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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 approach 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 deeper highest occupied molecular orbital levels and higher triplet energies. Here, we demonstrate successful sensitization of the triplet level of 1-chloro-9,10-bis(phenylethynyl)anthracene using the established formamidinium methylammonium lead triiodide perovskite, 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.

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.

Solid-state bulk lead halide perovskite thin films have recently shown progress as triplet sensitizers in infrared-to-visible photon upconversion (UC) schemes. Common systems pair lead halide perov...

Triplet sensitization of rubrene by bulk lead halide perovskites has recently resulted in efficient infrared-to-visible photon upconversion via triplet-triplet annihilation. Notably, this process occurrs under solar relavant fluxes, potentially paving the way toward integration with photovoltaic devices. In order to further improve the upconversion efficiency, the fundamental photophysical pathways at the perovskite/rubrene interface must be clearly understood to maximize charge extraction. Here, we utilize ultrafast transient absorption spectroscopy to elucidate the processes underlying the triplet generation at the perovskite/rubrene interface. Based on the bleach and photoinduced absorption features of the perovskite and perovskite/rubrene devices obtained at multiple pump wavelengths and fluences, along with their resultant kinetics, our results do not support charge transfer states or long-lived trap states as the underlying mechanism. Instead, the data points towards a triplet sensitization mechanism based on rapid extraction of thermally excited carriers on the picosecond timescale.

The mechanism and elemental composition that form the basis for the improved optical and electronic properties in mixed-ion lead halide perovskite solar cells are still not well understood compared...

The role electron-transport layers (ETLs) play in perovskite solar cells (PSCs) is still widely debated. Conduction band alignment at the perovskite/ETL interface has been suggested to be an import...

Photon upconversion via triplet-triplet annihilation creating light in the high energy regime of the visible spectrum could prove particularly useful in applications such as photocatalysis. Quantum-confined semiconductor nanocrystals have previously been shown to function as efficient triplet sensitizers in green-to-blue upconversion schemes, but an improvement in the apparent anti-Stokes shift of the upconversion scheme will be beneficial for future commercial applications. Additionally, both zero- and two-dimensional quantum-confined sensitizers have been investigated, but not one-dimensional nanomaterials. In this work, we fill a hole in the present field of photon upconversion by accomplishing both of these feats. Specifically, we introduce CdTe nanorods as a new class of triplet sensitizers for red-to-blue photon upconversion. When the triplet transmitter ligand (9-anthracenecarboxylic acid) and triplet annihilator (9,10-diphenylanthracene) are added to the nanorods, we observe efficient photon upconversion at a normalized upconversion efficiency of huc = 4.3% and a low threshold power of Ith = 93 mW/cm2. The introduction of one-dimensional triplet sensitizers could yield future research that effectively harnesses the unique properties of these materials allowing for new approaches for efficient photon upconversion, especially at large apparent anti-Stokes shifts.

Green-to-blue photon upconversion bears great potential in photocatalytic applications. However, current hybrid inorganic-organic upconversion schemes utilizing spherical CdSe nanocrystals are often limited by energetic polydispersity, low quantum yields and an additional tunneling barrier resulting from the necessity of surface-passivating inorganic shells. In this contribution, we introduce anisotropic CdSe nanoplatelets as triplet sensitizers. Here, quantum confinement occurs in only one direction, erasing effects stemming from energetic polydispersity. We investigate the triplet energy transfer from the CdSe nanoplatelets to the surface-bound triplet acceptor 9-anthracene carboxylic acid. We further focus on the influence of nanoplatelet stacking and singlet back transfer on the observed upconversion efficiency. We obtain an upconversion quantum yield of 5.4% at a power density of 11 W/cm2­ using the annihilator 9,10-diphenylanthracene, and a low efficiency threshold Ith of 237 mW/cm2.

A key debate involving mixed-cation lead mixed-halide perovskite thin-films relates to the effects of process conditions on film morphology and local performance of perovskite solar cells. In this contribution, we investigate the influence of precursor concentration on the film thickness, grain size, and orientation of these polycrystalline thin-films. We vary the molar concentration of the perovskite precursor containing Rb, Cs, MA, FA, Pb, I, and Br from 0.4 to 1.2 M. We use optical and electrical probes to measure local properties and correlate the effect of crystallographic orientation on the inter- and intragrain charge-carrier transport. We find that, with increasing precursor concentration, the grain size of the polycrystalline thin-films becomes larger and more faceted. Films with small grains show mostly random grain orientation angles, whereas films with large grains are oriented with {100} planes around an angle of 20° relative to the surface normal. These films with oriented large grains also ...

Semiconductor nanocrystals are a promising class of materials for a variety of novel optoelectronic devices, since many of their properties, such as the electronic gap and conductivity, can be controlled. Much of this control is achieved via the organic ligand shell, through control of the size of the nanocrystal and the distance to other objects. We here simulate ligand-coated CdSe nanocrystals using atomistic molecular dynamics, allowing for the resolution of novel structural details about the ligand shell. We show that the ligands on the surface can lie flat to form a highly anisotropic 'wet hair' layer as opposed to the 'spiky ball' appearance typically considered. We discuss how this can give rise to a dot-to-dot packing distance of one ligand length since the thickness of the ligand shell is reduced to approximately one-half of the ligand length for the system sizes considered here; these distances imply that energy and charge transfer rates between dots and nearby objects will be enhanced due to the thinner than expected ligand shell. Our model predicts a non-linear scaling of ligand shell thickness as the ligands transition from 'spiky' to 'wet hair'. We verify this scaling using TEM on a PbS nanoarray, confirming that this theory gives a qualitatively correct picture of the ligand shell thickness of colloidal quantum dots., 17 Pages, 9 Figures

Inspired by the rapid rise in efficiencies of lead halide perovskite (LHP) solar cells, lead-free alternatives are attracting increasing attention. In this work, we study the photovoltaic potential of solution-processed antimony (Sb)-based compounds with the formula A3Sb2I9 (A = Cs, Rb, and K). We experimentally determine bandgap magnitude and type, structure, carrier lifetime, exciton binding energy, film morphology, and photovoltaic device performance. We use density functional theory to compute the equilibrium structures, band structures, carrier effective masses, and phase stability diagrams. We find the A-site cation governs the structural and optoelectronic properties of these compounds. Cs3Sb2I9 has a 0D structure, the largest exciton binding energy (175 ± 9 meV), an indirect bandgap, and, in a solar cell, low photocurrent (0.13 mA cm–2). Rb3Sb2I9 has a 2D structure, a direct bandgap, and, among the materials investigated, the lowest exciton binding energy (101 ± 6 meV) and highest photocurrent (1....

Recently, we and others have proposed screening criteria for “defect-tolerant” photovoltaic (PV) absorbers, identifying several classes of semiconducting compounds with electronic structures similar to those of hybrid lead–halide perovskites. In this work, we reflect on the accuracy and prospects of these new design criteria through a combined experimental and theoretical approach. We construct a model to extract photoluminescence lifetimes of six of these candidate PV absorbers, including four (InI, SbSI, SbSeI, and BiOI) for which time-resolved photoluminescence has not been previously reported. The lifetimes of all six candidate materials exceed 1 ns, a threshold for promising early stage PV device performance. However, there are variations between these materials, and none achieve lifetimes as high as those of the hybrid lead–halide perovskites, suggesting that the heuristics for defect-tolerant semiconductors are incomplete. We explore this through first-principles point defect calculations and Shock...

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/organic interface in more detail and conclude that non-covalent interactions between the organic layer and perovskite result in surface trap passivation. In addition, band bending results in a charge space region at the perovskite/rubrene interface, which precharges the rubrene interface 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 precharged holes are consumed and a new equilibrium is reached, resulting in the previously investigated steady-state upconversion efficiency.

Green-to-blue photon upconversion bears great potential in photocatalytic applications. However, current hybrid inorganic-organic upconversion schemes utilizing spherical CdSe nanocrystals are limited by the additional tunneling barrier resulting from the necessity of surface-passivating shells. In this contribution, we introduce anisotropic CdSe nanoplatelets as triplet sensitizers. Here, quantum confinement occurs in only one direction, erasing effects stemming from energetic polydispersity. We investigate the triplet energy transfer from the CdSe nanoplatelets to the surface-bound triplet acceptor 9-anthracene in both solution and in solid-state upconversion devices fabricated by solution-casting. In solution, we obtain an upconversion quantum yield of (6±1)% at a power density of 11 W/cm2­using the annihilator 9,10-diphenylanthracene, and a low efficiency threshold Ithof 200 mW/cm2. Bilayer solid-state show low efficiency thresholds of 124 mW/cm2, however, suffer detrimental effects from parasitic low-energy excimer formation. This indicates that the overall brightness of the UC device and the Ithdo not necessarily correlate. This system provides a new avenue towards investigating the role of exciton transport on the upconversion mechanism.

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.

Chiral junctions of carbon nanotubes have the potential of serving as optically or electrically controllable switches. To investigate optoelectronic tuning of a chiral junction, we stamp carbon nanotubes onto a transparent gold surface and locate a tube with a semiconducting-metallic junction. We image topography, laser absorption at 532 nm, and measure I-V curves of the junction with nanometer spatial resolution. The bandgaps on both sides of the junction depend on the applied tip field (Stark effect), so the semiconducting-metallic nature of the junction can be tuned by varying the electric field from the STM tip. Although absolute field values can only be estimated because of the unknown tip geometry, the bandgap shifts are larger than expected from the tip field alone, so optical rectification of the laser and carrier generation by the laser must also affect the bandgap switching of the chiral junction.

Atomically flat, conductive, and transparent noble metal films are produced to extend the wavelength range of room-temperature single-molecule optical absorption detected by scanning tunneling microscopy (SMA-STM). Gold films grown on a platinum underlayer to 15 nm total thickness, deposited by electron beam evaporation onto c-plane sapphire substrates, show sufficient light transmission for backside illumination for laser-assisted STM experiments. Low resistance, transparency, and the atomically flat island surfaces make these good substrates for SMA-STM studies. Monte Carlo lattice kinetics were simulated to allow for a better understanding of the growth modes of the Pt–Au films and of the achieved morphologies. SMA-STM is detected for a quantum dot deposited by aerosol spraying onto Pt–Au films, demonstrating the suitability of such films for single-molecule absorption spectroscopy studies.