Deep Trapping Sites Research Articles

Fe-N Co-Doped BiVO4 Photoanode with Record Photocurrent for Water Oxidation.

Bismuth vanadate (BVO) ranks among the most promising photoanodes for photoelectrochemical (PEC) water splitting. Nonetheless, slow charge separation and transport, besides the sluggish water oxidation kinetics, are key barriers to its photoefficiency. Here, we present a co-doping strategy that significantly improves the charge separation performance of BVO photoanodes. We found that, under standard one sun illumination, the Fe-N co-doped BVO photoanode (Fe-N-BVO) by N-coordinated Fe precursor reaches a record photocurrent density of 7.01 mA cm-2 at 1.23 V vs RHE after modified a surface co-catalyst (FeNiOOH), and exhibits an outstanding stability. By contrast, much lower photocurrent density is obtained for the N-doped, Fe-doped and Fe/N-doped BVO photoanode with separated N and Fe precursors. The detailed experimental characterizations show that the high activity of the Fe-N co-doped BVO photoanode is attributed to the enhanced photo-induced bulk charge separation, as well as the accelerated surface water oxidation kinetics. XPS, EXAFS and DFT calculations clearly show that, instead of formation of deep trapping state in the individually doped BVO, the co-doping of Fe-N into BVO generates Fe-based electronic states just below the bottom of conduction band and N-derived states just above the top of valence band. Such modulations in electronic structure enable the efficient trap of the electrons and holes to enhance the separation of photo-induced carriers, but hinder the charge recombination originated from the deep trapping sites.

Fe−N Co‐Doped BiVO4 Photoanode with Record Photocurrent for Water Oxidation

AbstractBismuth vanadate (BVO) ranks among the most promising photoanodes for photoelectrochemical (PEC) water splitting. Nonetheless, slow charge separation and transport, besides the sluggish water oxidation kinetics, are key barriers to its photoefficiency. Here, we present a co‐doping strategy that significantly improves the charge separation performance of BVO photoanodes. We found that, under standard one sun illumination, the Fe−N co‐doped BVO photoanode (Fe−N−BVO) by N‐coordinated Fe precursor reaches a record photocurrent density of 7.01 mA cm−2 at 1.23 V vs RHE after modified a surface co‐catalyst (FeNiOOH), and exhibits an outstanding stability. By contrast, much lower photocurrent density is obtained for the N‐doped, Fe‐doped and Fe/N‐doped BVO photoanode with separated N and Fe precursors. The detailed experimental characterizations show that the high activity of the Fe−N co‐doped BVO photoanode is attributed to the enhanced photo‐induced bulk charge separation, as well as the accelerated surface water oxidation kinetics. XPS, EXAFS and DFT calculations clearly show that, instead of formation of deep trapping state in the individually doped BVO, the co‐doping of Fe−N into BVO generates Fe‐based electronic states just below the bottom of conduction band and N‐derived states just above the top of valence band. Such modulations in electronic structure enable the efficient trap of the electrons and holes to enhance the separation of photo‐induced carriers, but hinder the charge recombination originated from the deep trapping sites.

Nano‐Size Effects on Decay Dynamics of Photo‐Excited Polarons in CeO2

AbstractThe study of polaron dynamics in complex materials has garnered significant attention owing to its implications for various technological applications, including catalysis, solid‐state devices, and energy storage. This paper investigates the photo‐excited electron and hole polaron dynamics in cerium dioxide (CeO2) using time‐resolved X‐ray absorption spectroscopy, with an emphasis on the nano‐size effect. Additionally, density functional theory and multiplet calculations have been utilized to reveal the photo‐excited polaron dynamics in CeO2 single crystal (SC) and nanocrystal (NC). The electron polaron is observed to decay into a deep trap site with a short duration of ≈5 ps, while electrons in the traps stay for more than 1400 ps. The most significant observation is the behavior of holes in NC, which tends to stay longer (≈150 ps) compared to SC (<10 ps) suggesting hole existence more at the surface than at bulk. The fast dissociation of the electron polarons the prolonged lifetime of the electrons above the Fermi level and the enhanced hole lifetime at the surface are proposed to be among the various factors that influence the high reactivity of CeO2.

Scalable multilayered dielectric polymer film exhibiting significantly improved high-temperature energy density

Dielectric polymers, serving as crucial dielectric media in high-power-density energy storage devices, play a pivotal part in modern industries and electrical systems. However, the rapid degradation of breakdown strength and charge-discharge efficiency in elevated temperature environment imposes formidable limitations on the utilization of polymer dielectric under extreme conditions. Here, a series of polyetherimide/polysulfone alternating multilayer composite films are prepared using a non-equilibrium processing method, which effectively blocks the development of breakdown paths by the interface barriers in the multilayer structure. The deep trap sites within the interface capture the charge carriers excited at high temperatures, thus decreasing conduction loss and enhancing the efficiency and breakdown field strength of the dielectric polymer. Consequently, excellent capacitive performances including a high energy density of 5.4 J cm−3 with an efficiency exceeding 90% at 200 °C and cycle stability up to 106 cycles have been obtained. Furthermore, the multilayer polymer capacitors (MLPC) constructed from composite films also exhibit significant flexibility and thermal stability. This work provides valuable insights for the advancement of high-temperature energy storage polymers with commercial application value.

Durability enhancement of all-solid-state electrochromic devices by adjusting the charge density ratio between electrochromic and counter electrode layers

Owing to an increase in global warming, smart-window devices based on charge-balanced electrochromic devices (ECDs), which exhibit high potential to increase the thermal efficiency of buildings, have gained prominence. However, studies on the fabrication and cycling stability of charge-balanced ECDs are scarce. In this study, WO3 and NiOx films were deposited on indium–tin–oxide (ITO)-coated glass substrates by reactive direct-current magnetron sputtering, and the deposition time was varied to control the thickness and charge density of the thin films. Subsequently, the NiOx/ITO/glass and WO3/ITO/glass substrates were laminated with a Li-based polymeric electrolyte to fabricate all-solid-state ECDs comprising electrochromic (EC) and counter-electrode (CE) layers in charge-density ratios of 12.6, 6.4, 2.3, and 1.1. Changes in the electrochromic properties, device-layer microstructure, crystal structure, and elemental composition of the as-constructed ECDs before and after degradation were investigated to understand the influence of the charge-density ratio of the EC and CE layers on the long-term durability of ECDs. Increasing the charge-density ratio decreased the cycling stability of the device owing to changes in the microstructure and crystal structure of the NiOx layer in the microstructural deep-trap sites. Among all the ECDs, those comprising EC and CE layers with similar charge densities showed the most stable optical modulation and highest long-term durability. Finally, based on the aforementioned results, a degradation mechanism for charge-imbalanced all-solid-state ECDs was proposed. This study is expected to open new frontiers in designing optimal-performance electrochemical devices with a wide variety of potential applications.

Nano-scale charge trapping memory based on two-dimensional conjugated microporous polymer

There is a growing interest in new semiconductor nanostructures for future high-density high-performance flexible electronic devices. Two-dimensional conjugated microporous polymers (2D-CMPs) are promising candidates because of their inherent optoelectronic properties. Here, we are reporting a novel donor–acceptor type 2D-CMP based on Pyrene and Isoindigo (PI) for a potential nano-scale charge-trapping memory application. We exfoliated the PI polymer into ~ 2.5 nm thick nanoparticles (NPs) and fabricated a Metal–Insulator–Semiconductor (MIS) device with PI–NPs embedded in the insulator. Conductive AFM (cAFM) is used to examine the confinement mechanism as well as the local charge injection process, where ultrathin high-κ alumina supplied the energy barrier for confining the charge carrier transport. We have achieved a reproducible on-and-off state and a wide memory window (ΔV) of 1.5 V at a relatively small reading current. The device displays a low operation voltage (V < 1 V), with good retention (104 s), and endurance (103 cycles). Furthermore, a theoretical analysis is developed to affirm the measured charge carriers’ transport and entrapment mechanisms through and within the fabricated MIS structures. The PI–NPs act as a nanoscale floating gate in the MIS-based memory with deep trapping sites for the charged carriers. Moreover, our results demonstrate that the synthesized 2D-CMP can be promising for future low-power high-density memory applications.

Spiral-Structured Dielectric Polymers Exhibiting Ultrahigh Energy Density and Charge-Discharge Efficiency at High Temperatures.

The growing need for high-power and compact-size energy storage in modern electronic and electrical systems demands polymer film capacitors with excellent temperature capability. However, conventional polymer dielectrics feature dramatic deterioration in capacitive performance under concurrent high temperature and electric field because the high thermal stability traditionally relies on the conjugated, planar molecular segments in the polymer chains. Herein, inspired by the stable double helix structures of deoxyribonucleic acid, spiral-structured dielectric polymers that exhibit simultaneous high thermal stability and great capacitive performance are demonstrated. Both the experimental results and computational simulations confirm that the spiral groups serve to weaken the electrostatic molecular interaction, induce proper molecular chain stacking structure, and regulate the charge transfer process by breaking the conjugated planes and introducing deep trap sites. The resultant polymer exhibits the maximum discharged energy densities of 7.29 and 6.13 Jcm-3 with the charge-discharge efficiency above 90% at 150 and 200°C, respectively, more than ten times those of the original dielectric at the same conditions. Here a completely new dimension is offered for the molecular design of polymers, giving rise to well-balanced thermal and dielectric properties, and ultimately the desired capacitive energy storage performance at high temperatures.

Thermal stimulated structural transformation of cubic Zn0.78Cd0.22S nanoparticles to ZnO nano-hexagons: Tailoring of optical band gap and emission spectra for optoelectronic implementations

Ternary alloys of Zn0.78Cd0.22S nanoparticles (NPs) are synthesized via the facile co-precipitation technique. The as-synthesized sample exhibits a zincblende-type cubic phase with an average crystalline size of 2 nm. Thermal annealing and UV irradiation are utilized as post-treatment processes for tailoring the optical properties of Zn0.78Cd0.22S NPs. The as-synthesized sample exhibits a stable cubic phase up to 400 °C, during which partial phase transformation to a hexagonal structure is observed at a higher temperature of 500 °C. The oxidation of Zn0.78Cd0.22S NPs to mixed oxide phases with the majority of ZnO begins at 600 °C which induces morphology transformation to a relatively large nano-hexagon with a single crystalline domain size. The increase of the annealing temperature is accompanied by a decrease of Zn0.78Cd0.22S NPs optical band gap (Eg) due to the weakness of size confinement as well as the formation of localized states below the mobility band edges. The brief UV irradiation results in the increase of Eg whereas a further increase in exposure time is accompanied by a reduction of Eg. The photoluminescence (PL) spectrum of the as-synthesized sample covers a wide spectral range from UV to visible. Thermal annealing has a slight effect on the PL emission at high excitation energy, whereas low excitation energy reveals higher sensitivity to deep-state emission. Thermal oxidation incorporates a high concentration of oxygen-related defects that induce strong enhancement in the green emission at the expense of UV emission. This indicates the thermal-induced bleaching of shallow trapping sites and the evolution of other deep trapping or recombination sites.

Corona Poling Induced Phase Transition to Highly Polar Phase in P(VDF-TrFE-CFE) Dielectric and Charge Transport of Organic Field-Effect Transistors.

Increasing the number of charge carriers flowing through the charge transport channel to improve the electrical performance of organic field-effect transistors (OFETs) is important because it leads to a low driving voltage and a high drain current value. This paper proposes a new strategy, the corona poling process, to enhance the electrical performance of OFETs using an external electric field when forming a dielectric film using a PVDF-based high-k dielectric terpolymer, P(VDF-TrFE-CFE). A corona poling process was applied to align the dipoles with high-k dielectric molecules and improve the capacitance, thereby increasing the number of charge carriers. Through this process, by observing the phase transition of a PVDF dielectric through a corona poling process in the GIWAXS data, the phase transition through an external electric field was thoroughly revealed for the first time. As a result, the capacitance of high-k dielectric films can be improved, and the amount of charge carriers can be increased by a simple corona poling process. In addition, to reduce the effect of deep trap sites caused by the dipole alignment, a thin low-k dielectric, polystyrene (PS), was introduced between the active and high-k dielectric layers to provide trap site passivation, thereby increasing the electrical performance of the OFET. Therefore, through this strategy, using a diketopyrrolopyrrole (DPP)-based donor-acceptor (D-A) copolymer as an active material of OFET, the average saturation region hole mobility was improved from 0.34 to 0.60 cm2/Vs. Thus, the electrical performances of the OFETs were improved by enhancing the capacitance through the corona poling process and reducing the charge carrier trap sites introduced by the high-k and low-k bi-layer dielectric layer. Importantly, this work offers a new strategy for the post-treatment to improve electrical performance of organic devices.

Effects of the cementite morphology on the hydrogen trapping behavior in the pipeline steel

PurposeThe purpose of this study is to investigate the effects of the cementite morphology on the hydrogen trapping behavior in low-alloy pipeline steel.Design/methodology/approachIn this study, the hydrogen trapping behavior in low-alloy pipeline steel was quantitatively studied by a combination of microstructural observations, electrochemical hydrogen permeation experiments and thermal desorption spectroscopy (TDS) analyses.FindingsP-1 and P-2 steels are two samples with different microstructures. The morphology of cementite precipitates in the P-1 and P-2 steels was different. Lamellar cementite is present in P-2 steel and only granular cementite in P-1 steel, which led to a better irreversible hydrogen trapping ability of P-2 steel, which was confirmed by subsequent hydrogen permeation and TDS experiments.Originality/valueThe study of these deep hydrogen trap sites is helpful in improving the hydrogen embrittlement resistance of low-alloy pipeline steels.

Thermal Aging Properties of 500 kV AC and DC XLPE Cable Insulation Materials.

Despite similar material composition and insulation application, the alternating current (AC) cross-linked polyethylene (XLPE) and direct current (DC) XLPE materials cannot replace each other due to different voltage forms. Herein, this work presents a systematical investigation into the effects of thermal aging on the material composition and properties of 500 kV-level commercial AC XLPE and DC XLPE materials. A higher content of antioxidants in the AC XLPE than in the DC XLPE was experimentally demonstrated via thermal analysis technologies, such as oxidation-induced time and oxidation-induced temperature. Retarded thermal oxidation and suppression of space charge effects were observed in thermally aged AC XLPE samples. On the other hand, the carbonyl index of DC XLPE dramatically rose when thermal aging was up to 168 h. The newly generated oxygen-containing groups provided deep trapping sites (~0.95 eV) for space charges and caused severe electric field distortion (120%) under -50 kV/mm at room temperature in the aged DC XLPE samples. For the unaged XLPE materials, the positive space charge packets were attributed to the residue crosslinking byproducts, even after being treated in vacuum at 70 °C for 24 h. Thus, it was reasoned that the DC XLPE material had a lower crosslinking degree to guarantee fewer crosslinking byproducts. This work offers a simple but accurate method for evaluating thermal oxidation resistance and space charge properties crucial for developing high-performance HVDC cable insulation materials.

Tailoring well-ordered, highly crystalline carbon nitride nanoarrays via molecular engineering for efficient photosynthesis of H2O2

Small-scale on-site artificial photosynthesis of H2O2 from O2 and H2O is an ideal sustainable route. In particularly, g-C3N4 is a very popular catalyst, nevertheless, its photocatalytic activity is severely inhibited by the random migration and rapid recombination of photogenerated carriers. Herein, a well-ordered highly-crystalline g-C3N4 nanoarray with conjugated electron donor-acceptor structure (denoted as PDI/CNA) is rationally designed for efficient H2O2 production to imitate the photosynthesis of natural plants. Both experimental and DFT investigations demonstrate that the tailored PDI/CNA effectively improve charges utilization via eliminating deep defect trapping sites, and reduce its Gibbs free energy (ΔG) of rate-determining step (*HOOH→H2O2). As a result, the optimized PDI/CNA exhibits a superior H2O2 production rate of 1605.32 μmol g−1 h−1 and a high apparent quantum yield of 27.18% (λ = 400 nm). This work sheds light on promoting H2O2 photosynthesis by regulating the crystalline structure of g-C3N4 and rationally designing spatially separated redox centers.

(Invited, Digital Presentation) Properties of Defects That Determine the Charge Carrier Dynamics in Photocatalysts

Defect engineering of photocatalysts has been intensively studied as a way to improve their activity. It is reported that introducing oxygen vacancies into TiO2 and SrTiO3 improve the activity of photocatalytic water splitting. On the other hand, the effects of oxygen vacancies on WO3 photocatalyst have not yet been elucidated sufficiently, though WO3 is one of the most appealing visible-light-responsive photocatalysts. Herein, we have investigated photocarrier dynamics in WO3 powder by using a transient absorption spectroscopy from mid-infrared to visible wavelength range. We found that electrons deeply trapped by defect states decayed within 1 ns, which is in contrast to the case of TiO2 and SrTiO3. The decay of the deeply trapped electrons is further accelerated by increasing oxygen vacancies through the reduction process. This result suggests that the deep trapping states associated with oxygen vacancies in WO3 work as a recombination center. On the other hand, long-life free/shallowly trapped electrons were increased when the WO3 powder was mildly reduced, whereas they decreased when it was reduced too heavily. These results indicate that shallow trapping sites in WO3 elongate photocarrier lifetime, but the effect of recombination acceleration by deep trapping sites becomes dominant when too much oxygen vacancies are introduced. Our study revealed the positive and negative aspects of defects in WO3, and highlighted the importance of appropriate defect control on improving the photocatalytic activity.

Investigation of XLPE Cable Insulation Using Electrical, Thermal and Mechanical Properties, and Aging Level Adopting Machine Learning Techniques.

Hydrothermal and chemical aging tests on a 230 kV cross-linked polyethylene (XLPE) insulation cable were carried out in the present study to evaluate the degradation and aging levels qualitatively. The samples were subjected to water aging at a temperature of 80 °C, and in an aqueous ionic solution of CuSO4 at room temperature. The diffusion coefficient results indicated that the ion migration was not at the same rate in the aging conditions. The diffusion coefficient–D–of the sample immersed in an aqueous CuSO4 solution was lower than the hydrothermally aged specimens. The hydrophobicity of aged specimens decreased considerably compared to unaged samples. The distribution of trapped charges was quantitatively characterized. The presence of shallow trap energy states were observed in unaged XLPE, whereas the deep trap sites were noticed in aged specimens. In addition, the charge trap characteristics were different for positive and negative charge deposition. Various material characterization techniques, viz. dynamic mechanical analysis (DMA), tensile, contact angle, and LIBS, were further employed on the aged and virgin specimens. The tensile behavior of the hydrothermally aged specimen was degraded due to the oxidised regions, which had formed a weak spot against the mechanical stress. Reduced glass transition temperature and increased loss tangent measurements were noticed for aged specimens over their unaged counterparts. Machine learning techniques, such as the principal component analysis (PCA) and the artificial neural network (ANN) analysis, were performed on LIBS spectral data of the samples to classify the aging mechanisms qualitatively.

High-temperature Breakdown Performance Improvement of Polypropylene Films Based on Micromorphology Control

In this paper, a modification method of polypropylene (PP) films is proposed for capacitors by micro doping of carboxylated cellulose nanocrystals (C-CNCs). Results prove that crystallization process of films is promoted, due to the entanglement effect of acicular ultra-structures of C-CNCs on PP molecular chains. With a proper doping content (0.01 wt%), the thermal properties are elevated, and the DC conductivity decreases by raising crystallinity and limiting carrier movement. Modified films possess a restricted dielectric loss at low frequencies because of regular microstructures and decreased conduction loss. Based on DC experiments at different temperatures, the breakdown strength of C-CNC/PP films shows an increase by approximately 51% at 85 °C, basically equaled to the level of pure PP at 25 °C. The mechanism is attributed to deep trap sites, which are introduced by the large crystal region and result in short free path in carrier transport. This novel PP film shows a great potential for application under thermal-electrical compound field in power systems.

Dielectric Property Improvement of Polypropylene Films Doped with POSS for HVDC Polymer Film Capacitors

This paper focuses on the effects of the nano Polyhedral oligomericsilsesquioxanes (POSS) with three similar molecular structures on the thermal and electrical properties of polypropylene (PP) films, aiming to propose a comprehensive modification method. After doping with micro amount of nano POSS, the crystallinity and regularity of films are elevated. Correspondingly, PP with optimized microstructure has the lowest conductivity, due to the interaction between the nanoparticles and the matrix, as well as the strong binding force of the crystal region to the carriers. The loss of the sample is restricted, especially in the low frequency region, since the combined effect of polarization and conduction. The DC breakdown strength of the modified PP is higher than that of the PP, with an increase of above 20% at 25-85 °C. Based on quantum chemical calculations, the energy level distributions are analyzed. By selecting appropriate additives, deep trap sites can be introduced to catch carriers, preventing the breaks of polymer molecular chains. This modification of PP films shows huge potential in the improvement of dielectric properties in the field of DC capacitors.

Crystallization Morphology-Dependent Breakdown Strength of Polypropylene Films for Converter Valve Capacitor

In this paper, a novel modification method of polypropylene (PP) films is proposed in the field of metallized film capacitors for converter valves. An organic crystallization accelerator with good dispersion improves the micromorphology of PP films. The doping content of the organic crystallization accelerator is optimized based on breakdown experiments under DC voltage. The DC breakdown strength is 584.8 kV/mm, an increase of 19.6%, compared with that of the original film. Under DC, DC superimposed harmonics, and DC superimposed pulse voltages, the modified PP film has successfully withstood the tests, showing stable advantages in breakdown properties without increasing the conduction loss. Trap analysis and theoretical modeling were performed to clarify the mechanism of improving electrical performances based on crystallization control. The entanglement layer introduced by the organic crystallization accelerator helps to expand the crystal area, resulting in deep trap sites and limitation of carrier migration. This research can provide a reference for the PP performance optimization for metallized film capacitors of converter valves.

Polaron Trapping and Migration in Iron-Doped Lithium Niobate

Photoinduced charge transport in lithium niobate for standard illumination, composition and temperature conditions occurs by means of small polaron hopping either on regular or defective lattice sites. Starting from Marcus-Holstein’s theory for polaron hopping frequency we draw a quantitative picture illustrating two underlying microscopic mechanisms besides experimental observations, namely direct trapping and migration-accelerated polaron trapping transport. Our observations will be referred to the typical outcomes of transient light induced absorption measurements, where the kinetics of a polaron population generated by a laser pulse then decaying towards deep trap sites is measured. Our results help to rationalize the observations beyond simple phenomenological models and may serve as a guide to design the material according to the desired specifications.

Photoinduced Synaptic Behavior of InxTiyO Thin Film Transistors

AbstractHerein, InxTiyO films are successfully deposited via the atomic layer deposition method, which involves sub‐cycles of In2O3 and TiO2 application at a growth temperature of 200 °C. InxTiyO films are an excellent alternative to In2O3 films for use in channels of thin film transistors (TFTs), and can be used to avoid issues such as metal‐like conduction characteristics and undesirable negative shifts. Adjusting the addition of TiO2 to In2O3 enables modulation of the cut‐off wavelength in the UV region. However, the addition of TiO2 adversely affects the on‐current level. The TiO2 content in the InxTiyO films is optimized based on photosensitivity and current level, wherein the films are used as the channel layer in photo‐TFTs; consequently, a photo‐synaptic behavior is achieved. The InxTiyO film‐based memory devices are programmed and erased using UV light and gate voltage, respectively, wherein deep trap sites at the interface between the InTiO and Al2O3 layers facilitate the retention of charge during memory operation. The memory on/off ratio deteriorates slightly with a lapse in retention time of 4 × 104 s after 20 program/erase (P/E) cycles. Moreover, in the InxTiyO‐based TFTs, excellent linearity is achieved during potentiation due to a good photo‐synaptic behavior.

Effects of Hindered Phenolic Antioxidants on Space Charge and Breakdown Properties of Polypropylene

This paper focuses on the effects of hindered phenolic antioxidants AO300 and AO736 with similar molecular structure on the electrical properties of isotactic polypropylene (iPP). Experiments of conductivity, space charge distribution, and DC breakdown strength after the hetero-polarity DC prestress are performed. The experimental results show that these two antioxidants can increase the conductivity-temperature coefficient, reduce the accumulation of space charge and improve the DC breakdown strength after the hetero-polarity DC prestress of iPP. By calculating the molecular orbitals of these two antioxidants, it is found that the antioxidants introduce local states in the forbidden band of iPP matrix to capture high-energy charges. Besides, the bond dissociation energy (BDE) of the hydrogen-oxygen bond in AO736 is lower than that in AO300, representing a stronger ability of proton transfer, which scavenges the radicals, inhibits the growth of microvoids and prevents the process of breakdown. It is concluded that the improvement of space charge and breakdown properties is attributed to the coupling effects of deep trap sites and radicals scavenging introduced by antioxidant. This research shows that AO736 has potential applications in PP insulation.