Search

Perovskite quantum dots (PQDs) have many properties that make them attractive for optoelectronic applications, including expanded compositional tunability and crystallographic stabilization. While they have not achieved the same photovoltaic (PV) efficiencies of top-performing perovskite thin films, they do reproducibly show high open circuit voltage (VOC) in comparison. Further understanding of the VOC attainable in PQDs as a function of surface passivation, contact layers, and PQD composition will further progress the field and may lend useful lessons for non-QD perovskite solar cells. Here, we use photoluminescence-based spectroscopic techniques to understand and identify the governing physics of the VOC in CsPbI3 PQDs. In particular, we probe the effect of the ligand exchange and contact interfaces on the VOC and free charge carrier concentration. The free charge carrier concentration is orders of magnitude higher than in typical perovskite thin films and could be tunable through ligand chemistry. Tuning the PQD A-site cation composition via replacement of Cs+ with FA+ maintains the background carrier concentration but reduces the trap density by up to a factor of 40, reducing the VOC deficit. These results dictate how to improve PQD optoelectronic properties and PV device performance and explain the reduced interfacial recombination observed by coupling PQDs with thin-film perovskites for a hybrid absorber layer.

The design of photocatalysts with hierarchical pore sizes is an effective method to improve mass transport, enhance light absorption, and increase specific surface area. Moreover, the construction of a heterojunction at the interface of two semiconductor photocatalysts with suitable band positions plays a crucial role in separating and transporting charge carriers. Herein, ZIF-8 and urea are used as precursors to prepare hierarchically porous ZnO/g-C3N4 S-scheme heterojunction photocatalysts through a two-step calcination method. This S-scheme heterojunction photocatalyst shows high activity toward photocatalytic H2O2 production, which is 3.4 and 5.0 times higher than that of pure g-C3N4 and ZnO, respectively. The mechanism of charge transfer and separation within the S-scheme heterojunction is studied by Kelvin probe, in situ irradiated X-ray photoelectron spectroscopy (ISI-XPS), and electron paramagnetic resonance (EPR). This research provides an idea of designing S-scheme heterojunction photocatalysts with hierarchical pores in efficient photocatalytic hydrogen peroxide production.

Recently, photoassisted charging has been demonstrated as a green and sustainable approach to successfully enhance the capacitance of supercapacitors with low cost and good efficiency. However, their light-induced capacitance enhancement is relatively low and is lost quickly when the illumination is off. In this work, a novel active material system is developed for supercapacitors with the photoassisted charging capability by the decoration of a small amount of Bi2WO6 nanoparticles on an h-WO3 submicron rod surface in situ, which forms a typical type II band alignment heterostructure with a close contact interface through the co-sharing of W atoms between h-WO3 submicron rods and Bi2WO6 nanoparticles. The photogenerated charge carrier separation and transfer are largely enhanced in the h-WO3/Bi2WO6 submicron rod electrode, which subsequently allows more charge carriers to participate in its photoassisted charging process to largely enhance its capacitance improvement under simulated solar illumination than that of the h-WO3 submicron rod electrode. Furthermore, the h-WO3/Bi2WO6 submicron rod electrode could retain its photoinduced capacitance enhancement in the dark for an extended period of time from the photocatalytic memory effect. Thus, our work provides a solution to the two major drawbacks of reported supercapacitors with the light-induced capacitance enhancement property, and supercapacitors based on active materials with the photocatalytic memory effect could be utilized in various technical fields.

SnO2 films as a promising electron transport layer (ETL) have been widely used in planar-type perovskite solar cells to achieve an impressive improvement in the conversion efficiency. However, compared with a mesoporous ETL, the interfacial charge carrier transfer of the SnO2 ETL is severely limited due to the issues of oxygen vacancy defects and crystal lattice mismatch between SnO2 and the perovskite, which generally leads to the growth of randomly stacked and porous perovskite layers and subsequently impacts the charge transport and transfer properties. In this work, we developed a facile approach by inducing a bifunctional molecule, β-alanine, into the SnO2 ETL, which can serve as a bridge to modulate the interfacial charge transfer and the perovskite crystallization kinetics. Benefited by the interfacial β-alanine, we grew a highly orientational perovskite layer that exhibited superior charge transport properties. Meanwhile, the β-alanine caused an intimate connection between the perovskite and SnO2 to enhance the interfacial charge transfer. As a result, the power conversion efficiency (PCE) of the β-alanine-modified device achieved a much-improved value of 19.67% and showed high reproducibility. This work provides a way for developing a high-performance ETL toward the scalable fabrication of highly efficient PSCs.

Single-crystalline organic semiconductors exhibiting band transport have opened new possibilities for the utilization of efficient charge carrier conduction in organic electronic devices. The epitaxial growth of molecular materials is a promising route for the realization of well-crystallized organic semiconductor p–n junctions for optoelectronic applications enhanced by the improved charge carrier mobility. In this study, the formation of a high-quality crystalline interface upon “quasi-homoepitaxial” growth of bis(trifluoromethyl)dimethylrubrene (fmRub) on the single-crystal surface of rubrene was revealed by using out-of-plane and grazing-incidence X-ray diffraction techniques. Ultraviolet photoelectron spectroscopy results indicated abrupt electronic energy levels and the occurrence of band bending across this quasi-homoepitaxial interface. This study verifies that the minimization of the lattice mismatch enhances the crystalline qualities at the heterojunctions even for van der Waals molecular condensates, potentially opening an untested route for the realization of high-mobility organic semiconductor optoelectronics.

Colloidal semiconductor nanoplatelets (NPLs) are chemical versions of well-studied quantum wells (QWs). For QWs, gating and carrier doping are standard tools to manipulate their optical, electric, or magnetic properties. It would be highly desirable to use pure chemical methods to dope extra charge carriers into free-standing colloidal NPLs to achieve a similar level of manipulation. Here we report colloidal n-doped CdSe and CdSe/ZnS NPLs achieved through a photochemical doping method. The extra electrons doped into the conduction band edges are evidenced by exciton absorption bleaches recoverable through dedoping and the appearance of new intersub-band transitions in the near-infrared. A high surface ligand coverage is the key to successful doping; otherwise, the doped electrons can be depleted likely by unpassivated surface cations. Large trion binding energies of 20-30 meV are found for the n-doped CdSe NPLs, which, in contrast, are reduced by 1 order of magnitude in CdSe/ZnS core/shell NPLs due to dielectric screening. Furthermore, we identify a long-lived negative trion with a lifetime of 1.5-1.6 ns that is likely dominated by radiative recombination.

Quantum defects have been shown to play an essential role in nonradiative recombination in metal halide perovskites (MHPs). Nonetheless, the processes of charge transfer assisted by defects are still ambiguous. Herein, we theoretically study the nonradiative multiphonon processes among different types of quantum defects in MHPs using Markvart's model for the induced mechanisms of electron-electron and electron-phonon interactions. We find that the charge carrier can transfer between the neighboring levels of the same type of shallow defects by multiphonon processes, but it will be distinctly suppressed with an increase in the defect depth. For the nonradiation multiphonon transitions between donor- and acceptor-like defects, the processes are very fast and not sensitive to the defect depth, which provides a possible explanation for the phenomenon of blinking of photoluminescence spectra. We also discuss the temperature dependence of these multiphonon processes and find that their variational trends depend on the comparison of the Huang-Rhys factor with the emitted phonon number. These theoretical results not only fill some of the gaps in defect-assisted nonradiative processes in the perovskite materials but also provide deeper physical insights into producing higher-performance perovskite-based devices.

Zinc oxide (ZnO) nanomaterials are promising components for chemical and biological sensors and photocatalytic conversion and operate as electron collectors in photovoltaic technologies. Many of th...

The generation and transport processes of charge carriers in bilayer organic photovoltaics (OPVs), which rely on a suitable interfacial energy alignment between the donor and acceptor molecules, we...

It is critical to investigate the charge carrier gradient generation in semiconductor junctions with an asymmetric configuration, which can open a new platform for developing lateral photovoltaic and self-powered devices. This paper reports the generation of a charge carrier gradient in a 3C-SiC/Si heterojunction with an asymmetric electrode configuration. 3C-SiC/Si heterojunction devices with different electrode widths were illuminated by laser beams (wavelengths of 405, 521, and 637 nm) and a halogen bulb. The charge carrier distribution along the heterojunction was investigated by measuring the lateral photovoltage generated when the laser spot scans across the 3C-SiC surface between the two electrodes. The highest lateral photovoltage generated is 130.58 mV, measured in the device with an electrode width ratio of 5 and under 637 nm wavelength and 1000 μW illumination. Interestingly, the lateral photovoltage was generated even under uniform illumination at zero bias, which is unusual for the lateral photovoltage, as it can only be generated when unevenly distributed photogenerated charge carriers exist. In addition, the working mechanism and uncovered behavior of the lateral photovoltaic effect are explained based on the generation and separation of electron-hole pairs under light illumination and charge carrier diffusion theory. The finding further elaborates the underlying physics of the lateral photovoltaic effect in nano-heterojunctions and explores its potential in developing optoelectronic sensors.

Tin chalcogenides (SnX, X = S, Se)-based heterostructures (HSs) are promising materials for the construction of low-cost optoelectronic devices. Here, we report the synthesis of a SnSe/CdSe HS using the controlled cation exchange reaction. The (400) plane of SnSe and the (111) plane of CdSe confirm the formation of an interface between SnSe and CdSe. The Type I band alignment is estimated for the SnSe/CdSe HS with a small conduction band offset (CBO) of 0.72 eV through cyclic voltammetry measurements. Transient absorption (TA) studies demonstrate a drastic enhancement of the CdSe biexciton signal that points toward the hot carrier transfer from SnSe to CdSe in a short time scale. The fast growth and recovery of CdSe bleach in the presence of SnSe indicate charge transfer back to SnSe. The observed delocalization of carriers in these two systems is crucial for an optoelectronic device. Our findings provide new insights into the fabrication of cost-effective photovoltaic devices based on SnSe-based heterostructures.

Ammonium ions (NH4+), as non-metallic charge carriers, have spurred great research interest in the realm of aqueous batteries. Unfortunately, most inorganic host materials used in these batteries are still limited by the sluggish diffusion kinetics. Here, we report a unique hydrogen bond chemistry to employ covalent organic frameworks (COFs) for NH4+ ion storage, which achieves a high capacity of 220.4 mAh g-1 at a current density of 0.5 A g-1. Combining the theoretical simulation and materials analysis, a universal mechanism for the reaction of nitrogen and oxygen bridged by hydrogen bonds is revealed. In addition, we explain the solvation behavior of NH4+, leading to a relationship between redox potential and desolvation energy barrier. This work provides a new insight into NH4+ ion storage in host materials based on hydrogen bond chemistry. This mechanism can be leveraged to design and develop COFs for electrochemical energy storage.

Mechanistic understanding of the photogenerated charge carrier dynamics in modified semiconductor photoanodes is vital for the efficient enhancement of photoelectrochemical (PEC) water splitting. Here, an in situ femtosecond (fs)-transient absorption spectroscopy (TAS) assisted spectroelectrochemistry technique is used to probe the behavior of charge carriers in rutile TiO2 nanorod photoanodes under the different applied potentials and different density of surface polaron states that can be tuned via direct electrochemical protonation. We interpreted the background absorption with long-time decay in terms of polaron-mediated ultrafast electron trapping. The depleted surface polaron states on rutile TiO2 nanorods can trap photogenerated electrons and endow them with a long lifetime; thus, increasing the polaron state density can enhance the charge separation efficiency and the photocurrent density of the TiO2 nanorod electrode.

Z-scheme heterojunctions are fundamentally promising yet practically appealing for photocatalytic hydrogen (H2) production owing to the enhanced redox power, spatial separation of charge carriers, and broad-spectrum solar light harvesting. The charge-transfer dynamics at Z-scheme heterojunctions can be accelerated by inserting charge-transfer mediators at the heterojunction interfaces. In this study, we introduce Au nanoparticle mediators in the Z-scheme W18O49/g-C3N4 heterostructure, which enables an improved H2 production rate of 3465 μmol/g·h compared with the direct Z-scheme W18O49/g-C3N4 (1785 μmol/g·h) under 1 sun irradiation. The apparent quantum yields of H2 production with W18O49/Au/g-C3N4 are 3.9% and 9.3% at 420 and 1200 nm, respectively. The improved photocatalytic H2 production activity of W18O49/Au/g-C3N4 is attributable to the triple-channel charge-transfer mechanism: channel I─Z-scheme charge transfer facilitates charge separation and increased redox power of the photoexcited electrons; channels II and III─the localized surface plasmon resonances from Au (channel II) and W18O49 (channel III) enable light harvesting extension from visible to near-infrared wavelengths.

Identification and passivation of defect-induced electron-hole recombination centers are currently crucial for improving the efficiency of hybrid perovskite solar cells. Besides general intrinsic defects, experimental reports have indicated that hydrogen interstitials are also abundant in hybrid perovskite layers; however, few reports have evaluated the effect of such defects on the charge carrier recombination and device efficiencies. Here, we reveal that under I-poor synthesis conditions, the negatively charged monatomic hydrogen interstitial, Hi-, will form in the prototypical CH3NH3PbI3 perovskite layer, acting as a detrimental deep-level defect, which leads to efficient electron-hole recombination and lowers the cell performance. We further rationalize that Br doping can mitigate the large atomic displacement caused by the presence of Hi- and hence suppress the formation of the deep localized state. The results advance the knowledge of the deep-level defects in hybrid perovskites and provide useful information for enhancing solar cell performance by defect engineering.

The functional diversification and adaptability of the elementary switching units of computational circuits are disruptive approaches for advancing electronics beyond the static capabilities of conventional complementary metal-oxide-semiconductor-based architectures. Thereto, in this work the one-dimensional nature of monocrystalline and monolithic Al-Ge-based nanowire heterostructures is exploited to deliver charge carrier polarity control and furthermore to enable distinct programmable negative differential resistance at runtime. The fusion of electron and hole conduction together with negative differential resistance in a universal adaptive transistor may enable energy-efficient reconfigurable circuits with multivalued operability that are inherent components of emerging artificial intelligence electronics.

ConspectusPerovskite solar cells (PSCs) have, in recent years, become one of the most in-depth photovoltaic materials in many different disciplines due to their long-range charge carrier diffusion ...

The ionic transport in nanoscale channels with the critical size comparable to ions and solvents shows excellent performance on electrochemical desalination, ion separation, and supercapacitors. However, the key quantity ionic conductivity (σ) in the nanochannel that evaluates how easily the electric current is driven by an external voltage is still unknown because of the challenges in experimental measurement. In this work, we present an atomistic simulation-based study, which shows that how the ion concentration, nanoconfinement, and heterogeneous solvation modify the ionic conductivity in a two-dimensional graphene nanochannel. We find that σ in the confined channel is lower than that in the bulk (σb) at the same concentration along with enhanced ion-ion correlation. However, surprisingly, the local σ near the channel wall is more conductive than σb and is about 2-3 folds of the inner layer due to the highly concentrated charge carriers. Based on the layered feature of σ along the width of the channel, we propose a model that contains two dead (or depletion) layers, two highly conductive layers, and one inner layer to describe the ionic dynamics in the nanochannels. Our findings may open the way to unique nanofluidic functionalities, such as energy harvesting/storage and controlling transport at single-molecule and ion levels using the liquid layer near the wall.

In situ UV-vis-NIR spectroelectrochemistry has been intensively used to evaluate the electronic transitions during the charging/discharging process of π-conjugated polymers. However, the type of charge carrier and the mechanisms of their transport, remains still a point of discussion. Herein, the coupling between UV-vis-NIR spectroscopy and in situ electrochemical-conductance measurements is proposed to compare the doping process of three different thiophene-based conducting polymers. The simultaneous monitoring of electrical and absorption properties, associated with low energy electronic transitions characteristic for polarons and bipolarons, was achieved. In addition, this method allows evaluating the reversible charge trapping mechanism of poly-3,4-o-xylendioxythiophene (PXDOT), caused by the formation of σ-dimers, making it a very useful tool to determine relevant physicochemical properties of conductive materials.

Low efficient transfer of photogenerated charge carriers to redox sites along with high surface reaction barrier is a bottleneck problem of photocatalytic H2O overall splitting. Here, in the absence of cocatalysts, H2O overall splitting has been achieved by single-atomic S vacancy hexagonal CdS with a spin polarization electric field (PEF). Theoretical and experimental results confirm that single-atomic S vacancy-induced spin PEF with opposite direction to the Coulomb field accelerates charge carrier transport dynamics from the bulk phase to surface-redox sites. By systematically tuning the spin PEF intensity with single-atomic S vacancy content, common pristine CdS is converted to a photocatalyst that can efficiently complete H2O overall splitting by releasing a great number of H2 bubbles under natural solar light. This work solves the bottleneck of solar energy conversion in essence by single atom vacancy engineering, which will promote significant photocatalytic performance enhancement for commercialization.

Two-dimensional (2D) photocatalytic material is a vital project for modern solar energy conversion and storage. Despite a vast family of potential 2D photocatalysts that is demonstrated, their commercial applications are severely limited because of fast photogenerated electron-hole recombination. Here, based on first-principles, we propose a general paradigm to boost the separation of photoexcited charge carriers in 2D photocatalysts by stacking engineering. Taking the emerging water splitting photocatalyst MoSi2N4 as an example, we show that specific interlayer stacking-induced electric polarization plays a significant role in altering the electronic properties and thus the suppressed recombination rate of photoexcited carriers. Moreover, we find that the catalytic performance can be further controlled by vertical strain. These generalized findings not only highlight the importance of stacking-induced electric polarization but also offer new prospects for the design and application of 2D photocatalysts.

Revealing the nature of intrinsic defects that act as charge-carrier trapping centers for persistent luminescence (PersL) in inorganic phosphors remains a crucial challenge from an experimental perspective. It was recently reported that Bi3+-doped LiREGeO4 (RE = Sc, Y, Lu) compounds displayed strong ultraviolet-A PersL at ∼360 nm with a duration of tens of hours at room temperature. However, the mechanistic origin of the PersL remains to be unveiled. Herein, we carried out a systematic study on optical transitions, formation energies, and charge-transition levels of dopants and intrinsic point defects in these compounds using hybrid density functional theory calculations. The results show that the efficient charging by 254 nm is due to the D-band transition of Bi3+ and hence the charge carriers pertinent to PersL are electrons originating from the dopants which are involved in the trapping and detrapping processes. The main electron-trapping centers are antisite defects GeLi0, interstitial defects Lii0, and dopants Bi2+, with the former one responsible for the strong PersL and the latter two for its long-time duration. These findings are further confirmed by comparison with calculated results for isostructural NaLuGeO4 and LiLuSiO4, based on which the roles of Li and Ge elements in forming intrinsic defects with appropriate trap depths for PersL are clarified. Our results not only assist in the understanding of experimental observations but also provide a theoretical basis for the rational design of novel PersL phosphors containing lithium and germanium in the host compound.

Lead-halide perovskites have established a firm foothold in photovoltaics and optoelectronics due to their steadily increasing power conversion efficiencies approaching conventional inorganic single-crystal semiconductors. However, further performance improvement requires reducing defect-assisted, nonradiative recombination of charge carriers in the perovskite layers. A deeper understanding of perovskite formation and associated process control is a prerequisite for effective defect reduction. In this study, we analyze the crystallization kinetics of the lead-halide perovskite MAPbI3-xClx during thermal annealing, employing in situ photoluminescence (PL) spectroscopy complemented by lab-based grazing-incidence wide-angle X-ray scattering (GIWAXS). In situ GIWAXS measurements are used to quantify the transition from a crystalline precursor to the perovskite structure. We show that the nonmonotonous character of PL intensity development reflects the perovskite phase volume, as well as the occurrence of the defects states at the perovskite layer surface and grain boundaries. The combined characterization approach enables easy determination of defect kinetics during perovskite formation in real-time.

Among the parameters determining the efficiency of an organic solar cell, the open-circuit voltage ($V_\text{OC}$) is the one with most room for improvement. Existing models for the description of $V_\text{OC}$ assume that photogenerated charge carriers are thermalized. Here, we demonstrate that quasi-equilibrium concepts cannot fully describe $V_\text{OC}$ of disordered organic devices. For two representative donor:acceptor blends it is shown that $V_\text{OC}$ is actually 0.1-0.2 V higher than it would be if the system was in thermodynamic equilibrium. Extensive numerical modeling reveals that the excess energy is mainly due to incomplete relaxation in the disorder-broadened density of states. These findings indicate that organic solar cells work as nonequilibrium devices, in which part of the photon excess energy is harvested in the form of an enhanced $V_\text{OC}$., Comment: Final version; title changed; journal reference added

Charge transport in three-dimensional metal-halide perovskite semiconductors is due to a complex combination of ionic and electronic contributions, and its study is particularly relevant in light of their successful applications in photovoltaics as well as other opto- and microelectronic applications. Interestingly, the observation of field effect at room temperature in transistors based on solution-processed, polycrystalline, three-dimensional perovskite thin films has been elusive. In this work, we study the time-dependent electrical characteristics of field-effect transistors based on the model methylammonium lead iodide semiconductor and observe the drastic variations in output current, and therefore of apparent charge carrier mobility, as a function of the applied gate pulse duration. We infer this behavior to the accumulation of ions at the grain boundaries, which hamper the transport of carriers across the FET channel. This study reveals the dynamic nature of the field effect in solution-processed metal-halide perovskites and offers an investigation methodology useful to characterize charge carrier transport in such emerging semiconductors.

Metal-oxide semiconductors (MOS) are widely utilized for catalytic and photocatalytic applications in which the dynamics of charged carriers (e.g., electrons, holes) play important roles. Under operation conditions, photoinduced surface oxygen vacancies (PI-SOV) can greatly impact the dynamics of charge carriers. However, current knowledge regarding the effect of PI-SOV on the dynamics of hole migration in MOS films, such as titanium dioxide, is solely based upon volume-averaged measurements and/or vacuum conditions. This limits the basic understanding of hole-vacancy interactions, as they are not capable of revealing time-resolved variations during operation. Here, we measured the effect of PI-SOV on the dynamics of hole migration using time-resolved atomic force microscopy. Our findings demonstrate that the time constant associated with hole migration is strongly affected by PI-SOV, in a reversible manner. These results will nucleate an insightful understanding of the physics of hole dynamics and thus enable emerging technologies, facilitated by engineering hole-vacancy interactions.

Nanoscale oxide layer protected semiconductor photoelectrodes show enhanced stability and performance for solar fuels generation, although the mechanism for the performance enhancement remains unclear due to a lack of understanding of the microscopic interfacial field and its effects. Here, we directly probe the interfacial fields at p-GaP electrodes protected by n-TiO2 and its effect on charge carriers by transient reflectance spectroscopy. Increasing the TiO2 layer thickness from 0 to 35 nm increases the field in the GaP depletion region, enhancing the rate and efficiency of interfacial electron transfer from the GaP to TiO2 on the ps time scale as well as retarding interfacial recombination on the microsecond time scale. This study demonstrates a general method for providing a microscopic view of the photogenerated charge carrier's pathway and loss mechanisms from the bulk of the electrode to the long-lived separated charge at the interface that ultimately drives the photoelectrochemical reactions.

Excitons in Bridgman grown halide perovskite CsPbBr3 single crystals were examined using photoluminescence (PL) spectroscopy to determine the nature of the electronic states. The photoluminescence intensity was strongly temperature-dependent and depended upon the specific exciton band. At low temperatures intrinsic disorder and its related shallow below bandgap tail states determine the emission properties. Photoluminescence at low temperature revealed the presence of several strong bands at the band edge that is attributed to free or trapped/bound excitons. This PL emission results from strong electron-phonon coupling with an average phonon energy Eph of 6.5 and 27.4 meV for the emissions, comparable to that observed in other perovskites. The Huang-Rhys parameter S was calculated to be 3.81 and 1.51, indicating strong electron-phonon coupling. The interactions between electrons and phonons produce small polarons that tend to bind charge carriers and result in trapped/bound excitons. The transient photoluminescence response of each specific band was studied, and the results indicated a multiphonon recombination process. Average PL lifetimes of ∼17 ns for free excitons and ∼38 ns for trapped/bound excitons were determined. The observed edge states could be associated with native defects such as vacancies and interstitials, as well as twinning due to the cubic-to-tetragonal phase transition in CsPbBr3. Elimination of the trapping sites for binding excitons could lead to improved charge transport mobilities, carrier lifetimes, and detector properties in this system.

Organic photovoltaics are typically composed of at least four different materials, including the donor and acceptor components of the bulk heterojunction, the interfacial layers at each electrode, the electrodes themselves, and solution additives that may persist in the final sandwich structure. The interplay of surface energies between these different layers is profoundly complex, as the deposition and annealing of one layer on top of another may be influenced by the surface energy of these interfaces. While the energy levels of one layer with respect to adjacent layers are important to facilitate charge separation and collection at the electrodes, the relative surface energies of the interfaces in contact with the multicomponent bulk heterojunction can be beneficial or disadvantageous, or be neutral, with respect to the performance of the OPV device. Because the bulk heterojunction is a mixture of donor and acceptor polymers and/or small molecules, the accumulation of one of the components on the underlying electrode interface can be driven by surface energy considerations. A donor- or acceptor-rich interface may affect charge carrier flow to the electrode, thus affecting the overall efficiency. Here, ITO/PEDOT:PSS electrodes in forward organic photovoltaic devices are treated with five different thin interfacial layers to change the relative surface energy of this electrode with respect to the adjacent bulk heterojunction. Contact angle measurements with four probe liquids enable calculation of the surface energies, and the results are compared with the performance of forward-biased organic photovoltaic devices. Time-of-flight secondary ion mass spectrometry results substantiate the predictions of gradients in the bulk heterojunction layers, and grazing-incidence wide-angle X-ray scattering measurements show the impact on the polymer crystallites. Thus, a simple algorithm based on surface energy considerations may inform which interfacial layer for a given bulk heterojunction in an organic photovoltaic device can be the most appropriate.

The design of a photoanode with a bridging strategy that can enhance the charge injection and transport in a heterojunction can be an efficient approach to separate the photogenerated charge carriers and enhance the water oxidation kinetics. Aiming at such issues, herein we propose a BiVO4/GQDs/CoSn-LDH (layered double hydroxide) photoanode, which leads to the formation of a p-n heterojunction with bridged graphene quantum dots (GQDs) to accelerate the photoelectrochemical (PEC) performance. The BiVO4/GQDs/CoSn-LDH photoanode exhibits a maximum photocurrent density of 4.15 mA/cm2, which is ∼3-fold higher than for the pristine BiVO4 photoanode with an ∼250 mV cathodic shift in the onset potential. A faradaic yield of ∼91% confirms that the obtained photocurrent is mainly due to water oxidation. A mechanistic study based on the electrochemical impedance (EIS), charge separation, and charge injection efficacy measurements reveals that the introduction of GQDs between BiVO4 and CoSn-LDH provides a continuous conducting network to extract holes from the BiVO4 surface and efficiently inject into the CoSn-LDH surface for the water oxidation reaction.

Solution-processed metal oxide (MO) thin films have been extensively studied for use in thin-film transistors (TFTs) due to their high optical transparency, simplicity of fabrication methods, and high electron mobility. Here, we report, for the first time, the improvement of the electronic properties of solution-processed indium oxide (InOx) films by the subsequent addition of an organic p-type semiconductor material, here 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), yielding organic-inorganic hybrid TFTs. The addition of TIPS-pentacene not only improves the electron mobility by enhancing the charge carrier percolation pathways but also improves the electronic and temporal stability of the IDS(VG) characteristics as well as reduces the number of required spin-coating steps of the InOx precursor solution. Very interestingly, the introduction of 10 nm TIPS-pentacene films on top of 15 nm InOx layers allows the fabrication of either enhancement- or depletion-mode devices with only minimal changes to the fabrication process. Specifically, we find that when the TIPS-pentacene layer is added on top of the source/drain electrodes, resulting in devices with embedded source/drain electrodes [embedded electrode TFTs (EETFTs)], the devices exhibit an enhancement-mode behavior with an average mobility (μ) of 6.4 cm2 V-1 s-1, a source-drain current ratio (Ion/Ioff) of around 105, and a near-zero threshold voltage (VTH). When on the other hand the TIPS-pentacene layer is added before the source-drain electrodes, i.e., in top-contact electrode TFTs (TCETFTs), a very clear depletion mode behavior is observed with an average μ of 6.3 cm2 V-1 s-1, an Ion/Ioff ratio of over 105, and a VTH of -80.3 V. Furthermore, a logic inverter is fabricated combining the enhancement (EETFTs)- and depletion (TCETFTs)-mode transistors, which shows a potential for the construction of organic-inorganic hybrid electronics and circuits.

Lead-free metal halide perovskites are environmentally friendly and have favorable electro-optical properties; however, their efficiencies are significantly below the theoretical limit. Using ab initio nonadiabatic molecular dynamics, we show that common intrinsic defects accelerate nonradiative charge recombination in CsSnI3 without creating midgap traps. This is in contrast to Pb-based perovskites, in which many defects have little influence on and even prolong carrier lifetimes. Sn-related defects, such as Sn vacancies and replacement of Sn with Cs are most detrimental, since Sn removal breaks the largest number of bonds and strongly perturbs the Sn-I lattice that supports the carriers. The defects increase the nonadiabatic electron-vibrational coupling and interact strongly with free carrier states. Point defects associated with I atoms are less detrimental, and therefore, CsSnI3 synthesis should be performed in Sn rich conditions. The study provides an atomistic rationalization of why lead-free CsSnI3 exhibits lower photovoltaic efficiency compared to some lead-based perovskites.

Using unsupervised machine learning on the trajectories from a nonadiabatic molecular dynamics simulation with time-dependent Kohn-Sham density functional theory, we elucidated the structural parameters with the largest influence on nonradiative recombination of charge carriers in CsPbI3, which forms the basis for solar energy and optoelectronic applications. The I-I-I angles between PbI6 octahedra, followed by the Cs-I distance, have the strongest impact on the bandgap and the nonadiabatic coupling. The importance of the Cs-I distance is unexpected, because Cs does not contribute to electron and hole wave functions. The nonadiabatic coupling is most influenced by static properties, which is also surprising, given its explicit dependence on atomic velocities.

With a proper band gap of ∼2.4 eV for solar light absorption and suitable valence band edge position for oxygen evolution, scheelite-monoclinic bismuth vanadate (BiVO4) has become one of the most attractive photocatalysts for efficient visible-light-driven photoelectrochemical (PEC) water splitting. Several studies have indicated that surface modification of BiVO4 with a cocatalyst such as NiFe layered double hydroxide (LDH) can significantly increase the PEC water splitting performance of the catalyst. Herein, we experimentally investigated the charge transfer dynamics and charge carrier recombination processes by scanning electrochemical microscopy (SECM) with the feedback mode on the surface of BiVO4 and BiVO4/NiFe-LDH as model samples. The ratio of rate constants for photogenerated hole (kh+0) to electron (ke-0) via the photocatalyst of BiVO4/NiFe-LDH reacting with the redox couple is found to be five times larger than that of BiVO4 under illumination. In this case, the ratio of the rate constants kh+0/ke-0 stands for the interfacial charge recombination process. This implies the cocatalyst NiFe-LDH suppresses the electron back transfer greatly and finally reduces the surface recombination. Control experiments with cocatalysts CoPi and RuOx onto BiVO4 further verify this conclusion. Therefore, the SECM characterization allows us to make an overall analysis on the function of cocatalysts in the PEC water splitting system.

We describe the synthesis and electrochemical analysis of the phenyl siloxane-hybridized phosphotungstate Keggin-type polyoxometalate (POM) TBA3[PW11O39(SiC6H5)2O] (TBA3W11SiPh) and its performance as the charge carrier in nonaqueous redox flow batteries (RFBs). The hybridized POM is synthesized by modification of the parent POM [PW12O40]3–, increasing its saturation concentration in acetonitrile by 2 orders of magnitude over that of the parent compound (600 mmol dm–3 for TBA3W11SiPh vs less than1 mmol dm–3 for TBA3[PW12O40]). Electrochemical analysis of TBA3W11SiPh reveals four one-electron, quasi-reversible, redox couples between −0.60 and −2.50 V vs Ag+|Ag, prompting us to explore its application as a dual-function charge carrier in symmetric RFBs. The stability of TBA3W11SiPh is investigated in several symmetric RFBs, and the system demonstrates high coulombic efficiency (98%), voltage efficiency (89%), and energy efficiency (87%) during redox cycling. We show that capacity fade due to oxidation-state imbalance can be counteracted by rereduction of electrolytes. These results demonstrate that organic–inorganic hybridization of POMs offer opportunities for the development of highly soluble multielectron redox electrolytes that operate across a wide range of potentials, expanding the available range of charge carriers for high-energy RFBs.

Synchrotron-based X-ray spectroscopic and microscopic techniques are used to identify the origin of enhancement of the photoelectrochemical (PEC) properties of BiVO4 (BVO) that is coated on ZnO nanodendrites (hereafter referred to as BVO/ZnO). The atomic and electronic structures of core-shell BVO/ZnO nanodendrites have been well-characterized, and the heterojunction has been determined to favor the migration of charge carriers under the PEC condition. The variation of charge density between ZnO and BVO in core-shell BVO/ZnO nanodendrites with many unpaired O 2p-derived states at the interface forms interfacial oxygen defects and yields a band gap of approximately 2.6 eV in BVO/ZnO nanocomposites. Atomic structural distortions at the interface of BVO/ZnO nanodendrites, which support the fact that there are many interfacial oxygen defects, affect the O 2p-V 3d hybridization and reduce the crystal field energy 10Dq ∼2.1 eV. Such an interfacial atomic/electronic structure and band gap modulation increase the efficiency of absorption of solar light and electron-hole separation. This study provides evidence that the interfacial oxygen defects act as a trapping center and are critical for the charge transfer, retarding electron-hole recombination, and high absorption of visible light, which can result in favorable PEC properties of a nanostructured core-shell BVO/ZnO heterojunction. Insights into the local atomic and electronic structures of the BVO/ZnO heterojunction support the fabrication of semiconductor heterojunctions with optimal compositions and an optimal interface, which are sought to maximize solar light utilization and the transportation of charge carriers for PEC water splitting and related applications.

The energy band gaps of Pb halide perovskites are higher than the optimal band gap required for single-junction solar cells, governed by the Shockley-Queisser radiative limit. The pure Sn and Pb-Sn mixed-based perovskites have drawn significant attention due to their ability to lead to lower band gaps and open a new door for all perovskite tandem applications. There has been continuous progress toward the rapid improvement in the power conversion efficiency of Sn and Pb-Sn mixed-based perovskite solar cells (PSCs). Along with efforts for efficiency, it is worth analyzing the in-depth recombination dynamics for further development of Sn-based PSCs. The lower bimolecular recombination rate constant (k) is often attributed to the high performance of PSCs. Herein, we study the role of "B" cations in charge carrier recombination dynamics (CCRD) of ABX3 (A = MA+, FA+, and Cs+; B = Pb2+, Sn2+, and X = I-)-based PSCs. We fabricated p-i-n configuration-based FA0.95Cs0.05PbI3 (pure Pb), MA0.20FA0.75Cs0.05SnI3 (pure Sn), and (MAPbI3)0.4(FASnI3)0.6 (Pb-Sn mixed) PSCs and compared the CCRD of all the three PSCs. We optimized the Sn-based perovskite thin film (pure Sn) in terms of moisture and thermal stability in order to minimize the error due to perovskite degradation. We note that despite having lower open-circuit voltage (VOC), a pure Sn-based PSC shows lower k than that of Pb-Sn mixed and pure Pb-based PSCs, which is a contradictory result. This slow relaxation lifetime of the charge carrier in Sn-based PSCs can be correlated with recombination through the defect states without introducing the quasi-Fermi-level splitting. Furthermore, our results suggest that the rate law of charge carrier decay has nonlinear dependence of k on n in Sn-based PSCs, whereas it is linear in the other two cases.

Ultrahigh charge separation was observed in Bi4O5I2/Bi5O7I two-dimensional (2D)/one-dimensional (1D) hierarchical structures (HSs) constructed by selective growth of 2D monocrystalline Bi4O5I2 nanoplates on the electron-accumulating (100) facet of 1D monocrystalline Bi5O7I nanobelts. In addition to the presence of type-II heterojunction between Bi4O5I2 and Bi5O7I elementary entities in 2D/1D HSs, the type-II (100)/(001) surface heterojunction in Bi5O7I nanobelt substrates was also confirmed by means of density functional theory (DFT) calculations and selective photoreduction/oxidation deposition experiments. The synergistic effect of two kinds of heterojunctions in Bi4O5I2/Bi5O7I 2D/1D HSs endowed them with ultrahigh charge carrier separation and transfer characteristics. In contrast with the control sample (BB40-C) constructed by growing Bi4O5I2 nanoplates on whole four sides of Bi5O7I nanobelts, Bi4O5I2/Bi5O7I 2D/1D HSs demonstrated significantly enhanced charge transfer between Bi5O7I nanobelt substrates and Bi4O5I2 nanoplates, owing to respective electron and hole accumulations on (100) and (001) facets of Bi5O7I substrates caused by (100)/(001) surface heterojunction. The enhanced separation behavior was successfully verified by steady/transient-state photoluminescence, electrochemical techniques, and photocatalytic degradation experiments. Based on the above effective charge separation of Bi4O5I2/Bi5O7I 2D/1D HSs as well as the routine advantages for 2D/1D HSs, such as the excellent charge transport in monocrystalline elementary entities, much higher specific surface area, and enhanced light absorption by multiple reflections, the optimal BB40 HSs demonstrated ultrahigh photocatalytic performance than the control samples, whose apparent rates for Rhodamine B [or tetracycline hydrochloride (TC)] degradation were 7.1 (2.9 for TC), 10.3 (4.7 for TC), and 2.2 (1.7 for TC) times those of pristine Bi5O7I nanobelts, Bi4O5I2 nanoplates, and BB40-C, respectively. It is hoped that this crystal facet selection during the heterostructure construction in this work could provide a new strategy or some enlightenment for the exploration of highly active 2D/1D HSs or other-dimensional heterostructure nanomaterials applied in the fields of photocatalysts, solar cells, sensors, and others.

Degenerately doped metal-oxide nanocrystals (NCs) show localized surface plasmon resonances (LSPRs) that are tunable via their tunable excess charge-carrier densities. Modulation of excess charge carriers has also been used to control magnetism in colloidal doped metal-oxide NCs. The addition of excess delocalized conduction-band (CB) electrons can be achieved through aliovalent doping or by postsynthetic techniques such as electrochemistry or photodoping. Here, we examine the influence of charge-compensating aliovalent dopants on the potentials of excess CB electrons in free-standing colloidal degenerately doped oxide NCs, both experimentally and through modeling. Taking Sn4+:In2O3 (ITO) NCs as a model system, we use spectroelectrochemical techniques to examine differences between aliovalent doping and photodoping. We demonstrate that whereas photodoping introduces excess CB electrons by raising the Fermi level relative to the CB edge, aliovalent impurity substitution introduces excess CB electrons by stabilizing the CB edge relative to an externally defined Fermi level. Significant differences are thus observed electrochemically between spectroscopically similar delocalized CB electrons compensated by aliovalent dopants and those compensated by surface cations (e.g., protons) during photodoping. Theoretical modeling illustrates the very different potentials that arise from charge compensation via aliovalent substitution and surface charge compensation. Spectroelectrochemical titrations allow the ITO NC band-edge stabilization as a function of Sn4+ doping to be quantified. Extremely large capacitances are observed in both In2O3 and ITO NCs, making these NCs attractive for reversible charge-storage applications.

Facile and scalable fabrication of α-Fe2O3 photoanodes using a precursor solution containing FeIII ions and 1-ethylimidazole (EIm) in methanol was demonstrated to afford a rigidly adhered α-Fe2O3 film with a controllable thickness on a fluorine-doped tin oxide (FTO) substrate. EIm ligation to FeIII ions in the precursor solution brought about high crystallinity of three-dimensionally well-interconnected nanoparticles of α-Fe2O3 upon sintering. This is responsible for the 13.6 times higher photocurrent density (at 1.23 V vs reference hydrogen electrode (RHE)) for photoelectrochemical (PEC) water oxidation on the α-Fe2O3 (w-α-Fe2O3) photoanode prepared with EIm compared with that (w/o-α-Fe2O3) prepared without EIm. The w-α-Fe2O3 photoanode provided the highest charge separation efficiency (ηsep) value of 27% among the state-of-the-art pristine α-Fe2O3 photoanodes, providing incident photon-to-current conversion efficiency (IPCE) of 13% at 420 nm and 1.23 V vs RHE. The superior ηsep for the w-α-Fe2O3 photoanode is attributed to the decreased recombination of the photogenerated charge carriers at the grain boundary between nanoparticles, in addition to the higher number of the catalytically active sites and the efficient bulk charge transport in the film, compared with w/o-α-Fe2O3.

Polarity often refers to the charge carrier type of a semiconductor or the charging state of a functional group, generally dominating their functionality and performance. Herein we uncover a spontaneous and stochastic polarity-flipping phenomenon in monolayer WSe2, which randomly switches between the n-type and p-type states and is essentially triggered by fluctuating carrier flows from or to the adjacent WS2 monolayer. We have traced such fluctuating carrier flows by interfacial photocurrent measurements in a zero-bias two-terminal device. Such polarity flipping results in switching between the negative and positive correlations between the emission intensities of WS2 and WSe2 in the heterobilayer, which is further well-controlled by the electrostatic gate-tuning experiments in a capacitor-structure device. Our work not only demonstrates giant and intermittent carrier flows through long-range coupling in 2D heterostructures and a consequent spontaneous polarity flipping phenomenon but also provides a two-emitter system with a switchable correlation sign that could project future applications in optical logic devices.