We present a high-resolution photoluminescence study of Er-doped SiO2 sensitized with Si nanocrystals (Si NCs). Emission bands originating from recombination of excitons confined in Si NCs and of internal transitions within the 4f-electron core of Er3+ ions, and a band centered at lambda = 1200nm have been identified. Their kinetics have been investigated in detail. Based on these measurements, we present a comprehensive model for energy transfer mechanisms responsible for light generation in this system. A unique picture of energy flow between subsystems of Er3+ and Si NCs is developed, yielding truly microscopic information on the sensitization effect and its limitations. In particular, we show that most of the Er3+ ions available in the system are participating in the energy exchange. The long standing problem of apparent loss of optical activity of majority of Er dopants upon sensitization with Si NCs is clarified and assigned to appearance of a very efficient energy exchange mechanism between Si NCs and Er3+ ions. Application potential of SiO2:Er sensitized by Si NCs is discussed in view of the newly acquired microscopic insight.
We have fabricated UV-sensitive photodetectors based on colloidal CdS nanocrystals and graphene. The nanocrystals act as a sensitizer layer that improves light harvesting leading to high responsivity of the detector. Despite the slow relaxation of the photogenerated charges in the nanocrystal film, faster processes allowed to detect pulses up to a repetition rate of 2 kHz. We have performed time-resolved analysis of the processes occurring in our hybrid system, and discuss possible photo-induced charge transfer mechanisms.
We report an optically gated transistor composed of CdSe nanocrystals (NCs), sensitized with the dye Zinc beta-tetraaminophthalocyanine for operation in the first telecom window. This device shows a high ON/OFF ratio of six orders of magnitude in the red spectral region and an unprecedented 4.5 orders of magnitude at 847 nm. By transient absorption spectroscopy, we reveal that this unexpected infrared sensitivity is due to electron transfer from the dye to the CdSe NCs within 5 ps. We show by time-resolved photocurrent measurements that this enables fast rise times during near-infrared optical…
We report on the effect of ligand exchange of copper sulphide selenide as well as copper selenide nanocrystals with the organic pi-system Cobalt beta-tetraaminophthalocyanine and analyse changes in the structural, optical as well as electric properties of thin films of these hybrid materials. A strong ligand interaction with the surface of the nanocrystals is revealed by UV-vis absorption and Raman spectroscopy. Grazing-incidence small-angle X-ray scattering studies show a significant contraction in the interparticle distance upon ligand exchange. For copper-deficient copper selenide, this con…
Nanocrystals based on metal-halide perovskites offer a promising material platform for highly efficient lighting. Using transient optical spectroscopy, we study excitation recombination dynamics in manganese-doped CsPb(Cl,Br)3 perovskite nanocrystals. We find an increase in the intrinsic excitonic radiative recombination rate upon doping, which is typically a challenging material property to tailor. Supported by ab initio calculations, we can attribute the enhanced emission rates to increased exciton localization through lattice periodicity breaking from Mn dopants, which increases exciton eff…
Doping of semiconductors by impurity atoms enabled their widespread technological application in micro and opto-electronics. For colloidal semiconductor nanocrystals, an emerging family of materials where size, composition and shape-control offer widely tunable optical and electronic properties, doping has proven elusive. This arises both from the synthetic challenge of how to introduce single impurities and from a lack of fundamental understanding of this heavily doped limit under strong quantum confinement. We develop a method to dope semiconductor nanocrystals with metal impurities providin…
Robust control over the carrier type is fundamental for the fabrication of nanocrystal-based optoelectronic devices, such as the p-n homojunction, but effective incorporation of impurities in semiconductor nanocrystals and its characterization is highly challenging due to their small size. Herein, InAs nanocrystals, post-synthetically doped with Cd, serve as a model system for successful p-type doping of originally n-type InAs nanocrystals, as demonstrated in field-effect transistors (FETs). Advanced structural analysis, using atomic resolution electron microscopy and synchrotron X-ray absorpt…
Si nanocrystals have been extensively studied because of their novel properties and their potential applications in electronic, optoelectronic, photovoltaic, thermoelectric and biological devices. These new properties are achieved through the combination of the quantum confinement of carriers and the strong influence of surface chemistry. As in the case of bulk Si the tuning of the electronic, optical and transport properties is related to the possibility of doping, in a controlled way, the nanocrystals. This is a big challenge since several studies have revealed that doping in Si nanocrystals…
Structural, magnetic, and optical properties of zinc- and copper- substituted nickel ferrite nanocrystals
铁氧体纳米晶由于其丰富的物理性质而成为人们感兴趣的材料。在这里，我们将掺杂剂Zn和Cu添加到镍铁氧体纳米晶体Ni 1-xMxFe 2 O 4（0<=x<=1，M{ \in }{Cu，Zn}）中，并表征样品的相关性质如何相应地改变。基本上，这些掺杂导致Fe+3离子重排到两个预先存在的八面体和四面体位置。事实上，这，我们表明，诱导相关的磁性掺杂样品。在Cu掺杂的情况下，Jahn-Teller效应也出现了，我们通过样品的FTIR光谱来识别。此外，我们发现掺杂样品的晶格参数增加，以及掺杂样品的超顺磁性行为，而Jahn-Teller效应排除了CuFe 2 O 4纳米晶体中类似的行为。采用室温光致发光法研究了Zn和Cu掺杂对镍铁氧体纳米晶光学性质的影响。
Enhancement of the lifetime of metastable states in Er-doped Si nanocrystals by external coloured noise
分析了不同噪声强度和相关时间下，在外部色噪声源存在下掺铒硅纳米晶亚稳态能级寿命的变化.激子动力学模拟的一组唯象速率方程，考虑到所有可能的现象，固有的能量状态的Si纳米晶体和Er $^{3+}$离子在硅氧化物的主机材料。通过荧光和能量转移的协同上转换研究了Er原子在第一激发能级$^4$ I $_{13/2}$的初始布居数的衰减，研究了Er原子的电子退激发.我们的结果表明，在较宽的噪声强度和关联时间范围内，$^4$ I $_{13/2}$能级的退激过程被减慢.此外，一个非单调的行为的寿命与波动的幅度被发现，其特征在于由一个最大的变化值的噪声相关时间可比的去激时间。本文还讨论了色噪声对$^4$ I $_{13/2}$能级激活的能量转移上转换效率的间接影响。
We apply a stochastic version of an optimally tuned range-separated hybrid functional to provide insight on the electronic properties of P- and B- doped Si nanocrystals of experimentally relevant sizes. We show that we can use the range-separation parameter for undoped systems to calculate accurate results for dopant activation energies. We apply this strategy for tuning functionals to study doped nanocrystals up to 2.5 nm in diameter at the hybrid functional level. In this confinement regime, the P- and B- dopants have large activation energies and have strongly localized states that lie deep…
Lanthanide-Dependent Clustering in Yb$^{3+}$/Ln$^{3+}$ Co-Doped CaF$_2$ Nanocrystals: Correlating Spectroscopic Signatures with DFT Insights
University of Canterbury（坎特伯雷大学）；The Dodd-Walls Centre for Photonic and Quantum Technologies（光子与量子技术多德沃尔斯中心）；University of Science and Technology of China（中国科学技术大学）；Fayetteville State University（费耶特维尔州立大学）；Henan University of Technology（河南工业大学）
Copper binary compounds are often intrinsic p-type semiconductors due to the presence of Cu(I) vacancies, with corresponding hole carriers in the valence band. If the free carrier concentration is high enough, localized plasmon resonances can be sustained in nanocrystals, with frequencies in the infra-red (<1 eV), with respect to the typical resonances seen in the visible range in the case of metals (Ag, Au, ...). The localization of the resonances can be demonstrated with scanning transmission electron energy loss spectroscopy (STEM-EELS) by combining high spatial and high energy resolutions.…
Nitrogen-doped Nanoporous Carbon Membranes Functionalized with Co/CoP Janus-type nanocrystals as Hydrogen Evolution Electrode in Both Acid and Alkaline Environment
自负载型电催化剂的制备及其直接作为能量转换电极的应用是材料化学和能源领域的研究热点。在此，我们报告了一种合成策略，以制备独立的分层结构，氮掺杂的纳米多孔石墨碳膜功能化与Janus型Co/CoP纳米晶体（称为HNDCM-Co/CoP），这是成功地应用于作为一个高效的，无粘合剂的电极在析氢反应（HER）。HNDCM-Co/CoP具有石墨化程度高、微孔/介孔/大孔三维连通、氮掺杂均匀、Co/CoP纳米晶分散性好以及薄碳层对纳米晶的限制作用等结构优点，在酸性和碱性条件下均表现出优异的电催化活性和长期运行稳定性。作为实际使用的概念验证，在我们的实验室中制备尺寸为5.6cm X 4cm X 60 μ π ι的HNDCM-Co/CoP的宏观片。在太阳能电池的驱动下，在碱性条件下（pH 14）进行水的电还原，并以16 ml/min的速率产生H2，表明其作为现实生活中的能量转换系统的潜力。
Understanding the interplay between the structural, chemical and physical properties of nanomaterials is crucial for designing new devices with enhanced performance. In this regards, doping of metal oxides is a general strategy to tune size, morphology, charge, lattice, orbital and spin degrees of freedoms and has been shown to affect nanomaterials properties for photoelectrochemical water splitting, batteries, catalysis, magnetic applications and optics. Here we report the role of lattice small polaron in driving the morphological transition from nearly isotropic to nanowire crystals in Si do…
Tuning of the electronic properties of pre-synthesized colloidal semiconductor nanocrystals (NCs) by doping plays a key role in the prospect of implementing them in printed electronics devices such as transistors, and photodetectors. While such impurity doping reactions have already been introduced, the understanding of the doping process, the nature of interaction between the impurity and host atoms, and the conditions affecting the solubility limit of impurities in nanocrystals are still unclear. Here, we used a post-synthesis diffusion based doping reaction to introduce Ag impurities into I…
Degenerately doped semiconductor nanocrystals (NCs) exhibit a localized surface plasmon resonance (LSPR) in the infrared range of the electromagnetic spectrum. Unlike metals, semiconductor NCs offer tunable LSPR characteristics enabled by doping, or via electrochemical or photochemical charging. Tuning plasmonic properties through carrier density modulation suggests potential applications in smart optoelectronics, catalysis, and sensing. Here, we elucidate fundamental aspects of LSPR modulation through dynamic carrier density tuning in Sn-doped Indium Oxide NCs. Monodisperse Sn-doped Indium Ox…
Yb3+-doped inorganic metal-halide perovskites (Yb3+:CsPbX3, X = Cl, Br) have recently been discovered to display highly efficient quantum cutting, in which the energy from individual blue or UV photons absorbed by the material is re-emitted in the form of pairs of near-infrared photons by Yb3+ dopants. Experimental photoluminescence quantum yields approaching 200{%} have been reported. As the first quantum-cutting materials that combine such high photoluminescence quantum yields with strong, broadband absorption in the visible, these materials offer unique opportunities for enhancing the effic…
Metal-halide perovskite nanocrystals have demonstrated excellent optoelectronic properties for light-emitting applications. Isovalent doping with various metals (M2+) can be used to tailor and enhance their light emission. Although crucial to maximize performance, an understanding of the universal working mechanism for such doping is still missing. Here, we directly compare the optical properties of nanocrystals containing the most commonly employed dopants, fabricated under identical synthesis conditions. We show for the first time unambiguously and supported by first principles calculations …
Heterovalent substitution of toxic lead is an increasingly popular design strategy to obtain environmentally sustainable variants of the exciting material class of halide perovskites. Perovskite nanocrystals (NCs) obtained through solution-based methods exhibit exceedingly high optical quality. Unfortunately, most of these synthesis routes still require reaction under inert gas and at very high temperatures. Herein we present a novel synthesis routine for lead-free double perovskite NCs. We combine hot injection and ligand-assisted reprecipitation (LARP) methods to achieve a low-temperature an…
All-inorganic lead halide perovskite nanocrystals (NCs) show potential in optoelectronic devices, though their stability and efficiency have yet to improve. In this work, we explore the effect of bivalent metal site doping on the optoelectronic properties of CsPbX$_3$ (X = Br, Cl) perovskite NCs. First, the Pb$^{2+}$ ions in pristine CsPbBr$_3$ NC are partially substituted by Mn$^{2+}$ ions, and the alkaline earth metal strontium is then doped on both pristine and Mn$^{2+}$-substituted particles. The structural and photophysical properties of the pristine and the three doped NC variants have b…
Co-doped with calcium, europium and erbium ions lanthanum vanadate crystalline nanoparticles are synthesized and investigated with a goal to clarify the mechanisms of calcium and erbium impurities effects on europium ions luminescence and to find compositions with enhanced luminescence intensity. The XRD analysis reveals dependence of crystal structure on dopants concentration: monoclinic crystal phase is observed for low dopant concentrations and content of tetragonal crystal phase increases with dopant concentrations increase. The SEM investigation reveals formation of nanoparticles with two…
Low power photon upconversion (UC) based on sensitized triplet-triplet annihilation (sTTA) is considered as the most promising upwards wavelength-shifting technique to enhance the light harvesting capability of solar devices by recovering the low-energy tail of the solar spectrum. Semiconductor nanocrystals (NCs) with conjugated organic ligands have been proposed as broadband sensitizers for extending the light-harvesting capability of sTTA-UC molecular absorbers. Key to their functioning is efficient energy transfer (ET) from the NC to the triplet state of the ligands that sensitizes the trip…
Precursor stoichiometry controls dopant structure, defect chemistry, and valence in Mn-doped ZnGa$_2$O$_4$ nanocrystals
HUN-REN Wigner Research Centre for Physics（匈牙利科学院维格纳物理研究中心）；Institute for Solid State Physics and Optics（凝聚态物理与光学研究所）；Budapest University of Technology and Economics（布达佩斯科技经济大学）；University of Notre Dame（圣母大学）
Manganese (Mn)-doped ZnS nanocrystals (NCs) have been extensively explored for optical applications with the advantages of low toxicity, large Stokes shifts, and enhanced thermal and environmental stability. Although numerous studies on Mn-doped ZnS dots, rods, and wires have been reported, the literature related to Mn-doped ZnS nanoplatelets (ZnS:Mn NPLs) is scarce. Here, we present the first example of direct doping of Mn2+ ions into ZnS NPLs via the nucleation-doping strategy. The resulting ZnS:Mn NPLs exhibit Mn luminescence, indicative for successful doping of the host ZnS NPLs with Mn2+ …
Mn2+-doped semiconductor nanocrystals with tuned location and concentration of Mn2+ ions can yield diverse coupling regimes, which can highly influence their optical properties such as emission wavelength and photoluminescence (PL) lifetime. However, investigation on the relationship between the Mn2+ concentration and the optical properties is still challenging because of the complex interactions of Mn2+ ions and the host and between the Mn2+ ions. Here, atomically flat ZnS nanoplatelets (NPLs) with uniform thickness were chosen as matrixes for Mn2+ doping. Using time-resolved (TR) PL spectros…
Electron conduction through bare metal oxide nanocrystal (NC) films is hindered by surface depletion regions resulting from the presence of surface states. We control the radial dopant distribution in tin-doped indium oxide (ITO) NCs as a means to manipulate the NC depletion width. We find in films of ITO NCs of equal overall dopant concentration that those with dopant-enriched surfaces show decreased depletion width and increased conductivity. Variable temperature conductivity data shows electron localization length increases and associated depletion width decreases monotonically with increas…
