Search

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.

In a recent work, Nguyen et al. used trSMA-STM to probe electron-phonon dynamics within single carbon dots with nanometer resolution on a picosecond timescale. This promising technique opens up novel avenues to understand fluorescence quantum yield variations in carbon-dot ensembles.

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.

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.

Summary Studying nanoscale photophysical processes is mandatory to fully understand the complex optoelectronic properties in semiconductor materials used in photovoltaics and light emitting diodes. In this perspective, we target specific scanning probe techniques, which combine scanning tunneling microscopy (STM) with optical methods to unravel the localized optoelectronic properties of semiconductors under realistic electric and optical fields, down to the nanoscale. Combining optical spectroscopy with STM yields a powerful platform that allows for simultaneous imaging of the surface morphology and the electronic structure down to the atomic level, a resolution that is otherwise not accessible due to the optical diffraction limit. Incident wavelengths spanning the electromagnetic spectrum from the terahertz region to X-rays have been coupled into the STM tip-sample junction to investigate the nanoscale properties of semiconductor materials, whereas the reverse process of luminescence can give insight on local recombination processes. Imagine the potential of a tool capable of detecting both localized absorption and spontaneous and stimulated emission processes of semiconductor materials at the nanoscale. The role of every atom, defect, or electronic interaction could be disentangled, tailored, or harnessed to its maximum capacity.

Incorporating a low dimensional LD perovskite capping layer on top of a perovskite absorber, improves the stability of perovskite solar cells PSCs . However, in the case of mixed halide perovskites, which can undergo halide segregation into single halide perovskites, a systematic study of the capping layer s effect on mixed halide perovskite absorber is still lacking. This study bridges this gap by investigating how the 1D perovskite capping layers on top of MAPb IxBr1 amp; 8722;x 3 x 0, 0.25, 0.5, 0.75, 1 absorbers affect the films stability. We utilize a new method, dissimilarity matrix, to investigate the image based stability performance of capping absorber pair compositions across time. This method overcomes the challenge of analyzing various film colors due to bandgap difference in mixed halide perovskites. We also discover that the intrinsic absorber stability plays an important role in the overall stability outcome, despite the capping layer s support. Within the 55 unique capping absorber pairs, we observe a notable 1D perovskite material, 1 methoxynaphthalene 2 ethylammonium chloride 2MeO NEA Cl or 9 Cl , that improves the stability of MAPbI3 and MAPb I0.5Br0.5 3 by at least 8 and 1.5 times, respectively, compared to bare films under elevated humidity and temperature. Surface photovoltage results also show that the accumulation of electrostatic charges on the film surface depends on the capping layer type, which could contribute to the acceleration deceleration of degradation

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.

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, as well as an increased driving force for charge transfer.

Summary We investigate the rubrene triplet sensitization by perovskite thin films based on methylammonium formamidinium lead triiodide (MAFA) of varying thicknesses. The power-law dependence of both the MAFA photoluminescence (PL) intensity and upconverted emission is tracked as a function of the incident power density. Bimolecular triplet-triplet annihilation (TTA) exhibits a unique power-law dependence with a slope change from quadratic-to-linear at the threshold Ith. The underlying MAFA PL power-law dependence dictates the power law of the upconverted PL: (1) below Ith, the slope of the upconverted PL is twice the value of the MAFA PL; (2) above Ith, it follows the same power law as the underlying recombination of mobile electrons and holes in the MAFA films. We find that the Ith shifts to subsolar incident laser powers when increasing the MAFA thickness above 30 nm. For the thickest MAFA film of 380 nm we find an upconversion threshold of Ith = 7.1 mW/cm2.

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...

Upconversion via triplet-triplet annihilation could efficiently generate ultraviolet light. In a recent work, Harada et al. have doubled the existing visible-to-UV upconversion efficiency and demonstrated a new record using a new triplet annihilator, yielding efficient upconversion using even low-energy LEDs.

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.

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. A silicon and tetracene solar cell employing singlet fission uses an eight-angstrom-thick hafnium oxynitride interlayer to promote efficient triplet transfer, increasing the efficiency of the cell.

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.

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.

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

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.

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...

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

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.

High internal quantum efficiency semiconductor nanocrystal (NC)-based photon upconversion devices are currently based on a single monolayer of active NCs. Devices are therefore limited in their external quantum efficiency based on the low number of photons absorbed. Increasing the number of photons absorbed is expected to increase the upconversion efficiency, yet experimentally increasing the number of layers does not appreciably increase the upconverted light output. We unravel this mystery by combining kinetic modeling and transient photoluminescence spectroscopy. The inherent energetic disorder stemming from the polydispersity of the NCs means that the kinetics are governed by a stochastic transfer matrix. By drawing the rates from a probabilistic distribution and constructing a reaction network with realistic connectivity, we are able to fit complex photoluminescence traces with a very simple model. We use this model to explain the thickness-dependent performance of the upconversion devices and can attribute the reduced efficiencies to the low excitonic diffusivity of the exciton within the NC layers and increased back transfer of the created singlets from the organic annihilator rubrene. We suggest some avenues for overcoming these limitations in future devices.

The conversion of energy within materials has many applications. If one could convert the energy of a blue photon into two lower-energy particles, or into two red photons, solar cells could be fabricated much more efficiently. On the other hand, if one could combine the energy of two particles to form higher-energy particles, it could be used to activate a chemical reaction, for example, releasing a drug or sensitizing a standard silicon camera for infrared light.

Lead halide perovskites have emerged as promising absorber materials over the last decade to increase the efficiency of photovoltaics beyond its current limits. However, to further optimize the performance of perovskites more detailed studies need to be performed, which allow for the correlation of film morphology and local electronic properties at the nanoscale. Here, we present a scanning tunneling microscopy (STM) approach to probe the effect of an applied electric field of a methylammonium formamidinium lead triiodide perovskite thin film on the film response by current–voltage spectroscopy, current imaging tunneling spectroscopy, differential conductance mapping, and x-ray absorption spectroscopy by means of synchrotron x-ray STM. We find a strong correlation between the measurement conditions and the obtained current–voltage characteristics when imaging under opposite bias polarities. In particular, we find similarities to already observed poling effects for lead halide perovskites, which result in either a positively or negatively charged interface due to ion and vacancy migration. Our results provide insight into the influence of measurement conditions such as bias polarity on the performance assessment of perovskite thin films by STM.

Lead halide-based perovskite thin films have attracted great attention due to the explosive increase in perovskite solar cell efficiencies. The same optoelectronic properties that make perovskites ideal absorber materials in solar cells are also beneficial in other light-harvesting applications and make them prime candidates as triplet sensitizers in upconversion via triplet-triplet annihilation in rubrene. In this contribution, we take advantage of long carrier lifetimes and carrier diffusion lengths in perovskite thin films, their high absorption cross sections throughout the visible spectrum, as well as the strong spin-orbit coupling owing to the abundance of heavy atoms to sensitize the upconverter rubrene. Employing bulk perovskite thin films as the absorber layer and spin-mixer in inorganic/organic heterojunction upconversion devices allows us to forego the additional tunneling barrier owing from the passivating ligands required for colloidal sensitizers. Our bilayer device exhibits an upconversion efficiency in excess of 3% under 785 nm illumination.

The same optical and electronic properties that make perovskite thin films ideal absorber materials in photovoltaic applications are also beneficial in photon upconversion devices. In this contribution, we investigate the rubrene-triplet sensitization by perovskite thin films based on methylammonium formamidinium lead triiodide (MAFA). To elucidate the role of trap states which affect the free carrier lifetimes, we fabricate MAFA perovskite thin films with three different thicknesses. By measuring the change in the photoluminescence properties under different excitation fluences, we find that the prevalent recombination mechanism shifts from monomolecular for thinner films to bimolecular recombination for thicker MAFA films, indicating a reduction in shallow trap-assisted recombination. The addition of rubrene shows a passivating effect on the MAFA surface, but adds an additional quenching pathway due to charge transfer to the triplet state of rubrene. We observe that the threshold for efficient triplet-triplet annihilation shifts to lower incident powers with increasing MAFA thickness, which suggests that the charge transfer to the triplet state competes with non-radiative trap filling. Hence, injection of free electrons and holes into the upconverting organic semiconductor can provide a new avenue for sensitization of rubrene, and may allow us to move away from the necessity of efficient excitonic singlet-to-triplet converters.

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.

Perovskite solar cells (PSCs) are very promising lab-scale technologies to deliver inexpensive solar electricity. Low-temperature, planar PSCs are of particularly interest for large-scale deployment due to their inherent suitability for flexible substrates and potential for silicon/perovskite tandems. So far, planar PSCs have been prone to large current-voltage hysteresis and low stabilized power output due to a number of issues associated with this kind of device configuration. We find that the suppression of the yellow-phase impurity (∂-FAPbI3) present in formamidium-based perovskites, by RbI addition, contributes to low hysteresis, higher charge carrier mobility, long-lived carrier lifetimes and a champion stabilized power output of 20.3% using SnOx as the electron selective contact. We study the effects of these impurities on the transient behavior that defines hysteresis and its relation to ionic movement. In addition, we find that the formation of a RbPbI3 phase does not significantly affect the charge carrier lifetimes and consequently the performance of the devices. This brings new physical insights onto the role of different impurities in perovskite solar cells, which make these materials so remarkable., US Department of Energy, Office of Science, Office of Basic Energy Sciences (award no. DE-SC0001088)

Hybrid interfaces combining inorganic and organic materials underpin the operation of many optoelectronic and photocatalytic systems and allow for innovative approaches to photon up- and down-conversion. However, the mechanism of exchange-mediated energy transfer of spin-triplet excitons across these interfaces remains obscure, particularly when both the macroscopic donor and acceptor are composed of many separately interacting nanoscopic moieties. Here, we study the transfer of excitons from colloidal lead sulfide (PbS) nanocrystals to the spin-triplet state of rubrene molecules. By reducing the length of the carboxylic acid ligands on the nanocrystal surface from 18 to 4 carbon atoms, thinning the effective ligand shell from 13 to 6 Å, we are able to increase the characteristic transfer rate by an order of magnitude. However, we observe that the energy transfer rate asymptotes for shorter separation distances (≤10 Å) which we attribute to the reduced Dexter coupling brought on by the increased effective dielectric constant of these solid-state devices when the aliphatic ligands are short. This implies that the shortest ligands, which hinder long-term colloidal stability, offer little advantage for energy transfer. Indeed, we find that hexanoic acid ligands are already sufficient for near-unity transfer efficiency. Using nanocrystals with these optimal-length ligands in an improved solid-state device structure, we obtain an upconversion efficiency of (7 ± 1)% with excitation at λ = 808 nm.

Bismuth-based compounds have recently gained increasing attention as potentially nontoxic and defect-tolerant solar absorbers. However, many of the new materials recently investigated show limited photovoltaic performance. Herein, one such compound is explored in detail through theory and experiment: bismuth oxyiodide (BiOI). BiOI thin films are grown by chemical vapor transport and found to maintain the same tetragonal phase in ambient air for at least 197 d. The computations suggest BiOI to be tolerant to antisite and vacancy defects. All-inorganic solar cells (ITO|NiO x |BiOI|ZnO|Al) with negligible hysteresis and up to 80% external quantum efficiency under select monochromatic excitation are demonstrated. The short-circuit current densities and power conversion efficiencies under AM 1.5G illumination are nearly double those of previously reported BiOI solar cells, as well as other bismuth halide and chalcohalide photovoltaics recently explored by many groups. Through a detailed loss analysis using optical characterization, photoemission spectroscopy, and device modeling, direction for future improvements in efficiency is provided. This work demonstrates that BiOI, previously considered to be a poor photocatalyst, is promising for photovoltaics., National Science Foundation (U.S.) (Grant CBET-1605495), United States. Department of Energy. Office of Basic Energy Sciences (Grant DE-SC0001088), National Science Foundation (U.S.) (Grant DMF-08019762)

The relationship between charge-carrier lifetime and the tolerance of lead halide perovskite (LHP) solar cells to intrinsic point defects has drawn much attention by helping to explain rapid improvements in device efficiencies. However, little is known about how charge-carrier lifetime and solar cell performance in LHPs are affected by extrinsic defects (i.e., impurities), including those that are common in manufacturing environments and known to introduce deep levels in other semiconductors. Here, we evaluate the tolerance of LHP solar cells to iron introduced via intentional contamination of the feedstock and examine the root causes of the resulting efficiency losses. We find that comparable efficiency losses occur in LHPs at feedstock iron concentrations approximately 100 times higher than those in p-type silicon devices. Photoluminescence measurements correlate iron concentration with nonradiative recombination, which we attribute to the presence of deep-level iron interstitials, as calculated from first-principles, as well as iron-rich particles detected by synchrotron-based X-ray fluorescence microscopy. At moderate contamination levels, we witness prominent recovery of device efficiencies to near-baseline values after biasing at 1.4 V for 60 s in the dark. We theorize that this temporary effect arises from improved charge-carrier collection enhanced by electric fields strengthened from ion migration toward interfaces. Our results demonstrate that extrinsic defect tolerance contributes to high efficiencies in LHP solar cells, which inspires further investigation into potential large-scale manufacturing cost savings as well as the degree of overlap between intrinsic and extrinsic defect tolerance in LHPs and "perovskite-inspired" lead-free stable alternatives.

Single-molecule experiments based on Forster resonant energy transfer (FRET) or on single molecule absorption spectroscopy (SMA) are now capable of studying energy funneling, exciton blockade, singlet fission, and a variety of other processes that involve multiple photoactive groups interacting on a single molecular backbone. Here, we present synthesis and optical characterization of a new dendron functionalized with two green donor dyes (Cy3) and one red acceptor dye (Cy5) through flexible linkers. We describe in detail the synthesis of the conjugated network and the flexible dye coupling. Characterization of the dendron and of control molecules with fewer donors or no acceptor by ensemble absorption and emission spectroscopy shows that the system is capable of light harvesting, producing an intramolecular FRET signal from the acceptor greater than expected from a single donor. We also investigate intramolecular energy transfer upon UV excitation of the conjugated backbone. The photophysical behavior of this light harvesting dendron can be rationalized by a simple Forster/superexchange model. Simulations and scanning tunneling microscopy of single dendron molecules show that the dyes can fold over onto the dendron, creating a heterogeneous distribution of conformations suitable for single molecule studies of light harvesting.

We analyze the optical, chemical, and electrical properties of chemical vapor deposition (CVD) grown hexagonal boron nitride (h-BN) using the precursor ammonia-borane ($H_3N-BH_3$) as a function of $Ar/H_2$ background pressure ($P_{TOT}$). Films grown at $P_{TOT}$ less than 2.0 Torr are uniform in thickness, highly crystalline, and consist solely of h-BN. At larger $P_{TOT}$, with constant precursor flow, the growth rate increases, but the resulting h-BN is more amorphous, disordered, and $sp^3$ bonded. We attribute these changes in h-BN grown at high pressure to incomplete thermolysis of the $H_3N-BH_3$ precursor from a passivated Cu catalyst. A similar increase in h-BN growth rate and amorphization is observed even at low $P_{TOT}$ if the $H_3N-BH_3$ partial pressure is initially greater than the background pressure $P_{TOT}$ at the beginning of growth. h-BN growth using the $H_3N-BH_3$ precursor reproducibly can give large-area, crystalline h-BN thin films, provided that the total pressure is under 2.0 Torr and the precursor flux is well-controlled., 45 pages including the supporting information, in print at Chemistry of Materials 2016

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.

Correction for ‘Colloidal atomic layer deposition growth of PbS/CdS core/shell quantum dots’ by Michel Nasilowski et al., Chem. Commun., 2017, 53, 869–872.