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Perovskite light-emitting diodes (PeLEDs) have undergone rapid development in the last several years with external quantum efficiencies (EQEs) reaching over 21%. However, most PeLEDs still suffer from severe efficiency roll-off (droop) at high injection current densities, thus limiting their achievable brightness and presenting a challenge to their use in laser diode applications. In this work, we show that the roll-off characteristics of PeLEDs are affected by a combination of charge injection imbalance, nonradiative Auger recombination, and Joule heating. To realize ultrabright and efficient PeLEDs, several strategies have been applied. First, we designed an energy ladder to balance the electron and hole transport. Second, we optimized perovskite materials to possess reduced Auger recombination rates and improved carrier mobility. Third, we replaced glass substrates with sapphire substrates to better dissipate joule heat. Finally, by applying a current-focusing architecture, we achieved PeLEDs with a record luminance of 7.6 Mcd/m2. The devices can be operated at very high current densities (J) up to ∼1 kA/cm2. Our work suggests a broad application prospect of perovskite materials for high-brightness LEDs and ultimately a potential for solution-processed electrically pumped laser diodes.

The recent ExecutiveOrder by President Trump attempting to ban temporarily the citizens of seven countries (Iran, Iraq, Libya, Somalia, Sudan, Syria, and Yemen) from entering the United States is having significant consequences within the country and around the world. The Order poses a threat to the health and vitality of science, barring students and scientists from these countries from traveling to the United States to study or to attend conferences. In preventing those members of the international scientific community from traveling beyond U.S. borders without guaranteed safe return, the Executive Order demeans them; in so doing, it demeans us all. Universities and research communities are especially impacted, as major universities have students and often faculty holding passports from one of these seven countries. This temporary ban would affect refugees fleeing war-torn areas, challenging the long-standing notion that the United States is a safe haven for those fleeing persecution and war in addition to being a magnet for talent from every corner of the world. The pages of this journal reflect the geographic, ethnic, and cultural diversity that underpins great science. The ban impacts domestic and global scientific efforts and communities. Science succeeds through the cooperation between collections of individuals and teams around the world discovering and learning from each other. To ensure rapid scientific progress, open communication and exchange between scientists are essential. As scientists, engineers, and clinicians, we have benefited from open interactions and collaborations with visitors and students from all parts of the world as well as through scientific publications and discussions at scientific meetings.

We use high-resolution, spatially resolved, laser beam induced current, confocal photoluminescence, and photoconductive atomic force microscopy (pcAFM) measurements to correlate local solar cell performance with spatially heterogeneous local material properties in methylammonium lead triiodide (CH3NH3PbI3) perovskite solar cells. We find that, for this material and device architecture, the photocurrent heterogeneity measured via pcAFM on devices missing a top selective contact with traditional Au-coated tips is significantly larger than the photocurrent heterogeneity observed in full devices with both electron- and hole-selective extraction layers, indicating that extraction barriers at the Au/perovskite interface are ameliorated by deposition of the organic charge extraction layer. Nevertheless, in completed, efficient device structures (PCE ≈ 16%) with state-of-the-art nickel oxide and [6,6]-phenyl-C61-butyric acid (PCBM) methyl ester contacts, we observe that the local photoluminescence (PL) is weakly ...

We study light-induced dynamics in thin films comprising Ruddlesden-Popper phases of the layered 2D perovskite (C4H9NH3)2PbI4. We probe ionic and electronic carrier dynamics using two complementary scanning probe methods, time-resolved G-mode Kelvin probe force microscopy and fast free time-resolved electrostatic force microscopy, as a function of position, time, and illumination. We show that the average surface photovoltage sign is dominated by the band bending at the buried perovskite-substrate interface. However, the film exhibits substantial variations in the spatial and temporal response of the photovoltage. Under illumination, the photovoltage equilibrates over hundreds of microseconds, a time scale associated with ionic motion and trapped electronic carriers. Surprisingly, we observe that the surface photovoltage of the 2D grain centers evolves more rapidly in time than at the grain boundaries. We propose that the slower evolution at grain boundaries is due to a combination of ion migration occurring between PbI4 planes, as well as electronic carriers traversing grain boundary traps, thereby changing the time-dependent band unbending at grain boundaries. These results provide a model for the photoinduced dynamics in 2D perovskites and are a useful basis for interpreting photovoltage dynamics on hybrid 2D/3D structures.

Moisture, in the form of ambient humidity, has a significant impact on methylammonium lead halide perovskite films. In particular, due to the hygroscopic nature of the methylammonium component, moisture plays a significant role during film formation. This issue has so far not been well understood and neither has the impact of moisture on the physical properties of resultant films. Herein, we carry out a comprehensive and well-controlled study of the effect of moisture exposure on methylammonium lead halide perovskite film formation and properties. We find that films formed in higher humidity atmospheres have a less continuous morphology but significantly improved photoluminescence, and that film formation is faster. In photovoltaic devices, we find that exposure to moisture, either in the precursor solution or in the atmosphere during formation, results in significantly improved open-circuit voltages and hence overall device performance. We then find that by post-treating dry films with moisture exposure, we can enhance photovoltaic performance and photoluminescence in a similar way. The enhanced photoluminescence and open-circuit voltage imply that the material quality is improved in films that have been exposed to moisture. We determine that this improvement stems from a reduction in trap density in the films, which we postulate to be due to the partial solvation of the methylammonium component and "self-healing" of the perovskite lattice. This work highlights the importance of controlled moisture exposure when fabricating high-performance perovskite devices and provides guidelines for the optimum environment for fabrication. Moreover, we note that often an unintentional water exposure is likely responsible for the high performance of solar cells produced in some laboratories, whereas careful synthesis and fabrication in a dry environment will lead to lower-performing devices.

We use correlated confocal and wide-field fluorescence microscopy to probe the interplay between local variations in charge carrier recombination and charge carrier transport in methylammonium lead triiodide perovskite thin films. We find that local photoluminescence variations present in confocal imaging are also observed in wide-field imaging, while intensity-dependent confocal measurements show that the heterogeneity in nonradiative losses observed at low excitation powers becomes less pronounced at higher excitation powers. Both confocal and wide-field images show that carriers undergo anisotropic diffusion due to differences in intergrain connectivity. These data are all qualitatively consistent with trap-dominated variations in local photoluminescence intensity and with grain boundaries that exhibit varying degrees of opacity to carrier transport. We use a two-dimensional kinetic model to simulate and compare confocal time-resolved photoluminescence decay traces with experimental data. The simulations further support the assignment of local variations in nonradiative recombination as the primary cause of photoluminescence heterogeneity in the films studied herein. These results point to surface passivation and intergrain connectivity as areas that could yield improvements in perovskite solar cells and optoelectronic device performance.

We apply a combination of photoswitch-modified DNA and AFM-based pulling measurements to study the force-induced melting of double-stranded DNA in the unzipping geometry. We measure the differences in peak rupture force for azobenzene-modified DNA, as the incorporated azobenzenes are photoswitched reversibly between the trans and the cis form. Fitting our rupture force versus loading rate data, we obtain off rate (koff) at zero force values in the range of ∼10 s(-1). We show that the change in peak rupture force and koff induced by destabilizing the DNA duplex depends on the position of the destabilizing azobenzene photoswitch relative to the force-loading site. When the azobenzenes are proximal to the unzipping end, the decrease in peak force and koff upon azobenzene photoisomerization is significantly larger than when the azobenzene is distal to the site of force loading. We interpret these results as experimental evidence supporting the picture that the destabilization of a double-stranded DNA by a photoswitch isomerization is localized to a small bubble around the photoswitch.

Plasmonic metal nanoparticles have been used to enhance the performance of thin-film devices such as organic photovoltaics based on polymer/fullerene blends. We show that silver nanoprisms accumulate long-lived negative charges when they are in contact with a photoexcited bulk heterojunction blend composed of poly(3-hexylthiophene)/phenyl-C61-butyric acid methyl ester (P3HT/PCBM). We report both the charge modulation and electroabsorption spectra of silver nanoprisms in solid-state devices and compare these spectra with the photoinduced absorption spectra of P3HT/PCBM blends containing silver nanoprisms. We assign a previously unidentified peak in the photoinduced absorption spectra to the presence of photoinduced electrons on the silver nanoprisms. We show that coating the nanoprisms with a 2.5 nm thick insulating layer can completely inhibit this charging. These results may inform methods for limiting metal-mediated losses in plasmonic solar cells.

We use frequency-modulated electrostatic force microscopy to track changes in cantilever quality factor (Q) as a function of photochemical damage in a model organic photovoltaic system poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] (PTB7) and 3'H-cyclopropa[8,25][5,6]fullerene-C71-D5h(6)-3'-butanoic acid, 3'-phenyl-, methyl ester (PC71BM). We correlate local Q factor imaging with macroscopic device performance and show that, for this system, changes in cantilever Q correlate well with changes in external quantum efficiency and can thus be used to monitor local photochemical damage over the entire functional lifetime of a PTB7:PC71BM solar cell. We explore how Q imaging is affected by the choice of cantilever resonance frequency. Finally, we use Q imaging to elucidate the differences in the evolution of nanoscale structure in the photochemical damage occurring in PTB7:PC71BM solar cells processed with and without the solvent additive 1,8-diiodooctane (DIO). We show that processing with DIO not only yields a preferable morphology for uniform performance across the surface of the device but also enhances the stability of PTB7:PC71BM solar cells-an effect that can be predicted based on the local Q images.

In this study, we demonstrate how the vertical morphology of bulk heterojunction solar cells, with an active layer consisting of self-assembled poly(3-hexylthiophene) (P3HT) nanowires and phenyl-C(61)-butyric acid methyl ester (PCBM), can be beneficially influenced. Most device fabrication routes using similar materials employ an annealing step to influence active layer morphology, but this process can create an unfavorable phase migration where P3HT is driven toward the top of the active layer. In contrast, we demonstrate devices that exhibit an increase in relative fullerene concentration at the top of the active layer by introducing the donor phase as a solid nanowire in the active layer solution and altering the pre-spin drying time. X-ray photoelectron spectroscopy and conductive and photoconductive atomic force microscopy provide detailed images of how the surface of the active layer can be influenced; this is done by tracking the concentration and alignment of P3HT and PCBM domains. Using this new procedure, devices are made with power conversion efficiencies surpassing 2%. Additionally, we show that nanowires grown in the presence of the fullerene perform differently than those that are grown and mixed separately; exposure to the nanowire during self-assembly may allow the fullerene to coat nanowire surfaces and influence the photocurrent within the device.

We report studies of bulk heterojunction solar cells composed of self-assembled poly(3-butylthiophene) nanowires (P3BT-nw) as the donor component with a fullerene acceptor. We show that the nanostructure of these devices is the single most important variable determining their performance, and we use a combination of solvent and thermal annealing to control it. A combination of conductive and photoconductive atomic force microscopy provides direct connections between local nanostructure and overall device performance. Films with a dense random web of nanowires cause the fullerene to aggregate in the interstices, giving a quasi-ordered interpenetrating heterojunction with high short-circuit current density (10.58 mA/cm(2)), but relatively low open circuit voltage (520 mV). Films with a low density of nanowires result in a random bulk heterojunction composed of small crystalline PCBM and P3BT phases. Fewer nanowires result in higher open circuit voltage (650 mV) but lower current density (6.02 mA/cm(2)). An average power conversion efficiency of 3.35% was achieved in a structure which balances these factors, with intermediate nanowire density. The best photovoltaic performance would be realized in a material structure which maintains the interpenetrating network of nanowires and fullerene phases (high current density), but avoids the device bridging we observe, and the recombination and shunt losses associated with it (high open-circuit voltage).

We use photoluminescence (PL) quenching and photoinduced absorption (PIA) spectroscopy to study charge transfer in bulk heterojunction blends of PbSe quantum dots with the semiconducting polymers poly-3-hexylthiophene (P3HT) and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-para-phenylene vinylene] (MDMO-PPV). PIA spectra from the PbSe blends are compared to spectra from similar blends of the polymers with phenyl-C(61)-butyric acid methyl ester (PCBM) and blends with CdSe quantum dots. We find that the MDMO-PPV PL is quenched, and the PL lifetime is shortened upon addition of PbSe quantum dots, while the PL of the P3HT is unaffected upon blending. However, for PbSe blends with both polymers, the PIA spectra show very little polaronic signal, suggesting that few, if any, long-lived charges are being produced by photoinduced charge transfer.

Solution-processable semiconductor materials ranging from conjugated polymers and small organic molecules to colloidal inorganic nanoparticles are being studied for applications in both low-cost solar cells and photodetectors. High-quality thin films of many inorganic semiconductors can be prepared by techniques such as chemical vapor deposition, molecular beam epitaxy, and atomic layer deposition. In contrast, preparing device-quality films of inorganic materials from colloidal solutions can be more difficult due to the challenge of achieving well-defined doping, controlled trap densities, and reproducible surface chemistry. Nevertheless, solution deposition using colloidal precursors is an attractive goal because of the potential for low-cost, large-area processing. In recent years, a great deal of effort has focused on the colloidal synthesis of wide-band-gap metal oxides such as TiO(2), visible-absorbing II-VI compounds such as CdSe, and small-band-gap materials such as PbSe. Much of the work on visible- and IR-absorbing photodetectors has been done on materials containing metals such as Cd and Pb. A new paper in this issue demonstrates photoconductive detectors made from Cu-containing In(2)S(3) nanoplates. The incorporation of Cu into the In(2)S(3) nanoplates leads to a significant decrease in the lifetime of the photoexcited carriers, resulting in significantly faster response times for the photodetectors processed from colloidal solution.

Solution processable methanofullerene-based solar cells are the most widely studied class of organic photovoltaics (OPVs). The evolution of the electronic properties with solvent vapor annealing (SVA) in polyfluorene-copolymer and [6,6]phenyl-C61-butyric acid methyl ester (PCBM) blended OPVs is studied using various scanning probe techniques: light beam induced current spectroscopy (LBIC), conductive atomic force microscopy (c-AFM), and photoconductive AFM (pc-AFM). We demonstrate that SVA improves the power conversion efficiency by 40% while forming mesoscopic PCBM crystallites and a approximately 3 nm copolymer-rich overlayer at the cathode interface. We find that the large crystallites created during annealing do not directly improve the local performance of the device, but instead attribute the performance improvement to the ripened blend morphology and an increase in the hole mobility of the copolymer in comparison to the unannealed blend. The PCBM-rich aggregates act as a sink for excess PCBM, although excess PCBM is initially required to form the appropriate structural features prior to the annealing process.