Sensitization of silicon by singlet exciton fission in tetracene.

Silicon dominates contemporary solar cell technologies1. But when absorbing photons, silicon (like other semiconductors) wastes energy in excess of its bandgap2. Reducing these thermalization losses and enabling better sensitivity to light is possible by sensitizing the silicon solar cell using singlet exciton fission, in which two excited states with triplet spin character (triplet excitons) are generated from a photoexcited state of higher energy with singlet spin character (a singlet exciton)3-5. Singlet exciton fission in the molecular semiconductor tetracene is known to generate triplet excitons that are energetically matched to the silicon bandgap6-8. When the triplet excitons are transferred to silicon they create additional electron-hole pairs, promising to increase cell efficiencies from the single-junction limit of 29 per cent to as high as 35 per cent9. Here we reduce the thickness of the protective hafnium oxynitride layer at the surface of a silicon solar cell to just eight angstroms, using electric-field-effect passivation to enable the efficient energy transfer of the triplet excitons formed in the tetracene. The maximum combined yield of the fission in tetracene and the energy transfer to silicon is around 133 per cent, establishing the potential of singlet exciton fission to increase the efficiencies of silicon solar cells and reduce the cost of the energy that they generate.

Mixed halide bulk perovskite triplet sensitizers: Interplay between band alignment, mid-gap traps, and phonons.

Photon upconversion, particularly via triplet-triplet annihilation (TTA), could prove beneficial in expanding the efficiencies and overall impacts of optoelectronic devices across a multitude of technologies. The recent development of bulk metal halide perovskites as triplet sensitizers is one potential step toward the industrialization of upconversion-enabled devices. Here, we investigate the impact of varying additions of bromide into a lead iodide perovskite thin film on the TTA upconversion process in the annihilator molecule rubrene. We find an interplay between the bromide content and the overall device efficiency. In particular, a higher bromide content results in higher internal upconversion efficiencies enabled by more efficient charge extraction at the interface likely due to a more favorable band alignment. However, the external upconversion efficiency decreases as the absorption cross section in the near infrared is reduced. The highest upconversion performance is found in our study for a bromide content of 5%. This result can be traced back to a high absorption cross section in the near infrared and higher photoluminescence quantum yield in comparison to the iodide-only perovskite and an increased driving force for charge transfer.

Perovskite-sensitized upconversion bingo: Stoichiometry, composition, solvent, or temperature?

Triplet-triplet annihilation-based photon upconversion (UC) using bulk perovskite sensitizers has been previously shown to facilitate efficient UC at low fluences. However, the fabrication of the UC devices has not been fully optimized; thus, there is room for improvement. Here, we apply techniques that have been successful in enhancing the performance of perovskite solar cells in order to also improve perovskite-sensitized UC devices. In particular, we investigate the use of a post-fabrication thermal annealing step, overstoichiometric vs stoichiometric addition of PbI2 to the perovskite precursors, methylammonium vs formamidinium cation-rich lead halide perovskite compositions, and the use of different solvents for the annihilator molecules on the perovskite/annihilator interface. We find that excess PbI2 does not significantly affect the UC process, while the perovskite composition is crucial for the yield of extracted carriers across the interface. Comparing toluene and chlorobenzene, we find that the solvent used to deposit the annihilator is also a key factor in the overall device performance. Moreover, we find that thermal annealing of the whole device architecture significantly improves the UC performance by a factor of three.

Multiexciton Lifetimes Reveal Triexciton Emission Pathway in CdSe Nanocrystals.

Multiexcitons in emerging semiconducting nanomaterials play a critical role in potential optoelectronic and quantum computational devices. We describe photon resolved single molecule methods to directly probe the dynamics of biexcitons and triexcitons in colloidal CdSe quantum dots. We confirm that biexcitons emit from a spin-correlated state, consistent with statistical scaling. Contrary to current understanding, we find that triexciton emission is dominated by band-edge 1Se1S3/2 recombination rather than the higher energy 1Pe1P3/2 recombination.

Imaging Excited Orbitals of Quantum Dots: Experiment and Electronic Structure Theory.

Electronically excited orbitals play a fundamental role in chemical reactivity and spectroscopy. In nanostructures, orbital shape is diagnostic of defects that control blinking, surface carrier dynamics, and other important optoelectronic properties. We capture nanometer resolution images of electronically excited PbS quantum dots (QDs) by single molecule absorption scanning tunneling microscopy (SMA-STM). Dots with a bandgap of ∼1 eV are deposited on a transparent gold surface and optically excited with red or green light to produce hot carriers. The STM tip-enhanced laser light produces a large excited-state population, and the Stark effect allows transitions to be tuned into resonance by changing the sample voltage. Scanning the QDs under laser excitation, we were able to image electronic excitation to different angular momentum states depending on sample bias. The shapes differ from idealized S- or P-like orbitals due to imperfections of the QDs. Excitation of adjacent QD pairs reveals orbital alignment, evidence for electronic coupling between dots. Electronic structure modeling of a small PbS QD, when scaled for size, reveals Stark tuning and variation in the transition moment of different parity states, supporting the simple one-electron experimental interpretation in the hot carrier limit. The calculations highlight the sensitivity of orbital density to applied field, laser wavelength, and structural fluctuations of the QD.

Sub-nanometer glass surface dynamics induced by illumination.

Illumination is known to induce stress and morphology changes in opaque glasses. Amorphous silicon carbide (a-SiC) has a smaller bandgap than the crystal. Thus, we were able to excite with 532 nm light a 1 µm amorphous surface layer on a SiC crystal while recording time-lapse movies of glass surface dynamics by scanning tunneling microscopy (STM). Photoexcitation of the a-SiC surface layer through the transparent crystal avoids heating the STM tip. Up to 6 × 10(4) s, long movies of surface dynamics with 40 s time resolution and sub-nanometer spatial resolution were obtained. Clusters of ca. 3-5 glass forming units diameter are seen to cooperatively hop between two states at the surface. Photoexcitation with green laser light recruits immobile clusters to hop, rather than increasing the rate at which already mobile clusters hop. No significant laser heating was observed. Thus, we favor an athermal mechanism whereby electronic excitation of a-SiC directly controls glassy surface dynamics. This mechanism is supported by an exciton migration-relaxation-thermal diffusion model. Individual clusters take ∼1 h to populate states differently after the light intensity has changed. We believe the surrounding matrix rearranges slowly when it is stressed by a change in laser intensity, and clusters serve as a diagnostic. Such cluster hopping and matrix rearrangement could underlie the microscopic mechanism of photoinduced aging of opaque glasses.

Structure, function, and folding of phosphoglycerate kinase are strongly perturbed by macromolecular crowding.

We combine experiment and computer simulation to show how macromolecular crowding dramatically affects the structure, function, and folding landscape of phosphoglycerate kinase (PGK). Fluorescence labeling shows that compact states of yeast PGK are populated as the amount of crowding agents (Ficoll 70) increases. Coarse-grained molecular simulations reveal three compact ensembles: C (crystal structure), CC (collapsed crystal), and Sph (spherical compact). With an adjustment for viscosity, crowded wild-type PGK and fluorescent PGK are about 15 times or more active in 200 mg/ml Ficoll than in aqueous solution. Our results suggest a previously undescribed solution to the classic problem of how the ADP and diphosphoglycerate binding sites of PGK come together to make ATP: Rather than undergoing a hinge motion, the ADP and substrate sites are already located in proximity under crowded conditions that mimic the in vivo conditions under which the enzyme actually operates. We also examine T-jump unfolding of PGK as a function of crowding experimentally. We uncover a nonmonotonic folding relaxation time vs. Ficoll concentration. Theory and modeling explain why an optimum concentration exists for fastest folding. Below the optimum, folding slows down because the unfolded state is stabilized relative to the transition state. Above the optimum, folding slows down because of increased viscosity.

Generating spin-triplet states at the bulk perovskite/organic interface for photon upconversion.

Perovskite-sensitized triplet-triplet annihilation (TTA) upconversion (UC) holds potential for practical applications of solid-state UC ranging from photovoltaics to sensing and imaging technologies. As the triplet sensitizer, the underlying perovskite properties heavily influence the generation of spin-triplet states once interfaced with the organic annihilator molecule, typically polyacene derivatives. Presently, most reported perovskite TTA-UC systems have utilized rubrene doped with ∼1% dibenzotetraphenylperiflanthene (RubDBP) as the annihilator/emitter species. However, practical applications require a larger apparent anti-Stokes than is currently achievable with this system due to the inherent 0.4 eV energy loss during triplet generation. In this minireview, we present the current understanding of the triplet sensitization process at the perovskite/organic semiconductor interface and introduce additional promising annihilators based on anthracene derivatives into the discussion of future directions in perovskite-sensitized TTA-UC.

Mechanistic insight into CdSe nanoplatelet-sensitized upconversion: size and stacking induced effects.

CdSe nanoplatelets (NPLs) have been reported as triplet sensitizers for photon upconversion (UC). However, their UC quantum yields lag behind more conventional systems. Here, we take advantage of their one-dimensional quantum confinement to decouple effects caused by the energetic driving force and lateral size. A surprising anti-correlation between the power threshold Ith and the UC quantum yield based on the NPL size is found. We attribute this result to two distinct triplet-triplet annihilation mechanisms based on the NPL lateral dimension and degree of NPL stacking-mediated either by molecular diffusion or triplet energy diffusion.

Cool carriers: triplet diffusion dominates upconversion yield.

Perovskites have gained popularity both as the active material in photovoltaics and as bulk triplet sensitizers for solid-state triplet-triplet annihilation upconversion (TTA-UC). Prior to widespread implementation into commercial photovoltaics, an in-depth understanding of the environmental influences on device performance is required. To this point, the temperature-dependent structure-function properties of TTA-UC within methylammonium formamidinium lead triiodide (MAFA)/rubrene UC devices are explored. A strong temperature dependence of the underlying UC dynamics is observed, where the maximum UC efficiency is achieved at 170 K, reflecting the competition between triplet diffusion length, diffusion rate, and triplet-triplet encounter events. A combination of spectroscopic and structural methods and theoretical modelling illustrates that despite the significantly increased carrier lifetime of the perovskite at low temperatures, the TTA-UC dynamics are not governed by the underlying sensitizer properties but rather limited by the underlying triplet diffusion.

Recharging upconversion: revealing rubrene's replacement.

One of the major limitations of solid-state perovskite-sensitized photon upconversion to date is that the only annihilator successfully paired with the perovskite sensitizer has been rubrene, raising the question of whether this appraoch of triplet sensitization is universal or limited in scope. Additionally, the inherent energetic mismatch between the perovskite bandgap and the rubrene triplet energy has restricted the apparent anti-Stokes shift achievable in the upconversion process. To increase the apparent anti-Stokes shift for upconversion processes, anthracene derivates are of particular interest due to their higher triplet energies. Here, we demonstrate successful sensitization of the triplet state of 1-chloro-9,10-bis(phenylethynyl)anthracene using the established formamidinium methylammonium lead triiodide perovskite FA0.85MA0.15PbI3, resulting in upconverted emission at 550 nm under 780 nm excitation. We draw a direct comparison to rubrene to unravel the underlying differences in the upconversion processes.

Scratching the Surface: Passivating Perovskite Nanocrystals for Future Device Integration.

Metal halide perovskite materials have recently upended the field of photovoltaics and are aiming to make waves across a multitude of other fields and applications. Recently, perovskite nanocrystals have been synthesized and are rapidly outpacing traditional semiconductor nanocrystals in application driven fields due to their inherent defect tolerance and facile tunability, resulting in high photoluminescent quantum yields and efficient devices. Future improvements to perovskite nanocrystals toward device driven applications must come at the perovskite surface. The last half decade has resulted in considerable progress in tailoring the perovskite nanocrystal/ligand surface toward maximizing the optoelectronic performance. Here, we review the current progress and discuss how further improvements could be made to further improve this bright class of materials.

A Sensitizer of Purpose: Generating Triplet Excitons with Semiconductor Nanocrystals.

The process of photon upconversion promises importance for many optoelectronic applications, as it can result in higher efficiencies and more effective photon management. Upconversion via triplet-triplet annihilation (TTA) occurs at low incident powers and at high efficiencies, requirements for integration into existing optoelectronic devices. Semiconductor nanocrystals are a diverse class of triplet sensitizers with advantages over traditional molecular sensitizers such as energetic tunability and minimal energy loss during the triplet sensitization process. In this Perspective, we review current progress in semiconductor nanocrystal triplet sensitization, specifically focusing on the nanocrystal, the ligand shell which surrounds the nanocrystal, and progress in solid-state sensitization. Finally, we discuss potential areas of improvement which could result in more efficient upconversion systems sensitized by semiconductor nanocrystals. Specifically, we focus on the development of solid-state TTA upconversion systems, elucidation of the energy transfer mechanisms from nanocrystal to transmitter ligand which underpin the upconversion process and propose novel configurations of nanocrystal-sensitized systems.

Kitchen Spectroscopy: Shining a (UV) Light on Everyday Objects.

Fluorescent objects often lead to a sense of joy and intrigue. While the current COVID-19 pandemic limits the synthesis of "glowy things" like quantum dots, many household objects fluoresce, providing an opportunity to brighten your day while learning fundamental chemistry.

Engineering 3D perovskites for photon interconversion applications.

In this review, we highlight the current advancements in the field of triplet sensitization by three-dimensional (3D) perovskite nanocrystals and bulk films. First introduced in 2017, 3D perovskite sensitized upconversion (UC) is a young fast-evolving field due to the tunability of the underlying perovskite material. By tuning the perovskite bandgap, visible-to-ultraviolet, near-infrared-to-visible or green-to-blue UC has been realized, which depicts the broad applicability of this material. As this research field is still in its infancy, we hope to stimulate the field by highlighting the advantages of these perovskite nanocrystals and bulk films, as well as shedding light onto the current drawbacks. In particular, the keywords toxicity, reproducibility and stability must be addressed prior to commercialization of the technology. If successful, photon interconversion is a means to increase the achievable efficiency of photovoltaic cells beyond its current limits by increasing the window of useable wavelengths.

Correction: Engineering 3D perovskites for photon interconversion applications.

[This corrects the article DOI: 10.1371/journal.pone.0230299.].

Precharging Photon Upconversion: Interfacial Interactions in Solution-Processed Perovskite Upconversion Devices.

Recent advances in perovskite-sensitized photon upconversion via triplet-triplet annihilation (TTA) in rubrene have yielded several unanswered questions about the underlying mechanism and processes occurring at the interface. In particular, the near-infrared perovskite emission is not significantly quenched and a rapid reversible "photobleach" of the upconverted emission can be observed under fairly low excitation densities of 3.2 mW/cm2. In this contribution, we investigate the perovskite/rubrene interface in more detail and conclude that noncovalent interactions between the organic layer and the perovskite result in surface trap passivation. In addition, band bending results in a space charge region at the perovskite/rubrene interface, which "precharges" the rubrene with holes. Upon initial illumination, electrons can rapidly transfer to the excited triplet state of rubrene, followed by efficient TTA upconversion. As the device is continuously illuminated, the existing holes are consumed and a new equilibrium is reached, resulting in the previously investigated steady-state upconversion efficiency.

Monodisperse and Water-Soluble Quantum Dots for SWIR Imaging via Carboxylic Acid Copolymer Ligands.

Compared to the visible and near-infrared, the short-wave infrared region (SWIR; 1000-2000 nm) has excellent properties for in vivo imaging: low autofluorescence, reduced scattering, and a low-absorption cross-section of blood or tissue. However, the general adoption of SWIR imaging in biomedical research will be enhanced by a broader availability of versatile and bright contrast materials. Quantum dots (QDs) are bright and compact SWIR emitters with narrow size distributions and emission spectra, but their use is limited by the shortcomings of established ligand systems for SWIR QDs. Established ligands often result in SWIR probes with either limited colloidal stability, large size, or broad size distribution or a combination of all three. We present a polymeric QD ligand designed to be compatible with oleate-coated QDs. Our polymeric acid ligand is a copolymer bearing carboxylic acid anchoring groups and PEG-550 chains to solubilize the QD-ligand construct. After a mild and rapid ligand exchange, the resulting constructs are compact (<11 nm hydrodynamic diameter) and have narrow size distribution. Both qualities are preserved for several months in isotonic saline. The constructs are bright in vivo, and to demonstrate their suitability for imaging, we perform whole-body imaging and lymphatic imaging, including visualization of lymphatic flow.

Room-Temperature Phosphorescence and Low-Energy Induced Direct Triplet Excitation of Alq3 Engineered Crystals.

Crystal engineering is a practical approach for tailoring material properties. This approach has been widely studied for modulating optical and electrical properties of semiconductors. However, the properties of organic molecular crystals are difficult to control following a similar engineering route. In this Letter, we demonstrate that engineered crystals of Alq3 and Ir(ppy)3 complexes, which are commonly used in organic light-emitting technologies, possess intriguing functional properties. Specifically, these structures not only process efficient low-energy induced triplet excitation directly from the ground state of Alq3 but also can show strong emission at the Alq3 triplet energy level at room temperatures. We associate these phenomena with local deformations of the host matrix around the guest molecules, which in turn lead to a stronger host-guest triplet-triplet coupling and spin-orbital mixing.