Photoluminescence

光致发光
  • 文章类型: Journal Article
    有机硅酸盐玻璃(OSG)薄膜是现代电子器件中的重要组成部分,它们的电性能在器件性能中起着至关重要的作用。这篇全面的综述系统地研究了化学成分的影响,真空紫外线(VUV)照射,和等离子体处理对这些薄膜的电性能。通过对文献和实验结果的广泛调查,我们阐明了这些因素之间复杂的相互作用,以及由此产生的电导率变化,介电常数,OSG薄膜的击穿强度。主要关注领域包括掺入二氧化硅基质中的各种有机部分的影响,VUV辐照对薄膜性能的影响,以及各种等离子体处理技术引起的修饰。此外,讨论了控制这些现象的潜在机制,在不同环境条件下OSG薄膜中发生的复杂分子相互作用和结构重排的发光。表明,与先前报道的Fowler-Nordheim机制相比,相邻中性陷阱之间的声子辅助电子隧穿可以更准确地描述OSG低k材料中的电荷传输。此外,低k材料的质量显着影响泄漏电流的行为。在孔壁上保留残留致孔剂或吸附水的材料显示出与孔表面积和孔隙率直接相关的电导率。相反,无致孔剂材料,由Urbanowicz开发,表现出与孔隙率无关的泄漏电流。这强调了在理解这些材料的电特性时考虑内部缺陷(例如缺氧中心(ODC)或类似实体)的关键重要性。
    Organosilicate glass (OSG) films are a critical component in modern electronic devices, with their electrical properties playing a crucial role in device performance. This comprehensive review systematically examines the influence of chemical composition, vacuum ultraviolet (VUV) irradiation, and plasma treatment on the electrical properties of these films. Through an extensive survey of literature and experimental findings, we elucidate the intricate interplay between these factors and the resulting alterations in electrical conductivity, dielectric constant, and breakdown strength of OSG films. Key focus areas include the impact of diverse organic moieties incorporated into the silica matrix, the effects of VUV irradiation on film properties, and the modifications induced by various plasma treatment techniques. Furthermore, the underlying mechanisms governing these phenomena are discussed, shedding light on the complex molecular interactions and structural rearrangements occurring within OSG films under different environmental conditions. It is shown that phonon-assisted electron tunneling between adjacent neutral traps provides a more accurate description of charge transport in OSG low-k materials compared to the previously reported Fowler-Nordheim mechanism. Additionally, the quality of low-k materials significantly influences the behavior of leakage currents. Materials retaining residual porogens or adsorbed water on pore walls show electrical conductivity directly correlated with pore surface area and porosity. Conversely, porogen-free materials, developed by Urbanowicz, exhibit leakage currents that are independent of porosity. This underscores the critical importance of considering internal defects such as oxygen-deficient centers (ODC) or similar entities in understanding the electrical properties of these materials.
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  • 文章类型: Journal Article
    量子棱镜,一个新的结构,由许多量子线组成,其直径从底部到顶部逐渐减小,是我们研究的重点。量子线的这种分布导致色散发射光谱。光谱的红色边缘由体半导体的带隙宽度决定,蓝色边缘由棱镜顶部激子的量子大小决定。硅棱镜样品的PL光谱被弱和强光吸收激发。在弱吸收(hνex=1.2eV)时,PL光谱位于光谱的可见部分,从1.4eV到1.9eV,具有比Si晶体的带隙更高的能量。PL光谱的这种“蓝移”0.7eV是量子限制效应的特征。它是具有光学上转换的彩虹光谱。量子棱镜是一种新型的纳米光源,因为它取代了传统光谱仪中的两个元件:光源和色散元件。这些特征使得能够创建用于测量单个分子或病毒的吸收光谱的纳米光谱仪。
    A quantum prism, a new structure, consisting of many quantum wires with a diameter that gradually decreases from the base to the top, is the focus of our research. This distribution of quantum wires leads to a dispersive emitted spectrum. The red edge of the spectrum is determined by the band gap width of the bulk semiconductor, and the blue edge is determined by the quantum size of the excitons at the top of the prism. The PL spectrum of the silicon prismatic sample was excited by weak and strong light absorption. At weak absorption (hνex = 1.2 eV), the PL spectrum is located in the visible part of the spectrum, from 1.4 eV to 1.9 eV, with an energy higher than the band gap of the Si crystal. Such a \"blue shift\" of PL spectra by 0.7 eV is characteristic of the quantum confinement effect. It is a rainbow spectrum with an optical upconversion. The quantum prism is a new type of nano light source, as it replaces two elements in a conventional spectrometer: a light source and a dispersive element. These features enable to create a nano-spectrometer for measuring the absorption spectrum of individual molecules or viruses.
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  • 文章类型: Journal Article
    在这项研究中,开发了全芳香族聚醚砜,轴承蓝色,黄色,和橙红色π共轭半导体单元。卡巴唑-,蒽醌-,和苯并噻二唑基荧光团与二苯基砜部分共聚。另外使用了二苯基吡啶共聚单体,充当增溶单元和弱蓝色荧光基团。利用这个原理,高分子量的荧光聚芳醚,高达70kDa,被开发,显示成膜能力和高热稳定性,在普通有机物中保持优异的溶解性,非易失,和非氯化溶剂。通过共聚单体类型和比例的细微变化来实现发射颜色的微调。在可见光谱的蓝色或黄色区域发射的单发色团共聚物,而带有双发色团的三元共聚物在整个可见光谱中发射,导致白光发射。在环境条件下20wt%的极性非质子溶剂溶液允许荧光共聚醚的沉积和从非氯化溶剂印刷。评估所有聚醚的结构和光电性能,和选定的共聚物被成功地用于有机发光二极管(OLED)器件的发光层(EML),使用刚性或柔性基板。对于高达15V的偏置电压,在所有情况下都显示出显著的颜色稳定性。制造设备的国际委员会(CIE)位于蓝色(0.16,0.16),黄色(0.44,0.50),或可见光谱的白色区域(0.33,0.38),根据共聚单体的比例变化最小。本文开发的用于聚合物发光二极管(PLED)的半导体聚醚砜的通用方法导致了高达25g高分子量单批的发光聚合物的大规模生产,证明了这种方法的有效性,作为一种简单的工具,以促进大面积PLED覆盖的灵活和可印刷的EML的合成。
    In this study, fully aromatic polyether sulfones were developed, bearing blue, yellow, and orange-red π-conjugated semiconducting units. Carbazole-, anthracene-, and benzothiadiazole-based fluorophores are copolymerized with a diphenylsulfone moiety. A diphenylpyridine comonomer was additionally utilized, acting as both a solubilizing unit and a weak blue fluorescent group. Using this rationale, fluorescent polyarylethers with high molecular weights, up to 70 kDa, were developed, showing film formation ability and high thermal stability, while preserving excellent solubility in common organic, nonvolatile, and nonchlorinated solvents. Fine-tuning of the emission color was achieved through subtle changes of the comonomers\' type and ratio. Single-chromophore-bearing copolymers emitted in the blue or the yellow region of the visible spectrum, while the dual-chromophore-bearing terpolymers emitted throughout the visible spectrum, resulting in white light emission. Solutions of 20 wt% in polar aprotic solvents at ambient conditions allowed the deposition of fluorescent copolyethers and printing from non-chlorinated solvents. All polyethers were evaluated for their structural and optoelectronic properties, and selected copolymers were successfully used in the emitting layer (EML) of organic light-emitting diode (OLED) devices, using either rigid or flexible substrates. Remarkable color stability was displayed in all cases for up to 15 V of bias voltage. The Commission Internationale de L\'Eclairage (CIE) of the fabricated devices is located in the blue (0.16, 0.16), yellow (0.44, 0.50), or white region of the visible spectrum (0.33, 0.38) with minimal changes according to the ratio of the comonomers. The versatile methodology toward semiconducting polyethersulfones for polymer light-emitting diodes (PLEDs) developed herein led to the scaled-up production of luminescent polymers of up to 25 g of high-molecular-weight single batches, demonstrating the effectiveness of this approach as a straightforward tool to facilitate the synthesis of flexible and printable EMLs for large-area PLED coverage.
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  • 文章类型: Journal Article
    电子和空穴对的迁移行为决定了光致发光和光催化活性,这是半导体材料的两种不同性质。在合成方法的影响下,半导体材料的光致发光和光催化活性也表现出强烈的方法依赖性行为。在这次审查中,MMoO4、MWO4和MMoO4/MWO4的合成方法(M=Mg,Ca,首次综述了Sr和Ba)异质结复合材料及其光致发光和光催化活性。还综述了不同M离子对MMoO4/MWO4异质结复合材料光致发光和光催化活性的影响。还讨论了光致发光和光催化活性之间的内在相关机制。不同的M离子导致MMoO4/MWO4异质结复合材料中不同的配位环境,导致不同MMoO4/MWO4异质结复合材料的光致发光和光催化机理不同。该综述为今后MMoO4/MWO4异质结复合材料的研究提供了理论参考和技术指导。
    The migration behavior of electron and hole pairs determines both photoluminescence and photocatalytic activity, which are two distinct properties of semiconductor materials. The photoluminescence and photocatalytic activity of semiconductor materials also exhibit strong method-dependent behavior under the influence of synthesis methods. In this review, the synthesis methods of MMoO4, MWO4 and MMoO4/MWO4 (M = Mg, Ca, Sr and Ba) heterojunction composites and their photoluminescence and photocatalytic activities are reviewed for the first time. The effects of different M ions on the photoluminescence and photocatalytic activity of MMoO4/MWO4 heterojunction composites are also reviewed. There is also a discussion about the intrinsic correlation mechanism between photoluminescence and photocatalytic activity. Different M ions result in different coordination environments in MMoO4/MWO4 heterojunction composites, which leads to different photoluminescence and photocatalytic mechanisms of different MMoO4/MWO4 heterojunction composites. This review provides theoretical reference and technical guidance for future research on MMoO4/MWO4 heterojunction composites.
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  • 文章类型: Journal Article
    无应变GaAs锥壳量子点具有独特的形状,它允许通过外部电场和磁场对电荷载流子概率密度进行广泛的可调性。这里,使用仿真实验研究了横向电场对光发射的影响。模拟预测当受到横向电场时,电子和空穴形成横向偶极子。为了通过实验评估这一预测,我们将这些点整合在横向栅极几何形状中,并测量激子能量的斯塔克位移,激子强度,辐射寿命,和使用单点光致发光光谱的精细结构分裂(FSS)。相应的栅极电压依赖性显示出具有三个明显状态的非平凡趋势。我们假设各个主要过程是在低栅极电压U下的电荷载流子变形,介质U处的垂直电荷载流子位移,和高U的横向电荷载流子极化。横向极化形成偶极子,可以增强或补偿由QD形状各向异性引起的固有FSS,取决于电场的平面内方向。此外,数据表明,双激子峰可以被横向栅极电压抑制,我们假设表面电荷引起的额外垂直电场的存在。
    Strain-free GaAs cone-shell quantum dots have a unique shape, which allows a wide tunability of the charge-carrier probability densities by external electric and magnetic fields. Here, the influence of a lateral electric field on the optical emission is studied experimentally using simulations. The simulations predict that the electron and hole form a lateral dipole when subjected to a lateral electric field. To evaluate this prediction experimentally, we integrate the dots in a lateral gate geometry and measure the Stark-shift of the exciton energy, the exciton intensity, the radiative lifetime, and the fine-structure splitting (FSS) using single-dot photoluminescence spectroscopy. The respective gate voltage dependencies show nontrivial trends with three pronounced regimes. We assume that the respective dominant processes are charge-carrier deformation at a low gate voltage U, a vertical charge-carrier shift at medium U, and a lateral charge-carrier polarization at high U. The lateral polarization forms a dipole, which can either enhance or compensate the intrinsic FSS induced by the QD shape anisotropy, dependent on the in-plane orientation of the electric field. Furthermore, the data show that the biexciton peak can be suppressed by a lateral gate voltage, and we assume the presence of an additional vertical electric field induced by surface charges.
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  • 文章类型: Journal Article
    具有发光氧缺陷的单壁碳纳米管(SWNT)的共价官能化增加了它们的亮度,并使它们能够用作光学生物传感器或荧光探针,用于在第二生物学窗口(NIR-II)中的体内成像。然而,由于反应条件的受限窗口或需要用紫外光进行受控照射,获得具有高亮度的发光缺陷对于当前的功能化方法是具有挑战性的。这里,我们报告了一种通过类似Fenton反应引入发光氧缺陷的方法,该方法使用良性且廉价的化学物质,无需光照。(6,5)用这种方法官能化的水分散体中的SWNT显示明亮的E11*发射(1105nm),其具有比原始E11发射高3.2倍的峰强度和3%的可再现的光致发光量子产率。官能化可以在很宽的反应参数范围内进行,甚至在高浓度(100mgL-1)下使用未分类的纳米管原料,获得大量明亮发光的SWNT。我们进一步发现,引入的氧缺陷在光照下重排,这提供了对氧缺陷的结构和动力学的额外见解。最后,具有氧缺陷的超短SWNT的功能化也能够实现高光致发光量子产率。在与生物相容性聚乙二醇化磷脂或单链DNA进行表面活性剂交换后,它们的优异发射特性得以保留,使其适用于体内NIR-II成像和多巴胺传感。
    The covalent functionalization of single-walled carbon nanotubes (SWNTs) with luminescent oxygen defects increases their brightness and enables their application as optical biosensors or fluorescent probes for in vivo imaging in the second-biological window (NIR-II). However, obtaining luminescent defects with high brightness is challenging with the current functionalization methods due to a restricted window of reaction conditions or the necessity for controlled irradiation with ultraviolet light. Here, we report a method for introducing luminescent oxygen defects via a Fenton-like reaction that uses benign and inexpensive chemicals without light irradiation. (6,5) SWNTs in aqueous dispersion functionalized with this method show bright E11* emission (1105 nm) with 3.2 times higher peak intensities than the pristine E11 emission and a reproducible photoluminescence quantum yield of 3%. The functionalization can be performed within a wide range of reaction parameters and even with unsorted nanotube raw material at high concentrations (100 mg L-1), giving access to large amounts of brightly luminescent SWNTs. We further find that the introduced oxygen defects rearrange under light irradiation, which gives additional insights into the structure and dynamics of oxygen defects. Finally, the functionalization of ultrashort SWNTs with oxygen defects also enables high photoluminescence quantum yields. Their excellent emission properties are retained after surfactant exchange with biocompatible pegylated phospholipids or single-stranded DNA to make them suitable for in vivo NIR-II imaging and dopamine sensing.
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  • 文章类型: Journal Article
    半导体共轭聚合物(CP)在推进有机电子学方面至关重要,为太阳能电池和场效应晶体管提供可调谐的性能。这里,我们进行第一原理计算以研究单个顺式聚乙炔(cis-PA)低聚物及其集合。使用密度泛函理论(DFT)获得接地电子结构,通过计算电子和核自由度之间的非绝热耦合(NAC)来探索激发态动力学。我们使用Redfield理论计算电荷载流子和光致发光(PL)的非辐射弛豫。我们的发现表明电子比空穴弛豫得更快。与单一低聚物相比,低聚物的集合显示更快的松弛。计算的PL光谱显示了来自带间和带内跃迁的特征。合奏显示更宽的线宽,跃迁能量的红移,和较低的强度相比,单一的低聚物。这项比较研究表明,链之间的分散力和轨道杂交是PL变化的主要原因。它提供了对CP的基本行为和分子水平理解的见解,以设计更有效的光电器件。
    Semiconducting conjugated polymers (CPs) are pivotal in advancing organic electronics, offering tunable properties for solar cells and field-effect transistors. Here, we carry out first-principle calculations to study individual cis-polyacetylene (cis-PA) oligomers and their ensembles. The ground electronic structures are obtained using density functional theory (DFT), and excited state dynamics are explored by computing nonadiabatic couplings (NACs) between electronic and nuclear degrees of freedom. We compute the nonradiative relaxation of charge carriers and photoluminescence (PL) using the Redfield theory. Our findings show that electrons relax faster than holes. The ensemble of oligomers shows faster relaxation compared to the single oligomer. The calculated PL spectra show features from both interband and intraband transitions. The ensemble shows broader line widths, redshift of transition energies, and lower intensities compared to the single oligomer. This comparative study suggests that the dispersion forces and orbital hybridizations between chains are the leading contributors to the variation in PL. It provides insights into the fundamental behaviors of CPs and the molecular-level understanding for the design of more efficient optoelectronic devices.
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  • 文章类型: Journal Article
    壳聚糖是一种具有独特性质的生物聚合物,近几十年来在各个科学领域引起了广泛关注。尽管壳聚糖以其较差的电气和机械性能而闻名,人们对生产用碳基材料增强的壳聚糖基材料感兴趣,以赋予特殊的性能,如高导电性和高杨氏模量。这项研究描述了碳基材料的协同效应,如还原的氧化石墨烯和碳纳米管,在改善电气方面,光学,壳聚糖基薄膜的力学性能。我们的发现表明,还原氧化石墨烯的掺入会影响壳聚糖的结晶度,这极大地影响了薄膜的机械性能。然而,加入还原的氧化石墨烯-碳纳米管复合物不仅显著改善了机械性能,而且显著改善了光学和电学性能,如光致发光研究和采用四探针技术的电阻率测量所证明的。这是一个很有前景的新材料的合成,如生物聚合物薄膜,在光学领域的潜在应用,电气,和生物医学生物工程应用。
    Chitosan is a biopolymer with unique properties that have attracted considerable attention in various scientific fields in recent decades. Although chitosan is known for its poor electrical and mechanical properties, there is interest in producing chitosan-based materials reinforced with carbon-based materials to impart exceptional properties such as high electrical conductivity and high Young\'s modulus. This study describes the synergistic effect of carbon-based materials, such as reduced graphene oxide and carbon nanotubes, in improving the electrical, optical, and mechanical properties of chitosan-based films. Our findings demonstrate that the incorporation of reduced graphene oxide influences the crystallinity of chitosan, which considerably impacts the mechanical properties of the films. However, the incorporation of a reduced graphene oxide-carbon nanotube complex not only significantly improves the mechanical properties but also significantly improves the optical and electrical properties, as was demonstrated from the photoluminescence studies and resistivity measurements employing the four-probe technique. This is a promising prospect for the synthesis of new materials, such as biopolymer films, with potential applications in optical, electrical, and biomedical bioengineering applications.
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  • 文章类型: Journal Article
    在这项工作中,使用四种不同链长的伯胺合成了四种百里酚基苯并恶嗪,即甲胺,乙胺,1-丙胺,和1-丁胺,然后被命名为T-m,T-e,T-p,还有T-b,分别。通过光致发光研究其在丙酮中的溶液,检查了合成的百里酚基苯并恶嗪的光学性质。结果表明,当被275至315nm的激发波长照射时,所有制备的苯并恶嗪发出的最大波长为425至450nm的蓝光。发现最大激发波长为275nm。百里酚基苯并恶嗪的聚合是通过在不同条件下(160、180和200°C持续1小时)的热处理触发的。根据FTIR结果,热固化过程引入了OH峰的存在,其强度随着固化温度的增加而增加。关于TGA分析的百里酚基苯并恶嗪的热分解揭示了苯并恶嗪相对于N-取代基链长度的热稳定性的增强,如明显观察到的,在253至260°C的温度范围内的第一次热分解的变化。合成的苯并恶嗪衍生物进一步用于涂覆基材,例如,玻璃幻灯片。水接触角的研究表明,苯并恶嗪在表面的涂层改善了基材的疏水性,导致接触角从25.5°扩大到93.3°。此外,使用动电位极化技术检查了聚苯并恶嗪涂层的防腐蚀性能。结果表明,百里酚基聚苯并恶嗪的防腐效率高达99.99%。疏水和电化学研究均表明在防腐蚀涂层应用中使用苯并恶嗪的可行性。
    In this work, four thymol-based benzoxazines were synthesized using four primary amines with different chain lengths, namely methylamine, ethylamine, 1-propylamine, and 1-butylamine, which are then named T-m, T-e, T-p, and T-b, respectively. The optical properties of the synthesized thymol-based benzoxazines were examined via the photoluminescent study of their solutions in acetone. The results show that all the prepared benzoxazines emitted blue light with the maximum wavelengths from 425 to 450 nm when irradiated by the excitation wavelengths from 275 to 315 nm. The maximum excitation wavelengths are found to be 275 nm. The polymerization of the thymol-based benzoxazines is triggered by heat treatments with different conditions (160, 180, and 200 °C for 1 h). According to the FTIR results, the heat-curing process introduces a presence of the OH peak, of which intensity increases as the curing temperature increases. Thermal decompositions of thymol-based benzoxazines regarding TGA analyses reveal the enhancement of thermal stability of the benzoxazines with respect to the N-substituent chain length, as significantly observed the change in the first thermal decomposition at temperature ranged from 253 to 260 °C. Synthesized benzoxazine derivatives are further employed to coat the substrate, e.g., the glass slides. The investigation of the water contact angle shows that the coating of the benzoxazines onto the surface improves the hydrophobicity of the substrate, resulting in the enlargement of the contact angle from 25.5° to 93.3°. Moreover, the anticorrosion performance of the polybenzoxazine coatings is examined using potentiodynamic polarization techniques. The results illustrate the anticorrosion efficiency of the thymol-based polybenzoxazine up to 99.99%. Both hydrophobic and electrochemical studies suggest the feasibility for employing benzoxazines in anticorrosion coating applications.
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  • 文章类型: Journal Article
    回收的钠钙玻璃粉是一种可持续的材料,通常也被认为是水泥基复合材料中的填料。通过X射线光电子能谱(XPS)和光谱学分析了由于处理而引起的玻璃颗粒表面性质的变化。我们已经发现,在玻璃颗粒的表面上存在相对较高的碳污染水平(约30at。%),因此,对等离子体技术和热退火进行了表面清洁测试。室温等离子体处理不足以从回收的玻璃颗粒的表面去除碳污染物。相反,回收的钠钙玻璃颗粒的室温等离子体处理通过增加强度和加速光致发光的衰减而导致其室温光致发光(PL)的显着增强。室温等离子体处理后增强的蓝色PL归因于玻璃表面上存在碳污染以及相关的电荷表面和界面缺陷和界面状态。因此,我们提出了在UVLED下的蓝色光致发光作为一种快速且廉价的方法来指示玻璃颗粒表面上的碳污染。
    Recycled soda-lime glass powder is a sustainable material that is also often considered a filler in cement-based composites. The changes in the surface properties of the glass particles due to the treatments were analyzed by X-ray photoelectron spectroscopy (XPS) and optical spectroscopy. We have found that there is a relatively high level of carbon contamination on the surface of the glass particles (around 30 at.%), so plasma technology and thermal annealing were tested for surface cleaning. Room temperature plasma treatment was not sufficient to remove the carbon contamination from the surface of the recycled glass particles. Instead, the room temperature plasma treatment of recycled soda-lime glass particles leads to a significant enhancement in their room temperature photoluminescence (PL) by increasing the intensity and accelerating the decay of the photoluminescence. The enhanced blue PL after room-temperature plasma treatment was attributed to the presence of carbon contamination on the glass surface and associated charge surface and interfacial defects and interfacial states. Therefore, we propose blue photoluminescence under UV LED as a fast and inexpensive method to indicate carbon contamination on the surface of glass particles.
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