Achieving highly efficient long-wavelength phosphorescence emission of large singlet-triplet energy gap materials by host-guest doping

High-efficiency long-wavelength phosphorescence emissions of large singlet-triplet energy gap(ΔE_(ST))materials are essential for applications in biology and display.However,few long-wavelength phosphorescence emissions of largeΔE_(ST)materials have been reported due to the weak spin-orbit coupling(SOC)and strong non-radiative transitions.Herein,we develop a strategy to achieve highly efficient long-wavelength room temperature phosphorescence(RTP)emission of largeΔE_(ST)materials,which display bright red RTP emission with above 400μs lifetime and 6.5%phosphorescent quantum efficiency.Our experiments and theoretical calculations reveal that the fishbone-like packing and the zig-zag interactions provide favorable conditions for suppressing the non-radiative transitions of triplet state excitons,and heavy atoms effectively promote the intersystem crossing(ISC)process for highly efficient long-wavelength phosphorescence emission.The universality of the method for highly efficient long-wavelength RTP emission of largeΔE_(ST)materials was further investigated in various guests.Moreover,these materials with largeΔE_(ST)manifest the advantages of large color contrast on the display and utilization potentiality in information encryption.This strategy paves the way for the high contrast display and development of information encryption with RTP emission.

Sc-doped strontium iron molybdenum cathode for high-efficiency CO_(2)electrolysis in solid oxide electrolysis cell

Solid oxide electrolysis cells(SOECs)can effectively convert CO_(2)into high value-added CO fuel.In this paper,Sc-doped Sr_(2)Fe_(1.5)Mo_(0.3)Sc_(0.2)O_(6−δ)(SFMSc)perovskite oxide material is synthesized via solid-phase method as the cathode for CO_(2)electrolysis by SOECs.XRD confirms that SFMSc exhibits a stable cubic phase crystal structure.The experimental results of TPD,TG,EPR,CO_(2)-TPD further demonstrate that Sc-doping increases the concentration of oxygen vacancy in the material and the chemical adsorption capacity of CO_(2)molecules.Electrochemical tests reveal that SFMSc single cell achieves a current density of 2.26 A/cm^(2) and a lower polarization impedance of 0.32Ω·cm^(2) at 800°C under the applied voltage of 1.8 V.And no significant performance attenuation or carbon deposition is observed after 80 h continuous long-term stability test.This study provides a favorable support for the development of SOEC cathode materials with good electro-catalytic performance and stability.

Improved rate and cycling performances of Na_(3)V_(2)(PO_(4))_(2)F_(2)O by Ti^(3+/4+)doping with two oxidation states for sodium cathodes

Ti at the oxidation states of Ti^(3+)and Ti^(4+),was used to enhance the performance of Na_(3)V_(2)(PO_(4))_(2)F_(2)O by partially substituting vanadium.After doping Ti,the crystallographic volume is decreased due to the less radii of Ti^(3+/4+),and the valence of Ti is demonstrated identical to V.During sodium insertion in Ti-doped Na_(3)V_(2)(PO_(4))_(2)F_(2)O,the two discharge plateaus split into three because of the rearrangement of local redox environment.Consequently,the optimized Na_(3)V_(0.96)Ti_(0.04)(PO_(4))_(2)F_(2)O shows a specific capacity of 123 and 63 mA·h/g at 0.1C and 20C,respectively.After 350 cycles at 0.5C,the capacity is gradually reduced corresponding to a retention of 71.05%.The significantly improved performance is attributed to the rapid electrochemical kinetics,and showcases the strategy of replacing V^(3+/4+)with Ti^(3+/4+)for high-performance vanadium-based oxyfluorophosphates.

Realized stable BP-N at ambient pressure by phosphorus doping

Black-phosphorus-structured nitrogen(BP-N)is an attractive high-energy-density material.However,high-pressure-synthesized BP-N will decompose at low pressure and cannot be quenched to ambient conditions.Finding a method to stabilize it at 0 GPa is of great significance for its practical applications.However,unlike cubic gauche,layered polymeric,and hexagonal layered polymeric nitrogen(cg-N,LP-N,and HLP-N),it is always a metastable phase at high pressures up to 260 GPa,and decomposes into chains at 23 GPa.Here,on the basis of firstprinciples simulations,we find that P-atom doping can effectively reduce the synthesis pressure of BP-N and maintain its stability at 0 GPa.Uniform distribution of P-atom dopants within BP-N layers helps maintain the structural stability of these layers at 0 GPa,while interlayer electrostatic interaction induced by N-P dipoles enhances dynamic stability by eliminating interlayer slipping.Furthermore,pressure is conducive to enhancing the stability of BP-N and its doped forms by suppressing N-chain dissociation.For a configuration with 12.5%doping concentration,a gravimetric energy density of 8.07 kJ/g can be realized,which is nearly twice that of trinitrotoluene.

Mg doping reduced full width at half maximum of the near-band-edge emission in Mg doped ZnO films

Sol--gol method was employed to synthesize Mg doped ZnO films on Si substrates. The annealing temperature-dependent structure and optical property of the produced samples were studied. An interesting result observed is that increasing Mg concentration in the studied samples induces the full width at half maximum （FWHM） of their near-band-edge （NBE） emission decrease and the defect related emission of the corresponding sample suppresses drastically. The possible mechanism of the observed result is discussed.

Synthesis of nitrogen-doped single-walled carbon nanotubes and monitoring of doping by Raman spectroscopy

Nitrogen-doped single-walled carbon nanotubes （CNx-SWNTs） with tunable dopant concentrations were synthesized by chemical vapor deposition （CVD）, and their structure and elemental composition were characterized by using transmission electron microscopy （TEM） in combination with electron energy loss spectroscopy （EELS）. By comparing the Raman spectra of pristine and doped nanotubes, we observed the doping-induced Raman G band phonon stiffening and 2D band phonon softening, both of which reflect doping-induced renormalization of the electron and phonon energies in the nan- otubes and behave as expected in accord with the n-type doping effect. On the basis of first principles calculations of the distribution of delocalized carrier density in both the pristine and doped nanotubes, we show how the n-type doping occurs when nitrogen heteroatoms are substitutionally incorporated into the honeycomb tube-shell carbon lattice.

Fabrication of Pd-Nb bimetallic doped organosilica membranes by different metal doping routes for H_(2)/CO_(2) separation

Monometallic doping has proved its superiority in improving either permselectivity or H_(2) permeability of organosilica membranes for H_(2)/CO_(2) separation,but it is still challenging to break the trade-off effect.Herein,we report a series of Pd-Nb bimetallic doped 1,2-bis(triethoxysilyl)ethane(Pd-Nb-BTESE,PNB)membranes with different metal doping routes for simultaneously improving H_(2) permeance and H_(2)/CO_(2) permselectivity by the synergetic effects of Pd and Nb.The doped Pd can exist in the BTESE network as nanoparticles while the doped Nb is incorporated into BTESE network forming Nb-O-Si covalent bonds.The metal doping routes significantly influence the microstructure of PNB networks and gas separation performance of the PNB membranes.We found that the PNB membrane with Pd doping priority(PNB-Pd)exhibited the highest surface area and pore volume,comparing with Nb doping priority(PNB-Nb)or Pd-Nb simultaneous doping(PNB-PdNb).The PNB-Pd membrane could not only exhibit an excellent H_(2) permeance of~10^(−6) mol·m^(−2)·s^(−1)·Pa^(−1) but also a high H_(2)/CO_(2) permselectivity of 17.2.Our findings may provide novel insights into preparation of bimetallic doped organosilica membranes with excellent H_(2)/CO_(2) separation performance.

Confinement of sulfur-doped NiO nanoparticles into N-doped carbon nanotube/nanofiber-coupled hierarchical branched superstructures:Electronic modulation by anion doping boosts oxygen evolution electrocatalysis

The search for non-precious and efficient electrocatalysts towards the oxygen evolution reaction(OER)is of vital importance for the future advancement of multifarious renewable energy conversion/storage technologies.Electronic modulation via heteroatom doping is recognized as one of the most forceful leverages to enhance the electrocatalytic activity.Herein,we demonstrate a delicate strategy for the in-situ confinement of S-doped Ni O nanoparticles into N-doped carbon nanotube/nanofiber-coupled hierarchical branched superstructures(labeled as S-Ni O@N-C NT/NFs).The developed strategy simultaneously combines enhanced thermodynamics via electronic regulation with accelerated kinetics via nanoarchitectonics.The S-doping into Ni O lattice and the 1 D/1 D-integrated hierarchical branched carbon substrate confer the resultant S-Ni O@N-C NT/NFs with regulated electronic configuration,enriched oxygen vacancies,convenient mass diffusion pathways and superior architectural robustness.Thereby,the SNi O@N-C NT/NFs display outstanding OER properties with an overpotential of 277 m V at 10 m A cm^(-2)and impressive long-term durability in KOH medium.Density functional theory(DFT)calculations further corroborate that introducing S-dopant significantly enhances the interaction with key oxygenate intermediates and narrow the band gap.More encouragingly,a rechargeable Zn-air battery using an air-cathode of Pt/C+S-Ni O@N-C NT/NFs exhibits a lower charge voltage and preferable cycling stability in comparison with the commercial Pt/C+Ru O_(2)counterpart.This study highlighting the concurrent consideration of electronic regulation,architectural design and nanocarbon hybridization may shed light on the future exploration of economical and efficient electrocatalysts.

Preparation of Ta-Doped TiO2 Using Ta2O5 as the Doping Source

A novel method for preparing Ta-doped Ti02 via using Ta2 05 as the doping source is proposed. The preparation process combines the hydrothernlal fluorination of Ta2O5 and the subsequent formation of Ta-doped TiO2 sol. The results show that the doped sample annealed at 393 K generates an unstable intermediate NH4 TiOF3, which converts into anatase TiO2 with the increase of temperature. After annealing at ≥673K, the Ta-doped TiO2 nanocrystals with the grain size 〈20nm are obtained. Both the XRD and TG-DSC results confirm that Ta doping prevents the anatase-rutile crystal transition of TiO2. The band gap values of the doped samples, as obtained by UV-vis diffuse reflectance spectra, are smaller than that of pure anatase TiO2. The first-principle pseudopotential method calculations indicate that Ta5＋ lies in the TiO2 lattice at the interstitial position.

Influence of different Fe doping strategies on modulating active sites and oxygen reduction reaction performance of Fe, N-doped carbonaceous catalysts

Fe/N/C catalysts,synthesized through the pyrolysis of Fe-doped metal–organic framework (MOF) precursors,have attracted extensive attention owing to their promising oxygen reduction reaction (ORR) catalytic activity in fuel cells and/or metal-air batteries.However,post-treatments (acid washing,second pyrolysis,and so on) are unavoidable to improve ORR catalytic activity and stability.The method for introducing Fe^(3+) sources (anhydrous Fe Cl_(3)) into the MOF structure,in particular,is a critical step that can avoid time-consuming post-treatments and result in more exposed Fe-N_(x) active sites.Herein,three different Fe doping strategies were systematically investigated to explore their influence on the types of active sites formed and ORR performance.Fe-NC(Zn^(2+)),synthesized by one-step pyrolysis of Fe doped ZIF-8 (Zn^(2+)) precursor which was obtained by adding the anhydrous Fe Cl_(3)source into the Zn(NO_(3))_(2)·6H_(2)O/methanol solution before mixing,possessed the highest Fe-N_(x)active sites due to the high-efficiency substitution of Zn^(2+)ions with Fe^(3+) ions during ZIF-8 growth,the strong interaction between Fe^(3+) ions and N atoms of 2-Methylimidazole (2-MIm),and ZIF-8’s micropore confinement effect.As a result,Fe-NC(Zn^(2+)) presented high ORR activity in the entire p H range (p H=1,7,and 13).At p H=13,Fe-NC(Zn^(2+)) exhibited a half-wave potential (E1/2) of 0.95 V (vs.reversible hydrogen electrode),which was 70 m V higher than that of commercial Pt/C.More importantly,Fe-NC(Zn^(2+)) showed superior ORR stability in neutral media without performance loss after 5,000 cycles.A record-high open-circuit voltage(1.9 V) was obtained when Fe-NC(Zn^(2+)) was used as a cathodic catalyst in assembled Mg-air batteries in neutral media.The assembled liquid and all-solid Mg-air batteries with high performance indicated that Fe-NC(Zn^(2+)) has enormous potential for use in flexible and wearable Mg-air batteries.

Effects of Host Doping on Spectral and Long-Lasting Properties of Sm^(3+)-Doped Y_2O_2S

Gd- or Lu-doped long afterglow red phosphor Y2O2S：Sm^3＋ was synthesized using the high temperature flux fusion method. The obtained phosphors were analyzed using X-ray diffraction to determine the crystal structure, and the phase analyses show that the product is in single phase. The luminescence spectra and decay curve were measured on a Hitachi F-4500 fluorescence spectrophotometer. The decay time was determined on an ST-900PM weak light photometer. The analyses show that host doping of Lu improves both luminescence and decay time of the materials. The concentration of doped Lu and Sm was varied in order to determine the optimal condition and to synthesize the product with the best properties. The mechanism of the long afterglow was also briefly discussed.

A host-guest approach to fabricate metallic cobalt nanoparticles embedded in silk-derived N-doped carbon fibers for efficient hydrogen evolution

Hydrogen evolution reaction(HER) plays a key role in generating clean and renewable energy. As the most effective HER electrocatalysts, Pt group catalysts suffer from severe problems such as high price and scarcity. It is highly desirable to design and synthesize sustainable HER electrocatalysts to replace the Pt group catalysts. Due to their low cost, high abundance and high activities, cobalt-incorporated N-doped nanocarbon hybrids are promising candidate electrocatalysts for HER. In this report, we demonstrated a robust and eco-friendly host-guest approach to fabricate metallic cobalt nanoparticles embedded in N-doped carbon fibers derived from natural silk fibers. Benefiting from the onedimensional nanostructure, the well-dispersed metallic cobalt nanoparticles and the N-doped thin graphitized carbon layer coating, the best Cobased electrocatalyst manifests low overpotential(61 mV@10 mA/cm^2) HER activity that is comparable with commercial 20% Pt/C, and good stability in acid. Our findings provide a novel and unique route to explore high-performance noble-metal-free HER electrocatalysts.

Enhancing multifunctional photocatalysis with acetate-assisted cesium doping and unlocking the potential of Z-scheme solar water splitting

Graphitic carbon nitride(g-C_(3)N_(4))has been extensively doped with alkali metals to enlarge photocatalytic output,in which cesium(Cs)doping is predicted to be the most efficient.Nevertheless,the sluggish diffusion and doping kinetics of precursors with high melting points,along with imprecise regulation,have raised the debate on whether Cs doping could make sense.For this matter,we attempt to confirm the positive effects of Cs doping on multifunctional photocatalysis by first using cesium acetate with the character of easy manipulation.The optimized Csdoped g-C_(3)N_(4)(CCN)shows a 41.6-fold increase in visible-light-driven hydrogen evolution reaction(HER)compared to pure g-C_(3)N_(4) and impressive degradation capability,especially with 77%refractory tetracycline and almost 100%rhodamine B degradedwithin an hour.The penetration ofCs+is demonstrated to be a mode of interlayer doping,and Cs–N bonds(especially with sp^(2) pyridine N in C═N–C),along with robust chemical interaction and electron exchange,are fabricated.This atomic configuration triggers the broadened spectral response,the improved charge migration,and the activated photocatalytic capacity.Furthermore,we evaluate the CCN/cadmium sulfide hybrid as a Z-scheme configuration,promoting the visible HER yield to 9.02 mmol g^(−1) h^(−1),which is the highest ever reported among all CCN systems.This work adds to the rapidly expanding field of manipulation strategies and supports further development of mediating served for photocatalysis.

Effect of the Doping Layer Concentration on Optical Absorption in Si δ-Doped GaAs Layer

We study in this paper the intersubband optical absorption of Si doped GaAs layer for different applied electric fields and donors concentration. The electronic structure has been calculated by solving the Schr?dinger and Poisson equations self-consistently. From our results, it is clear that the subband energies and intersubband optical absorption are quite sensitive to the applied electric field. Also our results indicate that the optical absorption depends not only on the electric field but also on the donor’s concentration. The results of this work should provide useful guidance for the design of optically pumped quantum well lasers and quantum well infrared photo detectors (QWIPs).

Electronic structures and optical properties of Zn-dopedβ-Ga_2O_3 with different doping sites

The electronic structures and optical properties of intrinsic β-Ga2O3 and Zn-dopedβ-Ga2O3 are investigated by first-principles calculations. The analysis about the thermal stability shows that Zn-doped β-Ga2O3 remains stable. The Zn doping does not change the basic electronic structure of β-Ga2O3, but only generates an empty energy level above the maximum of the valence band, which is shallow enough to make the Zn-doped β-Ga2O3 a typical p-type semiconductor. Because of Zn doping, absorption and reflectivity are enhanced in the near infrared region. The higher absorption and reflectivity of ZnGa（2） than those of ZnGa（1） are due to more empty energy states of ZnGa（2） than those of ZnGa（1） near Ef in the near infrared region.

Enhancing the stability of Ni Fe-layered double hydroxide nanosheet array for alkaline seawater oxidation by Ce doping

Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.

Co-doped BaFe_(2)As_(2) Josephson junction fabricated with a focused helium ion beam

Josephson junction plays a key role not only in studying the basic physics of unconventional iron-based superconductors but also in realizing practical application of thin-film based devices,therefore the preparation of high-quality iron pnictide Josephson junctions is of great importance.In this work,we have successfully fabricated Josephson junctions from Co-doped BaFe_(2)As_(2)thin films using a direct junction fabrication technique which utilizes high energy focused helium ion beam(FHIB).The electrical transport properties were investigated for junctions fabricated with various He^(+)irradiation doses.The junctions show sharp superconducting transition around 24 K with a narrow transition width of 2.5 K,and a dose correlated foot-structure resistance which corresponds to the effective tuning of junction properties by He^(+)irradiation.Significant J_c suppression by more than two orders of magnitude can be achieved by increasing the He^(+)irradiation dose,which is advantageous for the realization of low noise ion pnictide thin film devices.Clear Shapiro steps are observed under 10 GHz microwave irradiation.The above results demonstrate the successful fabrication of high quality and controllable Co-doped BaFe_(2)As_(2)Josephson junction with high reproducibility using the FHIB technique,laying the foundation for future investigating the mechanism of iron-based superconductors,and also the further implementation in various superconducting electronic devices.

The effects of Zn vacancies on ferromagnetism in Cu-doped ZnO films controlled by oxygen pressure and Li doping

Zn0.99Cu0.01O films were studied experimentally and theoretically. The films were prepared by pulsed-laser deposition on Pt（111）/Ti/SiO2/Si substrates under various oxygen pressures to investigate the growth-dependence of the ferromagnetic properties. The structural, magnetic, and optical properties were studied, and it was found that all the samples possess a typical wurtzite structure, and that the films exhibit room-temperature ferromagnetism. The sample deposited at 600 ℃ and an oxygen pressure of 10 Pa showed a large saturation magnetization of 0.83 μB/Cu. The enhanced ferromagnetism in the （Cu, Li）-codoped ZnO is attributable to the existence of Zn vacancies （Vzn）, as shown by first-principles calcu- lations. The photoluminescence analysis demonstrated the existence of Vzn in both Zn0.99Cu0.01 O and （Cu, Li）-codoped ZnO thin films, and this plays an important role in the increase of ferromagnetism, according to the results of first-principles calculations.

Effects of N-doping concentration on the electronic structure and optical properties of N-doped β-Ga_2O_3

The electronic structures and the optical properties of N-doped β-Ga2O3 with different N-doping concentrations are studied using the first-principles method.We find that the N substituting O（1） atom is the most stable structure for the smallest formation energy.After N-doping,the charge density distribution significantly changes,and the acceptor impurity level is introduced above the valence band and intersects with the Fermi level.The impurity absorption edges appear to shift toward longer wavelengths with an increase in N-doping concentration.The complex refractive index shows metallic characteristics in the N-doped β-Ga2O3.

Effects of doping concentration on properties of Mn-doped ZnO thin films

This paper reports that the radio frequency magnetron sputtering is used to fabricate ZnO and Mn-doped ZnO thin films on glass substrates at 500 ℃. The Mn-doped ZnO thin films present wurtzite structure of ZnO and have a smoother surface, better conductivity but no ferromagnetism. The x-ray photoelectron spectroscopy results show that the binding energy of Mn2p3/2 increases with increasing Mn content slightly, and the state of Mn in the Mn-doped ZnO thin films is divalent. The chemisorbed oxygen in the Mn-doped ZnO thin films increases with increasing Mn doping concentration. The photoluminescence spectra of ZnO and Mmdoped ZnO thin films have a similar ultraviolet emission. The yellow green emissions of 4 wt.% and 10 wt.% Mn-doped thin films are quenched, whereas the yellow green emission occurs because of abundant oxygen vacancies in the Mn-doped ZnO thin films after 20 wt.% Mn doping. Compared with pure ZnO thin film, the bandgap of the Mn-doped ZnO thin films increases with increasing Mn content.