vertical overgrowth of the SnS seeds and with sharp lateral interfaces. Combined cathodoluminescence spectroscopy and ab initio calculations show the effects of small band offsets on carrier transport and radiative recombination near the interface. Further, the results demonstrate the possibility of forming atomically connected lateral interfaces across many van der Waals layers, which is promising for manipulating optoelectronics, photonics, and for managing charge- and thermal transport.

2D layered crystals↗
DOE OSTI2025

Nanoscale Strain and Octahedral Tilting Removes Structural and Nonradiative Defects in 2D-Templated FAPbI 3

The halide perovskite formamidinium lead iodide (FAPbI 3 ) is a prime candidate for photovoltaics due to its excellent optoelectronic properties, but its application has been limited due to its structural instability. The large size of the FA cation results in metastability of the photoactive cubic phase and a facile degradation into thermodynamically stable hexagonal phases at room temperature. Recently, the incorporation of two-dimensional (2D) Ruddlesden-Popper halide perovskite seeds into a FAPbI 3 precursor solution was shown to template the growth of and stabilize cubic FAPbI 3 . Here, in this study, we investigate the nanoscale structural and optoelectronic mechanisms behind the observed bulk stabilization using synchrotron-based X-ray microscopies. Nanoprobe X-ray diffraction reveals 2D-templated FAPbI 3 films exhibit an average compressive strain normal to the substrate of -3.3%, 2-fold larger than that of MACl-stabilized FAPbI 3 . This compression creates locally templated regions composed of tetragonal-phase FAPbI 3 distributed nonuniformly throughout the film with fewer crystalline defects than purely cubic regions. Scanning X-ray excited optical luminescence (X-ray analog of photoluminescence) reveals that this local templating results in increased radiative recombination and red-shifted band edge and emission. Our results provide insight into the microscopic mechanism for the phase stabilization of FAPbI 3 using 2D perovskites as templates.

X-ray diffraction↗
DOE OSTI2023

Origins of Photoluminescence Instabilities at Halide Perovskite/Organic Hole Transport Layer Interfaces

Metal halide perovskites are promising for optoelectronic device applications; however, their poor stability under solar illumination remains a primary concern. While the intrinsic photostability of isolated neat perovskite samples has been widely discussed, it is important to explore how charge transport layers—employed in most devices—impact photostability. Here, in this paper, we study the effect of organic hole transport layers (HTLs) on light-induced halide segregation and photoluminescence (PL) quenching at perovskite/organic HTL interfaces. By employing a series of organic HTLs, we demonstrate that the HTL’s highest occupied molecular orbital energy dictates behavior; furthermore, we reveal the key role of halogen loss from the perovskite and subsequent permeation into organic HTLs, where it acts as a PL quencher at the interface and introduces additional mass transport pathways to facilitate halide phase separation. In doing so, we both reveal the microscopic mechanism of non-radiative recombination at perovskite/organic HTL interfaces and detail the chemical rationale for closely matching the perovskite/organic HTL energetics to maximize solar cell efficiency and stability.

14 SOLAR ENERGY↗
DOE OSTI2024

Ag Intercalation in Layered Cs 3 Bi 2 Br 9 Perovskite for Enhanced Light Emission with Bound Interlayer Excitons

Cesium bismuth bromide (CBB) has garnered considerable attention as a vacancy-ordered layered perovskite with notable optoelectronic applications. However, its use as a light source has been limited due to its weak photoluminescence (PL). Here, we demonstrate metal intercalation as a novel approach to engineer the room-temperature PL of CBB using experimental and computational methods. Ag, when introduced into CBB, occupies vacant sites in the spacer region, forming octahedral coordination with surrounding Br anions. First-principles density functional theory calculations reveal that intercalated Ag represents the most energetically stable Ag species compared to other potential forms, such as Ag substituting Bi. The intercalated Ag forms a strong polaronic trap state close to the conduction band minimum and quickly captures photoexcited electrons with holes remaining in CBB layers, leading to the formation of a bound interlayer exciton, or BIE. The radiative recombination of this BIE exhibits bright room-temperature PL at 600 nm and a decay time of 38.6 ns, 35 times greater than that of free excitons, originating from the spatial separation of photocarriers by half a unit cell separation distance. The BIE as a new form of interlayer exciton is expected to inspire new research directions for vacancy-ordered perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Unraveling the influence of non-fullerene acceptor molecular packing on photovoltaic performance of organic solar cells

In non-fullerene organic solar cells, the long-range structure ordering induced by end-group π–π stacking of fused-ring non-fullerene acceptors is considered as the critical factor in realizing efficient charge transport and high power conversion efficiency. Here, we demonstrate that side-chain engineering of non-fullerene acceptors could drive the fused-ring backbone assembly from a π–π stacking mode to an intermixed packing mode, and to a non-stacking mode to refine its solid-state properties. Different from the above-mentioned understanding, we find that close atom contacts in a non-stacking mode can form efficient charge transport pathway through close side atom interactions. The intermixed solid-state packing motif in active layers could enable organic solar cells with superior efficiency and reduced non-radiative recombination loss compared with devices based on molecules with the classic end-group π–π stacking mode. Our observations open a new avenue in material design that endows better photovoltaic performance.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Single-layered organic photovoltaics with double cascading charge transport pathways: 18% efficiencies

The chemical structure of donors and acceptors limit the power conversion efficiencies achievable with active layers of binary donor-acceptor mixtures. Here, using quaternary blends, double cascading energy level alignment in bulk heterojunction organic photovoltaic active layers are realized, enabling efficient carrier splitting and transport. Numerous avenues to optimize light absorption, carrier transport, and charge-transfer state energy levels are opened by the chemical constitution of the components. Record-breaking PCEs of 18.07% are achieved where, by electronic structure and morphology optimization, simultaneous improvements of the open-circuit voltage, short-circuit current and fill factor occur. The donor and acceptor chemical structures afford control over electronic structure and charge-transfer state energy levels, enabling manipulation of hole-transfer rates, carrier transport, and non-radiative recombination losses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Layer number dependent ferroelasticity in 2D Ruddlesden–Popper organic-inorganic hybrid perovskites

Ferroelasticity represents material domains possessing spontaneous strain that can be switched by external stress. Three-dimensional perovskites like methylammonium lead iodide are determined to be ferroelastic. Layered perovskites have been applied in optoelectronic devices with outstanding performance. However, the understanding of lattice strain and ferroelasticity in layered perovskites is still lacking. Here, using the in-situ observation of switching domains in layered perovskite single crystals under external strain, we discover the evidence of ferroelasticity in layered perovskites with layer number more than one, while the perovskites with single octahedra layer do not show ferroelasticity. Density functional theory calculation shows that ferroelasticity in layered perovskites originates from the distortion of inorganic octahedra resulting from the rotation of aspherical methylammonium cations. The absence of methylammonium cations in single layer perovskite accounts for the lack of ferroelasticity. These ferroelastic domains do not induce non-radiative recombination or reduce the photoluminescence quantum yield.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Traps and transport resistance are the next frontiers for stable non-fullerene acceptor solar cells

Stability is one of the most important challenges facing material research for organic solar cells (OSC) on their path to further commercialization. In the high-performance material system PM6:Y6 studied here, we investigate degradation mechanisms of inverted photovoltaic devices. We have identified two distinct degradation pathways: one requires the presence of both illumination and oxygen and features a short-circuit current reduction, the other one is induced thermally and marked by severe losses of open-circuit voltage and fill factor. We focus our investigation on the thermally accelerated degradation. Our findings show that bulk material properties and interfaces remain remarkably stable, however, aging-induced defect state formation in the active layer remains the primary cause of thermal degradation. The increased trap density leads to higher non-radiative recombination, which limits the open-circuit voltage and lowers the charge carrier mobility in the photoactive layer. Furthermore, we find the trap-induced transport resistance to be the major reason for the drop in fill factor. Our results suggest that device lifetimes could be significantly increased by marginally suppressing trap formation, leading to a bright future for OSC.

14 SOLAR ENERGY↗
DOE OSTI2023

Suppressing phase disproportionation in quasi-2D perovskite light-emitting diodes

Electroluminescence efficiencies and stabilities of quasi-two-dimensional halide perovskites are restricted by the formation of multiple-quantum-well structures with broad and uncontrollable phase distributions. Here, we report a ligand design strategy to substantially suppress diffusion-limited phase disproportionation, thereby enabling better phase control. We demonstrate that extending the π-conjugation length and increasing the cross-sectional area of the ligand enables perovskite thin films with dramatically suppressed ion transport, narrowed phase distributions, reduced defect densities, and enhanced radiative recombination efficiencies. Consequently, we achieved efficient and stable deep-red light-emitting diodes with a peak external quantum efficiency of 26.3% (average 22.9% among 70 devices and cross-checked) and a half-life of ~220 and 2.8 h under a constant current density of 0.1 and 12 mA/cm 2 , respectively. Our devices also exhibit wide wavelength tunability and improved spectral and phase stability compared with existing perovskite light-emitting diodes. These discoveries provide critical insights into the molecular design and crystallization kinetics of low-dimensional perovskite semiconductors for light-emitting devices.

14 SOLAR ENERGY↗
DOE OSTI2024

Grain engineering for efficient near-infrared perovskite light-emitting diodes

Metal halide perovskites show promise for next-generation light-emitting diodes, particularly in the near-infrared range, where they outperform organic and quantum-dot counterparts. However, they still fall short of costly III-V semiconductor devices, which achieve external quantum efficiencies above 30% with high brightness. Among several factors, controlling grain growth and nanoscale morphology is crucial for further enhancing device performance. This study presents a grain engineering methodology that combines solvent engineering and heterostructure construction to improve light outcoupling efficiency and defect passivation. Solvent engineering enables precise control over grain size and distribution, increasing light outcoupling to ~40%. Constructing 2D/3D heterostructures with a conjugated cation reduces defect densities and accelerates radiative recombination. The resulting near-infrared perovskite light-emitting diodes achieve a peak external quantum efficiency of 31.4% and demonstrate a maximum brightness of 929 W sr -1 m -2 . These findings indicate that perovskite light-emitting diodes have potential as cost-effective, high-performance near-infrared light sources for practical applications.

42 ENGINEERING↗
DOE OSTI2024

Diamine chelates for increased stability in mixed Sn–Pb and all-perovskite tandem solar cells

Perovskite tandem solar cells show promising performance but non-radiative recombination and its progressive worsening with time, especially in the mixed Sn–Pb low-bandgap layer, limit performance and stability. Here, in this study, we find that mixed Sn–Pb perovskite thin films exhibit a compositional gradient, with an excess of Sn on the surface – and we show this gradient exacerbates oxidation and increases the recombination rate. We find that diamines preferentially chelate Sn atoms, removing them from the film surface and achieving a more balanced Sn:Pb stoichiometry, making the surface of the film resistive to the oxidation of Sn. The process forms an electrically resistive low-dimensional barrier layer, passivating defects and reducing interface recombination. Further improving the homogeneity of the barrier layer using 1,2-diaminopropane results in more uniform distribution and passivation. Tandems achieve a power conversion efficiency of 28.8%. As a result, encapsulated tandems retain 90% of initial efficiency following 1000 hours of operating at the maximum power point under simulated one-sun illumination in air without cooling.

14 SOLAR ENERGY↗
DOE OSTI2023

Ultrafast vibrational control of organohalide perovskite optoelectronic devices using vibrationally promoted electronic resonance

Vibrational control (VC) of photochemistry through the optical stimulation of structural dynamics is a nascent concept only recently demonstrated for model molecules in solution. Extending VC to state-of-the-art materials may lead to new applications and improved performance for optoelectronic devices. Metal halide perovskites are promising targets for VC due to their mechanical softness and the rich array of vibrational motions of both their inorganic and organic sublattices. Here, we demonstrate the ultrafast VC of FAPbBr 3 perovskite solar cells via intramolecular vibrations of the formamidinium cation using spectroscopic techniques based on vibrationally promoted electronic resonance. The observed short (~300 fs) time window of VC highlights the fast dynamics of coupling between the cation and inorganic sublattice. First-principles modelling reveals that this coupling is mediated by hydrogen bonds that modulate both lead halide lattice and electronic states. Cation dynamics modulating this coupling may suppress non-radiative recombination in perovskites, leading to photovoltaics with reduced voltage losses.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Efficient and bright white light-emitting diodes based on single-layer heterophase halide perovskites

At present, electric lighting accounts for ~15% of global power consumption and thus the adoption of efficient, low-cost lighting technologies is important. Here, halide perovskites have been shown to be good emitters of pure red, green and blue light, but an efficient source of broadband white electroluminescence suitable for lighting applications is desirable. Here, we report a white light-emitting diode (LED) strategy based on solution-processed heterophase halide perovskites that, unlike GaN white LEDs, feature only one broadband emissive layer and no phosphor. Our LEDs operate with a peak luminance of 12,200 cd m –2 at a bias of 6.6 V and a maximum external quantum efficiency of 6.5% at a current density of 8.3 mA cm –2 . Systematic in situ and ex situ characterizations reveal that the mechanism of efficient electroluminescence is charge injection into the α phase of CsPbI 3 , α to δ charge transfer and α–δ balanced radiative recombination. Future advances in fabrication technology and mechanistic understanding should lead to further improvements in device efficiency and luminance.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Two-dimensional-lattice-confined single-molecule-like aggregates

Intermolecular distance largely determines the optoelectronic properties of organic matter. Conventional organic luminescent molecules are commonly used either as aggregates or as single molecules that are diluted in a foreigner matrix. They have garnered great research interest in recent decades for a variety of applications, including light-emitting diodes, lasers and quantum technologies, among others. However, there is still a knowledge gap on how these molecules behave between the aggregation and dilution states. Here we report an unprecedented phase of molecular aggregate that forms in a two-dimensional hybrid perovskite superlattice with a near-equilibrium distance, which we refer to as a single-molecule-like aggregate (SMA). By implementing two-dimensional superlattices, the organic emitters are held in proximity, but, surprisingly, remain electronically isolated, thereby resulting in a near-unity photoluminescence quantum yield, akin to that of single molecules. Moreover, the emitters within the perovskite superlattices demonstrate strong alignment and dense packing resembling aggregates, allowing for the observation of robust directional emission, substantially enhanced radiative recombination and efficient lasing. Molecular dynamics simulations together with single-crystal structure analysis emphasize the critical role of the internal rotational and vibrational degrees of freedom of the molecules in the two-dimensional lattice for creating the exclusive SMA phase. Furthermore, this two-dimensional superlattice unifies the paradoxical properties of single molecules and aggregates, thus offering exciting possibilities for advanced spectroscopic and photonic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Destructive reverse bias pinning in perovskite/silicon tandem solar modules caused by perovskite hysteresis under dynamic shading

In this work, we demonstrate how perovskite hysteresis can result in permanent reductions in power output in perovskite/silicon tandem modules—including irreversible hotspot-induced damage—from only brief periods of shading. We show that reverse bias events in which a perovskite cell is biased above a threshold voltage—which in this work we find to be as low as –1.1 V—produces a temporary reduction in power output that is of sufficient magnitude to keep the cell pinned in reverse bias after the shading event ends. As a hysteretic phenomena, this crucial failure mode may be overlooked by static models of perovskite-based solar cells. Higher reverse bias voltages exacerbate the temporary reduction in short-circuit photocurrent, which is also sensitive to the level of illumination under reverse bias. Numerical device modelling demonstrates that this effect is consistent with our understanding of perovskite hysteresis as a consequence of mobile ion-electron coupling controlling rates of non-radiative recombination over time. Measurements of the dynamic response of single-junction perovskite cells are extrapolated to two-terminal and four-terminal perovskite/silicon tandem module modelling. We validate these models with measurements from an equivalent electronic circuit that represents a two-terminal perovskite–silicon tandem mini module. Two module-level solutions are discussed that address this issue, which includes increasing the number of bypass diodes and choosing better suited silicon bottom cells with higher shunter resistance in two-terminal tandem modules.

14 SOLAR ENERGY↗
DOE OSTI2021

Exciton dissociation in quantum dots connected with photochromic molecule bridges

Here, we report modulation of exciton dissociation dynamics in quantum dots (QD) connected with photochromic molecules. Our results show that switching the configuration of photochromic molecules changes the inter-QD potential barrier height which has a major impact on the charge tunnelling and exciton dissociation. The switching of the dominant exciton decay pathway between the radiative recombination and exciton dissociation results in switchable photoluminescence intensity from QDs. Implications of our findings for optical memory and optical computing applications are discussed.

36 MATERIALS SCIENCE↗