Defect Band Research Articles

Synergism of defect and band engineering in ultra-thin metal free organic C(CN)3 nanosheet for efficient photocatalytic CO2 reduction

Photocatalytic CO2 conversion is an effective and promising strategy for alleviating carbon emissions and energy crisis. Herein, an aqueous ultrasonic method is applied to exfoliate bulk half metallic C(CN)3 into ultra-thin atomic layered C(CN)3 nanosheets. It found that after 20 h of ultrasonic treatment, the as-obtained C(CN)3-20 presents a significantly improved photocatalytic CO2 reduction activity. The CO production rate reaches 285.3 μmol g−1 h−1, fiftyfold of the bulk C(CN)3. The significant improvement in photocatalytic performance can be attributed to the following factors: (1) exfoliation reduces the particle size and increases the specific surface areas of the material. Thus, the atomic utilization efficiency is improved; (2) the bandgap of the material is enlarged after exfoliation, while suitable bandgap further promotes photocatalytic CO2 conversion; (3) the optimized surface defect concentration enhances the separation efficiency of photogenerated electrons and holes. This study demonstrates the synergistic effect of defect regulation and band engineering on photoelectric property modulation for metal-free organic C(CN)3, enabling highly selective and efficient CO2 photoconversion.

Simultaneous Growth Strategy of High-Optical-Efficiency GaN NWs on a Wide Range of Substrates by Pulsed Laser Deposition.

Here, we explore a catalyst-free single-step growth strategy that results in high-quality self-assembled single-crystal vertical GaN nanowires (NWs) grown on a wide range of common and novel substrates (including GaN, Ga2O3, and monolayer two-dimensional (2D) transition-metal dichalcogenide (TMD)) within the same chamber and thus under identical conditions by pulsed laser deposition. High-resolution transmission electron microscopy and scanning transmission electron microscopy (HR-STEM) and grazing incidence X-ray diffraction measurements confirm the single-crystalline nature of the obtained NWs, whereas advanced optical and cathodoluminescence measurements provide evidence of their high optical quality. Further analyses reveal that the growth is initiated by an in situ polycrystalline layer formed between the NWs and substrates during growth, while as its thickness increases, the growth mode transforms into single-crystalline NW nucleation. HR-STEM and corresponding energy-dispersive X-ray compositional analyses indicate possible growth mechanisms. All samples exhibit strong band edge UV emission (with a negligible defect band) dominated by radiative recombination with a high optical efficiency (∼65%). As all NWs have similar structural and optical qualities irrespective of the substrate used, this strategy will open new horizons for developing III-nitride-based devices.

Bandgap and its defect band analysis of flexoelectric effect in phononic crystal plates

The wave equations of a novel model for the electro-elastic Kirchhoff plate containing the flexoelectric effect are constructed using a variational formulation. Through an Improved Plane Wave Expansion (IPWE) approach, the proposed wave equations are then applied to examine the elastic wave bandgap and defect band in a phononic crystal plate structure without or with a defect. The results demonstrate that the flexoelectric effect on the bandgap is apparent when the structure is at the submicron scale and fades as the scale increases. Moreover, at all length scales, the magnitude of the bandgap varies dramatically with lattice length and inclusion volume ratio. This suggests that the frequency and broadness of the bandgap can be tuned by modifying the volume percentage of inclusion, plate size parameters and lattice length. The dispersion curves of the defect model and corresponding mode shape at the defect band are also studied, which can indicate the applicability of the current model incorporating flexoelectric effect in energy harvesting and wave focusing. The novel model and these findings would help the design of MEMS/NEMS devices for enhanced wave guiding when flexoelectric-based electro-elastic fields are involved.

Intrapulse in situ Raman probing of electron, phonon and structural dynamics in synthetic diamond excited by ultrashort laser pulses: Insights into atomistic structural damage

Synthetic Ib-diamond plate with a minor concentration of substitutional atomic nitrogen C-centers was exposed in its bulk by tightly focused 0.2-ps, 525-nm laser pulses, coming at 80-MHz repetition rate and nJ-level variable pulse energies. Stokes first-order Raman scattering line related to 1332-cm−1 optical phonon was observed in the transmitted laser spectra and its pulse energy-dependent intensity, position wavenumber and half-width were analyzed. The Raman intensity, along with the second-order Raman band (2200–2700 cm−1), demonstrated quadratic dependence on pulse energy due to three-photon inter-band absorption, transforming at higher energies into a linear dependence for saturated absorption of opaque dense electron-hole plasma. Under these conditions, first-order Raman scattering was related to a non-resonant spontaneous process, enhanced by plasma emission of seeding coherent optical phonons. The Raman wavenumber decreased versus pulse energy via photo-injection of plasma and then slowly increased due to the “electronic” stress, until its final drop upon the onset of self-accelerated decay of optical phonons into acoustic ones (quasi-heating). The Raman half-width increased versus pulse energy due to the optical-phonon decay during the 0.2-ps laser pulse. An additional Stokes Raman band of radiation-induced defects was observed in the range of 900–1200 cm−1, exhibiting its yield scaling with generation of energetic Auger electrons. At the maximal pulse energies (stronger intra-pulse quasi-heating) all Raman lines disappeared, implying ultrafast structural disordering in the diamond without graphitization.

Self‐Trapped Excitons‐Based Warm‐White Afterglow by Room‐Temperature Engineering toward Intelligent Multi‐Channel Information System

AbstractIn the era of intelligence, the output colors of foundational phosphors are expected to be controlled by programs, while current activators‐determined afterglow candidates with fixed spectral channel have limitations in creating customized colors. Here, a long‐lived warm‐white emission is successfully demonstrated originating from self‐trapped excitons (STEs) in non‐toxic Cs2NaInCl6:Ag,Bi, ranging from 400 to 850 nm, of which the afterglow color can be easily customized using filters. This investigation indicates that 3% of Ag alloying breaks the dark STEs and introduces traps for efficient afterglow, while 3% Bi doping further improves the quantum yield to ≈100% and greatly enhances afterglow by ≈100‐fold compared with the initial intensity, allowing for an impressive afterglow persistence of over 20,000 s. Intriguingly, the self‐trapped defect bands from Jahn‐Teller distortions are prolonged from hundreds of femtoseconds to several hours, and they are first detected in the steady‐state absorption spectra after the cessation of excitation sources, contributing to the concluded dynamic afterglow model for STEs. And its intelligent application is corroborated by designed multi‐channel information system. These findings offer a novel scheme for understanding dynamic luminescence of STEs and supply an exemplification of designing white afterglow phosphors.

Correlation between deep level traps and reverse recovery of GaAs p–i–n diodes before and after neutron irradiation

Using the deep-level transient spectroscopy and reverse recovery method, the minority carrier lifetime in the base n 0-layers of high-voltage GaAs p +–p 0–i–n 0–n +-diodes grown by the liquid phase epitaxy in argon atmosphere has been estimated before and after irradiation by neutrons with the energy of 1 MeV and the fluence of 1.6 × 1014 cm–2. Correlation between the values of the minority carrier lifetime determined by both methods was found. EL2 defects where shown to govern the dynamic switching characteristics of non-irradiated GaAs diodes, while the switching process in the irradiated diodes is determined by the acceptor-like states of defect bands located above the midgap, which are D– states of a three-charged donor. Having been irradiated with neutrons, the diodes revealed a significant decrease in the time of their reverse recovery upon changing the character of the diode switching from the “hard” mode to the “soft” one.

How do carbon dots with amine terminals help perovskite solar cells perform better?

Lead halide perovskite solar cells can be significantly improved with multifunctional additives such as carbon dots (CDs) with amine terminals via defect passivation and band alignment. Here, we determine rational guidelines for the usage of such quantum dots in perovskite solar cells by systematically studying their effects on crystal quality and carrier transport. The amine-terminated CDs homogeneously dispersed in precursors improve the crystal quality of perovskite films, but they reduce the hole mobility hampering hole extraction. In contrast, CDs deposited between the electron transport layer and active layer could promote spin-coated film quality and electron’s extraction efficiently. So, the approaches of the carbon dots in device alters semiconductor properties and energy level structure. Interface engineering achieve better crystal quality and energy level alignment, which in turn affects charge collection, thereby increasing current density and power conversion efficiency. According to the findings of this study, when considering defect passivation by additives, the energy band alignment of the device should also be considered, since this could change carrier dynamics and device performance differently.

Enhanced multi-band acoustic energy harvesting using double defect modes of Helmholtz resonant metamaterial

Acoustic metamaterials (AMs) based on phononic crystals have been widely employed for acoustic energy harvesting, for their capacity to amplify incident sound waves and transfer them to piezoelectric devices. By substituting a resonator unit with a piezoelectric material having distinct characteristics, the periodicity of the AM is locally disrupted, resulting in the generation of defect bands within the band gap. At the frequencies corresponding to these defect bands, the AM exhibits the phenomenon of local resonance, which concentrates the incident acoustic energy at the defect sites and significantly enhances the output power of the piezoelectric devices. Conventional AMs primarily consist of elastic resonators, which can be regarded as spring-mass systems. The elastic resonances of these resonators lead to local resonance in the AM and are utilized for single-band acoustoelectric conversion. In contrast, Helmholtz resonators (HRs), in addition to demonstrating mechanical resonance, generate acoustic resonance at specific frequencies. By combining AM with HRs, the resulting Helmholtz AM (HAM) achieves energy localization effects within two defect bands, thereby increasing the output power and broadening the operational frequency range of the AM. This study aims to investigate the energy localization in HAM with multiple point defects within the two defect bands through numerical simulations and experimental analysis. Multiple HRs are intentionally removed from the HAM to introduce these multi-point defects. The interaction of elastic waves localized within these defects further enhances the energy harvesting efficiency of the HAM. Comparing the voltage frequency response functions, it is observed that, in both the first and second band gaps, the output voltage of the three double-defect HAM structures surpasses that of the single-defect HAM. As the distance between the two defects decreases, the energy harvesting at the defect modes intensifies due to a stronger coupling effect.

The impact of buffer thickness upon the transport-limited buffer trapping effects in carbon-doped power GaN-on-Si devices

In this work, we focused on investigating the transport-limited trapping effects in GaN-on-Si buffer layers as well as impact of the thickness of buffer layers (TBuf) upon such effects. Vertical transport dynamics of charges within the buffer layers and their key energy levels are quantitatively and statistically investigated and analyzed. The results show that an increased TBuf diminishes both impurity conduction of the defect band formed by carbon doping as well as the injection of electrons from the substrate, greatly diminishing the current collapse and improving the stability of the device. Such enhancement is mainly attributed to the reduced vertical electric field within the thickened epitaxy, which provides an additional pathway to address the current collapse and yields more efficient power GaN-on-Si devices.

(Invited) High-Performance Field-Effect Transistors Based on Two-Dimensional Materials for VLSI Circuits

Introduction Nowadays, the scaling of silicon very large-scale integration(VLSI) technologies has reached channel thicknesses of 7nm. However, further downscaling becomes increasingly difficult as the gate electrostatics require a substantial reduction of the channel thickness to about a fourth of the gate length. As a result, the actual gate length of high-performance(HP) FETs at the current state-of-the-art amounts to 16nm and is projected to stall at 12nm for the 1.5nm node and the following nodes, according to the International Roadmap for Devices and Systems(IRDS)[1]. For these nodes, two-dimensional(2D) materials could have the potential to replace silicon as the channel material. They can maintain sizable mobilities at atomic thicknesses, thus providing enhanced gate control in stacked channel nanosheet transistor structures[2]. Even though FETs based on 2D materials hold the promise to serve as FETs at the front end of the line, numerous challenges still need to be overcome. Downscaling Dimensions For ultra-scaled device designs, 2D materials can be used as a channel in stacked nanosheet FETs. In such a structure, the 2D material is gated from both sides, as depicted in Fig.1(a). By stacking multiple double-gated channels on top of each other, the required on-current density of around 1mA/μm can be achieved[3]. The first experimental demonstrations have achieved sub-5nm gate lengths[4] or, in a different design, a gate pitch of only 42nm[5], meeting the requirements for the 1.5nm node. While these prototypes show that 2D FETs can be scaled down, they have been fabricated in a laboratory. Many challenges must be overcome before such small devices can be fabricated in industry-compatible batch processes which require a high yield and low variability. Contact Engineering In order to enable sufficiently high on-current densities, small contact resistances to 2D semiconductors are required, which are inhibited by the formation of Schottky barriers at the metal to semiconductor interface. Schottky contacts to 2D materials are so prevalent because there is, on one side, a lack of stable doping schemes, and on the other side, pronounced Fermi-level pinning at the metal-to-semiconductor interface. Semi-metallic bismuth contacts can provide low-resistive contacts to n-type MoS2 FETs, as the bismuth suppresses the metal-induced gap states which pin the Fermi-level[6]. This way, a small contact resistance of 123Ωμm has been achieved, reaching the IRDS limit for the 1.5nm node. While comparable results have been realized for antimony contacts to n-type FETs, low-resistive contacts to p-type FETs are more challenging. Gate Stack Design A good gate stack for 2D FETs must provide excellent gate control while maintaining small gate leakage currents, which requires a capacitive equivalent thickness(CET) smaller than 0.9 nm. At these small CETs, a small gate leakage can only be obtained with a high-dielectric constant gate insulator and sizable band offsets, rendering some insulators, e.g. hexagonal boron nitride, unsuitable. Simultaneously, the gate insulator should form a van-der Waals interface with the 2D semiconductor, as otherwise, interface traps degrade the carrier mobility and the sub-threshold slope[7]. Charge traps within the insulator are the root cause of the limited stability and reliability of 2D FETs, as seen by a large hysteresis in the transfer characteristics or in pronounced Bias Temperature Instabilities(BTI). The electrical stability can be improved, if the defect bands in the gate insulator are energetically far away from the semiconductor’s conduction and valence band edges, see Fig.1(b)[8]. Conclusions Despite all the progress achieved within the last decade, the challenges for VLSI integration of 2D materials are enormous. First, stacked 2D FETs with scaled dimensions still need to be realized at an industrial scale. Second, despite low contact resistance demonstrations for n-type FETs, the resistances for p-type FETs are one order of magnitude too high. Finally, one of the most serious obstacles is identifying a suitable gate stack. Even though promising combinations of insulators to semiconductors have been suggested, like Bi2O5Se/Bi2O2Se, CaF2/MoS2 or SrTiO3/MoS2, it is at the moment unclear, which of them provides the best performance. Acknowledgments The authors thank for funding from the European Research Council under grant agreement no. 101055379.

(Invited) Gate Stack Design for Field-Effect Transistors Based on Two-Dimensional Materials

1.Introduction Two-dimensional(2D) materials hold the promise to allow for ultrathin channels built of single atomic monolayers in ultimately scaled field-effect transistors (FETs). Due to this small thickness, an enhanced gate control is achieved while at the same time sizable mobilities in the 2D materials can be maintained[1]. In this way, the on-current density of the devices could potentially be increased to up to 1mA/μm by stacking six nanosheets on top of each other, combining p-type and n-type FETs in vertical integration. Even though FETs based on 2D materials hold a lot of promise, numerous challenges still need to be overcome. One of the most serious obstacles is the identification of a suitable gate stack. Over the last years, several insulators have been suggested, including layered insulators like hBN[2], ionic insulators like CaF2[3], amorphous high-k dielectrics like HfO2[4], see Fig.1. In addition, crystalline perovskites like SrTiO3[5] or native oxides like Bi2SeO5[6] have been explored. However, which of these materials provides the best performance is at the moment unclear and needs to be evaluated according to the criteria of scalability (Section 2), the minimization of charge traps (Section 3), and batch-processing compatible deposition technology for double-gated device designs (Section 4). 2.Scalable Gate Stacks High-performance FETs require a high on/off current ratio and steep subthreshold slopes. In order to preserve these characteristics in devices with ultimately scaled channel lengths, the insulator capacitance needs to be higher than 1.5μFcm-2, corresponding to a capacitive equivalent thickness smaller than 1nm. At the same time, if the insulator thickness becomes too small, the gate leakage current often easily exceeds the low-power limit of 0.015 Acm-2, thereby increasing the standby power consumption in the off-state. In fact, the gate leakage currents through thin hBN layers are high, rendering it unsuitable as a gate insulator for scaled FETs, while CaF2, HfO2 or Bi2SeO5 show promise[7]. 3.Minimizing Charge Traps The gate insulator should form a van der Waals interface with the 2D semiconductor, as otherwise, interface traps will degrade the carrier mobility and the sub-threshold slope[8]. Charge traps within the insulators cause limited stability and reliability of 2D FETs, as seen by a large hysteresis in the transfer characteristics or in Bias Temperature Instabilities. As a consequence, the stability can be enhanced if the defect bands in the gate insulator are energetically far away from the conduction and valence band edges[9]. Thus, the number of electrically active charge traps can be minimized by selecting a suitable combination of 2D semiconductor to insulator or by reducing the width of the defect bands by using crystalline insulators. 4.Deposition Technology Gate insulators need to be deposited on top of 2D semiconductors for top gate formation. However, the inert planes of 2D materials inhibit direct nucleation of insulators from the gaseous phase in an atomic layer deposition process. In this context, a promising approach is to use a self-assembled polymer monolayer to nucleate the precursors[4]. Molecular beam epitaxy is an alternative growth approach for gate insulators which offers the advantage of van der Waals epitaxy for layered materials, where the lattice-matching conditions are relaxed[10]. In order to avoid the growth of the insulator on top of the 2D semiconductor altogether the in-situ oxidation of the 2D semiconductor to its native oxide is a promising option, like for Bi2SeO5. 5.Conclusions Even though many novel insulator systems for 2D FETs have been proposed over the last couple of years, it is still unclear which of them best meets the requirements formulated. The most important questions to be addressed in the future will be to identify systems with reproducibly small interface and border trap densities and high thermal stability and to develop suitable batch-processing compatible top gate deposition methods for these material systems. Acknowledgments The authors thank for funding from the European Research Council under grant agreement no.101055379.

BaSn0.96-XZr0.04MXO3 (M = Mn, Fe or Co, x = 0, 0.02) for spin-based devices: Ferromagnetic properties

In this study, Zr and/or Mn, Fe or Co ions were used to induce a robust room temperature ferromagnetic nature in perovskite BaSnO3 for high performance information applications. Dilute magnetic semiconductor compositions with formula of BaSn0.96-XZr0.04MXO3 (M = Mn, Fe, Co, x = 0, 0.02) have been synthesized at 1150 °C. For all compositions, mono-phase of cubic BaSnO3 structure with very small impurities of SnO2 were recorded based on X-ray diffraction analysis. The relation between ionic size of dopants and crystal dimension of BaSnO3 suggests the of Sn4+-site by Zr4+, Mn2+, Fe2+ or Co2+ ions. Extended absorption tails to visible light region were found for BaSn0.94Zr0.04Mn0.02O3 and BaSn0.94Zr0.04Co0.02O3 samples, owing to strong defect band transition absorption. Due to the addition of Zr and/or Mn, Fe or Co ions high refine of BaSnO3 morphology from inhomogeneous large grains to well distribute small one were seen. The XPS results of BaSn0.96Zr0.04O3 and BaSn0.94Zr0.04Co0.02O3 samples confirm that Ba, Sn, O and Zr are in the oxidation states of +II, +IV, −II and +IV/+III, respectively. Magnetically, incorporation of 4 wt% Zr4+ ions (empty 4d-orbital) induced a full-saturated spin ferromagnetic order with saturation magnetization of 1.16 emu/g, retentivity of 0.11 emu/g and coercivity of 147 Oe. Also, codoping by Zr/Co ions stimulates a full-saturated spin ferromagnetic order with saturation magnetization of 1.36 emu/g, retentivity of 0.17 emu/g and coercivity of 149 Oe. The empty 4d-Zr4+ ions have high ability in reversing the diamagnetic nature of BaSnO3 to ferromagnetic one through interaction with oxygen vacancies. The outer 4d-shell of Zr and 3d-orbital of Co with the oxygen vacancies induce the strong magnetic exchange interaction. Through looking into the previous studies on the magnetic properties of BaSnO3, the recorded saturation magnetization of 4 wt% Zr and 4 wt% Zr + 2 wt% Co ions are remarkable values.

Symmetry-protected topological exceptional chains in non-Hermitian crystals

In non-Hermitian systems, defective band degeneracies called exceptional points can form exceptional lines (ELs) in 3D momentum space in the absence of any symmetries. However, whether the presence of symmetries can affect the EL configurations had rarely been discussed. Here we show that a natural orientation can be assigned to every EL according to the eigenenergy braiding around it, and we establish the source-free principle of ELs stating that the number of ELs ingoing and outgoing from the junction must be conserved. Based on this principle, we discover that three crystalline-symmetry-based mechanisms can stabilize the junction of ELs, resulting in the formation of various types of exceptional chains (ECs). We further demonstrate that ECs can be observed in prototypical non-Hermitian photonic crystals. Our results combine the effect of non-Hermitian spatiotemporal symmetry and topology to pave the way for understanding and manipulating the morphology of ELs in non-Hermitian crystalline systems.

Enhanced upconversion luminescence and single-band red emission in β-Ba2ScAlO5: Yb3+/Er3+ phosphor through doping Cu2+

This study reports on a single-band red upconversion emission of Er3+ in a pure-phase β-Ba2ScAlO5: Yb3+/Er3+ fluorescent powder by doping Cu2+. The optimum concentration of Cu2+ ions in β-Ba2ScAlO5: Yb3+/Er3+ powder was 0.20. The red and green emission intensity of β-Ba2ScAlO5: Yb3+/Er3+ sample with optimum concentration of Cu2+ ions increased by 19.1 and 3.6 times, respectively, relative to the β-Ba2ScAlO5:Yb3+/Er3+ material lacking Cu2+ ions. The red-green integral intensity ratio of the β-Ba2ScAlO5:Yb3+/Er3+/Cu2+ phosphor reached 141.9. The potential upconversion luminescence (UCL) mechanism was explored by analyzing the down-shift luminescence (DS) spectra, upconversion luminescence spectra, and upconversion fluorescence lifetime decay curves of Yb3+/Er3+/Cu2+ triple-doped β-Ba2ScAlO5. Enhanced red emission and green upconversion emission are achieved by energy transfer between defect band by the oxygen vacancy and Er3+ energy levels. This study's findings establish the foundation for developing novel phosphors with single UC red light emission, which has potential applications in illumination displays, optical thermometry, and biomedicine.

Structural optimization of inverted CsPbI2Br perovskite solar cells for enhanced performance via SCAPS-1D simulation

The CsPbI2Br material benefits perovskite solar cells (PSCs) by balancing their efficiency with chemical and thermal stability. Herein, we performed numerical modeling of a p-i-n structured PSCs employing different electron transport layers (ETLs). In order to optimize the ETL, the simulation results showed bilayer ETL (PCBM/SnO2) yielded the best device performance. Then, by tweaking the absorber layer’s defect density, thickness, electron affinity, and band gap, we optimized the device performance utilizing this bilayer ETL and yielded power conversion efficiency (PCE) of 12.51%, fill factor (FF) of 73.60%, open circuit voltage (V OC ) of 0.94 V, and short circuit current density (J SC ) of 17.94 mA cm−2. These CsPbI2Br perovskite-based devices would have outstanding thermal stability in a range from 253 K to 323 K. Another important observation in these PSCs is that interfacial defect density plays a crucial for regulating the V OC. We, therefore, anticipate that this research will aid in the development of extremely effective and stable inverted all inorganic PSCs.

Photogenerated Defect‐Transit Dual S‐Scheme Charge Separation for Highly Efficient Hydrogen Production

AbstractThe rational design of a step‐scheme (S‐scheme) heterojunctions in hybrid semiconductors by avoiding unwanted charge transport paths is considered as an attractive way to achieve high photocatalytic activity in hydrogen evolution reaction (HER). Here, a dual S‐scheme heterojunction formed in the lychee‐shaped W18O49/CdWO4/CdS nanostructures is proposed for improving the photocatalytic performance in HER under visible light irradiation. The remarkable activity in photocatalytic HER of W18O49/CdWO4/CdS is attributed to the unique structure and effective charge separation by the photoinduced defect‐transit dual S‐scheme mechanism and strong internal electric field. The measurements of X‐ray photoelectron spectroscopy (XPS), femtosecond transient absorption (fs‐TA) spectroscopy, and electron paramagnetic resonance (EPR) further confirm the photoinduced carrier transfer pathways following the dual S‐scheme mechanism. This research can provide a new strategy for designing the dual S‐scheme heterojunctions to improve photocatalytic performance through the defect band structure engineering.

Synthesis of Mesoporous Carbon Adsorbents Using Biowaste Crude Glycerol as a Carbon Source via a Hard Template Method for Efficient CO2 Capture.

Biowaste utilization as a carbon source and its transformation into porous carbons have been of great interest to promote environmental remediation owing to biowaste's cost-effectiveness and useful physicochemical properties. In this work, crude glycerol (CG) residue from waste cooking oil transesterification was employed to fabricate mesoporous crude glycerol-based porous carbons (mCGPCs) using mesoporous silica (KIT-6) as a template. The obtained mCGPCs were characterized and compared to commercial activated carbon (AC) and CMK-8, a carbon material prepared using sucrose. The study aimed to evaluate the potential of mCGPC as a CO2 adsorbent and demonstrated its superior adsorption capacity compared to AC and comparable to CMK-8. The X-ray diffraction (XRD) and Raman results clearly depicted the structure of carbon nature with (002) and (100) planes and defect (D) and graphitic (G) bands, respectively. The specific surface area, pore volume, and pore diameter values confirmed the mesoporosity of mCGPC materials. The transmission electron microscopy (TEM) images also clearly revealed the porous nature with the ordered mesopore structure. The mCGPCs, CMK-8, and AC materials were used as CO2 adsorbents under optimized conditions. The mCGPC adsorption capacity (1.045 mmol/g) is superior to that of AC (0.689 mmol/g) and still comparable to that of CMK-8 (1.8 mmol/g). The thermodynamic analyses of the adsorption phenomena are also carried out. This work demonstrates the successful synthesis of a mesoporous carbon material using a biowaste (CG) and its application as a CO2 adsorbent.

Two-in-One Electrons Trapped Fe-BiOCl-Vo Nanosheets for Promoting Photocatalytic-Fenton Degradation Performances of Phenol

Fe-BiOCl-Vo nanosheets with electron-capture centers of doped Fe and surface oxygen vacancies (Vo) for enhanced photocatalytic-Fenton performances were conducted. Compared with pristine BiOCl nanosheets, the band gap of the resulting Fe-BiOCl-Vo nanosheets was narrowed, and defective bands were introduced due to the Fe doping and Vo. Furthermore, the integrated electron trapping effect of Vo and doped Fe can efficiently drive charge transfer and separation. As a result, the photocatalytic-Fenton performances of phenol over Fe-BiOCl-Vo nanosheets were enhanced. The photocatalytic-Fenton performances of Fe-BiOCl-Vo nanosheets were enhanced two-fold and four-fold, respectively, as compared with the photocatalytic performances of Fe-BiOCl-Vo and pristine BiOCl nanosheets. During the photocatalytic-Fenton process, the multiple reactive species referring holes (h+), superoxide radicals (●O2−), and hydroxyl radicals (●OH) induced by the efficiently separated charge carriers and Fenton reaction played synergetic roles in phenol degradation and mineralization. This work provides a sophisticated structure design of catalysts for efficient charge transfer and separation, promoting photocatalytic-Fenton performance.

Cathodoluminescence and structural properties of ZnTe nanocrystals synthesized from Te/ZnO thin films

Highly mismatched alloys are of substantial interest for composition-dependent bandgap tunability for solar cell applications. Using low-energy ion implantation and subsequent thermal treatment, we have synthesized ZnTe nanocrystals from Te/ZnO bilayer thin films. However, only thermal treatment without ion implantation does not show any ZnTe nanocrystal characteristics that demonstrate the role of defects via ion implantation in nucleation growth. High-resolution transmission electron microscopy measurements confirmed the nanocrystalline growth of ZnTe and ZnTeO3 inside the mixed layer of ZnO and Te. From X-ray diffraction, it has been observed that a critical fluence of ions is required to produce a certain quantity of defects to assist in stoichiometric ZnTe formation. The absorption spectroscopy illustrates dual bandgap in the mixed alloys. Cathodoluminescence spectroscopy confirms two visible emission bands at 2.1 eV and 2.35 eV corresponding to the ZnTe and ZnO defect band along with the near band UV emission of ZnO at 3.26 eV. Such composition-dependent bandgap and light emission tunability from a mixed alloy are suitable for semiconductor device technology and energy harvesting.

Construction of Ultrasensitive Surface‐Enhanced Raman Scattering Substates Based on TiO2 Aerogels

AbstractRecent advances in surface‐enhanced Raman scattering (SERS) on semiconductor substrates offer this technology improved selectivity on top of other advantages, such as cost efficiency. However, the enhancement factor (EF) based on the semiconductors is still low compared with the noble metal substrates. Here, a new strategy of developing the semiconductor substrates based on aerogels is proposed for the first time. According to the modified Herzberg–Teller coupling rule, TiO2 aerogels are selected as the control object because of their large tunability. The surface area, amorphousness, and surface oxygen vacancy densities of TiO2 aerogels are regulated synergically. Due to the tuning of band structure, including band gap and defect band, multiresonant interband charge transfer (CT) pathways are generated and enhanced CT efficiency. A strong, intrinsically activated SERS effect is generated. Amorphous TiO2 aerogel with the highest surface oxygen vacancies shows a significant EF of 2.42 × 107, and TiO2 aerogels afford the large surface area and more active sites, which is conducive to promoting the adsorption of molecules. The aerogel‐based SERS is demonstrated to have wide applicability for ultrasensitive detection of explosives and organic dyes. The aerogel nanomaterials demonstrated here open a way for the construction of low‐cost and high‐sensitivity SERS substrate materials.