Nonresonant and Resonant Nonlinear Absorption of CdSe-Based Nanoplatelets

We present a comprehensive understanding of the nonlinear absorption characteristics of CdSe-based nanoplatelets(NPLs) synthesized by the solution-phase method and the colloidal atomic layer deposition approach through Z-scan techniques at 532 nm with picosecond pulses. The CdSe NPLs exhibit strong two-photon induced free carrier absorption(effective three-photon absorption) upon the nonresonant excitation, resulting in a remarkable optical limiting behavior with the limiting threshold of approximately 75 GW/cm~2. A nonlinear optical switching from saturable absorption(SA) to reverse saturable absorption(RSA) with increasing the laser intensity is observed when coating CdSe NPLs with a monolayer of CdS shell to realize the resonant absorption. The SA behavior originates from the ground state bleaching and the RSA behavior is attributed to the free carrier absorption.These findings explicitly demonstrate the potential applications of CdSe-based NPLs in nonlinear optoelectronics such as optical limiting devices, optical pulse compressors and optical switching devices.     

Doping and Surface Modification of Carbon Quantum Dots for Enhanced Functionalities and Related Applications

Carbon quantum dots (CQDs) are a unique class of 0D nanomaterials, featured by a graphitic core and shell layers saturated with hydrogen atoms and functional groups. CQDs are prepared through top-down and bottom-up strategies from natural and synthetic precursors. CQDs can be modified through chemical (e.g., surface functionalization/passivation, doping, etc.) and physical (e.g., core–shell architecture, composite material blending, etc.) strategies to control their properties. This review highlights the effect of such modifications on the photophysical properties of CQDs, such as photoluminescence (PL), absorbance, and relaxivity. The dependence of PL upon the size, orientation at the edges, surface and edge functionalization, doping, excitation wavelength, concentration, pH, aggregate formation, etc., are summarized along with the supporting theoretical evidence available in the literature. Also, this review outlines the recent advancements, and future prospective of optical (e.g., sensing, bioimaging, and fluorescent ink) and catalytic applications (e.g., photocatalysis and electrocatalysis) of CQDs enhanced through physical and chemical modifications of their structure and composition.     

表面配体和器件结构对PbS胶体量子点电池性能的影响

利用吸收光谱、傅里叶变换红外光谱和循环伏安等表征技术,分析了利用四丁基碘化铵(TBAI)和1,2-乙二硫醇(EDT)配体钝化处理的PbS胶体量子点的光学性质、表面化学及其能级结构,并在此基础上分别以PbS-TBAI薄膜、PbS-EDT薄膜和PbS-TBAI/PbS-EDT薄膜作为有源层制备了PbS胶体量子点/Zn O纳米粒子异质结太阳能电池,以比较研究表面配体和器件结构对器件光伏性能及其稳定性的影响。结果表明,TBAI和EDT均能与PbS胶体量子点表面原有的油酸配体实现良好置换,但是配体置换之后量子点表面均残留少量油酸分子; PbS-TBAI薄膜的导带底为-5.12 eV,价带顶为-3. 86 eV,而PbS-EDT薄膜的导带底为-4. 99 eV,价带顶为-3. 74 eV,后者相对前者出现了明显的能带上移; PbS-TBAI/PbS-EDT双配体器件的光伏性能最优,能量转化效率达到4. 43%;随着空气暴露时间的增加,PbS-TBAI/PbS-EDT双配体器件和PbS-TBAI单配体器件表现出相似的性能变化趋势,于3 d后达到最优光伏性能,而PbS-EDT单配体器件的空气稳定性差,3 d后的能量转换效率下降至初始效率的1/4。本工作的研究结果将不仅有助于加深对PbS胶体量子点电池性能变化规律的认识,而且有望促进该类电池制备技术的进一步优化。     

碳纳米管/二硒化钼有机玻璃的非线性吸收、非线性散射和光限幅特性

MoSe₂的禁带宽度较窄（1.1–1.5 eV）,且具有可调谐的激子光电效应,这样使其在光致发光、光电晶体管、太阳能电池和光学非线性等方面具有潜在的应用价值.然而,纯的MoSe₂的光生电子空穴复合率较高,限制了其在某些光学领域中的应用.通过设计MoSe₂的复合材料,可以降低材料的光生电子空穴复合率,从而扩展其应用领域.首先,通过热溶剂法合成CNT/MoSe₂复合材料;然后,通过浇铸法将其分散在甲基丙烯酸甲酯（MMA）中制备成有机玻璃,其中MMA会聚合成聚甲基丙烯酸甲酯（PMMA）,并利用改进的Z-扫描技术首次对CNT/MoSe₂/PMMA有机玻璃的非线性吸收、非线性散射和光限幅特性进行了研究.研究表明,随着输入能量的变化,通过调节输入能量,CNT/MoSe₂/PMMA有机玻璃表现出饱和吸收（SA）和从SA到反饱和吸收的转变.结合材料特性及应用条件要求,可以得到CNT/MoSe₂/PMMA有机玻璃在光学设备,如光学限制器和锁模/调Q激光器等方向具有较好的应用前景.     

Effects of solvent on nonlinear absorption properties of tetraphenylporphyrin compounds in the nanosecond regime

The nonlinear absorption properties of tetraphenylporphyrins (TPP) in different solvents and excitation intensities are investigated with nanosecond pulses by the Z-scan technique. The nonlinear absorption behaviour observed presents a distinct difference between in solvent mixtures and in pure solvents. A crossover from reverse saturable absorption (RSA) to saturable absorption (SA) and then again to RSA is observed with the increases of excitation intensity in chloroform and pyridine mixed solvents. However, porphyrin molecules in pure solvents show good RSA behaviour under the studied intensity range, no saturation absorption is observed with nanosecond excitation. Excited state absorption parameters and two-photon absorption coefficients are obtained by theoretical fit using rate equations for population densities in a seven-level energy scheme.     

GaN晶体在飞秒紫外波段激发下的可变非线性吸收效应和光动力学过程研究

采用Z扫描和泵浦-探测技术研究了GaN薄膜在370 nm时的非线性光学效应和非线性光动力学过程。首先,基于GaN薄膜的透射光谱,结合线性光学理论分析得到了其在370 nm的线性折射率n₀、线性吸收系数α₀、光学带隙E_g等线性光学性质。采用飞秒激光Z扫描技术,得到了不同光强激发下的Z扫描实验响应结果,结合非线性光学理论提取出GaN薄膜可变的光学非线性吸收效应。在激发光子能量接近GaN带隙情况下,低光强时材料表现为饱和吸收而高光强时为反饱和吸收,这是因为低光强下单光子吸收占主导而高光强下以单光子感应自由载流子吸收为主。闭孔Z扫描测量得到了GaN薄膜的三阶非线性折射系数为n₂=-(1.0±0.1)×10-3 cm2·GW-1,它几乎比传统非线性介质的高出一个数量级。为了探究上述非线性过程的动力学弛豫时间以及进一步探究GaN薄膜非线性光动力学过程的深层物理机制,采用了交叉偏振飞秒退相泵浦探测技术观察GaN薄膜的光激发载流子动力学弛豫过程。实验结果表明,在低光强下,饱和吸收效应来源于瞬态单光子吸收,高光强下单光子感应自由载流子吸收为非瞬态光动力学过程,其自由载流子弛豫时间约为17 ps。该工作将为GaN薄膜在紫外非线性纳米器件应用以及GaN薄膜非线性过程的机制分析理解提供新的思路。     

CdSe/CdS核/壳型纳米晶的光谱特性

以巯基乙酸为稳定剂制备了CdSe/CdS核／壳型纳米晶。用光吸收谱（Abs)、光致发光谱（PL）及光致发光激发谱（PLE）研究了CdS壳层对CdSe纳米晶电子结构，从而对其吸收和发光性能的影响。根据PL和PLE的结果以及带边激子精细结构的计算结果，我们用尺寸很小的纳米晶中所形成的基激缔合物解释了PL光谱与吸收边之间较大的Stokes位移。     

Fabrication and optical properties of 3D composite photonic crystals of core-shell structures

Three-dimensional (3D) composite colloidal photonic crystals with SiO₂ core and ZnO shell were fabricated on borosilicate glass (BSG) substrate by a two-stage deposition method. Scanning electron microscopy (SEM) measurements show that both the pre-deposited SiO₂ and SiO₂/ZnO core-shell structures are oriented with their (1 1 1) axes parallel to the substrates. Optical measurement reveals that the periodic arrays exhibit a photonic band gap in the (1 1 1) direction. The optical properties of SiO₂/ZnO core-shell structures strongly depend on the size dispersions of colloidal spheres and the intrinsic defects in the sample.     

Study of absorption spectrum and dynamics evaluation of the indocyanine‐green first singlet excited state

Excited state absorption and excited state dynamics of indocyanine‐green (ICG) dissolved in dymethyl sulfoxide were measured using white‐light continuum Z‐scan (WLCZScan) and white‐light continuum pump–probe (WLCPP) techniques. The excited state absorption spectrum, obtained through Z‐scan measurements, revealed saturable absorption (SA) for wavelengths longer than 630 nm, while reverse saturable absorption (RSA) appeared, as indicated by a band at approximately 570 nm. Both processes were modeled by a three‐energy‐level diagram, from which the excited state cross‐section values were determined. SA and RSA were also observed in pump–probe experiments, with a recovery time in the hundreds of picoseconds time scale due to the long lifetime of the first excited state of ICG. Such results contribute to the understanding of ICG optical properties, allowing application in photonics and medicine. Copyright © 2010 John Wiley & Sons, Ltd.     

Design and optimisation of multimode 1D photonic band gap waveguide

The modal characteristics of planar waveguides with photonic band gap guiding properties are studied. It is demonstrated that a slight deviation from the periodicity in the photonic band gap multilayers can result in multimode transmission within the guiding layer. Possible applications of the results for avoiding single mode regime destruction due to fabrication process imperfection, as well as for designing such waveguides for conventional and emerging new applications of multimode photonic devices, are pointed out.     

Design and optimisation of multimode 1d photonic band gap waveguide

The modal characteristics of planar waveguides with photonic band gap guiding properties are studied. It is demonstrated that a slight deviation from the periodicity in the photonic band gap multilayers can result in multimode transmission within the guiding layer. Possible applications of the results for avoiding single mode regime destruction due to fabrication process imperfection, as well as for designing such waveguides for conventional and emerging new applications of multimode photonic devices, are pointed out.     

Nanostructural effects on optical properties of tungsten inverse opal

Tungsten (W) photonic crystals are very attractive because of their potential applications in the conventional lighting field. In this work we show that W nanostructures have dominative effects on optical properties of W inverse opal. The nanoparticle structure of W phase can cause intensive optical absorption and breakdown of the photonic band gap; on the contrary, W inverse opal made from bulk and compact W phase would have weak absorption and possess a good photonic band gap. The results will throw a new light on the study and application of W photonic crystals and development of other photonic crystal and black-body materials. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

Temperature–Light Dual‐Responsive Au@PNIPAm Core‐Shell Microgel‐Based Optical Devices

Au nanoparticle (AuNP) core particles coated with a poly(N‐isopropylacrylamide) (pNIPAm) shell (Au@pNIPAm) are synthesized by seed mediated free radical polymerization. Subsequently, a temperature–light‐responsive photonic device is fabricated by sandwiching the Au@pNIPAm particles between two thin layers of Au. The optical device exhibits visual color and characteristic multipeak reflectance spectra, where peak position is primarily determined by the distance between two Au layers. Dual responsivities of the photonic device are achieved by combining the photothermal effect of AuNPs core (localized surface plasmon resonance (LSPR) effect) and the temperature responsivity of the pNIPAm shell. That is, the pNIPAm shell collapses as the temperature is increased above pNIPAm's lower critical solution temperature, either by direct heat input or heat generated by AuNPs' LSPR effect. To investigate the effect of AuNPs distribution in the microgels on the devices' photothermal responsivity, the Au@pNIPAm microgel‐based etalon devices are compared with that fabricated by AuNP‐doped pNIPAm‐based microgels; in terms of response kinetics and optical spectrum homogeneity. The uniform Au@pNIPAm microgel‐based devices show a fast response and exhibit a comparatively homogeneous spectrum over the whole slide. These materials can potentially find use in drug delivery systems, active optics, and soft robotics.     

EXCITED-STATE NONLINEAR ABSORPTION AND ITS APPLICATION IN PHOTONIC TECHNOLOGY

The main achievements in our research on the physical phenomena of the excited-state nonlinear absorption in a molecular system and its applications in photonic technology are described. In the first part of this paper, some energy-level models and rate-equations are used to explain various mechanisms of the excited-state nonlinear absorption under differ-ent conditions, such as reverse saturable absorption caused by the triplet and/or the singlet excited-state absorption; saturable absorption due to the first and/or the second singlet excited-state absorption; and the excited-state nonlinear absorption induced by two-photon absorption. The experimental results for metal-organic and C₆₀ materials irradiated by ps and ns laser pulses are consistent with the simulated curves of the transmittance versus flu-ences. In the second part, the applications of excited-state nonlinear absorption in photonic techniques including optical bistability, optical switching, optical limiting, optical modula-tion, optical logic and optical storage are introduced. The working principles of the photonic devices based on the excited-state nonlinear absorption are presented. The experimental characteristic curves are found in good agreement with the theoretical simulations for these devices.     

Band gap characteristics of plasma with periodically varying external magnetic field

The reflectance characteristics of a one-dimensional periodically magnetized plasma structure is studied by using the transfer matrix method. It is found that this system has the band gap characteristics of photonic crystals, so we also name it a plasma photonic crystal. The results show that the gap location and gap width can be controlled by the incident angle. If the external magnetic field is small, the gap location and gap width change significantly with incident angle, while they change only slightly when the external magnetic field is sufficiently large. The collision frequency has little effect on the gap location and gap width while it makes the amplitude of reflectance and transmission decrease. This new type of plasma photonic crystal could have potential applications in designing tunable photonic crystal devices.     

基于光子晶体异质结构的磁可调石墨烯多带吸收

石墨烯在光电子学领域具有广泛应用,但石墨烯的吸收率较低限制了其在某些方面的应用。为了改善单层石墨烯的吸收特性,在前人研究的基础上,设计了石墨烯和光子晶体异质结构构成的复合结构。利用4×4传输矩阵法研究了外磁场、费米能量和设计波长等参数对石墨烯吸收特性的影响。结果表明,所设计的光学结构使石墨烯既保持了原有的宽吸收带,还增加了数目可调的窄吸收带。由于考虑到磁光效应,石墨烯的吸收特性表现出一定的磁圆二色性。对于各吸收带,通常情况下左旋圆偏振光的吸收率要大于右旋圆偏振光的吸收率。但调节外磁场和费米能量,可使各吸收带具有99%以上的吸收,在一定的条件下,还可实现近完美的100%吸收。研究结果为光电子学领域中基于石墨烯的相关器件的设计提供了参考。     

Modification of the spontaneous emission of quantum dots near the surface of a three-dimensional colloidal photonic crystal

This paper demonstrates experimentally and numerically that a significant modification of spontaneous emission rate can be achieved near the surface of a three-dimensional photonic crystal.In experiments,semiconductor core-shell quantum dots are intentionally confined in a thin polymer film on which a three-dimensional colloidal photonic crystal is fabricated.The spontaneous emission rate of quantum dots is characterised by conventional and time-resolved photoluminescence (PL) measurements.The modification of the spontaneous emission rate,which is reflected in the change of spectral shape and PL lifetime,is clearly observed.While an obvious increase in the PL lifetime is found at most wavelengths in the band gap,a significant reduction in the PL lifetime by one order of magnitude is observed at the short-wavelength band edge.Numerical simulation reveals a periodic modulation of spontaneous emission rate with decreasing modulation strength when an emitter is moved away from the surface of the photonic crystal.It is supported by the fact that the modification of spontaneous emission rate is not pronounced for quantum dots distributed in a thick polymer film where both enhancement and suppression are present simultaneously.This finding provides a simple and effective way for improving the performance of light emitting devices.     

Analysis of two-dimensional photonic band gap structure with a rhombus lattice

The relative band gap for a rhombus lattice photonic crystal is studied by plane wave expansion method and high frequency structure simulator (HFSS) simulation. General wave vectors in the first Briliouin zone are derived. The relative band gap as a function of air-filling factor and background material is investigated, respectively, and the nature of photonic band gap for different lattice angles is analyzed by the distribution of electric energy. These results would provide theoretical instruction for designing optical integrated devices using photonic crystal with a rhombus lattice.     

光子晶体传输特性的时域精细积分法分析

将精细积分法应用于时域有限差分法中,提出了一种求解光子晶体传输特性的时域精细积分法,并对其计算精度及稳定性进行了分析.从一阶麦克斯韦方程出发,在空间上采用Yee元胞进行差分离散,结合吸收边界条件及激励源表达式将方程整理为标准的一阶常微分方程组形式.通过时间步长的精细划分和指数矩阵的加法定理,在时间上利用精细积分法对齐次微分方程进行积分求解,并结合激励向量的特解得到空间离散的场分量,最终通过傅里叶变换求得方程的解.利用时域精细积分法对光子晶体进行了实例计算,并将其结果分别与时域有限差分法和四阶龙格库塔法在精度、稳定性等方面进行了比较,结果表明时域精细积分法具有更高的计算精度,并且克服了时域有限差分法以及四阶龙格库塔法在计算稳定性上对时间步长的限制.提出的方法具有精确、稳定的特点,为光子晶体传输特性的研究提供了一种新的有效的分析方法.     

ZnCuInS/ZnS量子点光致发光温度依赖性研究

ZnCuInS/ZnS量子点是一种无重金属"绿色"半导体纳米材料。制备出了直径为2.9nm的ZnCuInS/ZnS核壳量子点。从ZnCuInS/ZnS量子点的吸收及光致发光光谱中可以看到,量子点的斯托克斯位移为410meV。这样大的斯托克斯位移表明,ZnCuInS/ZnS量子点的复合机制与缺陷能级有关。研究并计算了在辐射及非辐射驰豫过程的(Huang-Rhys)因子及平均声子能量。结果表明在50~373K范围内,能量带隙的变化以及光致发光光谱的增宽是分别由光从能带边缘向缺陷能级跃迁及载流子声子耦合导致的。