Multi-level non-volatile organic transistor-based memory using lithium-ion-encapsulated fullerene as a charge trapping layer

We report on multi-level non-volatile organic transistor-based memory using pentacene semiconductor and a lithium-ion-encapsulated fullerene (Li⁺@C₆₀) as a charge trapping layer. Memory organic field-effect transistors (OFETs) with a Si⁺⁺/SiO₂/Li⁺@C₆₀/Cytop/Pentacene/Cu structure exhibited a performance of p-type transistor with a threshold voltage (V_th) of −5.98 V and a mobility (μ) of 0.84 cm² V⁻¹ s⁻¹. The multi-level memory OFETs exhibited memory windows (ΔV_th) of approximate 10 V, 16 V, and 32 V, with a programming gate voltage of 150 V for 0.5 s, 5 s, and 50 s, and an erasing gate voltage of −150 V for 0.17 s, 1.7 s, and 17 s, respectively. Four logic states were clearly distinguishable in our multi-level memory, and its data could be programmed or erased many times. The multi-level memory effect in our OFETs is ascribed to the electron-trapping ability of the Li⁺@C₆₀ layer.     

Charge trapping in ultrathin Gd2O3 high-k dielectric

Charge trapping in ultrathin high-k Gd₂O₃ dielectric leading to appearance of hysteresis in C-V curves is studied by capacitance-voltage and current-voltage techniques. It was shown that the large leakage current at a negative gate voltage causes the generation of the positive charge in the dielectric layer, resulting in the respective shift of the C-V curve. The capture cross-section of the hole traps is around 2 × 10⁻²⁰ cm². The distribution of the interface states was measured by conductance technique showing the concentration up to 7.5 × 10¹² eV⁻¹ cm⁻² near the valence band edge.     

Optoelectronic properties of cubic BxInyGa1−x−yN alloys matched to GaN for designing quantum well Lasers: First-principles study within mBJ exchange potential

A Full-Potential Linearized Augmented Plane Wave calculation within density functional theory is performed to investigate the electronic and optical properties of cubic B_xIn_yGa_1−x−yN alloys matched to GaN with low-Boron content (x≤0.187). The exchange-correlation potential is treated by the local density approximation (LDA) to calculate the structural properties. The band structure and density of states of these compounds are well predicted by modified Becke–Johnson (mBJ) exchange potential compared to LDA and generalized gradient approximation (GGA). Also, the optical properties are calculated by the mBJ exchange potential. The computed structural parameters are found to be in good agreement with experimental and theoretical data. The B_xIn_yGa_1−x−yN alloy is expected to be lattice matched to GaN substrate for (x=0.125, y=0.187). The incorporation of B and In into GaN substrate allows the reduction of the band gap energy. The real and imaginary parts of the dielectric function, refractive index, reflectivity and absorption coefficient are discussed on the basis on the energy band structure and the calculated density of states. The optical properties of B_xIn_yGa_1−x−yN depend on the incorporated Boron content (with y=0.187). This means that B_xIn_yGa_1−x−yN could constitute an active layer in single quantum well for the design of high-efficiency solar cells and optoelectronic devices as Laser Diodes operating in the UV spectral region.     

Sulfur stoichiometry driven chalcopyrite and pyrite structure of spray pyrolyzed Cu-alloyed FeS2 thin films

We report on fabrication of Cu_xFe_1−xS₂ (CFS) thin films using chemical spray pyrolysis followed by post-sulfurization. Post-sulfurized CFS films were grown with compact and good crystalline texture. The sulfur stoichiometry in CFS films was found to be crucial for determination of its crystal structure. The sulfur deficient CFS films were driven to chalcopyrite CFS (CH-CFS) structure whereas the sulfur cured CFS films were grown with Cu-incorporated pyrite CFS (P-CFS) structure which was confirmed by X-ray diffraction and Raman spectroscopy analysis along with UV–vis spectroscopy measurement. Electrical characterizations of both types of CFS films revealed p-type conductivity with carrier concentration in the range of 10¹⁸–10²⁰ cm⁻³ and mobility of 0.5–9 cm² V⁻¹ s⁻¹. The band gaps of CFS films of CH-CFS structure (0.885–0.949 eV) were found to be less than that of P-CFS structure (0.966–1.156 eV), which indicates its potential application for thermoelectric and photovoltaic devices.     

Characterization of surface states in HCl-grown oxides using MOS transient currents

A fast transient current (TC) technique has been developed for the characterization of majority carrier charge emission from surface states using MOS capacitors excited by a voltage step-function. This technique, with appropriate choice of initial and final biasing conditions, allows a rapid determination of the density of surface states (N_ss) and their capture cross section values (σ_n) in preselected regions of band gap using suitable temperature ambients. A low temperature (113°K) was used for regions close to the bottom of conduction band and room temperature and moderately low temperatures were used for the mid-gap region. Results of transient current measurements were compared with those obtained from thermally stimulated current and low frequency C-V measurements. The MOS devices were fabricated using [100] oriented n-type (6–8 Ω-cm) silicon on n⁺ substrates with HCl added to the oxidizing ambient. The detectability limit of the TC technique has been found to be approximately 1 × 10¹⁰ cm^?2 eV^?1 for the device area used.     

Functionalized Poly(phenylene ether) with high thermal stability as flexible dielectrics and substrates for organic field-effect transistors

Extensive research efforts are devoted into seeking the thermally and mechanically durable dielectric materials for flexible electronics. In this work, a series of sulfonylated poly (phenylene ether)s (PPEs) were synthesized and served as gate dielectrics in the flexible OFET devices with crosslinked poly (2-allyl-6-methylphenol-co-2,6-dimethylphenol) (APPE) as substrate. The chemical structure, thermal, morphology, and dielectric properties were investigated, and the corresponding OFET devices were accordingly fabricated and characterized. We found that the discrepancy in sulfone content of PPE-xS renders the difference in thermal stability, surface polarity and dielectric constants. Among them, PPE-9kS with the highest sulfone content of 63% shows the best dielectric properties in the flexible OFET devices with hole mobility (μ_p) of 0.45 cm² V⁻¹ s⁻¹, outperforming its parent polymer without sulfone group (PPE-9k) with μ_p of 0.14 cm² V⁻¹ s⁻¹. Besides, the flexible device with PPE-9kS as dielectric exhibits highly retained device performance after cyclic bending or thermal treatment, which indicates the decent mechanical and thermal durability. The present study documents a practical methodology to fabricate a high-performance flexible OFET with excellent thermal and mechanical stability.     

Interface states in polyfluorene-based metal–insulator–semiconductor devices

Hybrid metal–insulator–semiconductor structures based on ethyl-hexyl substituted polyfluorene (PF2/6) as the active polymer semiconductor were fabricated on a highly doped p-Si substrate with Al₂O₃ as the insulating oxide layer. We present detailed frequency-dependent capacitance–voltage (C–V) and conductance–voltage characteristics of the semiconductor/insulator interface. PF2/6 undergoes a transition to an ordered crystalline phase upon thermal cycling from its nematic-liquid crystalline phase, confirmed by our atomic force microscope images. Thermal cycling of the PF2/6 films significantly improves the quality of the (PF2/6)/Al₂O₃ interface, which is identified as a reduced hysteresis in the C–V curve and a decreased interface state density (D_it) from ∼3.9 × 10¹² eV⁻¹ cm⁻² to ∼3.3 × 10¹¹ eV⁻¹ cm⁻² at the flat-band voltage. Interface states give rise to energy levels that are confined to the polymer/insulator interface. A conductance loss peak, observed due to the capture and emission of carriers by the interface states, fits very well with a single time constant model from which the D_it values are inferred.     

Spin-Phonon Scattering-Induced Low Thermal Conductivity in a van der Waals Layered Ferromagnet Cr2Si2Te6

Layered van der Waals (vdW) magnets are prominent playgrounds for developing magnetoelectric, magneto-optic, and spintronic devices. In spintronics, particularly in spincaloritronic applications, low thermal conductivity (κ) is highly desired. Herein, by combining thermal transport measurements with density functional theory calculations, this study demonstrates low κ down to 1 W m⁻¹ K⁻¹ in a typical vdW ferromagnet Cr₂Si₂Te₆. In the paramagnetic state, development of magnetic fluctuations way above T_c = 33 K strongly reduces κ via spin-phonon scattering, leading to low κ ≈ 1 W m⁻¹ K⁻¹ over a wide temperature range, in comparable to that of amorphous silica. In the magnetically ordered state, emergence of resonant magnon-phonon scattering limits κ below ≈2 W m⁻¹ K⁻¹, which will be three times larger if magnetic scatterings are absent. Application of magnetic fields strongly suppresses the spin-phonon scattering, giving rise to large enhancements of κ. This study's calculations well capture these complex behaviors of κ by taking the temperature- and magnetic-field-dependent spin-phonon scattering into account. Realization of low κ, which is easily tunable by magnetic fields in Cr₂Si₂Te₆, may further promote spincaloritronic applications of vdW magnets. This study's theoretical approach may also provide a generic understanding of spin-phonon scattering, which appears to play important roles in various systems.     

Direct synthesis of quaternary Cd(Zn,S)Se thin films: Effects of composition

In the present communication, the binary CdSe and quaternary Cd_1-xZn_xSe_1-yS_y (0 ≤ x = y ≤ 0.35) thin films were synthesized using a chemical bath deposition. Thin film deposition was carried out at the optimized conditions (pH = 10 ± 0.1, deposition temperature = 70 ± 0.1 °C, deposition time = 100 min and substrate rotation speed = 65 ± 2 rpm). X-ray diffraction studies confirmed hexagonal-wurtzite crystal structure with the formation of quaternary Cd(Zn, S)Se phase along with binary CdSe, CdS, ZnS and ZnSe, phases of the as-grown Cd_1-xZn_xSe_1-yS_y thin films. Elemental analysis showed presence of Cd²⁺, Zn²⁺, S^2- and Se^2- in the deposited films. Fourier transform infrared spectroscopy shown the bands at 911.15 cm⁻¹ – 901.62 cm⁻¹ which are assigned to the stretching frequency of Cd–Se bond. Scanning electron microscopy show transformation of the microstructure from globular crystallites to a rhomboid flake like network. The electrical conductivity was typically ≈ 10⁻⁷ Ω⁻¹ cm⁻¹. At low temperatures, the conduction was by variable range hopping, and this changed to thermally activated grain boundary dominated conduction for T > 350 K.     

A highly emissive distyrylthieno[3,2-b]thiophene based red luminescent organic single crystal: Aggregation induced emission,optical waveguide edge emission,and balanced ambipolar carrier transport

A highly emissive red luminescent single crystal which shows aggregation induced emission (AIE) property and optical waveguide edge emission based on small organic functional molecule, cyano-substituted 2,5-di((E)-styryl)thieno[3,2-b]thiophene (CNP2V2TT) has been prepared by the physical vapor transport (PVT) method. The fluorescence quantum efficiency of crystal is up to 37% and an emission peak maximum (λ_max) locates at 645 nm. Cystallographic data indicate that uniaxially oriented molecular packing with slipped face-to-face π-π stacking forms by the hydrogen bonding network among CNP2V2TT molecules. The single crystal FET devices were fabricated using Au and Ca as hole and electron injection electrodes, respectively. The molecular design, introducing cyano groups into molecular skeleton, effectively lower the LUMO level and achieve well-balanced ambipolar electron (0.13 cm² V⁻¹ s⁻¹) and hole (0.085 cm² V⁻¹ s⁻¹) mobilities.     

Thickness-dependent optoelectronic properties of CuCr0.93Mg0.07O2 thin films deposited by reactive magnetron sputtering

CuCr_0.93Mg_0.07O₂ thin films were successfully deposited by DC reactive magnetron sputtering at 1123 K from metallic targets. The influence of film thickness on the structural and optoelectronic properties of the films was investigated. X-ray diffraction (XRD) results revealed that all the films had a delafossite structure with no other phases. The optical and electrical properties were investigated by UV–VIS spectrophotometer and Hall measurement, respectively. It was found that the optoelectronic properties exhibited a thickness-dependent behavior. The optical band gap and the average transmittance of the films showed a monotonous decrease with respect to the increase in thickness. The average transmittance in the visible region decreased from 67% to 47% as the thickness increased from ~70 nm to ~280 nm. Simultaneously, the conductivity of the films fell from 1.40 S∙cm⁻¹ to 0.27 S∙cm⁻¹. According to Haacke's figure of merit (FOM), a film with a maximum FOM value of about 1.72×10⁻⁷ Ω⁻¹ can be achieved when the thickness is about 70 nm (σ≈ 1.40 S·cm⁻¹ and T_av. ≈67%).     

Spectroscopic differentiation between O-atom vacancy and divacancy defects,respectively, in TiO2 and HfO2 by X-ray absorption spectroscopy

Defect state features have been detected in second derivative O K edge spectra for thin films of nano-crystalline TiO₂ and HfO₂. Based on soft X-ray photoelectron band edge spectra, and the occurrence of occupied band edge 4f states in Gd(Sc,Ti)O₃, complementary spectroscopic features have been confirmed in the pre-edge (<530 eV) and vacuum continuum (>545 eV) regimes of O K edge spectra. Qualitatively similar spectral features have been obtained for thin films of HfO₂ and TiO₂, and these have been assigned to defect states associated with vacancies. The two electrons/removed O-atom are not distributed uniformly over the TM atoms defining the vacancy geometry, but instead are localized in equivalent d-states: a d² state for a Ti monovacancy and a d⁴ state for a Hf divacancy. This new model for electronic structure provides an unambiguous way to differentiate between monovacancy and divacancy arrangements, as well as immobile (or fixed) and mobile vacancies.     

Properties of fluorine-doped tin oxide films prepared by an improved sol-gel process

Fluorine-doped tin oxide (FTO) films were prepared by an improved sol-gel process, in which FTO films were deposited on glass substrates using evaporation method, with the precursors prepared by the conventional sol-gel method. The coating and sintering processes were combined in the evaporation method, with the advantage of reduced probability of films cracking and simplified preparation process. The effects of F-doping contents and structure of films on properties of films were analyzed. The results showed the performance index (Φ_TC=3.535×10⁻³ Ω⁻¹ cm) of the film was maximum with surface resistance (R_sh) of 14.7 Ω cm⁻¹, average transmittance (T) of 74.4% when F/Sn=14 mol%, the reaction temperature of the sol was 50 °C, and the evaporation temperature was 600 °C in muffle furnace, and the film has densification pyramid morphology and SnO_2−xF_x polycrystalline structure with tetragonal rutile phase. Compared with the commercial FTO films (Φ_TC=3.9×10⁻³ Ω⁻¹ cm, R_sh=27.4 Ω cm⁻¹, T=80%) produced by chemical vapor deposition (CVD) method, the Φ_TC value of FTO films prepared by an improved sol-gel process is close to them, the electrical properties are higher, and the optical properties are lower.     

Band gap tailoring and yellow band emission of Cd0.9−xMnxZn0.1S (x=0 to 0.05) nanoparticles: Influence of Mn concentration

Cd_0.9-xMn_xZn_0.1S nanoparticles with x=0 to 0.05 were prepared by a simple chemical co-precipitation method at room temperature. Crystal structure and optical properties of the synthesized nanoparticles have been analyzed by X-ray diffraction (XRD) and UV–visible spectrophotometer. XRD confirmed the phase singularity of the synthesized material, which also confirmed the formation of Cd–Mn–Zn–S solid solution rather than secondary phase formation. Energy dispersive X-ray spectra showed the presence of Cd, Zn, Mn and S in the synthesized samples. The observed higher absorbance and lower transmittance of Mn-doped Cd_0.9Zn_0.1S than Cd_0.9Zn_0.1S is due to the size effect and also the defect states induced by Mn. The decrease in energy gap at Mn=0.01 is due the ‘sp–d’ exchange interactions between band electrons in CdS and the localized ‘d’ electrons of the Mn²⁺ ions. The increase in energy gap after Mn=0.01 can be explained by the excessive carriers generated by the impurity atoms. Fourier transform infrared spectroscopy (FTIR) illustrated the vibration modes of Cd–Zn–Mn–S between the wave number 530 cm⁻¹ and 780 cm⁻¹. Mn=0.01 doped sample exhibits a relatively high PL intensity and covers most of the visible region than the other samples; so desirable for LED application. The intensity ratio of the green band (GB) to Mn-related yellow band (YB) is decreased after Mn=0.01 which may be due the size effect or reduction of surface defect at higher doping concentrations.     

The Edge Effects Boosting Hydrogen Evolution Performance of Platinum/Transition Bimetallic Phosphide Hybrid Electrocatalysts

Platinum (Pt) is regarded as a promising electrocatalyst for hydrogen evolution reaction (HER). However, its application in an alkaline medium is limited by the activation energy of water dissociation, diffusion of H⁺, and desorption of H*. Moreover, the formation of effective structures with a low Pt usage amount is still a challenge. Herein, guided by the simulation discovery that the edge effect can boost local electric field (LEF) of the electrocatalysts for faster proton diffusion, platinum nanocrystals on the edge of transition metal phosphide nanosheets are fabricated. The unique heterostructure with ultralow Pt amount delivered an outstanding HER performance in an alkaline medium with a small overpotential of 44.5 mV and excellent stability for 80 h at the current density of −10 mA cm⁻². The mass activity of as-prepared electrocatalyst is 2.77 A mg⁻¹_Pt, which is 15 times higher than that of commercial Pt/C electrocatalysts (0.18 A mg⁻¹_Pt). The density function theory calculation revealed the efficient water dissociation, fast adsorption, and desorption of protons with hybrid structure. The study provides an innovative strategy to design unique nanostructures for boosting HER performances via achieving both synergistic effects from hybrid components and enhanced LEF from the structural edge effect.     

Controlling the electrical characteristics of Au/n-Si structures by interfacial insulator layer

Admittance (C–V and G/ω–V) measurements of Au/n-Si (metal–semiconductor, MS) and Au/SnO₂/n-Si (metal–insulator–semiconductor, MIS) structures were carried out between 1 kHz and 1 MHz at room temperature to investigate the interfacial insulator layer effect on the electrical characteristics of Au/n-Si structures. Experimental results showed that MIS structure's capacitance (C) values, unlike those of MS structure, became stable especially at high frequencies in the accumulation region. Also, the insulator layer caused structure's shunt resistance (R_sh) to increase. It was found that series resistance (R_s) is more effective in the accumulation region at high frequencies after the correction was applied to C and G/ω data to eliminate the R_s effect. The density of interface states (D_is) was obtained using Hill–Coleman method, D_is values MIS structure was obtained smaller than those of MS structure. Results indicate that interfacial insulator layer brings about some improvements in electrical characteristics of Au/n-Si structures.     

Controllable thin-film morphology and structure for 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8BTBT) based organic field-effect transistors

Organic field-effect transistors (OFETs) based on organic semiconductor material 2,7-dioctyl[1]benzothieno[3,2-b] benzothiophene (C8BTBT) as the active layer were fabricated by using organic molecular beam deposition (OMBD) and solution-processed methods, in which the C8BTBT thin-film morphology could be well controlled. In OMBD method, C8BTBT thin-film morphology could be controlled by the thickness of organic semiconductor layer and the deposition rate, of which the high-quality C8BTBT thin film was obtained at a thickness of about 20 nm and at a deposition rate of 1.2 nm/min, resulting in an obvious mobility improvement from 2.8 × 10⁻³ cm² V⁻¹ s⁻¹ to 1.20 cm² V⁻¹ s⁻¹. While in the solution-processing, C8BTBT thin-film morphology and thickness are related to the spin-coating speed and the substrate position in spin coater, i.e., in-centre and off-centre position. The off-centre spin-coating with an optimized speed produced large-size domain C8BTBT thin film and accordingly resulted in a mobility of 1.47 cm² V⁻¹ s⁻¹. Furthermore, an additive polystyrene (PS) was added into C8BTBT solution could further improve the thin-film morphology with more metal-stable phase as well as improve the interface contact with the substrate SiO₂, resulting in the highest mobility up to 3.56 cm² V⁻¹ s⁻¹. The research suggested that C8BTBT-based OFETs with the mobility over 1.20 cm² V⁻¹ s⁻¹ could be fabricated by using both OMBD and solution-processed methods through the thin-film morphology and structure optimization, which shows the potential applications in high-performance flexible and printed electronics.     

Structural,electronic and elastic properties of wurtzite-structured TlxAl1−xN alloys from first principles

Structural, electronic and elastic properties of wurtzite-structured thallium aluminum nitride (Tl_xAl_1−xN) across the entire alloy composition range have been studied using first-principles pesudopotential plane-wave density functional calculations. The alloy's lattice constants obey Vegard's law well. Band-gap bowing coefficients show very strong composition dependence. Elastic constants and their aggregate elastic modulus change continuously with Tl-concentrations varying from 0 up to 100%. A transition from brittle fracture to plastic flow occurs in Tl_xAl_1−xN alloys at about x=0.33. Further, elastic wave velocity and Debye temperature all monotonically decrease with increasing Tl concentration. Our calculated results for the binary cases, aluminum nitride (AlN) and thallium nitride (TlN), are in good agreement with previously reported data.     

In Situ Topochemical Transformation of ZnIn2S4 for Efficient Photocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran

Photocatalytic selective oxidation of 5-hydroxymethylfurfural (HMF) coupled H₂ production offers a promising approach to producing valuable chemicals. Herein, an efficient in situ topological transformation tactic is developed for producing porous O-doped ZnIn₂S₄ nanosheets for HMF oxidation cooperative with H₂ evolution. Aberration-corrected high-angle annular dark-field scanning TEM images show that the hierarchical porous O-ZIS-120 possesses abundant atomic scale edge steps and lattice defects, which is beneficial for electron accumulation and molecule adsorption. The optimal catalyst (O-ZIS-120) exhibits remarkable performance with 2,5-diformylfuran (DFF) yields of 1624 µmol h⁻¹ g⁻¹ and the selectivity of >97%, simultaneously with the H₂ evolution rate of 1522 µmol h⁻¹ g⁻¹. Mechanistic investigations through theoretical calculations show that O in the O-ZIS-120 lattice can reduce the oxidation energy barrier of hydroxyl groups of HMF. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) results reveal that DFF^* (C₄H₂(CHO)₂O^*) intermediate has a weak interaction with O-ZIS-120 and desorb as the final product. This study elucidates the topotactic structural transitions of 2D materials simultaneously with electronic structure modulation for efficient photocatalytic DFF production.     

Properties of amorphous CdS-crystalline Si junctions

Junctions between amorphous a-CdS and crystalline n-Si have been prepared. It is found that the junctions are rectifying with a coefficient k_r = 10²−10³ at room temperature. The temperature dependence of k_r, the J-V characteristics and the spectral intensity dependence of the photocurrent have been measured. The results are interpreted on the basis of carrier injection from c-Si to a-CdS and the assumption that C₁⁻ states in a-CdS define the reverse current flow. An energy band diagram of the heterojunction is proposed.