RESUMEN

The short charge-carrier diffusion length (LD ) (100-300 nm) in organic bulk heterojunction (BHJ) impedes the further improvement in power conversion efficiency (PCE) of organic solar cells (OSCs), especially for thick-film (>400 nm) devices matching with industrial solution processing. Here a facile method is developed to efficiently increase LD and then improve PCEs of OSCs via introducing a fullerene liquid crystal, F1, into the active layer. F1 combines the inherent high electron mobility of fullerene and strong self-assembly capacity of liquid crystal, providing a fast channel for charge-carrier transport and reducing energetic disorder and trap density in BHJ film via enhancing crystallization. Typically, in PM6:Y6:F1 BHJ, the enhanced charge-carrier mobility (>10-2 cm-2 V-1 s-1 ) and prolonged charge-carrier lifetime (55.3 µs) are acquired to realize the record LD of 1.6 or 2.4 µm for electron or hole, respectively, which are much higher than those of the PM6:Y6 binary sample and comparable to or even better than those values reported for some inorganic/hybrid materials, such as CuInx Ga(1- x ) Se2 (CIGS) and perovskite thin films. Benefitting from the micrometer-scale LD , the PM6:Y6:F1 ternary OSCs sustain a remarkable PCE of 15.23% with the active layer thickness approaching 500 nm.

RESUMEN

Covalent organic frameworks (COFs)-based photocatalysts have received growing attention for photocatalytic hydrogen (H2 ) production. One of the big challenges in the field is to find ways to promote energy/electron transfer and exciton dissociation. Addressing this challenge, herein, a series of olefin-linked 2D COFs is fabricated with high crystallinity, porosity, and robustness using a melt polymerization method without adding volatile organic solvents. It is found that regulation of the spatial distances between the acceptor units (triazine and 2, 2'-bipyridine) of COFs to match the charge carrier diffusion length can dramatically promote the exciton dissociation, hence leading to outstanding photocatalytic H2 evolution performance. The COF with the appropriate acceptor distance achieves exceptional photocatalytic H2 evolution with an apparent quantum yield of 56.2% at 475 nm, the second highest value among all COF photocatalysts and 70 times higher than the well-studied polymer carbon nitride. Various experimental and computation studies are then conducted to in-depth unveil the mechanism behind the enhanced performance. This study will provide important guidance for the design of highly efficient organic semiconductor photocatalysts.

RESUMEN

Solution-processed metal-based halide perovskites have taken a dominant position for perovskite optoelectronics including light emission and X-ray detection; however, the toxicity of the included heavy metals severely restricts their applications for wearable, lightweight, and transient optoelectronic devices. Here, the authors describe investigations of large (4 × 6 × 2 mm3 ) 3D metal-free perovskite MDABCO-NH4 I3 (MDBACO = methyl-N'-diazabicyclo[2.2.2]octonium) single crystal and its charge recombination and extraction behavior for light emission and X-ray detection. Unlike conventional 3D metal-based perovskites, this lightweight and biocompatible perovskite large crystal is processed from aqueous solution at room temperature, and can achieve both an extremely long carrier lifetime up to ≈1.03 µs and the formation of self-trapped excited states for luminescence. These features contribute to a photoluminescence quantum yield (PLQY) as high as ≈53% at room temperature and an X-ray sensitivity up to 1997 ± 80 µC Gy cm-2 at 50 V bias (highest among all metal-free detectors). The ability to tune the perovskite band gap by modulating the structure under high pressure is also demonstrated, which opens up applications for the crystal as colored emitters. These attributes make it a molecular alternative to metal-based perovskites for biocompatible and transient optoelectronics.

Asunto(s)

RESUMEN

Metal-free halide perovskites, as a specific category of the perovskite family, have recently emerged as novel semiconductors for organic ferroelectrics and promise the wide chemical diversity of the ABX3 perovskite structure with mechanical flexibility, light weight, and eco-friendly processing. However, after the initial discovery 17 years ago, there has been no experimental information about their charge transport properties and only one brief mention of their optoelectronic properties. Here, growth of large single crystals of metal-free halide perovskite DABCO-NH4 Br3 (DABCO = N-N'-diazabicyclo[2.2.2]octonium) is reported together with characterization of their instrinsic optical and electronic properties and demonstration, of metal-free halide perovskite optoelectronics. The results reveal that the crystals have an unusually large semigap of ≈16 eV and a specific band nature with the valence band maximum and the conduction band minimum mainly dominated by the halide and DABCO2+ , respectively. The unusually large semigap rationalizes extremely long lifetimes approaching the millisecond regime, leading to very high charge diffusion lengths (tens of µm). The crystals also exhibit high X-ray attenuation as well as being lightweight. All these properties translate to high-performance X-ray imaging with sensitivity up to 173 µC Gyair -1 cm-2 . This makes metal-free perovskites novel candidates for the next generation of optoelectronics.

RESUMEN

Wavelength-dependent (i.e. penetration-depth-dependent) lateral photocurrent (i LP ) measurement has been used to extract depth-resolved L c profiles, where L c is the minority carrier collection length by diffusion. The extracted L c depth-profiles can be used to determine the minority carrier diffusion length and back-surface recombination velocity in Cu(In,Ga)Se2 (CIGS) thin film solar cells (Chung, 2019). During the measurement of i LP , the CIGS thin film is generally exposed to air. The CIGS thin films can be degraded by air exposure (Metzger et al., 2009). Therefore, it will be helpful to know the effect of air exposure time of CIGS thin films on the i LP values to properly estimate the electrical quality of CIGS thin films.

RESUMEN

Tandem photovoltaics, combining absorber layers with two distinct band gap energies into a single device, provide a practical solution to reduce thermalization losses in solar energy conversion. Traditionally, tandem devices have been assembled using two-terminal (2-T) or four-terminal (4-T) configurations; the 2-T limits the tandem performance due to the series connection requiring current matching, while the standard 4-T configuration requires at least three transparent electrical contacts, which reduce the total collected power due to unavoidable parasitic absorption. Here, we introduce a novel architecture based on a nanoscale back-contact for a thin-film top cell in a three terminal (3-T) configuration. Using coupled optical-electrical modeling, we optimize this architecture for a planar perovskite-silicon tandem, highlighting the roles of nanoscale contacts to reduce the required perovskite electronic quality. For example, with an 18% planar silicon base cell, the 3-T back contact design can reach a 32.9% tandem efficiency with a 10 µm diffusion length perovskite material. Using the same perovskite quality, the 4-T and 2-T configurations only reach 30.2% and 24.8%, respectively. We also confirm that the same 3-T efficiency advantage applies when using 25% efficient textured silicon base cells, where the tandems reach 35.2% and 32.8% efficiency for the 3-T, and 4-T configurations, respectively. Furthermore, because our design is based on the individual subcells being back-contacted, further improvements can be readily made by optimizing the front surface, which is left free for additional antireflective coating, light trapping, surface passivation, and photoluminescence outcoupling enhancements.

RESUMEN

The minority carrier diffusion length (LD) is a crucial property that determines the performance of light absorbers in photoelectrochemical (PEC) cells. Many transition-metal oxides are stable photoanodes for solar water splitting but exhibit a small to moderate LD, ranging from a few nanometers (such as α-Fe2O3 and TiO2) to a few tens of nanometers (such as BiVO4). Under operating conditions, the temperature of PEC cells can deviate substantially from ambient, yet the temperature dependence of LD has not been quantified. In this work, we show that measuring the photocurrent as a function of both temperature and absorber dimensions provides a quantitative method for evaluating the temperature-dependent minority carrier transport. By measuring photocurrents of nonstoichiometric rutile TiO2-x nanowires as a function of wire radius (19-75 nm) and temperature (10-70 °C), we extract the minority carrier diffusion length along with its activation energy. The minority carrier diffusion length in TiO2-x increases from 5 nm at 25 °C to 10 nm at 70 °C, implying that enhanced carrier mobility outweighs the increase in the recombination rate with temperature. Additionally, by comparing the temperature-dependent photocurrent in BiVO4, TiO2, and α-Fe2O3, we conclude that the ratio of the minority carrier diffusion length to the depletion layer width determines the extent of temperature enhancement, and reconcile the widespread temperature coefficients, which ranged from 0.6 to 1.7% K-1. This insight provides a general design rule to select light absorbers for large thermally activated photocurrents and to predict PEC cell characteristics at a range of temperatures encountered during realistic device operation.

RESUMEN

Organometal halide perovskite has emerged as a promising material for solar cells and optoelectronics. Although the long diffusion length of photogenerated carriers is believed to be a critical factor responsible for the material's high efficiency in solar cells, a direct study of carrier transport over long distances in organometal halide perovskites is still lacking. We fabricated highly oriented crystalline CH3NH3PbI3 (MAPbI3) thin-film lateral transport devices with long channel length (∼120 µm). By performing spatially scanned photocurrent imaging measurements with local illumination, we directly show that the perovskite films prepared here have very long transport lengths for photogenerated carriers, with a minority carrier (electron) diffusion length on the order of 10 µm. Our approach of applying scanning photocurrent microscopy to organometal halide perovskites may be further used to elucidate the carrier transport processes and the vastly different carrier diffusion lengths (∼100 nm to 100 µm) in different types of organometal halide perovskites.

RESUMEN

We investigate solution-grown single-crystal methylammonium lead iodide (MAPbI3) nanowires and nanoplates with spatially resolved photocurrent mapping. Sensitive perovskite photodetectors with Schottky contacts are fabricated by directly transferring the nanostructures on top of prepatterned gold electrodes. Scanning photocurrent microscopy (SPCM) measurements on these single-crystal nanostructures reveal a minority charge carrier diffusion length up to 21 µm, which is significantly longer than the values observed in polycrystalline MAPbI3 thin films. When the excitation energy is close to the bandgap, the photocurrent becomes substantially stronger at the edges of nanostructures, which can be understood by the enhancement of light coupling to the nanostructures. These perovskite nanostructures with long carrier diffusion lengths and strong photonic enhancement not only provide an excellent platform for studying their intrinsic properties but may also boost the performance of perovskite-based optoelectronic devices.

RESUMEN

Light trapping in subwavelength semiconductor nanowires (NWs) offers a promising approach to simultaneously reducing material consumption and enhancing photovoltaic performance. Nevertheless, the absorption efficiency of a NW, defined by the ratio of optical absorption cross section to the NW diameter, lingers around 1 in existing NW photonic devices, and the absorption enhancement suffers from a narrow spectral width. Here, we show that the absorption efficiency can be significantly improved in NWs with higher refractive indices, by an experimental observation of up to 350% apparent external quantum efficiency in lead sulfide NW resonators, a 3-fold increase compared to Si NWs. Furthermore, broadband absorption enhancement is achieved in single tapered NWs, where light of various wavelengths is absorbed at segments with different diameters. Overall, the single NW Schottky junction solar cells benefit from optical resonance, near bandgap open circuit voltage, and long minority carrier diffusion length, demonstrating power conversion efficiency comparable to Si and III-V single NW coaxial p-n junction cells but with much simpler fabrication processes.

RESUMEN

Nanowires have large surface areas that create new challenges for their optoelectronic applications. Lithographic processes involved in device fabrication and substrate interfaces can lead to surface defects and substantially reduce charge carrier lifetimes and diffusion lengths. Here, we show that using a bridging method to suspend pristine nanowires allows for circumventing detrimental fabrication steps and interfacial effects associated with planar device architectures. We report electron diffusion lengths up to 2.7 µm in bridged silicon nanowire devices, much longer than previously reported values for silicon nanowires with a diameter of 100 nm. Strikingly, electron diffusion lengths are reduced to only 45 nm in planar devices incorporating nanowires grown under the same conditions. The highly scalable silicon nanobridge devices with the demonstrated long diffusion lengths may find exciting applications in photovoltaics, sensing, and photodetectors.