Understanding Trap States in InP and GaP Quantum Dots through Density Functional Theory.

The widespread application of III-V colloidal quantum dots (QDs) as nontoxic, highly tunable emitters is stymied by their high density of trap states. Here, we utilize density functional theory (DFT) to investigate trap state formation in a diverse set of realistically passivated core-only InP and GaP QDs. Through orbital localization techniques, we deconvolute the dense manifold of trap states to allow for detailed assignment of surface defects. We find that the three-coordinate species dominate trapping in III-V QDs and identify features in the geometry and charge environment of trap centers capable of deepening, or sometimes passivating, traps. Furthermore, we observe stark differences in surface reconstruction between InP and GaP, where the more labile InP reconstructs to passivate three-coordinate indium at the cost of distortion elsewhere. These results offer explanations for experimentally observed trapping behavior and suggest new avenues for controlling trap states in III-V QDs.

Highly Efficient and Stable Inverted Perovskite Solar Cell Using Pure δ-FAPbI3 Single Crystals.

Pure δ-formamidinium lead triiodide (δ-FAPbI3 ) single crystal for highly efficient perovskite solar cell (PCS) with long-term stability is prepared by a new method consisting of liquid phase reaction of FAI and PbI2 in N,N-dimethyl formamide and antisolvent crystallization using acetonitrile. In this method, the incorporation of any impurity into the crystal is excluded by the molecular recognition of the crystal growth site. This pure crystal is used to fabricate α-FAPbI3 inverted PSCs which showed excellent power conversion efficiency (PCE) due to much-reduced trap-states. The champion device exhibited a high PCE of 23.48% under the 1-Sun condition. Surface-treated devices with 3-(aminomethyl)pyridine showed a significantly improved PCE of 25.07%. In addition, the unencapsulated device maintained 97.22% of its initial efficiency under continuous 1-Sun illumination for 1,000 h at 85 °C in an N2 atmosphere ensuring long-term thermal and photo stabilities of PSCs, whereas the control device kept only 89.93%.

Enhanced Charge Separation for Efficient Photocatalytic H2 Production by Long-Lived Trap-State-Induced Interfacial Charge Transfer.

Photogeneration of charge carriers in semiconductors provides the scientific fundamental for photocatalytic water splitting. However, an ongoing challenge is the development of a new mechanism promoting charge carrier separation. Here we propose a trap-state-induced interfacial charge-transfer transition mechanism (TSICTT), in which electrons in long-lived trap states recombine with holes on the valence band (VB) of the semiconductor, thus prolonging the electron lifetime. We demonstrate this concept in the Sr4Al14O25:Eu2+, Dy3+/CdS (SAO/CdS) heterostructure, where trapped electrons with a lifetime of up to several hours in the SAO persistent luminescence phosphor (PLP) can continuously consume holes on the VB of CdS nanoparticles (NPs). We discover that the interfacial interaction and the work function difference between SAO and CdS are crucial for the TSICTT, which finally contributes to the improved H2 production from 34.4 to 1212.9 µmol gCdS-1 h-1 under visible-light irradiation. This model introduces a new strategy to manipulate charge carrier transport for the effective utilization of solar energy.

Physics of defects in metal halide perovskites.

Metal halide perovskites are widely used in optoelectronic devices, including solar cells, photodetectors, and light-emitting diodes. Defects in this class of low-temperature solution-processed semiconductors play significant roles in the optoelectronic properties and performance of devices based on these semiconductors. Investigating the defect properties provides not only insight into the origin of the outstanding performance of perovskite optoelectronic devices but also guidance for further improvement of performance. Defects in perovskites have been intensely studied. Here, we review the progress in defect-related physics and techniques for perovskites. We survey the theoretical and computational results of the origin and properties of defects in perovskites. The underlying mechanisms, functions, advantages, and limitations of trap state characterization techniques are discussed. We introduce the effect of defects on the performance of perovskite optoelectronic devices, followed by a discussion of the mechanism of defect treatment. Finally, we summarize and present key challenges and opportunities of defects and their role in the further development of perovskite optoelectronic devices.

Mapping Trap Dynamics in a CsPbBr3 Single-Crystal Microplate by Ultrafast Photoemission Electron Microscopy.

For versatile lead-halide perovskite materials, their trap states, both in the bulk and at the surface, significantly influence optoelectronic behaviors and the performance of the materials and devices. Direct observation of the trap dynamics at the nanoscale is necessary to understand and improve the device design. In this report, we combined the femtosecond pump-probe technique and photoemission electron microscopy (PEEM) to investigate the trap states of an inorganic perovskite CsPbBr3 single-crystal microplate with spatial-temporal-energetic resolving capabilities. Several shallow trap sites were identified within the microplate, while the deep traps were resolved throughout the surface. The results revealed high-defect tolerance to the shallow traps, while the surface dynamics were dominated by the surface deep traps. The ultrafast PEEM disclosed a full landscape of fast electron transfer and accumulation of the surface trap states. These discoveries proved the excellent electronic properties of perovskite materials and the importance of surface optimization.

Optical and Material Characteristics of MoS2/Cu2O Sensor for Detection of Lung Cancer Cell Types in Hydroplegia.

In this study, n-type MoS2 monolayer flakes are grown through chemical vapor deposition (CVD), and a p-type Cu2O thin film is grown via electrochemical deposition. The crystal structure of the grown MoS2 flakes is analyzed through transmission electron microscopy. The monolayer structure of the MoS2 flakes is verified with Raman spectroscopy, multiphoton excitation microscopy, atomic force microscopy, and photoluminescence (PL) measurements. After the preliminary processing of the grown MoS2 flakes, the sample is then transferred onto a Cu2O thin film to complete a p-n heterogeneous structure. Data are confirmed via scanning electron microscopy, SHG, and Raman mapping measurements. The luminous energy gap between the two materials is examined through PL measurements. Results reveal that the thickness of the single-layer MoS2 film is 0.7 nm. PL mapping shows a micro signal generated at the 627 nm wavelength, which belongs to the B2 excitons of MoS2 and tends to increase gradually when it approaches 670 nm. Finally, the biosensor is used to detect lung cancer cell types in hydroplegia significantly reducing the current busy procedures and longer waiting time for detection. The results suggest that the fabricated sensor is highly sensitive to the change in the photocurrent with the number of each cell, the linear regression of the three cell types is as high as 99%. By measuring the slope of the photocurrent, we can identify the type of cells and the number of cells.

Improving the Power-Conversion Efficiency through Alloying in Common Anion CdZnX (X=S, Se) Nanocrystal Sensitized Solar Cells.

In this paper, we have investigated the possibility of utilizing CdZnS and CdZnSe alloy nanocrystals (NCs) as sensitizers in quantum-dot solar cells (QDSCs). The alloy NCs were synthesized by a high-temperature hot injection method and subsequently characterized through high photoluminescence quantum yield, along with larger size compared to binary NCs. Femtosecond transient absorption measurements revealed long-lived charge carriers in the alloy structure due to more structural rigidity and less defect states. Finally, the solar-cell efficiencies of the CdZnS (CdZnSe) NCs were found to be 3.05 % (3.69 %) as compared to 1.23 % (3.12 %) efficiencies for CdS (CdSe) NCs. Thus, common anion ternary NCs have been successfully utilized for solar-cell assembly and can be helpful for constructing tandem solar cells to harvest the high-energy portion of solar radiation.

Fluorometric sensing of oxygen using manganese(II)-doped zinc sulfide nanocrystals.

Manganese(II)-doped zinc sulfide nanocrystals (Mn:ZnS NCs) with dual-emission fluorescence (peaks at 445 nm and 590 nm under 330 nm excitation), good water stability and low toxicity were synthesized by hot injection. The fluorescence intensity of both emission bands of the nanocrystals can change rapidly by the content of gaseous and dissolved oxygen. The process is fully reversible. Compared with the maximum intensity of Mn:ZnS sensing film in 100% nitrogen, the emission of the blue emission decreases by 72% in the presence of 100% oxygen, and the yellow emission by 32%. Response is linear in the presence of 3% to 12% of oxygen percentage in gas. For water-dissolved oxygen, the linear response occurs between 0.54 and 11.4 mg·L-1. Graphical abstractMn-doped ZnS NCs with dual-emission fluorescence were synthesized by hot-injection method. The reversible and rapid sensing characteristics of Mn-doped ZnS NCs to oxygen were studied, and the possible sensing mechanism was investigated.

Defect-Induced Conical Intersections Promote Nonradiative Recombination.

We apply multireference electronic structure calculations to demonstrate the presence of conical intersections between the ground and the first excited electronic states of three silicon nanocrystals containing defects characteristic of the oxidized silicon surface. These intersections are accessible upon excitation at visible wavelengths and are predicted to facilitate nonradiative recombination with a rate that increases with decreasing particle size. This work illustrates a new framework for identifying defects responsible for nonradiative recombination.

Enhanced NO2 Sensitivity of Vertically Stacked van der Waals Heterostructure Gas Sensor and Its Remarkable Electric and Mechanical Tunability.

Nanodevices based on van der Waals heterostructures have been predicted, and shown, to have unprecedented operational principles and functionalities that hold promise for highly sensitive and selective gas sensors with rapid response times and minimal power consumption. In this study, we fabricated gas sensors based on vertical MoS2/WS2 van der Waals heterostructures and investigated their gas sensing capabilities. Compared with individual MoS2 or WS2 gas sensors, the MoS2/WS2 van der Waals heterostructure gas sensors are shown to have enhanced sensitivity, faster response times, rapid recovery, and a notable selectivity, especially toward NO2. In combination with a theoretical model, we show that it is important to take into account created trapped states (flat bands) induced by the adsorption of gas molecules, which capture charges and alter the inherent built-in potential of van der Waals heterostructure gas sensors. Additionally, we note that the performance of these MoS2/WS2 heterostructure gas sensors could be further enhanced using electrical gating and mechanical strain. Our findings highlight the importance of understanding the effects of altered built-in potentials arising from gas molecule adsorption induced flat bands, thus offering a way to enhance the gas sensing performance of van der Waals heterostructure gas sensors.

Eliminating the Burn-in Loss of Efficiency in Organic Solar Cells by Applying Dimer Acceptors as Supramolecular Stabilizers.

The meta-stable active layer morphology of organic solar cells (OSCs) is identified as the main cause of the rapid burn-in loss of power conversion efficiency (PCE) during long-term device operation. However, effective strategies to eliminate the associated loss mechanisms from the initial stage of device operation are still lacking, especially for high-efficiency material systems. Herein, the introduction of molecularly engineered dimer acceptors with adjustable thermal transition properties into the active layer of OSCs to serve as supramolecular stabilizers for regulating the thermal transitions and optimizing the crystallization of the absorber composites is reported. By establishing intimate π-π interactions with small-molecule acceptors, these stabilizers can effectively reduce the trap-state density (Nt) in the devices to achieve excellent PCEs over 19%. More importantly, the low Nt associated with an initially optimized morphology can be maintained under external stresses to significantly reduce the PCE burn-in loss in devices. This research reveals a judicious approach to improving OPV stability by establishing a comprehensive correlation between material properties, active-layer morphology, and device performance, for developing burn-in-free OSCs.

Coexistence of the Band Filling Effect and Trap-State Filling in the Size-Dependent Photoluminescence Blue Shift of MAPbBr3 Nanoparticles.

The size-dependent photoluminescence (PL) blue shift in organometal halide perovskite nanoparticles has traditionally been attributed to quantum confinement effects (QCEs), irrespective of nanoparticle size. However, this interpretation lacks rigor for nanoparticles with diameters exceeding the exciton Bohr radius (rB). To address this, we investigated the PL of MAPbBr3 nanoparticles (MNPs) with diameters ranging from ~2 to 20 nm. By applying the Brus equation and Burstein-Moss theory to fit the PL and absorption blue shifts, we found that for MNPs larger than rB, the blue shift is not predominantly governed by QCEs but aligns closely with the band filling effect. This was further corroborated by a pronounced excitation-density-dependent PL blue shift (Burstein-Moss shift) at high photoexcitation densities. Additionally, trap-state filling was also found to be not a negligible origin of the PL blue shift, especially for the smaller MNPs. The time-resolved PL spectra (TRPL) and excitation-density-dependent TRPL are collected to support the coexistence of both filling effects by the high initial carrier density (~1017-1018 cm-3) and the recombination dynamics of localized excitons and free carriers in the excited state. These findings underscore the combined role of the band filling and trap-state filling effects in the size-dependent PL blue shift for solution-prepared MNPs with diameters larger than rB, offering new insights into the intrinsic PL blue shift in organometal halide perovskite nanoparticles.

Anisotropic Growth of Centimeter-Size CsCu2 I3 Single Crystals with Ultra-Low Trap Density for Aspect-Ratio-Dependent Photodetectors.

Low-dimensional ternary copper iodide metal halide with strong quantum confinement effects has made great progress in optoelectronic fields. However, efficient regulation of anisotropic growth of metal halides single crystal still remains a great challenge. Herein, 2 cm size CsCu2 I3 single crystals with tunable aspect ratio and the trap states (ntrap ) as low as 5.38 × 109  cm-3 are fabricated by optimized anti-solvent vapor-assisted method, in which the growth cycle is shortened by half. Evidenced by real-time observation and the LaMer growth model, the rapid and anisotropic growth mechanism is ascribed to preferential 1D growth, promoted by high concentration and fast vapor rate. Furthermore, the aspect-ratio-dependent optoelectronic performance is observed, the on-off ratio for 2 cm CsCu2 I3 single crystal are enhanced 350 times compared with those of short and thick single crystal, which shows ultrahigh on-off ratio of 1570, D* of 1.34 × 1012  Jones, Rλ of 276.94 mA W-1 , t rise /t decay of 0.37 and 1.08 ms, and EQE of 95.53%, which are clearly at very high level among lead-free perovskite-based photodetectors. This study not only provides a new strategy for overcoming anisotropic growth limitations of low-dimensional metal halides, but also paves a way for high-performance optoelectronic applications.

Precursor Chemistry Enables the Surface Ligand Control of PbS Quantum Dots for Efficient Photovoltaics.

The surface ligand environment plays a dominant role in determining the physicochemical, optical, and electronic properties of colloidal quantum dots (CQDs). Specifically, the ligand-related electronic traps are the main reason for the carrier nonradiative recombination and the energetic losses in colloidal quantum dot solar cells (CQDSCs), which are usually solved with numerous advanced ligand exchange reactions. However, the synthesis process, as the essential initial step to control the surface ligand environment of CQDs, has lagged behind these post-synthesis ligand exchange reactions. The current PbS CQDs synthesis tactic generally uses lead oxide (PbO) as lead precursor, and thus suffers from the water byproducts issue increasing the surface-hydroxyl ligands and aggravating trap-induced recombination in the PbS CQDSCs. Herein, an organic-Pb precursor, lead (II) acetylacetonate (Pb(acac)2 ), is used instead of a PbO precursor to avoid the adverse impact of water byproducts. Consequently, the Pb(acac)2 precursor successfully optimizes the surface ligands of PbS CQDs by reducing the hydroxyl ligands and increasing the iodine ligands with trap-passivation ability. Finally, the Pb(acac)2 -based CQDSCs possess remarkably reduced trap states and suppressed nonradiative recombination, generating a certified record Voc of 0.652 V and a champion power conversion efficiency (PCE) of 11.48% with long-term stability in planar heterojunction-structure CQDSCs.

Trap or Triplet? Excited-State Interactions in 2D Perovskite Colloids with Chromophoric Cations.

Movement of energy within light-harvesting assemblies is typically carried out with separately synthesized donor and acceptor species, which are then brought together to induce an interaction. Recently, two-dimensional (2D) lead halide perovskites have gained interest for their ability to accommodate and assemble chromophoric molecules within their lattice, creating hybrid organic-inorganic compositions. Using a combination of steady-state and time-resolved absorption and emission spectroscopy, we have now succeeded in establishing the competition between energy transfer and charge trapping in 2D halide perovskite colloids containing naphthalene-derived cations (i.e., NEA2PbX4, where NEA = naphthylethylamine). The presence of room-temperature triplet emission from the naphthalene moiety depends on the ratio of bromide to iodide in the lead halide sublattice (i.e., x in NEA2Pb(Br1-xIx)4), with only bromide-rich compositions showing sensitized emission. Photoluminescence lifetime measurements of the sensitized naphthalene reveal the formation of the naphthalene triplet excimer at room temperature. From transient absorption measurements, we find the rate constant of triplet energy transfer (kEnT) to be on the order of ∼109 s-1. At low temperatures (77 K) a new broad emission feature arising from trap states is observed in all samples ranging from pure bromide to pure iodide composition. These results reveal the interplay between sensitized triplet energy transfer and charge trapping in 2D lead halide perovskites, highlighting the need to carefully parse contributions from competing de-excitation pathways for optoelectronic applications.

Transient Measurements and Simulations Correlate Exchange Ligand Concentration and Trap States in Colloidal Quantum Dot Photodetectors.

Colloidal quantum dot (CQD) photodetectors (PDs) can detect wavelengths longer than the 1100 nm limit of silicon because of their highly tunable bandgaps. CQD PDs are acutely affected by the ligands that separate adjacent dots in a CQD-solid. Optimizing the exchange solution ligand concentration in the processing steps is crucial to achieving high photodetector performance. However, the complex mix of chemistry and optoelectronics involved in CQD PDs means that the effects of the exchange solution ligand concentration on device physics are poorly understood. Here we report direct correspondence between simulated and experimental transient photocurrent responses in CQD PDs. For both deficient and excess conditions, our model demonstrated the experimental changes to the transient photocurrent aligned with changes in trap state density. Combining transient photoluminescence, absorption, and photocurrent with this simulation model, we revealed that different mechanisms are responsible for the increased trap density induced by excess and deficient active layer ligand concentrations.

Tracing the Si Dangling Bond Nanopathway Evolution ina-SiNx:H Resistive Switching Memory by the Transient Current.

With the big data and artificial intelligence era coming, SiNx-based resistive random-access memories (RRAM) with controllable conductive nanopathways have a significant application in neuromorphic computing, which is similar to the tunable weight of biological synapses. However, an effective way to detect the components of conductive tunable nanopathways in a-SiNx:H RRAM has been a challenge with the thickness down-scaling to nanoscale during resistive switching. For the first time, we report the evolution of a Si dangling bond nanopathway in a-SiNx:H resistive switching memory can be traced by the transient current at different resistance states. The number of Si dangling bonds in the conducting nanopathway for all resistive switching states can be estimated through the transient current based on the tunneling front model. Our discovery of transient current induced by the Si dangling bonds in the a-SiNx:H resistive switching device provides a new way to gain insight into the resistive switching mechanism of the a-SiNx:H RRAM in nanoscale.

Borosilicate glasses containing CdS/ZnS QDs: A heterostructured composite with enhanced degradation of IC dye under visible-light.

The glass system SiO2-B2O3-Na2O3-ZnO containing 2 wt% CdS and 1 wt% ZnS was synthesized by the conventional melt quench method. Glass transition temperature and crystallization temperature was determined from Differential thermal analysis (DTA) measurement to optimize heat-treatment. The amorphous structure of the glass was confirmed by the X-ray diffraction (XRD) measurement. Glasses were heat-treated by optimized heat-treatment schedule to grow CdS/ZnS QDs and crystalline phases of CdS and ZnS were confirmed by the XRD measurement. High-Resolution Transmission Electron Microscopy (HRTEM) was used to determine the size and shape of quantum dots (QDs) grown in the glass matrix. The optical band gap was calculated from the absorption spectra and found to decrease with increase in size of QDs. Electron-hole recombination rate was studied using a decay time and impedance analyzer. Prepared samples were tested as a photocatalyst under sunlight for the degradation of indigo carmine (IC) dye and photodegradation efficiency was found to be 73.6 % and 87.2 % for samples CZ1 and CZ4 respectively. No significant change is observed in degradation efficiency even for 4 cycles which confirms the stability of prepared glasses for dye degradation.

Probing Intrinsic Defect-Induced Trap States and Hopping Transport in Two-Dimensional PdSe2 Semiconductor Devices.

Palladium diselenide (PdSe2), as an emerging two-dimensional (2D) layered material, is gaining growing attention in nanoelectronics and optoelectronics due to its thickness-dependent band gap, high carrier mobility, and good air stability. However, its asymmetric pentagon structure is inclined to breed defects. Herein, the intrinsic Se vacancy-induced trap states and their influence on the hopping transport in PdSe2 are systematically investigated. We provide direct evidence that Se vacancies exist in the fresh PdSe2 samples, which results in the localized trapping states inside the band gap. For the few-layer PdSe2, at 77 K, the trap density (Dit) near the midgap is about 2.2 × 1013 cm-2 eV-1, whereas at 295 K, the Dit value increases to ∼7.1 × 1013 cm-2 eV-1. By comparison, the multilayer PdSe2 shows nonobvious temperature-dependent trap behaviors with almost unchanged Dit values of ∼8.1 × 1012 cm-2 eV-1 at midgap in the temperature range between 77 and 295 K. Thus, trap states in the few-layer PdSe2 are more vulnerable to temperature effect. Transport measurements demonstrated that both few-layer and multilayer PdSe2 field-effect transistor (FET) devices show n-type dominant ambipolar behaviors. The electron mobility in the multilayer PdSe2 FET is nearly 15-fold higher than that in the few-layer PdSe2 FET at 315 K, probably owing to the decreased effective mass and suppression of charge impurity scattering in the thicker channel material. However, both FET devices exhibit variable-range hopping over a temperature range from 77 to 240 K and thermally activated hopping at temperatures above 240 K. The hopping transport mechanism is strongly associated with the Se vacancy-induced localized states with poor screening and strong potential fluctuations. This study reveals the important role of structural defects in tailoring and improving the charge transport properties of PdSe2.

High-Efficiency Thickness-Insensitive Organic Solar Cells with an Insulating Polymer.

Achieving high-efficiency thick-film bulk heterojunction (BHJ) organic solar cells (OSCs) with thickness-independent power conversion efficiencies (PCEs) in a wide thickness range is still a challenge for the roll-to-roll printing techniques. The concept of diluting the transport sites within BHJ films with insulating polymers can effectively eliminate charge trapping states and optimize the charge transport. Herein, we first adopted the concept with insulating polypropylene (PP) in the efficient non-fullerene system (PM6:Y6) and demonstrated its potential to fabricate thick-film OSCs. The PP can form an insulating matrix prior to PM6 and Y6 within the BHJ film, resulting in an enhanced molecular interaction and isolated charge transport by expelling Y6 molecules. We thus observed reduced trap state density and improved charge transport properties in the PP-blended device. At around 300 nm, the PM6:Y6:PP device enjoys a high PCE of 15.5% and achieves over 100% of the efficiency of the optimal thin-film device, which is significantly improved compared to the binary PM6:Y6 counterpart. This research promotes an effective strategy with insulating polymers and provides knowledge of commercial production with response to the roll-to-roll technique demands.