OsSi2电子结构及介电性能的第一性原理研究

采用基于密度泛函理论的第一性原理,研究了硅基异质外延的OsSi_2的电子结构和介电性能。结果表明,在1.010nm≤a≤1.030nm范围内,OsSi_2始终为间接带隙的能带结构,且带隙值随晶格常数a的增大而逐渐减小;当晶格常数a为1.020nm时,体系处于稳定平衡态,此时OsSi_2具有0.625eV的间接带隙能量值;OsSi_2的价带主要由Os的5d、5p和Si的3s、3p态电子构成,导带主要由Si的3s、3p和Os的5d、6s态电子构成;OsSi_2在外延稳定平衡态及其附近的介电函数实部和虚部变化趋近一致,与块体OsSi_2相比,OsSi_2在外延稳定平衡态下的介电函数曲线相对往低能区飘移,OsSi_2的介电峰减少且介电峰强度明显增强。     

Effect of Si addition on the precipitation of Al<Superscript>2</Superscript>Cu-phase in Al-Cu-Si thin films

The effects of Si addition and of deposition temperature on the precipitation processes of Al²Cu (θ) and Si particles in Al-Cu-Si alloy films were studied with in-situ hot stage transmission electron microscopy (TEM). Deposition of an Al-1.5Cu-1.5Si (wt%) film at 305∘C, in the three-phase, Al(α)-Al²Cu-Si region resulted in formation of fine, uniformly distributed spherical θ -phase particles due to the coprecipitation of the θ and Si phase particles during deposition. For deposition in the two-phase, Al(α)-Si region (435∘C), fine θ -phase particles precipitated during wafer cooldown, while coarse Si nodules formed at the sublayer interface during deposition. In-situ heat treatment of the film revealed that excess Si existed in a supersaturated Al matrix. Si addition decreased film susceptibility to corrosion induced by the θ -phase precipitates, since extensive Cu segregation can be reduced by coprecipitation at 305∘C and the Al matrix supersaturated with Si reduced galvanic action with respect to the θ -phase precipitate.     

A liquid phase anion-exchange approach to high-quality all-inorganic halide perovskite micro- and nanowires

All-inorganic halide perovskite nanowires (NWs) are promising materials due to they have broad application prospects in the field of optoelectronics, with mixed-halide perovskite nanowires can change the optoelectronic properties by adjusting the halide ratio. Here, we experimentally investigated the two-process governed anion-exchange reaction in single-crystalline CsPbX₃ micro- and nanowires. The critical parameters affecting the outcome of the reaction are identified as the reaction temperature, reaction time, and precursor concentrations. Upon examining the photoluminescence and morphology of the NWs, high-quality NWs were obtained by optimizing these critical parameters. The bandgap of the NWs can be tuned over the entire visible spectra (430–700 nm). In addition, photodetectors incorporating single NWs were fabricated, which demonstrated excellent responsivity under illumination. Our results expand the validity of liquid-phase anion exchange to the microscale, and lay the basis for liquid-processed optoelectronics and displays.

     

Optical properties of undoped and oxygen doped CuCl films on silicon substrates

Semiconductor photonic emitters operating in the UV range remain an elusive goal. Attention has focused mainly on III-Nitrides. However, a large lattice constant difference between the III-Nitride layers and the compatible substrates results in high densities of misfit dislocations and consequently the device performance is adversely affected. An alternative novel material system, γ-CuCl on silicon, is investigated. Properties of the exciton luminescence from vacuum deposited undoped and oxygen doped CuCl films on Si are studied using temperature dependent photoluminescence spectroscopy. Oxygen doping degrades the optical quality and introduces an intermediate state leading to negative thermal quenching behaviour.     

Atomic layer deposition of nanocrystallite arrays of copper(I) chloride for optoelectronic structures

Zinc blende structure γ-copper(I) chloride is a wide bandgap semiconductor with high exciton and biexciton binding energies. γ-CuCl has applications in UV-wavelength optoelectronic structures which can exploit these characteristics, such as 4-wave mixing and optical bistability. For these purposes, a controllable method of achieving thin films and nanocrystallite arrays is necessary. Atomic layer deposition (ALD) of nanocrystallites and thin films of γ-CuCl under restricted conditions has previously been demonstrated. This paper greatly extends the previous work and unequivocally confirms that ALD growth takes place over a range of deposition parameters, as characterised by growth saturation with increasing precursor dose, deposition rate independent of temperature and linear growth rate once a complete film has been formed. Arrays of nanocrystallites of different sizes can be controllably deposited by varying the number of ALD cycles within the initial nucleation region. In this region two distinct growth regimes have been observed depending on the length of the post-chloride precursor purge pulse. Long purge time results in retarded nucleation whereas short pulse time shows enhanced nucleation compared to a strictly linear process. The zinc blende γ-CuCl phase was confirmed with both X-ray analysis and also the signature excitonic Z_1,2 and Z₃ peaks in optical absorption, with no evidence of other impurities. This demonstrates that ALD is a suitable technique for the controllable deposition of thin films and arrays of nanocrystallites of CuCl which may facilitate the use of CuCl in thin film or nanocluster form for further exploration in optoelectronic and photonic applications.     

Up-conversion luminescence in Er/Yb-codoped PbTiO3 perovskite obtained via Pechini method

Efficient infrared-to-visible conversion by Er³⁺/Yb³⁺-codoped PbTiO₃ perovskite will be reported. The process is observed under 980 nm laser diode (GaAs:Si) excitation and results in the generation of green (∼555 nm) and red (∼655 nm) emission. The main mechanism that allows for up-conversion is attributed the energy transfer among Yb and Er ions in excited states. The power up-conversion efficiency for red emission is predominant in this material. The results illustrate the large potential of this new class of material for photonic applications involving optoelectronics devices.     

Influence of target to substrate distance on the sputtered CuCl film properties

CuCl is a potential candidate for UV optoelectronic devices due to its superior optical properties and lattice matching with Si. Stoichiometric CuCl thin films of polycrystalline nature were grown by RF magnetron sputtering technique. The effect of varying the target to substrate distance on the compositional, structural and optoelectronic properties of the sputtered films was analysed. A critical target to substrate distance (d_ts) was observed and the film properties were clearly different above and below this distance. Based on the film properties, the optimum spacing of d_ts = 6 cm was found to yield stoichiometric and high optical quality films. The existence of more than one chemical bonding state was identified in nonstoichiometric, chlorine rich, films by analysing the Cu 2p_3/2 core level XPS spectra. Chlorine rich samples were found to show a noticeable emission from deep levels at ∼ 515 nm in cathodoluminescence (CL) spectroscopy. An exciton mediated sharp UV luminescence (385 nm) emission was realized at room temperature in the stoichiometric CuCl thin films.     

Structural, dielectric, impedance and optical properties of CaBi2B2O7 glasses and glass-nanocrystal composites

Optically clear glasses were fabricated by quenching the melt of CaCO₃–Bi₂O₃–B₂O₃ (in equimolecular ratio). The amorphous and glassy characteristics of the as-quenched samples were confirmed via the X-ray powder diffraction (XRD) and differential scanning calorimetric (DSC) studies. These glasses were found to have high thermal stability parameter (S). The optical transmission studies carried out in the 200–2500 nm wavelength range confirmed both the as-quenched and heat-treated samples to be transparent between 400 nm and 2500 nm. The glass-plates that were heat-treated just above the glass transition temperature (723 K) for 6 h retained ≈60% transparency despite having nano-crystallites (≈50–100 nm) of CaBi₂B₂O₇ (CBBO) as confirmed by both the XRD and transmission electron microscopy (TEM) studies. The dielectric properties and impedance characteristics of the as-quenched and heat-treated (723 K/6 h) samples were studied as a function of frequency at different temperatures. Cole–Cole equation was employed to rationalize the impedance data.     

Solid-phase crystallization of β-FeSi2 thin film in Fe/Si structure

Dependence of solid-phase growth of β-FeSi₂ thin films on the crystal orientation of Si substrates has been investigated by using a-Fe (thickness: 20 nm)/c-Si(100), (110) and (111) stacked structures. X-ray diffraction (XRD) measurements suggested that the substrate orientation dependence of the formation rate of β-FeSi₂ was as follows: (100)>(111)>(110). This dependence can be explained on the basis of the lattice mismatch between β-FeSi₂ and Si substrates, i.e., the lattice mismatch between β-FeSi₂(100) and Si(100), β-FeSi₂(110) or (101) and Si(111), and β-FeSi₂(010) or (001) and Si(110) of 1.4-2.0%, 5.3-5.5% and 9.2%, respectively. The substrate orientation dependence of solid-phase growth becomes relatively remarkable for very thin films.     

Epitaxial growth of Fe3Si/CaF2/Fe3Si magnetic tunnel junction structures on CaF2/Si(111) by molecular beam epitaxy

The Fe₃Si(24 nm)/CaF₂(2 nm)/Fe₃Si(12 nm) magnetic tunnel junction (MTJ) structures were grown epitaxially on CaF₂/Si(111) by molecular beam epitaxy (MBE). The 12-nm-thick Fe₃Si underlayer was grown epitaxially on CaF_2/Si(111) at approximately 400 °C; however, the surface of the Fe₃Si film was very rough, and thus a lot of pinholes are considered to exist in the 2-nm-thick CaF₂ barrier layer. The average roughness (Ra) of the CaF₂ barrier layer was 7.8 nm. This problem was overcome by low-temperature deposition of Fe and Si at 80 °C on CaF₂/Si(111), followed by annealing at 250 °C for 30 min to form the Fe₃Si layer. The Ra roughness was significantly reduced down to approximately 0.26 nm. A hysteresis loop with coercive field H_c of approximately 25 Oe was obtained in the magnetic field dependence of Kerr rotation at room temperature (RT).     

2D Perovskite Sr2Nb3O10 for High-Performance UV Photodetectors

2D perovskites, due to their unique properties and reduced dimension, are promising candidates for future optoelectronic devices. However, the development of stable and nontoxic 2D wide-bandgap perovskites remains a challenge. 2D all-inorganic perovskite Sr₂Nb₃O₁₀ (SNO) nanosheets with thicknesses down to 1.8 nm are synthesized by liquid exfoliation, and for the first time, UV photodetectors (PDs) based on individual few-layer SNO sheets are investigated. The SNO sheet-based PDs exhibit excellent UV detecting performance (narrowband responsivity = 1214 A W⁻¹, external quantum efficiency = 5.6 × 10⁵%, detectivity = 1.4 × 10¹⁴ Jones @270 nm, 1 V bias), and fast response speed (t_rise ≈ 0.4 ms, t_decay ≈ 40 ms), outperforming most reported individual 2D sheet-based UV PDs. Furthermore, the carrier transport properties of SNO and the performance of SNO-based phototransistors are successfully controlled by gate voltage. More intriguingly, the photodetecting performance and carrier transport properties of SNO sheets are dependent on their thickness. In addition, flexible and transparent PDs with high mechanical stability are easily fabricated based on SNO nanosheet film. This work sheds light on the development of high-performance optoelectronics based on low-dimensional wide-bandgap perovskites in the future.     

Sintering mechanisms in YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7−<Emphasis Type="Italic">x</Emphasis></Subscript> superconducting ceramics

The densification of ceramic compacts of YBa₂Cu₃O_7−x (123) was studied with a vertical dilatometer. The runs effected under isothermal conditions (ISO) covered the 920–970^∘C range and were performed under static air atmosphere. Also, controlled heating rate (CHR) runs, from about 800 to 1050^∘C, were conducted at 5^∘C/min under either flowing oxygen or static air. The ISO data could be satisfactorily fitted by the solution-precipitation (SP) model giving an activation enthalpy of 221 kJ/mol. Furthermore, the CHR data for 920–970^∘C was also fitted with the same model giving 207 kJ/mol as the activation energy. From analysis of CHR data, the initial stage sintering is driven by solid state sintering between 827–894^∘C (823–908^∘C in O₂). Then, in the interval 902–920^∘C (914–934^∘C in O₂) the intermediate stage driven by grain growth (GG), competes with the rearrangement process associated to the presence of a liquid phase. This last process applied because the next sintering stage in the range 922–970^∘C (938–990^∘C in O₂ flow) could be fitted by the SP model with an activation enthalpy of 207 kJ/mol (229 kJ/mol in O₂). In the range 972–995^∘C (990–1014^∘C in O₂), the solid state (GG) intermediate stage mechanism and/or viscous flow competes with the SP process.     

Rib waveguides based on Zn-substituted LiNbO3 films grown by liquid phase epitaxy

The fabrication of epitaxially grown Zn-substituted LiNbO₃ (Zn:LiNbO₃) waveguide films and rib waveguides is reported and detailed investigations about microstructure, morphology and optical waveguide properties are provided. Zn:LiNbO₃ films were grown on congruent X-cut LiNbO₃ substrates by a modified liquid phase epitaxy in solid–liquid coexisting solutions. The homogeneously Zn-substituted films exhibit high crystalline perfection and extremely flat surfaces with averaged surface roughness of rms = 0.2–0.3 nm. At the film/substrate interface a Zn-containing transient layer has been observed, which allows the growth of elastically strained Zn:LiNbO₃ film lattices. X-ray diffraction reciprocal-space measurements prove the pseudomorphic film growth. The refractive index difference between substrate and film depends on the zinc substitution content, which increase with rising growth temperatures. For films with 5.3 mol% Zn (Δn_o ≈ +5 × 10⁻³) only ordinary ray propagation was observed, while for films with 7.5 mol% Zn (Δn_o ≈ +8 × 10⁻³, Δn_e ≈ +5 × 10⁻³) both modes, TM and TE propagate. Stress-induced refractive index changes are in the order of Δn ≈ 10⁻⁴. In rib waveguide microstructures singlemode propagation with nearly symmetrical field distribution has been observed. To demonstrate the potential of the proton exchange-assisted dry-etching technique interferometer microstructures were fabricated.     

Solid solutions of metastable tetragonal ZrO2 and Ce3ZrO8 in the system ZrO2-CeO2

In the system ZrO₂-CeO₂, metastable t-ZrO₂ solid solutions containing up to 30 mol% CeO₂ crystallize at temperatures of 385–430 °C from amorphous materials prepared by the hydrazine method. Crystalline Ce₃ZrO₈ solid solutions are formed in as-prepared powders between 30–75 mol % CeO₂. The variation of the lattice parameters of both solid solutions is determined as a function of CeO₂ content. The value of the lattice parameter of pure Ce₃ZrO₈ (cubic) is a = 0.5342 nm. Detailed characterization of the Ce₃ZrO₈ powder has been performed. Crystallite size and particle size are strongly dependent on the heating temperature. Specific surface areas do not drop below 40 m²g^–1 until the heating temperature is above 1000°C.     

Kinetic study of the reaction between copper(I) chloride and commercial silicon or silicides

The reaction of CuCl with silicon containing as impurities Al, Fe, Ca and Ti or with some silicides (Si₂Ca, Si₂Fe, Si₂Ti) has been investigated in the temperature range 250–310 °C. For the reaction between CuCl and commercial Si, it has been found that at 282 °C, the aluminium promotes the reaction between Cu₃Si and CuCl while its rate of consumption is greatly decreased by the presence of iron impurity. The combined action of these two impurities improves the quantity of the copper-silicon alloy formed. In the presence of silicides, the reaction with CuCl leads to copper formation with a high degree of dispersion.     

Structural and Optical Properties of Co-Doped ZnO Thin Films

Co-doped zinc oxide thin films (Zn_1–xCo_xO) have been deposited on c-plane sapphire substrates by dual-beam pulsed laser deposition. The films have lattice parameters similar to that of ZnO, and the lattice parameters are closely distributed. The films grew along a preferred direction, following the epitaxial relationship Zn_1–xCo_xO (0001)substrate (0001). Excitonic emission was suppressed at higher Co-dopant concentration in ZnO because of increase in the distortion of host lattice and defects. When more Zn is replaced by Co, more impurity levels are developed within the bandgap, and more defect are generated. Under our experimental conditions, the bandgap of the films tends to increase with increasing dopant concentration.     

Design and Synthesis of CdHgSe/HgS/CdZnS Core/Multi-Shell Quantum Dots Exhibiting High-Quantum-Yield Tissue-Penetrating Shortwave Infrared Luminescence

Cd_xHg_1−xSe/HgS/Cd_yZn_1−yS core/multi-shell quantum dots (QDs) exhibiting bright tissue-penetrating shortwave infrared (SWIR; 1000–1700 nm) photoluminescence (PL) are engineered. The new structure consists of a quasi-type-II Cd_xHg_1−xSe/HgS core/inner shell domain creating luminescent bandgap tunable across SWIR window and a wide-bandgap Cd_yZn_1−yS outer shell boosting the PL quantum yield (QY). This compositional sequence also facilitates uniform and coherent shell growth by minimizing interfacial lattice mismatches, resulting in high QYs in both organic (40–80%) and aqueous (20–70%) solvents with maximum QYs of 87 and 73%, respectively, which are comparable to those of brightest visible-to-near infrared QDs. Moreover, they maintain bright PL in a photocurable resin (QY 40%, peak wavelength ≈ 1300 nm), enabling the fabrication of SWIR-luminescent composites of diverse morphology and concentration. These composites are used to localize controlled amounts of SWIR QDs inside artificial (Intralipid) and porcine tissues and quantitatively evaluate the applicability as luminescent probes for deep-tissue imaging.     

Cathodoluminescence of CuCl Powder

The cathodoluminescence behavior of CuCl powder was studied in the temperature range 80–400 K. The cathodoluminescence spectrum of CuCl was found to contain bands peaked at 393.5, 700, 780, and 830 nm and to vary significantly with temperature. An anomalous temperature-induced shift of the Z ₃ exciton emission was revealed.     

Preferred orientation of AlN plates prepared by chemical vapour deposition of AlCl3 + NH3 system

Aluminium nitride (AlN) plates about 1 mm thick (maximum) were prepared by chemical vapour deposition (CVD) at the maximum deposition rate of 430 nm s⁻¹ using AlCl₃, NH₃ and H₂ gases at deposition temperatures,T _dep, of 873–1473 K. The effects of deposition conditions on the preferred orientation, morphology and micro-structure were investigated. WhenT _dep was less than 1073 K, the resulting CVD AlN plates contained some impurity chlorine and the aluminium content exceed the nitrogen content. WhenT _dep exceeded 1173 K, no chlorine was detected, and the Al/N atomic ratio matched the stoichiometric value. The lattice parameters (a=0.311 nm,c=0.4979 nm) and density (3.26×10³ kgm⁻³) were in agreement with values reported previously. The crystal planes oriented parallel to the substrates changed from (1 1 ˉ2 0) to (1 0 ˉ1 0) to (0001) with increasing total gas pressure (P _tot) and decreasingT _dep. This tendency is discussed thermodynamically and is explained by the change of supersaturation in the gas phase.     

Growth of n-type γ-CuCl with improved carrier concentration by pulsed DC sputtering: Structural, electronic and UV emission properties

γ Copper (I) chloride is naturally a direct band gap, zincblende and p-type semiconductor material with much potential in linear and non-linear optical applications owing to its large free excitonic binding energy. In order to fabricate an efficient electrically pumped emitter, a combination of both p-type and n-type semiconductor materials will be required. In this study, we report on the growth of n-type γ-CuCl with improved carrier concentration by pulsed DC magnetron sputtering of CuCl/Zn target. An improvement of carrier concentration up to an order of ~ 9.8 × 10¹⁸ cm^− 3, which is much higher than the previously reported (~ 10¹⁶ cm^− 3), has been achieved. An enhancement in crystallinity of CuCl along the (111) orientation and its consistency with the morphological studies have also been investigated as an effect of doping. Influence of Zn wt.% in the sputtering target on the Hall mobility and resistivity of the doped films is explored. The strong ultraviolet emission of doped films is confirmed using room temperature and low temperature photoluminescence studies.