Suppressed Lattice Disorder for Large Emission Enhancement and Structural Robustness in Hybrid Lead Iodide Perovskite Discovered by High-Pressure Isotope Effect

The soft nature of organic–inorganic halide perovskites renders their lattice particularly tunable to external stimuli such as pressure, undoubtedly offering an effective way to modify their structure for extraordinary optoelectronic properties. Here, using the methylammonium lead iodide as a representative exploratory platform, it is observed that the pressure-driven lattice disorder can be significantly suppressed via hydrogen isotope effect, which is crucial for better optical and mechanical properties previously unattainable. By a comprehensive in situ neutron/synchrotron-based analysis and optical characterizations, a remarkable photoluminescence (PL) enhancement by threefold is convinced in deuterated CD₃ND₃PbI₃, which also shows much greater structural robustness with retainable PL after high peak-pressure compression–decompression cycle. With the first-principles calculations, an atomic level understanding of the strong correlation among the organic sublattice and lead iodide octahedral framework and structural photonics is proposed, where the less dynamic CD₃ND₃⁺ cations are vital to maintain the long-range crystalline order through steric and Coulombic interactions. These results also show that CD₃ND₃PbI₃-based solar cell has comparable photovoltaic performance as CH₃NH₃PbI₃-based device but exhibits considerably slower degradation behavior, thus representing a paradigm by suggesting isotope-functionalized perovskite materials for better materials-by-design and more stable photovoltaic application.     

Probing the effect of R-cation radii on structural,vibrational, optical,and dielectric properties of rare earth (R=La,Pr, Nd) aluminates

The present study correlates the effect of R-cation radii on structural, vibrational, optical, and dielectric properties of rhombohedral rare earth aluminates RAlO₃ (R = La, Pr, Nd). The polycrystalline samples of RAlO₃ have been synthesized using sol-gel synthesis technique. Pure rhombohedral phase of RAlO₃ samples has been confirmed with X-ray diffraction. Systematic decrements in the lattice parameter, bond length, and bond angle have been observed, giving rise to structural distortion due to decrease in ionic radii of R-cation. The phononic properties of RAlO₃ have been investigated through Raman spectroscopy, where the degree of distortion of AlO₆ octahedra can be analyzed with the peak position of E_g and A_1g modes. An increase in the energy bandgap with decreasing R-cation radii shows an interconnection with the decrease in Al–O bond length. Interestingly, the decreasing dielectric constant with decreasing ionic radii of R-cation has been correlated with the difference in electronegativity of cation(R³⁺)-anion(O^2?) pair. Also, a positive linear relationship between dielectric constant and energy bandgap has been investigated using Penn model.     

Halogenation effect promoted low bandgap polymers based on asymmetric isoindigo unit with low energy loss

To optimize the energy levels of the structural framework of isoindigo polymers, a series of asymmetric isoindigo based low bandgap polymers with chlorine, fluorine and thiazole substituents was constructed and their optical, electrochemical and photovoltaic properties were comparatively evaluated for the impact of different substitutions. In comparison with the polymer based on 2,2'‐bithiophene and isoindigo unit (PTi) with non‐substituted bithiophene as the donor moiety, the highest occupied molecular orbital energy level for the newly synthesized polymers is significantly decreased, and in turn an improvement of the open‐circuit voltage (V_OC) is noted in the corresponding photovoltaic devices. More importantly, combined with a low bandgap of 1.32 eV, the energy losses (E_loss) could be reduced to 0.61 eV for polymer based on chlorinated 2,2'‐bithiophene and isoindigo unit (PCl). In addition, the halogen moieties are observed to be superior in device fabrication and give better values than the thiazole substituent. Both fluorinated and chlorinated polymer donors exhibited improved performance compared with the original polymer PTi. Consequently, this work not only presents the influence of different electron withdrawing substituents on the physicochemical and photovoltaic performance, but also backs the concept of how to reduce the energy loss via the heteroatom effect. © 2020 Society of Chemical Industry     

Constraint effect caused by graphene on in situ grown Gr@WO3 -nanobrick hybrid material

This work reported the abnormal constraint effect of graphene on the structural and optical properties of in situ grown Gr@WO₃ nanobrick (NB) hybrid nanomaterials. Stable hybrid Gr@WO₃ nanomaterials were synthesized through a one-step hydrothermal method, in which different graphene contents (0.1, 0.3 and 0.5 wt%) were directly introduced into the precursor solution of tungsten oxide. The existence of graphene in the nucleation phase of tungsten oxide NB decreased the crystallite size from 49.5 nm to 45.3 nm, increased the microstrain from 1.10% to 1.44% and the optical bandgap of the hybrid samples from 2.68 eV to 2.78 eV, and reduced the radiative recombination efficiency of tungsten oxide NB. The hybridization between graphene and tungsten oxide NBs was confirmed by X-ray diffraction and Raman scattering analysis. The optical properties of materials were studied based on the absorbance and diffuse reflectance spectra. In this work, we also proposed a reliable method to estimate the optical bandgap of the sample from the diffuse reflectance spectrum. These findings would introduce an alternative method of fabrication and enhance the understanding of in situ hybrid materials.     

Structural,electrical, optical and dielectric properties of yttrium substituted cadmium ferrites prepared by Co-Precipitation method

The yttrium substituted cadmium ferrites having composition Cd_1-xY_xFe₂O₄ (X = 0.00, 0.125, 0.250, 0.375, 0.500) were synthesized by the co-precipitation method and sintered at 1100 °C for 6 h. Structural, morphological, electrical, optical and dielectric characteristics were explored by XRD, SEM, EDS, FTIR, I–V two probes, UV–Vis and LCR techniques.XRD results confirmed the cubic structure of spinel ferrites. A decrease in lattice constants of the prepared samples was observed with the substitution of Y ions and was attributed to the difference in ionic radii of Y³⁺ (0.95 Å) and Cd²⁺ (0.97 Å) ions. Cationic distributions, ionic radii of both tetrahedral and octahedral sites, tolerance factor, oxygen positional parameters, bond lengths, interatomic distances, positional parameters and bond length angles were calculated from XRD data. The morphology of the prepared ferrites was studied using SEM and results ratified the XRD results. EDS confirmed the presence of all inserted elements in Cd_1-xY_xFe₂O₄ composition. DC resistivity and drift mobility of soft-ferrites were found to be increased from 1.047 × 10⁸–4.822 × 10¹⁰ Ω-cm and 5.87 × 10⁻¹² – 1.045 × 10⁻¹⁴ cm²V⁻¹s⁻¹, respectively, at 523 K with yttrium content confirming the behavior of semiconductor materials. The optical band gap energy calculated from the UV–Vis pattern of the Cd_1-xY_xFe₂O₄ system was decreased from 3.6011 to 2.8153 eV. DC resistivity and optical band gaps exposed inverse relation. FTIR results revealed lower and upper-frequency absorption bands in the ranges of 419.31–417.01 cm⁻¹ and 540.95–565.70 cm⁻¹, respectively. Dielectric constant and dielectric losses were in decreasing order, while ac conductivity revealed rising behavior with increasing frequency. Results showed the potential of yttrium doped Cd nanoferrites for applications in high-frequency microwave absorbing devices.     

B2O3-K2O-Sb2O3系统玻璃的光学折射率及带隙

高折射率和非线性光学玻璃可以用于高速光开关、光学存储器、新型光纤和光学运算元件等，其研究受到各国科技工作者的高度重视，本文采用熔融淬冷法制备了组成为(85-x)B₂O₃-15K₂O-xSb₂O₃(x=70, 75, 80, 85)的4组玻璃，测试了玻璃样品的密度、折射率、热学性能、拉曼光谱和吸收光谱，利用玻璃样品的吸收光谱计算了其直接允许光学带隙、间接允许光学带隙及Urbach能量。结果表明：随着Sb₂O₃含量的增加，玻璃样品的密度从4.445g/cm³逐渐增加到4.767g/cm³，折射率从1.9438增加到2.0058，玻璃转变温度从291℃降低到260℃，玻璃析晶温度从463℃降低到370℃，直接光学带隙从3.2775eV降低到3.1379eV，间接光学带隙从3.1444eV降低到3.0256eV，Urbach能量从0.137eV逐渐减小到0.107eV。说明Sb₂O₃-K₂O-B₂O₃系统玻璃可以作为新型的非线性光学玻璃候选材料之一。     

Ga掺杂ZnO薄膜的MOCVD生长及其特性

利用低压MOCVD技术在(0002)蓝宝石上外延获得高质量的ZnO∶Ga单晶薄膜,并研究了Ga的不同掺杂浓度对材料电学和光学特性的影响．当Ga/Zn气相摩尔比为3.2 at%时,ZnO(0002)峰半高宽仅为0.26°,载流子浓度高达2.47e19cm－3,透射率高于90%;当载流子浓度升高时,吸收边出现明显的Burstein-Moss蓝移效应．同时室温光致发光谱显示,紫外峰位随载流子浓度的增加而发生红移,峰形展宽,这和Ga高掺杂所引起的能带重整化效应有关．当Ga/Zn比达到6.3 at%时,由于高掺杂浓度下Ga的自补偿效应导致载流子浓度下降．     

UHV-CVD生长的SiGe多量子阱在热光电池领域的应用

为了验证SiGe多量子阱的能带向直接带隙结构转变[1]和进一步探索其在热光电池领域的应用,采用先进的超高真空化学气相沉积系统生长出高质量的SiGe多量子阱外延层,并对其进行多次反射红外线吸收谱的测量.测量结果说明吸收峰接近黑体辐射峰1450nm波长,跃迁几率有所增加,这将大幅度提高热光电池的吸收效率,同时也为SiGe多量子阱中量子效应的存在提供了实验依据.     

柱形光子晶体波导中偏振光的传输模式和禁带特征

利用光波在一维有限周期柱型光子晶体波导中径向受限的条件,推导出TE波和TM波2种偏振光在一维有限周期柱型光子晶体波导中各个传输模式满足的关系式。研究了各个传输模式的特征,计算出TE波和TM波传输各模式的禁带随周期数、模式量子数、圆柱半径以及入射角的变化规律,得出了一维有限周期柱型光子晶体波导中TE波和TM波各传输模式带隙的结构。