Charge Carrier Transport Research Articles

Surface Lattice Engineering Enables Efficient Inverted Perovskite Solar Cells

AbstractState‐of‐the‐art inverted perovskite solar cells (PSCs) have exhibited considerable promise for commercialization due to their prospective stability. However, the intricate crystallization of halide perovskite, especially for multi‐component perovskites, not only distorts the surface lattice from its ideal form but also introduces numerous unsaturated dangling bonds to form surface defects, which can easily lead to reduced stability and poor performance. Herein, a surface lattice engineering is developed by coupling surface unsaturated ions and regulating ion bonding lengths/angles to achieve efficient and stable inverted PSCs. The renovated surface lattice not only eliminates shallow/deep level defects on the surface of perovskite, but also enhances photo/thermal stability of the materials. Moreover, the surface lattice engineering contributes to uniform potential surface, and improves energy‐level alignment at the interfaces of the perovskite and C60 carrier transport layer, enhancing charge carrier extraction and transportation. Finally, the champion PSC delivers an impressive efficiency of 25.82% (certified 25.5%). Moreover, these PSCs exhibit excellent operational stability, retaining 94% initial efficiency after more than ≈1 000h maximum power point test.

Roll-to-Roll Manufactured Polyetherimide Nanocomposite With Different Diameters of SiO2 Nanoparticles Exhibiting Improved High-Temperature Dielectric Energy Storage Performance.

To enhance the high-temperature energy storage performance of the polymer-based dielectric film, inorganic nanofillers with large band gaps are much more effective and have been widely adopted. However, the impact of nanoparticle diameters on the dielectric properties of polymer nanocomposites has been less studied. Herein, silicon dioxide nanoparticles (SiO2-NPs)with varying diameters (20, 60, 120, 200nm) prepared by the sol-gel method are incorporated in the PEI matrix to form PEI/SiO2 nanocomposites. The characterization results reveal a distinct correlation between the dielectric properties of polyetherimide (PEI) composites and the diameters of SiO2-NPs. Leakage current density analysis and breakdown strength simulations indicate that SiO2-NPs with smaller diameters generate more deep traps that impede the transport of charge carriers, especially under high temperatures. Notably, PEI/20nm-SiO2 exhibits a high discharged energy density of 4.4 J cm-3 with an efficiency of 90% at 150°C. Furthermore, PEI/SiO2 films with 10µm in thickness are manufactured by a large-scale solution casting process. The continuously prepared PEI/20nm-SiO2 film exhibits a discharged energy density of 3.2 J cm-3 with an efficiency of 90% at 150°C. This study not only provides a strategy for the design of high-performance dielectric polymer composites but also offers a large-scale high-temperature dielectric film for practical use.

High-Performance perovskite quantum dots light-emitting diodes with hole transport layer engineering and synergetic outcoupling enhancement

Perovskite quantum dot light-emitting diodes (PeQLEDs) are frequently considered as the most promising alternatives to organic light-emitting diodes (OLEDs). However, the efficiency of PeQLEDs remains inferior to OLEDs due to suboptimal charge carrier transport and intrinsic light outcoupling efficiency (ηout). Herein, a combination of hole transport layer (HTL) engineering and substrate engineering is demonstrated to improve the charge injection and ηout of PeQLEDs. To replace the conventional PEDOT:PSS, a novel HTL bilayer based on modified PEDOT:PSS and PVK with a lower refractive index and fewer trap densities at the HTL-QDs interface is developed. Additionally, this study identifies the ideal thickness of ITO for achieving optimal ηout of PeQLEDs through optical simulations and experimental validation. Based on the synergistic use of HTL bilayer and 70-nm-thick ITO, the PeQLEDs achieved an optimal external quantum efficiency of 17.96 % at a luminance of 1763 cd/m2 and 15.19 % at 8300 cd/m2 without using any external outcoupling structure, indicating a low efficiency roll-off.

Positional Isomerism of Aromatic Heterocyclic Spacer Cations in Two-Dimensional Dion-Jacobson Hybrid Perovskites.

Ligand engineering of aromatic heterocyclic cations in two-dimensional (2D) Dion-Jacobson (DJ) perovskites has been widely explored in recent years. In this study, how the positional isomers of aromatic heterocyclic cations tune the lattice of 2D perovskites, thereby influencing the transport and recombination dynamics of charge carriers, has been investigated through nonadiabatic molecular dynamics simulations. We demonstrate that the meta-substituted 3-(aminomethyl)pyridinium (3AMPY) cations greatly reduce the strength of electron-vibration coupling since the strong hydrogen-bonding network introduced by the changes in the arrangement of spacer cations significantly suppresses the structural thermal fluctuations. Compared to the para-substituted 4-(aminomethyl)pyridinium (4AMPY) cation, using the asymmetric 3AMPY as a spacer cation can achieve improved in-plane transport performance, enhanced thermal stability, and suppressed charge carrier recombination through weakening electron-vibration interactions. Our results explain the observed lifetime difference between the two types of DJ-phase perovskites in experiments and provide new guidance for optimizing the performance of perovskite devices.

A Review on Pulsed Laser Preparation of Quantum Dots in Colloids for the Optimization of Perovskite Solar Cells: Advantages, Challenges, and Prospects.

In recent years, academic research on perovskite solar cells (PSCs) has attracted remarkable attention, and one of the most crucial issues is promoting the power conversion efficiency (PCE) and operational stability of PSCs. Generally, modification of the electron or hole transport layers between the perovskite layers and electrodes via surface engineering is considered an effective strategy because the inherent structural defects between charge carrier transport layers and perovskite layers can be reshaped and modified by adopting the functional nanomaterials, and thus the charge recombination rate can be naturally decreased. At present, large amounts of available nanomaterials for surface modification of the perovskite films are extensively investigated, mainly including nanocrystals, nanorods, nanoarrays, and even colloidal quantum dots (QDs). In particular, as unique size-dependent nanomaterials, the diverse quantum properties of colloidal QDs are different from other nanomaterials, such as their quantum confinement effects, quantum-tunable effects, and quantum surface effects, which display great potential in promoting the PCE and operational stability of PSCs as the charge carriers in perovskite layers can be effectively tuned by these quantum effects. However, preparing QDs with a neat and desirable size remains a technical difficulty, even though the present chemical engineering is highly advanced. Fortunately, the rapid advances in laser technology have provided new insight into the precise preparation of QDs. In this review, we introduce a new approach for preparing the QDs, namely pulsed laser irradiation in colloids (PLIC), and briefly highlight the innovative works on PLIC-prepared QDs for the optimization of PSCs. This review not only highlights the advantages of PLIC for QD preparation but also critically points out the challenges and prospects of QD-based PSCs.

Tunable electronic and optical properties of a type-II GaP/SiH van der Waals heterostructure as photocatalyst: A first-principles study

In this study, a novel GaP/SiH heterostructure was successfully predicted and constructed. Subsequently, an in-depth and systematic investigation was conducted to explore its structural, electronic, transport and optical properties. The calculated structural performance results revealed that the GaP/SiH heterostructure was a typical type-II van der Waals heterostructure, exhibiting excellent energy stability, mechanical stability and thermodynamic stability. In particular, the formation of the GaP/SiH heterostructure significantly reduced the bandgap of the materials to 2.24eV, and the type-II energy band arrangement effectively suppressed the recombination of photogenerated carriers. Furthermore, the biaxial and vertical strains could finely modulate the electronic structure of the GaP/SiH heterojunction. The electron mobility of the GaP/SiH heterostructure was measured to be 1573.91 cm2 V⁻1 s⁻1, indicating its superior charge carrier transport capabilities. Meanwhile, the GaP/SiH heterostructure also exhibited excellent optical absorption performance in the visible and UV region up to 2.34 × 106 cm−1. Thus, the GaP/SiH heterostructure will be a strong candidate for photocatalytic applications due to its excellent light absorption properties, electrical properties, and stability.

Impedance Spectroscopy Study of Charge Transfer in the Bulk and Across the Interface in Networked SnO2/Ga2O3 Core–Shell Nanobelts in Ambient Air

Metal oxide core–shell fibrous nanostructures are promising gas-sensitive materials for the detection of a wide variety of both reducing and oxidizing gases. In these structures, two dissimilar materials with different work functions are brought into contact to form a coaxial heterojunction. The influence of the shell material on the transportation of the electric charge carriers along these structures is still not very well understood. This is due to homo-, hetero- and metal/semiconductor junctions, which make it difficult to investigate the electric charge transfer using direct current methods. However, in order to improve the gas-sensing properties of these complex structures, it is necessary to first establish a good understanding of the electric charge transfer in ambient air. In this article, we present an impedance spectroscopy study of networked SnO2/Ga2O3 core–shell nanobelts in ambient air. Tin dioxide nanobelts were grown directly on interdigitated gold electrodes, using the thermal sublimation method, via the vapor–liquid–solid (VLS) mechanism. Two forms of a gallium oxide shell of varying thickness were prepared via halide vapor-phase epitaxy (HVPE), and the impedance spectra were measured at 189–768 °C. The bulk resistance of the core–shell nanobelts was found to be reduced due to the formation of an electron accumulation layer in the SnO2 core. At temperatures above 530 °C, the thermal reduction of SnO2 and the associated decrease in its work function caused electrons to flow from the accumulation layer into the Ga2O3 shell, which resulted in an increase in bulk resistance. The junction resistance of said core–shell nanostructures was comparable to that of SnO2 nanobelts, as both structures are likely connected through existing SnO2/SnO2 homojunctions comprising thin amorphous layers.

Ions-induced Assembly of Perovskite Nanocomposites for Highly Efficient Light-Emitting Diodes with EQE Exceeding 30.

Metal halide perovskites, a cost-effective class of semiconductos, hold great promise for display technologies that demand high-efficiency, color-pure light-emitting diodes (LEDs). Early research on three-dimensional (3D) perovskites showed low radiative efficiencies due to modest exciton binding energies. To inprove luminescence, reducing dimensionality or grain size has been a common approach. However, dividing the perovskite lattice into smaller units may hinder carrier transport, compromising electrical performance. Moreover, the increased surface area introduce additional surface trap states, leading to greater non-radiative recombination. Here, an ions-induced growth method is employed to assembe lattice-anchored perovskite nanocomposites for efficient LEDs with high color purity. This approach enables the nanocomposite thin films, composed of 3D CsPbBr3 and its variant of zero-dimensional (0D) Cs4PbBr6, to feature significant low trap-assisted nonradiative recombination, enhanced light out-coupling with a corrugated surface, and well-balanced charge carrier transport. Based on the resultant 3D/0D perovskite nanocomposites, the perovskite LEDs (PeLEDs) achieving an remarkable external quantum efficiency of 31.0% at the emission peak of 521 nm with a narrow full width at half-maximum of only 18 nm. This sets a new benchmark for color purity in high performance PeLED research, highlighting the significant advantage of this approach.

Electrical properties and evaluation of band tail states in Mg doped p-type multilayer hBN

A series of Mg doped p-type multi-layered hBN films were prepared by atmospheric pressure chemical vapor deposition. Temperature dependent conductivity measurements were performed from 0.1 Hz to 10 MHz to analyze the characteristics of tail states close to the valence band edge. Jonscher's power law (Aωs) is successfully applied to understand charge carrier transport through these states. In this work, exponent S increases from 0.6 → 0.8, 0.8 → 0.995, and 1.4 → 1.6 for samples B (precursor temperature, 750 °C), D (850 °C), and E (900 °C), indicating that non-overlapping small polaron tunneling dominates to 548 K. Polaron binding energies of 0.2–0.40 eV and tunneling distances <4.9 Å are calculated, confirming transport through localized states. The density of states near the Fermi level N(EF) was extracted from a fit to the AC conductivity data, yielding values of 1015 and 1017eV−1cm−3 as the precursor temperature increases. Singular Mg acceptor levels of 74, 30, and 17 meV are identified for each sample. A hole concentration from 6.5 × 1017 to 1 × 1018 cm−3 and carrier mobility from 18 to 25 cm2/V s is measured at 300 K. From RC fitting, carrier recombination lifetimes of 1.2, 0.4, and 0.35 μs are determined. Fermi's golden rule is used to determine an optical joint density of states of 1.1 × 1021 eV−1 cm−3 at a band edge. Overall, we show that AC conductivity is an effective method to evaluate midgap states in 2D (two-dimensional) materials at EF and p-type hBN possesses sufficient electrical properties to be integrated into a wide range of semiconductor applications.

Transient Electroluminescence Spectroscopy in Planar Electroluminescent Devices

AbstractThe emergence of planar electroluminescent diodes (including polymer light‐emitting diodes, organic light‐emitting diodes, quantum‐dot light‐emitting diodes, and perovskite light‐emitting diodes) is causing a revolution in displays, lighting, and wearable electronic devices. Continuous advancement in the comprehension and management of charge carrier dynamics in these devices has led to several significant breakthroughs, including diodes with ultrahigh luminance, memory devices, and amplified spontaneous emission. Transient electroluminescence (TrEL) spectroscopy is a relative powerful technology to investigate charge dynamics, including transport, distribution, and storage of charge carriers, in electrically‐driven planar light‐emitting diodes (LEDs). The aim of this review is to revisit the principle and applications of TrEL spectroscopy in planar electroluminescent diodes, and to evaluate the reliability of various parameters extracted using this technology. A particular focus is on electroluminescence response time, charge‐carrier transport and storage, and exciton species. First, the principle and equipment system of the TrEL, as well as specific attention during TrEL measurements are described in detail, following by the applications TrEL spectroscopy in planar LEDs. Further development on the TrEL technology is discussed in the third section. Finally, a summary and outlook for the TrEL are shown and challenges faced by the TrEL spectroscopy are also highlighted.

Ingenious development of bandgap engineered MIL-101(Fe) core-shell supported on SnO2/ZnO heterojunction and its photocatalytic activity towards azo dye degradation: Process optimization and mechanistic insight

Water pollution is a pressing global concern, exacerbated by industrial effluents containing hazardous azo-dyes such as Trypan blue (TB) and Methyl orange (MO), which contaminate water bodies and threaten ecosystems. The scarcity of pure water intensifies the urgency to develop effective remediation strategies to tackle the toxic dye pollutants. In the present work, an attempt has been made to fabricate and utilize a novel ternary MOF-based SnO2/ZnO@MIL-101(Fe) photocatalyst for the removal of TB and MO dyes from an aqueous medium. The photocatalyst was characterized using various analytical techniques, like XRD, FTIR, UV–vis DRS, PL, SEM, TEM, and XPS, which provide insights into the composites’ crystal structure, morphology, and optical properties, which are crucial for understanding their photocatalytic behavior. The photocatalytic performance of the heterojunction was investigated under various reaction parameters such as catalyst dosage, initial concentration of dyes, and light irradiation time. The results demonstrated the superior performance of the SnO2/ZnO@MIL-101(Fe) composites in degrading the mono-azo and di-azo dyes under visible light irradiation via a photo-fenton process. The maximum degradation efficiency of 97.44 % and 98.8 % were obtained for TB and MO within 30 and 55 min, respectively. Furthermore, the change in the total organic carbon (TOC) was monitored to verify the degree of mineralization of the azo dyes. The extremely high dye degradation activity and TOC removal can be attributed to the formation of a suitable heterojunction interface between the components of the photocatalyst, leading to effective charge carrier transport and the generation of active radicals. Finally, based on the radical scavenging experiments, ESR, and VB-XPS analysis, a plausible mechanism for the photodegradation process was derived. This research contributes to the advancement of sustainable water treatment technologies by providing insights into the design, fabrication, and utilization of novel composites for efficient remediation of dye-contaminated wastewater.

Tailoring Diversified Peripheral Anchor Groups in Spirofluorene‐Dithiolane‐Based Hole Transporting Materials for Efficient Organic and Perovskite Solar Cells from First‐Principle

AbstractThis quantum mechanical approach recommends push–pull molecular engineering to fabricate hole‐transporting materials (HTMs) for photovoltaic cells. It integrates acceptor moieties via thiophene to fluorene core, resulting in five novel HTMs (SFD‐1 to SFD‐5). The results exhibit that derivative HTMs show excellent coherence in excitation, dispersion, and transportation of charge carriers, ensuring robust hole mobility. The anchor moieties functionalized HTMs unveil excellent band alignment with perovskite with fitting HOMO energy levels (−4.93–−5.35 eV), less optical absorption in visible portion ( < 520). This acceptor integration has improved the hole mobility in derivatives, accredited to the smaller hole reorganization energy (0.14–0.68 eV), and greater hole transfer integral (0.22–0.33 eV). The transition density matrix analysis exhibited robust electronic coupling, subtler charge carrier overlapping and greater charge transfer length (7.48–13.73 Å). This resulted in an excellent upsurge in intrinsic charge transference (70.75–92.70%) and smaller exciton binding energy, leading to easier exciton dissociation, and fewer recombination fatalities. However, an adequate variation in dipole moment (4.04 D to 16.34 D) and Gibbs solvation‐free energy (−18.06 to −21.89 kcal mol−1) ensures facile film formation and processability. In conclusion, this approach recommends these flourene‐based HTMs are highly desireable for forthcoming solar cell technology.

Achieving Efficient Intrinsically Stretchable Organic Photovoltaics with a Conjugated and Elastomeric Dual‐Network Morphology

AbstractStretchable organic photovoltaics (OPVs) are pivotal for advancing conformable electronics, yet achieving both efficient and intrinsically stretchable OPVs remains a significant challenge. The main issue is maintaining electronic and mechanical properties under deformation. Here, a ternary blend system, PTzBI‐oF:PYIT:EVA is presented, incorporating ethylene‐vinyl acetate (EVA) to establish a conjugated and elastomeric dual‐network morphology. The elastomer network dissipates applied stress, preserving the crystalline packing of the conjugated network and enabling improved mechanical stability of charge carrier generation and transport. Specifically, with 15% EVA content, the ternary blend achieved a power conversion efficiency (PCE) of 15.28% in rigid devices and exhibited a crack onset strain of 17.23%. Notably, the stretchable OPVs retained over 80% of their initial PCE under 30% strain. These findings underscore the potential of conjugated and elastomeric dual‐network morphology in developing high‐performance stretchable electronics for various applications.

Enhanced Performance and Stability of Perovskite Solar Cells Through Surface Modification with Benzocaine Hydrochloride.

Current development of inverted p-i-n perovskite solar cells (PSCs), with nickel oxide as the hole transport layer, is progressing toward lower net costs, higher efficiencies, and superior stabilities. Unfortunately, the high density of defect-based traps on the surface of perovskite films significantly limits the photoelectric conversion efficiency and operational stability of perovskite solar cells. Finding cost-effective interface modifiers is crucial for the further commercial development of p-i-n PSCs. In the present work, we report a passivation strategy using a multifunctional molecule, benzocaine hydrochloride (BHC), which is shown to reduce defect density and enhance the photovoltaic performance and stability of the resultant p-i-n PSCs. It has been revealed that BHC strongly interacts with perovskite precursor components and triggers the evolution of the perovskite absorber film morphology and enables improved surface energy level alignment, thus promoting charge carrier transport and extraction. These properties are beneficial for improving open-circuit voltage (VOC) and fill factor (FF). Our results show that the photoelectric conversion efficiency (PCE) of p-i-n PSCs with nickel oxide as the hole transport layer increased from an initial 20.0% to 22.1% after being passivated with BHC, and these passivated devices also exhibited improved stability. DFT calculations reveal the unusual ability of the BHC passivant to improve band alignment while also preventing the accumulation of holes at the interface. In this work, the advantages of BHC passivation are demonstrated by linking theoretical calculations with optical and electrical characterizations.

Formamidinium lead iodide perovskite photovoltaics with MoS2 quantum dots

We present the formation of a composite film made out of formamidinium lead iodide (FAPI) and molybdenum disulphide quantum dots (MoS2 QDs) and propose a corresponding photovoltaic device architecture based on a ‘type-I’ alignment of the two materials’ electronic energy levels. The introduction of the MoS2 QDs has not compromised the overall crystallinity of the FAPI film and the composite absorber has shown improved stability. We report on the benefits of this composite film and energy band arrangement as the photogenerated carriers in MoS2 QDs, both positive and negative, are injected into the FAPI host matrix, resulting in an increased current density of 24.19 mA cm−2 compared to a current density of 19.83 mA cm−2 for the control device with FAPI only. The corresponding photoconversion efficiency increases from 12.6 to 15.0%. We also show that inclusion of MoS2 QDs in FAPI films resulted in a notable improvement in the fill factor and open-circuit voltage of the solar cells. Most importantly, MoS2 QDs enhanced the film stability by reducing defect formation and acting as passivating agents that minimize recombination losses and improve charge carrier transport. Our results suggest that a composite film in a type-I device architecture can introduce benefits for both future developments in perovskite solar cells and effectively tackling the longstanding challenges of carrier transport in QDs solar cells.

Air-Processed Efficient Cesium-Based Two-Dimensional Perovskite Solar Cells Based on Asymmetric Chiral Ammonium Salts.

Cesium-based two-dimensional (2D) perovskites with attractive phase and environmental stability have broad application prospects in single-junction and tandem perovskite solar cells (PSCs). However, the severe nonradiative recombination and significant energy losses due to disordered phase orientations and phase distributions greatly hinder the carrier transport performance of cesium-based 2D PSCs and severely limit their photovoltaic performance. Here, we employ an asymmetric chiral spacer cation source, (R)-α-phenylethylamine acrylate (R-α-PEAAA), to prepare high-quality 2D cesium-based films with uniform phase distribution and high out-of-plane orientation by air processing, resulting in efficient carrier transport. More importantly, the asymmetric chiral spacer R-α-PEA has a stronger dipole moment than its isomer (PEA), which can regulate the dielectric properties of cesium-based 2D perovskites and promote charge dissociation. In addition, the chiral R-α-PEA can optimize the morphology and out-of-plane orientation of perovskite films, reduce trap density and nonradiative recombination loss, and optimize energy level alignment, thus enhancing carrier transport. As a result, cesium-based 2D PSCs (R-α-PEA2Cs4Pb5I16, n = 5) achieved a record power conversion efficiency of 19.71% and the unencapsulated device maintained over 90% efficiency after 1500 h of continuous light exposure and ambient storage (35 ± 5% relative humidity). This study provides an idea for the development of chiral 2D perovskite with efficient charge carrier transport toward efficient and stable cesium-based 2D PSCs.

Electrochemistry Beyond Solutions: Modeling Particle Self-Crowding of Nanoparticle Suspensions.

Nanoparticle suspensions hold promise to transform functionality of next-generation electrochemical systems including batteries, capacitors, wastewater treatment, and sensors, challenging the limits of existing electrochemical models. Classical solution-based electrochemistry assumes that charge is transported and transferred by point-like carriers. Herein, we examine the electrochemistry of a model aqueous suspension of nondissolvable electroactive nanoparticles over a wide concentration range using a rotating disk electrode. Past a concentration and rotation rate threshold, the electrochemistry deviates from solution theory with a maximum attainable current due to particle "self-crowding" where reacted particles on the electrode surface reduce the area accessible for charge transfer by unreacted particles. The observed response is rationalized with an analytical model considering the physical adsorption/desorption kinetics and interfacial transport of nondissolvable finite-size charge carriers. Experimental validation shows the model to be applicable across a range of electrode sizes and thus suitable for engineering electrochemical systems employing nondissolvable nanoparticle suspensions.

Modulating long-lived ultrafast charge carrier recombination in type-I MoS2/CdS photocatalyst achieving optimal H2 evolution

Maximizing charge carrier efficiency is crucial for enhancing photocatalyst systems’ capacity to achieve outstanding photocatalytic hydrogen evolution (PHE). Herein, an I-type CdS nanorod/MoS2 nanoflowers heterojunction was successfully fabricated and kinetic transportof charge carriers was being investigated with electron paramagnetic resonance (EPR) analysis, surface photovoltage (SPV), femtosecond transient absorption (fs-TA) measurements and related density functional theory (DFT) calculations, etc. The in-situ dynamic study conducted using fs-TA reveals that the optimal CdS/MoS2 ratio (3CM), when excited by a 380 nm pump, exhibits a quasi-discrete exciton hot carrier cooling time of 0.35 picoseconds (ps), with interfacial electron transfer occurring in approximately 21.90 ps. In this context, MoS2 enhances the efficiency of interfacial electron transfer by passivating surface shallow trapped states, which were observed to be only 8.62 ps in pure CdS. Moreover, the kinetic coupling of long-lived charge separation (approximately 4440 ps) within the 3CM heterojunction, across various ratios of CdS/MoS2, is identified as a key factor in enhancing visible-light-driven PHE. This enhancement achieves remarkable rates of up to 31.094 mmol h-1 g-1, surpassing the performance of physically mixed CdS-MoS2 without chemical bonding by an impressive factor of 31. Our findings highlight the importance of tailored cocatalyst ratios in modulating the charge recombination for enhanced photocatalytic activity.

Linking Electronic and Structural Disorder Parameters to Carrier Transport in a Modern Conjugated Polymer.

Understanding charge transport in conjugated polymers is crucial for the development of next-generation organic electronic applications. It is presumed that structural disorder in conjugated polymers originating from their semicrystallinity, processing, or polymorphism leads to a complex energetic landscape that influences charge carrier transport properties. However, the link between polymer order parameters and energetic landscape is not well established experimentally. In this work, we successfully link statistical surveys of the local polymer electronic structure with paracrystalline structural disorder, a measure of statistical fluctuations away from the ideal polymer packing structure. We use scanning tunneling microscopy/spectroscopy to measure spatial variability in electronic band edges in PM6 films, a high-performance conjugated polymer, and find that films with higher paracrystallinity exhibit greater electronic disorder, as expected. In addition, we show that macroscopic charge carrier mobility in field effect transistors and and trap influence in hole-only diode devices is positively correlated with these microscopic structural and electronic parameters.

Heterophase homojunction construction by amorphous TiOx and N–TiO2 photoanode for oxygen evolution reaction kinetics and charge carriers’ transportation enhancement

Photoelectrochemical (PEC) water splitting by TiO2 photoanode for clean hydrogen production is limited by the poor charge separation and inert oxygen evolution reaction (OER) kinetics issues for now. In this work, a band-matched heterophase homojunction (TiOx/N–TiO2) by amorphous TiOx and N-doped TiO2 nanotube arrays is constructed by two-step anodic oxidation and impregnation. The photocurrent density of TiOx/N–TiO2 reaches 0.69 mA/cm2 at 1.23 V vs. RHE, which is 1.86 folds than bare TiO2. The enhanced charge carriers' injection/separation efficiency, smaller Tafel slope (37.79 mF dec−1) and larger electrochemical active surface area (ECSA) (1.98 mF cm−2) of TiOx/N–TiO2 indicate that N doping and heterophase homojunction with amorphous TiOx effectively facilitate the surface OER kinetics and charge carriers' transportation. TiOx/N–TiO2 is annealed with a transformation of the surface amorphous TiOx layer into anatase TiO2 (a-TiOx/N–TiO2) to study the role of amorphous TiO2 in PEC water splitting. The photocurrent density and applied bias photon-to-current efficiency (ABPE) for a-TiOx/N–TiO2 decrease, even lower than the pristine TiO2. This is due to the reduction of surface oxygen vacancies, which causes the slowdown of OER kinetics and the weakening of charge carrier transportation ability. That is favorable for a better understanding of the OER kinetics and charge carriers’ transportation enhancement mechanism by the surficial modification on the semiconductor during the PEC water splitting.