Charge Trapping Sites Research Articles

2D Ti3C2Tx-MXene and its superstructures as dual-function electrodes for triboelectric nanogenerators for self-powered electronics

Selecting distinct materials to design a tribopositive and tribonegative electrode pair for a triboelectric nanogenerator (TENG) device is a challenging task, as the interfacial electric field causes surface charges to diffuse into the air or within the material itself, leads to charge deterioration. To address these challenges, there is a strong demand for engineered materials and electrode designs that enable effective charge accumulation and trapping to regulate their performance optimally. Herein, we introduce a unique electrode design for a contact-separation (CS) mode triboelectric nanogenerator TENG featuring multilayered Ti3C2Tx MXene/Kapton as tribonegative electrodes. For the tribopositive electrode, we developed an innovative synthesis strategy to create MXene-seeded layered TiO2 superstructures/PVA-based tribopositive electrodes. After optimization of both triboelectric layers, the optimized TENG showed an open-circuit voltage (Voc) ∼ 120 V, short-circuit current (Isc) ∼ 25 μA, and power density of 5.66 W·m−2. The surface terminations groups in highly conductive black MXene nanosheets and the oxygen vacancies in TiO2-layered superstructures provide abundant charge accumulation and trapping sites due to organized multilayered structures at both ends. Moreover, the induced polarization in the tribopositive layer due to the hybrid film could further hinder the free electrons’ drift to the bottom electrode, preventing charge recombination. The optimized TENG was tested as a pressure sensor to monitor different sensitive physiological movements of the human body. Further application of the designed TENG has been revealed by humidity sensing characteristics, powering LEDs, stopwatches, pedometers, and swiftly charging micro-capacitors by utilizing direct output power. By employing a controlled synthesis strategy, our approach leverages the unique properties of MXenes to function as both tribo-positive and tribonegative electrodes within the same device. This dual-function capability simplifies material selection and enhances overall device performance, presenting a transformative solution for next-generation TENG applications.

Synergistic Passivation of Bulk and Interfacial Defects Improves Efficiency and Stability of Inverted Perovskite Solar Cells

Defects both in bulk and at the interfaces serve as charge trapping sites for nonradiative recombination and as ion migration pathways, resulting in degradation of perovskite solar cell efficiency and stability. In this work, a strategy for simultaneous passivation of both bulk and interfacial defects is reported. For bulk passivation polystyrene (PS) is used as an additive in the perovskite precursor which reduces the structural defects by forming larger defect‐free grains. While the F‐PEAI cation is used to passivate the interfacial defects, present at both perovskite HTL/ETL interfaces. Furthermore, by conducting control measurements with just bulk modification (PS), just interface modification (F‐PEAI), and a combination of both, the role of individual defect passivation strategies is decoupled. As a result of simultaneous bulk as well as interfacial passivation, the modified perovskite solar cell shows the highest efficiency of 22.32% with a high Voc of 1.14 V and fill factor of 80%. Moreover, the cells have excellent stability retaining 92% and 99% of their initial efficiency after 1008 h and 560 h under ISOS‐ D1 and D2 storage conditions. These results highlight the importance of simultaneous bulk and interfacial passivation for improving solar cell efficiency and stability.

A novel simulation of space charge decay dynamics after removing the voltage in epoxy resin composites

Abstract Epoxy resin serves as a critical insulating component in ultra-high voltage dry direct current bushings. However, the accumulation of space charges within the epoxy resin, a byproduct of charge mobility, poses a significant risk to the reliability and operational safety of bushings. Conventional space charge attenuation models, especially after voltage removal, have limited use in simulations aimed at understanding this phenomenon. This study introduces an improved model integrating the bipolar charge transport mechanism with space charge decay based on the hopping conduction mechanism and Schottky’s theorem, establishes a theoretical framework for predicting the space charge behavior following voltage removal, and conducts a simulation to investigate the decay process within the internal structure of epoxy resin and measure the residual charges after voltage removal using the pulsed electro-acoustic method. The experimental data validate the accuracy of the proposed model and theoretical assumptions. The findings show that the remaining negative charges after voltage removal are not enhanced by the field enhancement; the anodic positive and cathodic positive charges are distributed in two-segment discontinuous traps, whereas the negative charges are distributed in one-segment traps. The model identifies two distinct trapping sites for anodic and cathodic positive charges, and one trapping site for negative charges. After voltage removal, when the field strength exceeded 40 kV mm−1, positive charges exist near the upper and lower electrodes, and negative charges exist near the center of the specimen. The consistency between the simulated predictions and experimental data proves the effectiveness of the proposed model in accurately simulating the space charge decay in epoxy materials after voltage removal.

Polymer Coating Enabled Carrier Modulation for Single-Walled Carbon Nanotube Network Inverters and Antiambipolar Transistors.

The control of the performance of single-walled carbon nanotube (SWCNT) random network-based transistors is of critical importance for their applications in electronic devices, such as complementary metal oxide semiconducting (CMOS)-based logics. In ambient conditions, SWCNTs are heavily p-doped by the H2O/O2 redox couple, and most doping processes have to counteract this effect, which usually leads to broadened hysteresis and poor stability. In this work, we coated an SWCNT network with various common polymers and compared their thin-film transistors' (TFTs') performance in a nitrogen-filled glove box. It was found that all polymer coatings will decrease the hysteresis of these transistors due to the partial removal of charge trapping sites and also provide the stable control of the doping level of the SWCNT network. Counter-intuitively, polymers with electron-withdrawing functional groups lead to a dramatically enhanced n-branch in their transfer curve. Specifically, SWCNT TFTs with poly (vinylidene fluoride) coating show an n-type mobility up to 61 cm2/Vs, with a decent on/off ratio and small hysteresis. The inverters constructed by connecting two ambipolar TFTs demonstrate high gain but with certain voltage loss. P-type or n-type doping from polymer coating layers could suppress unnecessary n- or p-branches, shift the threshold voltage and optimize the performance of these inverters to realize rail-to-rail switching. Similar devices also demonstrate interesting antiambipolar performance with tunable on and off voltage when tested in a different configuration.

A Mechanism of Resistance Switching in CNT Based Memory Devices

Carbon nanotubes (CNTs) show promise for high energy efficiency electronic devices due to their high electrical conductivity. One possible application is in the fabrication of resistance-change computer memory, where the application of an external electrical bias can use a CNT layer as the switching element in a RAM cell. Memory cells of this type have been extensively demonstrated, where the electrical resistance of a switching layer of CNTs can be reversibly controlled by the application of external bias [1].To better understand these devices, we have developed a nanoscale model of their electrical switching. Towards this end, first-principles calculations of the electrical conductivity of CNT-CNT junctions were performed using the Density Functional Tight Binding (DFTB) in combination with the Non-Equilibrium Greens functions (NEGF) approach, enabling an improved understanding of the tunnelling of electrons across a range of CNT junctions [2]. These results demonstrate that the conductivity of CNT contacts depends on the overlap area between nanotubes and exponentially on the distances between the carbon atoms of the interacting CNTs. Secondly, we employed coarse-grained molecular dynamics [3,4] to produce nanoscale dense CNT film models like those used in the devices. We devise a set of metrics for characterising the structural properties of CNT films, and apply them to a set of model films designed to mimic those used in microelectronics devices. In order to understand how the geometrical properties of CNTs affect the film structure, we analyse films with different CNT chirality and length distributions. Unlike previous studies that focused on relatively low-density systems below ∼0.4 g/cm3, we also consider films with density of ∼0.6 g/cm3, as employed in experimentally fabricated CNT-based NRAM devices. By adding amorphous carbon to the film models, in varying amounts, we are then able to assess its effects. Finally, these two elements were combined to produce electrical simulations of the conductivity of the CNT films connected to TiN electrodes. These electrodes are shown to be partially oxidized during the device fabrication. The electrical conductivity in a device is characterized by formation of conduction paths formed by CNTs between the electrodes and connected via the CNT junctions. The conductivity is modulated by charging of CNTs and amorphous carbon present in the film.Using these simulations, we propose a resistance switching mechanism in TiN/CNT/TiN devices based on the physical movement of CNTs. During the initial operation of the device, oxygen is released from the oxidized bottom electrode and this readily reacts with individual CNTs to form charge trapping sites. Once these sites have become charged, they enable controllable movement of CNTs at the bottom electrode under the application of electric field. By reversibly connecting and disconnecting such CNTs from the bottom electrode, the electrical conductivity through the CNT film as a whole can be controlled.

Small sized of anion doping effect on semiconducting single-walled carbon nanotube network for field-effect transistors

Carbon nanotubes have shown great promise for high-performance, large-area, solution processable field-effect transistors due to their exceptional charge transport properties. In this study, we utilize the spin-coating method to form networks from selectively sorted semiconducting single-walled carbon nanotubes (s-SWNTs), aiming for scalable electronic device fabrication. The one-dimensional nature of s-SWNTs, however, introduces significant roughness and charge trap sites, hindering charge transport due to the van der Waals gap (∼0.32 nm) between nanotubes. Addressing this, we explored the effects of anion doping on the spin-coated s-SWNT random network, with a focus on the influence of the small size of halogen anions (0.13–0.22 nm) on these electronic properties. Raman and ultraviolet–visible–near-infrared optical spectroscopy results indicate that smaller anions significantly enhance doping effects through strong non-covalent anion–π interactions, improving charge transport and carrier injection efficiency in s-SWNTs, especially for n-type operation. This improvement is inversely proportional to the size of the halogen anions, with the smallest anion (fluorine) effectively transitioning the electrical characteristics of the s-SWNT network from ambipolar to n-type by reducing both junction and contact resistances through anion doping, based on anion–π interaction.

Artificial nociceptor based on interface engineered ferroelectric volatile memristor

Recent advancements in neuromorphic computing driven by memristors, which emulate biological synapses and neurons, have spurred the development of innovative information technologies. To extend memristor applications to artificial nervous systems, electronic receptors are crucial for converting external stimuli into signals for the internal nervous system. Key requirements for integrating neuron devices into neuromorphic computing include achieving threshold behavior, minimizing power consumption, and ensuring compatibility with complementary metal-oxide semiconductor (CMOS) technology. Hafnium-based ferroelectric memristors are known for their robust ferroelectric properties at nanoscales and compatibility with CMOS technology. However, their non-volatile resistive switching has historically limited their suitability for neuron sensory applications requiring threshold switching. This study demonstrates threshold switching behavior in a TiN/Hf0.67Zr0.33O2(HZO)/TiOx/TiN heterostructure by incorporating a nanoscale TiOx interfacial layer as an oxygen reservoir. This layer facilitates the formation of oxygen vacancies within the ferroelectric HZO layer, serving as internal charge trap sites. As a result, hafnium-based ferroelectric memristors exhibit volatile switching characteristics, enabling them to function as nociceptive devices through internal charge trapping and detrapping mechanisms. These volatile memristors are suitable for artificial nociceptor systems requiring responses such as threshold detection, relaxation, allodynia, and hyperalgesia to external stimuli. This capability opens avenues for developing advanced humanoid robots capable of rapid adaptation and response in challenging environments such as outer space or hazardous conditions, leveraging real-time sensory processing for effective operation and survival.

Harnessing Persistent Photocurrent in a 2D Semiconductor-Polymer Hybrid Structure: Electron Trapping and Fermi Level Modulation for Optoelectronic Memory.

Recently, 2D semiconductor-based optoelectronic memory has been explored to overcome the limitations of conventional von Neumann architectures by integrating optical sensing and data storage into one device. Persistent photocurrent (PPC), essential for optoelectronic memory, originates from charge carrier trapping according to the Shockley-Read-Hall (SRH) model in 2D semiconductors. The quasi-Fermi level position influences the activation of charge-trapping sites. However, the correlation between quasi-Fermi level modulations and PPC in 2D semiconductors has not been extensively studied. In this study, we demonstrate optoelectronic memory based on a 2D semiconductor-polymer hybrid structure and confirm that the underlying mechanism is charge trapping, as the SRH model explains. Under light illumination, electrons transfer from polyvinylpyrrolidone to p-type tungsten diselenide, resulting in high-level injection and majority carrier-type transitions. The quasi-Fermi level shifts upward with increasing temperature, improving PPC and enabling optoelectronic memory at 433 K. Our findings offer valuable insights into optimizing 2D semiconductor-based optoelectronic memory.

Highly sensitive and selective detection of dopamine using atomic layer deposited HfO2 ultra-thin films

The development of non-enzymatic and binder-free biosensors plays a vital role, and it possesses main benefits for effective biomolecule recognition with high sensitivity and preferred selectivity. Herein, an atomic layer deposition (ALD) was employed to develop the hafnium oxide (HfO2) nanofilm on silicon (Si) for fabricating binder-free selective and sensitive determination of the non-enzymatic electrochemical dopamine sensor. The prepared HfO2 nanofilm selectively acted as a local dopamine binding site because of the hydrophobic-hydrophobic interaction between fabricated film and dopamine, electrostatic attraction between negatively charged hydroxyl group on film surfaces, and positively charged amino group of dopamine. The developed insufficient oxygen vacancies on the HfO2 could have behaved as a charge-trapping site for better sensing properties. The developed sensor demonstrated excellent realization in sensing dopamine with a very low detection limit (0.4 pM) and swift response time of 3s which is quite precise compared with various reported literature. The fabricated HfO2/Si electrode sensor has exhibited high sensitivity, stability, and repeatability. The selectivity of dopamine sensors was at least three orders greater than other interfering biomolecules. This work proposes the essential track for the practical realization of dopamine detection in human serum and biomedical applications.

Electrical Double-Layer Transistors Comprising Block Copolymer Electrolytes for Low-Power-Consumption Photodetectors.

Electrical double-layer transistors (EDLTs) have received extensive research attention owing to their exciting advantages of low working voltage, high biocompatibility, and sensitive interfacial properties in ultrasensitive portable sensing applications. Therefore, it is of great interest to reduce photodetectors' operating voltage and power consumption by utilizing photo-EDLT. In this study, a series of block copolymers (BCPs) of poly(4-vinylpyridine)-block-poly(ethylene oxide) (P4VP-b-PEO) with different compositions were applied to formulate polyelectrolyte with indigo carmine salt in EDLT. Accordingly, PEO conduces ion conduction in the BCP electrolyte and enhances the carrier transport capability in the semiconducting channel; P4VP boosts the photocurrent by providing charge-trapping sites during light illumination. In addition, the severe aggregation of PEO is mitigated by forming a BCP structure with P4VP, enhancing the stability and photoresponse of the photo-EDLT. By optimizing the BCP composition, EDLT comprising P4VP16k-b-PEO5k and indigo carmine provides the highest specific detectivity of 2.1 × 107 Jones, along with ultralow power consumptions of 0.59 nW under 450 nm light illumination and 0.32 pW under dark state. The results indicate that photo-EDLT comprising the BCP electrolyte is a practical approach to reducing phototransistors' operating voltage and power consumption.

Dynamic Reconfiguration and Local Polarization of NiFe-Layered Double Hydroxide-Bi2MoO6- x Heterojunction for Enhancing Piezo-Photocatalytic Nitrogen Oxidation to Nitric Acid.

Constructing heterojunctions with vacancies has garnered substantial attention in the field of piezo-photocatalysis. However, the presence of interfacial vacancies can serve as charge-trapping sites, leading to the localization of electrons and hindering interfacial charge transfer. Herein, dual oxygen vacancies in the NiFe-layered double hydroxide and Bi2MoO6- x induced interfacial bonds have been designed for the piezo-photocatalytic N2 oxidation to NO3 -. Fortunately, it achieves sensational nitric acid production rates (7.23mg g-1 h-1) in the absence of cocatalysts and sacrificial agents, which is 6.03 times of pure Bi2MoO6 that under ultrasound and light illumination. Theoretical and experimental results indicate that interfacial bonds act as "charge bridge" and "strain center" to break the carrier local effect and negative effects with piezocatalysis and photocatalysis for promoting exciton dissociation and charge transfer. Moreover, the strong electronic interaction of the interfacial bond induces internal reconstruction under ultrasound for promoting the local polarization and adsorption of N2, which accelerates the fracture of the N≡N bonds and reduces the activation energy of the reaction. The research not only establishes a novel approach for optimizing the combined effects of piezo-catalysis and photocatalysis, but also achieves equilibrium between the synergistic impacts of vacancies and heterojunctions.

Tailoring the Molecular Planarity of Perylene Diimide-Based Third Component toward Efficient Ternary Organic Solar Cells.

Incorporating a third component into binary organic solar cells (b-OSCs) has provided a potential platform to boost power conversion efficiency (PCEs). However, gaining control over the non-equilibrium blend morphology via the molecular design of the perylene diimide (PDI)-based third component toward efficient ternary organic solar cells (t-OSCs) still remains challenging. Herein, two novel PDI derivatives are developed with tailored molecular planarity, namely ufBTz-2PDI and fBTz-2PDI, as the third component for t-OSCs. Notably, after performing a cyclization reaction, the twisted ufBTz-2PDI with an amorphous character transferred to the highly planar fBTz-2PDI followed by a semi-crystalline character. When incorporating the semi-crystalline fBTz-2PDI into the D18:L8-BO system, the resultant t-OSC achieved an impressive PCE of 18.56%, surpassing the 17.88% attained in b-OSCs. In comparison, the addition of amorphous ufBTz-2PDI into the binary system facilitates additional charge trap sites and results in a deteriorative PCE of 14.37%. Additionally, The third component fBTz-2PDI possesses a good generality in optimizing the PCEs of several b-OSCs systems are demonstrated. The results not only provided a novel A-DA'D-A motif for further designing efficient third component but also demonstrated the crucial role of modulated crystallinity of the PDI-based third component in optimizing PCEs of t-OSCs.

Electronic and optical properties of pyrochlore Re2Ti2O7 (Re = Sm and Eu) from first-principles

Rare-earth titanate oxides are believed to be prospective functional materials for photocatalytic and photoluminescent applications because of their excellent optical properties and thermal stability of their physical properties. However, the relationships between optical properties and photoelectron trapping mechanisms are unclear. Herein, the structure, electronic, and optical properties of pyrochlore-structure Re2Ti2O7 (Re = Sm and Eu) were investigated using the first-principles approach with the Hubbard parameter U (GGA + U). The calculated bandgap is 2.5 eV for Sm2Ti2O7 and 2.4 eV for Eu2Ti2O7, which is in good agreement with the experimental observation. The results indicate that the strongly localized f states at the top of valence band are charge-trapping sites for photoexcitation of Re2Ti2O7, where electrons can absorb photon energy and transfer from the valence band to the conduction band, resulting in the photocatalytic and/or fluorescent effects in the visible and early UV regions. The important optical parameters, dielectric function ε(ω), refractive index n(ω), extinction coefficient k(ω), reflectivity R(ω), absorption coefficient I(ω), optical conductivity σ(ω), and electron energy-loss L(ω) were studied in detail, indicating that these optical parameters of Sm2Ti2O7 and Eu2Ti2O7 are insensitive to the ultra-violet (UV) radiation, but both Sm2Ti2O7 and Eu2Ti2O7 exhibit excellent optical properties in the visible and early UV regions. This work provides a clear understanding on the photoelectron trapping mechanism of pyrochlore-structure Re2Ti2O7, which will help to improve the photocatalytic and photoluminescent performance of Re2Ti2O7 and broaden their applications.

Low-frequency noise behaviors of quasi-two-dimensional electron systems based on complex oxide heterostructures

We report the low-frequency noise behaviors in quasi-two-dimensional (quasi-2D) electron systems based on complex oxide heterostructures. First, the surface 2D electron gas (2DEG) on SrTiO3 (STO) exhibits the 1/fα-type current power spectral density (PSD) with α∼1.39. The non-unity exponent α indicates the discrepancy between the depth distributions of electrons and oxygen vacancies in the STO substrate. Second, the amorphous LaAlO3/KTaO3 (LAO/KTO) interface, another quasi-2D electron system, shows Lorentzian components of PSD at a high-frequency region around 1 kHz, implying that the amorphous overlayer can provide additional shallow charge-trapping sites to the quasi-2D electrons in the crystalline KTO substrate. Lastly, ultrathin SrRuO3 (SRO) film grown on STO substrate exhibits the Lorentzian components of PSD at a low-frequency region around 200 Hz. The slight suppression of the fast charge trapping is attributed to the intrinsic band bending at the interface between film and substrate. These results will provide a guideline for understanding the defect-induced charge trapping and the relevant electron dynamics in the quasi-2D electron systems as well as the oxide-based electronic materials in general.

Unifying and Suppressing Conduction Losses of Polymer Dielectrics for Superior High-Temperature Capacitive Energy Storage.

Superior high-temperature capacitive performance of polymer dielectrics is critical for the modern film capacitor demanded in the harsh-environment electronic and electrical systems. Unfortunately, the capacitive performance degrades rapidly at elevated temperatures owing to the exponential growth of conduction loss. The conduction loss is mainly composed of electrode and bulk-limited conduction. Herein, the contribution of surface and bulk factors is unified to conduction loss, and the loss is thoroughly suppressed. The experimental results demonstrate that the polar oxygen-containing groups on the surface of polymer dielectrics can act as the charge trap sites to immobilize the injected charges from electrode, which can in turn establish a built-in field to weaken the external electric field and augment the injection barrier height. Wide bandgap aluminum oxide (Al2 O3 ) nanoparticle fillers can serve as deep traps to constrain the transport of injected or thermally activated charges in the bulk phase. From this, at 200 °C, the discharged energy density with a discharge-charge efficiency of 90% increases by 1058.06% from 0.31 J cm-3 for pristine polyetherimide to 3.59 J cm-3 for irradiated composite film. The principle of simultaneously inhibiting the electrode and bulk-limited conduction losses could be easily extended to other polymer dielectrics for high-temperature capacitive performance.

Enhancement of dielectric properties of the La2NiO4-CuO terpolymer nanocomposites by modified SiC nanofiller

This work investigates the enhancement of dielectric properties of La2NiO4-CuO terpolymer nanocomposites using surface modified SiC nanoparticles as fillers. SiC nanoparticles were subjected to acid treatment and annealing at 1000 °C to tailor the surface chemistry. Acid treatment involved immersing the SiC powder in a mixture of H2SO4 and HNO3 acids and sonicating for 30 min, followed by stirring at 60 °C for 6 h. Annealing was carried out at 1000 °C for 2 h in an inert argon atmosphere. La2NiO4 and CuO nanoparticles were synthesized by sol-gel and precipitation techniques respectively, with average particle sizes of 20–40 nm and 10–15 nm confirmed by XRD and FESEM. Nanocomposites were fabricated by dispersing 2–10 wt% of untreated, acid treated and annealed SiC nanoparticles in a La2NiO4-CuO mixture solution, using PVDF as the polymer matrix. Impedance spectroscopy revealed that addition of 5 wt% acid treated SiC resulted in the highest dielectric constant of 42 at 1 kHz, in comparison to 25 for the unfilled polymer. This was attributed to increased interfacial polarization arising from uniform dispersion of nanoparticles and abundant charge trapping sites introduced by the SiC filler.

Enhanced Charge Separation in Nanoporous BiVO4 by External Electron Transport Layer Boosts Solar Water Splitting.

The optimization of charge transport with electron-hole separation directed toward specific redox reactions is a crucial mission for artificial photosynthesis. Bismuth vanadate (BiVO4 , BVO) is a popular photoanode material for solar water splitting, but it faces tricky challenges in poor charge separation due to its modest charge transport properties. Here, a concept of the external electron transport layer (ETL) is first proposed and demonstrated its effectiveness in suppressing the charge recombination both in bulk and at surface. Specifically, a conformal carbon capsulation applied on BVO enables a remarkable increase in the charge separation efficiency, thanks to its critical roles in passivating surface charge-trapping sites and building external conductance channels. Through decorated with an oxygen evolution catalyst to accelerate surface charge transfer, the carbon-encased BVO (BVO@C) photoanode manifests durable water splitting over 120h with a high current density of 5.9mAcm-2 at 1.23V versus the reversible hydrogen electrode (RHE) under 1sun irradiation (100mWcm-2 , AM 1.5G), which is an activity-stability trade-off record for single BVO light absorber. This work opens up a new avenue to steer charge separation via external ETL for solar fuel conversion.

Over- and Undercoordinated Atoms as a Source of Electron and Hole Traps in Amorphous Silicon Nitride (a-Si3N4).

Silicon nitride films are widely used as the charge storage layer of charge trap flash (CTF) devices due to their high charge trap densities. The nature of the charge trapping sites in these materials responsible for the memory effect in CTF devices is still unclear. Most prominently, the Si dangling bond or K-center has been identified as an amphoteric trap center. Nevertheless, experiments have shown that these dangling bonds only make up a small portion of the total density of electrical active defects, motivating the search for other charge trapping sites. Here, we use a machine-learned force field to create model structures of amorphous Si3N4 by simulating a melt-and-quench procedure with a molecular dynamics algorithm. Subsequently, we employ density functional theory in conjunction with a hybrid functional to investigate the structural properties and electronic states of our model structures. We show that electrons and holes can localize near over- and under-coordinated atoms, thereby introducing defect states in the band gap after structural relaxation. We analyze these trapping sites within a nonradiative multi-phonon model by calculating relaxation energies and thermodynamic charge transition levels. The resulting defect parameters are used to model the potential energy curves of the defect systems in different charge states and to extract the classical energy barrier for charge transfer. The high energy barriers for charge emission compared to the vanishing barriers for charge capture at the defect sites show that intrinsic electron traps can contribute to the memory effect in charge trap flash devices.

Nitrogen‐Doped Carbon Quantum Dots on Graphene for Field‐Effect Transistor Optoelectronic Memories

AbstractThe development of field‐effect transistor‐based (FET‐based) non‐volatile optoelectronic memories is vital toward innovations necessary to improve computer systems. In this work, for the first time, the unique charge‐trapping and charge‐retention properties of solution‐processed colloidal nitrogen‐doped carbon quantum dots (CQDs) are harnessed to achieve functional optoelectronic memories programmable by UV illumination with a multilevel writing possibility. Of particular note, long‐lasting memory function can be achieved thanks to the vast charge trapping sites provided by the N‐doped CQDs and the resultant photo‐gating effect is exercised on the graphene FET. The achieved memory can be erased by a positive gate bias which provides sufficient carriers to remove trapped charges through recombination. This study highlights the possibility to engineer high‐performance all‐carbon non‐volatile FET‐based optoelectronic memories through manipulating and coupling the charge‐trapping properties of colloidal CQDs and graphene.

Silicon oxynitride thin films by plasma-enhanced atomic layer deposition using a hydrogen-free metal-organic silicon precursor and N2 plasma

We investigated the growth mechanism of SiOxNy films deposited via plasma-enhanced atomic layer deposition at low temperatures (100–300 °C) using a tetraisocyanate silane (Si(NCO)4) precursor and N2 plasma. By using tetraisocyanate silane, which does not contain hydrogen, we were able to deposit SiOxNy with notably less hydrogen, around 3–5%, compared to using silicon precursors that contain hydrogen. Additionally, the precursor ligands, including oxygen, react with surface amine groups (-NH2) to form Si–N–O bonds. Therefore, by understanding the adsorption mechanism of the precursor and controlling the temperature that can affect the bond formation, we can successfully produce SiOxNy films without any oxidizing source. We utilized density functional theory to explore the adsorption mechanism during the deposition of SiOxNy films and proposed a possible adsorption pathway of the precursors and by-products on the surface. We also employed various characterization techniques, such as spectroscopic ellipsometry, X-ray photoelectron spectroscopy, X-ray reflectometry, secondary ion mass spectroscopy, and current-electric field and capacitance-voltage analyses to establish correlations between the composition and dielectric properties of the thin films. Increasing the deposition temperature results in an increased presence of stronger and more stable Si–N bonds compared to Si–O and O–N bonds. As a result, the dielectric constant of the SiOxNy film increased from 5.8 to 7.4, while the leakage current density decreased from 1.52 × 10−8 A/cm2 to 8.56 × 10−10 A/cm2. Additionally, the counterclockwise hysteresis decreased from 0.16 V to 0.07 V as the amount of hydrogen in the SiOxNy film decreased. This can be interpreted as a reduction in hydrogen impurities, which act as charge trapping sites within the film, leading to a decrease in hysteresis with increasing temperature.