Tuning light emission of PbS nanocrystals from infrared to visible range by cation exchange

Abstract

Colloidal semiconductor nanocrystals, with intense and sharp-line emission between red and near-infrared spectral regions, are of great interest for optoelectronic and bio-imaging applications. The growth of an inorganic passivation layer on nanocrystal surfaces is a common strategy to improve their chemical and optical stability and their photoluminescence quantum yield. In particular, cation exchange is a suitable approach for shell growth at the expense of the nanocrystal core size. Here, the cation exchange process is used to promote the formation of a CdS passivation layer on the surface of very small PbS nanocrystals (2.3 nm in diameter), blue shifting their optical spectra and yielding luminescent and stable nanostructures emitting in the range of 700–850 nm. Structural, morphological and compositional investigation confirms the nanocrystal size contraction after the cation-exchange process, while the PbS rock-salt crystalline phase is retained. Absorption and photoluminescence spectroscopy demonstrate the growth of a passivation layer with a decrease of the PbS core size, as inferred by the blue-shift of the excitonic peaks. The surface passivation strongly increases the photoluminescence intensity and the excited state lifetime. In addition, the nanocrystals reveal increased stability against oxidation over time. Thanks to their absorption and emission spectral range and the slow recombination dynamics, such highly luminescent nano-objects can find interesting applications in sensitized photovoltaic cells and light-emitting devices.     

Syntheses and applications of Mn-doped II-VI semiconductor nanocrystals

Luminescent Mn-doped II-VI semiconductor nanocrystals have been intensively investigated over the last ten years. Several semiconductor host materials such as ZnS, CdS, and ZnSe have been used for Mn-doped nanocrystals with different synthetic routes and surface passivation. Beyond studies of their fundamental properties including photoluminescence and size, these luminescent nanocrystals have now been tested for practical applications such as electroluminescent displays and biological labeling agents (biomarkers). Here, we first review ZnS:Mn, CdS:Mn/ZnS core/shell, and ZnSe:Mn nanocrystal systems in terms of their synthetic chemistries and photoluminescent properties. Second, based on ZnS:Mn and CdS:Mn/ZnS core/shell nanocrystals as electroluminescent components, direct current electroluminescent devices having a hybrid organic/inorganic multilayer structure are reviewed. Highly luminescent and photostable CdS:Mn/ZnS nanocrystals can further be used as the luminescent biomarkers and some preliminary results are also discussed here.     

Colloidal PbS nanocrystals with narrow photoluminescence spectra

Luminescent PbS nanocrystals have been synthesized by the colloidal method. PVA has been employed to modify the surface of prepared PbS nanocrystals and improve their optical properties. Optical and morphological characteristics of lead sulfide nanocrystals have been studied by high resolution electron microscopy and spectrophotometer. Optical absorption and photoluminescence (PL) studies of the PbS nanocrystals have shown the strong quantum confinement effects. For the first time, the prepared lead sulfide nanocrystals have emitted at 608 nm wavelength with narrow band width (21 nm) and high Stokes shift. Experimental results have shown that the surface charge traps have higher contribution to the optical properties of colloidal PbS nanocrystals and in our sample photoluminescence was due to hole relaxation. These properties made them a material with potential application in nanophotonics.     

Synthesis and oxidation of luminescent silicon nanocrystals from silicon tetrachloride by very high frequency nonthermal plasma

Silicon nanocrystals have recently attracted significant attention for applications in electronics, optoelectronics, and biological imaging due to their size-dependent optical and electronic properties. Here a method for synthesizing luminescent silicon nanocrystals from silicon tetrachloride with a nonthermal plasma is described. Silicon nanocrystals with mean diameters of 3-15 nm are synthesized and have a narrow size distribution with the standard deviation being less than 20% of the mean size. Control over crystallinity is achieved for plasma pressures of 1-12 Torr and hydrogen gas concentrations of 5-70% through adjustment of the plasma power. The size of nanocrystals, and resulting optical properties, is mainly dependent on the gas residence time in the plasma region. Additionally the surface of the nanocrystals is covered by both hydrogen and chlorine. Oxidation of the nanocrystals, which is found to follow the Cabrera-Mott mechanism under ambient conditions, is significantly faster than hydrogen terminated silicon due to partial termination of the nanocrystal surface by chlorine.     

Applications of quantum dots in optical fiber luminescent oxygen sensors

The potential applications of luminescent semiconductor nanocrystals to optical oxygen sensing are explored. The suitability of quantum dots to provide a reference signal in luminescence-based chemical sensors is addressed. A CdSe-ZnS nanocrystal, with an emission peak at 520 nm, is used to provide a reference signal. Measurements of oxygen concentration, which are based on the dynamic quenching of the luminescence of a ruthenium complex, are performed. Both the dye and the nanocrystal are immobilized in a solgel matrix and are excited by a blue LED. Experimental results show that the ratio between the reference and the sensor signals is highly insensitive to fluctuations of the excitation optical power. The use of CdTe, near-infrared quantum dots with an emission wavelength of 680 nm, in combination with a ruthenium complex to provide a new mechanism for oxygen sensing, is investigated. The possibility of creating oxygen sensitivity in different spectral regions is demonstrated. The results obtained clearly show that this technique can be applied to develop a wavelength division multiplexed system of oxygen sensors.     

Time-resolved photoluminescence spectroscopy of ligand-capped PbS nanocrystals

PbS nanocrystals are synthesized using colloidal techniques and have their surfaces capped with oleic acid. The absorption band edge of the PbS nanocrystals is tuned between 900 and 580?nm. The PbS nanocrystals exhibit tuneable photoluminescence with large non-resonant Stokes shifts of up to 500?meV. The magnitude of the Stokes shift is found to be dependent upon the size of PbS nanocrystals. Time-resolved photoluminescence spectroscopy of the PbS nanocrystals reveals that the photoluminescence has an extraordinarily long lifetime of 1?μs. This long fluorescence lifetime is attributed to the effect of dielectric screening similar to that observed in other IV-VI semiconductor nanocrystals.     

Highly efficient luminescence from a hybrid state found in strongly quantum confined PbS nanocrystals

We report that high quality PbS nanocrystals, synthesized in the strong quantum confinement regime, have quantum yields as high as 70% at room temperature. We use a combination of modelling and photoluminescence up-conversion to show that we obtain a nearly monodisperse size distribution. Nevertheless, the emission displays a large nonresonant Stokes shift. The magnitude of the Stokes shift is found to be directly proportional to the degree of quantum confinement, from which we establish that the emission results from the recombination of one quantum confined charge carrier with one localized or surface-trapped charge carrier. Furthermore, the surface state energy is found to lie outside the bulk bandgap so that surface-related emission only commences for strongly quantum confined nanocrystals, thus highlighting a regime where improved surface passivation becomes necessary.     

Properties of size-tuned PbS nanocrystals stabilized in a polymer template

Nanoclusters of PbS embedded in polymer matrices have recently been shown to have interesting optical properties with the capability of tuning the effective band gap over a wide spectral range. The results of a systematic investigation of the preparation and characterization of size-tuned PbS nanocrystals stabilized in the polymer nanotemplate of Nafion and their size-dependent physical properties are presented in this paper. These nanocrystals exhibit large characteristic blueshift in optical absorption from the bulk absorption onset value of 3020 nm. XRD and HRTEM measurements indicate the presence of PbS nanocrystals in the size range of 2-6 nm, in the regime of strong quantum confinement. Thermal and electrical properties of the polymer are found to be influenced to a great extent by the embedded PbS nanocrystals.     

Highly efficient (infra)red conversion of InGaN light emitting diodes by nanocrystals, enhanced by colour selective mirrors

Colloidal nanocrystal layers deposited onto the enclosure of InGaN light emitting diodes are demonstrated to operate as nano-phosphors for colour conversion with high colour stability. Depending on the choice of the nanocrystal material (either CdSe/ZnS or PbS nanocrystals are applied), the diode emission at 470?nm is converted to red or to infrared light, with similar quantum efficiencies. The colour conversion is further improved by dielectric mirrors with high reflectivity at the emission band of the nanocrystals, resulting in an almost doubling of the nanocrystal light extraction from the devices, which increases the nanocrystal device efficiency up to 19.1%.     

Effect of PbS nanocrystal concentration on the physical properties of a polymer–nanocrystal composite

Semiconductor nanocrystals doped in stable matrices such as polymers are of interest due to fundamental scientific aspects as well as their scope for technological applications. In the present investigation, PbS nanocrystals are synthesized in polyvinyl alcohol (PVA) matrix using a simple technique based on colloidal chemistry. Various concentrations of nanocrystalline PbS (with an average size of 4.5 nm) are loaded into the polymer to study the effect of PbS concentration on the optical, thermal and electrical properties of the composite. An increase in PbS content results in decrease in thermal stability and an increase in electrical conductivity, presumably resulting from interactions between the nanofiller and polymer. Considerations for designing composites with desired combinations of electrical, thermal, and optical properties to suit specific device operating environments are studied systematically.     

Surface passivation of CdS/Zn2SiO4 nanocomposites prepared by a wet chemical route

Highly luminescent CdS/Zn2SiO4 nanocrystals were prepared by a wet chemical method. The effect of surface passivation was observed in photoluminescence measurements of CdS nanocrystals embedded in colloidal nanocrystallite or amorphous Zn2SiO4 matrix. The resultant luminescent emission of as-prepared CdS/Zn2SiO4 nanocomposite thin films displays two distinct components. One is attributed to the band-edge emission and the other is due to the surface defects. The effect of aging on CdS/Zn2SiO4 nanocomposite thin films has been investigated, showing the active role of Zn2SiO4 matrix in modifying the surface states.     

Charge separation in type II tunneling structures of close-packed CdTe and CdSe nanocrystals

We report on charge separation between type II aligned CdTe and CdSe nanocrystals. Two types of electrostatically bound nanocrystal structures have been studied: first, clusters of nanocrystals hold together by Ca(II) ions in aqueous solution and, second, thin film structures of nanocrystals created with layer-by-layer deposition in combination with polyelectrolytes. In both types of structures, short interparticle distances of less than 1 nm have been achieved, whereby the isolating organic ligands on the nanocrystal surfaces and/or the polymer monolayers act as tunneling barriers between nanocrystals. We have observed an efficient quenching of photoluminescence and a reduced emission lifetime for CdTe nanocrystals in both types of type II heterostructures. This result is explained by a spatial charge separation of the photoexcited electron-hole pairs due to tunneling of charge carriers through the thin organic layer between CdTe and CdSe nanocrystals. Type II heterostructures demonstrated here may find future applications in photovoltaics.     

Enhanced radiative emission rate and quantum efficiency in coupled silicon nanocrystal-nanostructured gold emitters

We report local-field-enhanced light emission from silicon nanocrystals close to a film of nanoporous gold. We resolve photoluminescence as the gold-Si nanocrystal separation distance is varied between 0 and 20 nm and observe a fourfold luminescence intensity enhancement concomitant with increases in the coupled silicon nanocrystal/nanoporous gold absorbance cross section and radiative decay rate. A detailed analysis of the luminescence data indicated a local-field-enhanced quantum efficiency of 58% for the Si nanocrystals coupled to the nanoporous gold layer.     

A facile and green preparation of high-quality CdTe semiconductor nanocrystals at room temperature

One chemical reagent, hydrazine hydrate, was discovered to accelerate the growth of semiconductor nanocrystals (cadmium telluride) instead of additional energy, which was applied to the synthesis of high-quality CdTe nanocrystals at room temperature and ambient conditions within several hours. Under this mild condition the mercapto stabilizers were not destroyed, and they guaranteed CdTe nanocrystal particle sizes with narrow and uniform distribution over the largest possible range. The CdTe nanocrystals (photoluminescence emission range of 530-660?nm) synthesized in this way had very good spectral properties; for instance, they showed high photoluminescence quantum yield of up to 60%. Furthermore, we have succeeded in detecting the living Borrelia burgdorferi of Lyme disease by its photoluminescence image using CdTe nanocrystals.     

Characterization of CdTe nanocrystals during their synthesis in liquid paraffin: optical properties and particle growth

This article presents a systematic investigation of the optical properties and the growth process of CdTe nanocrystals during their hot-injection-based synthesis in liquid paraffin. Cadmium(II) stearate and tributylphosphine telluride are used as precursors. The as-obtained nanocrystals are characterized by transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS), X-ray powder diffraction (XRD), UV–vis absorbance, and fluorescence spectroscopy. The changes in optical absorbance and fluorescence during the nanocrystal synthesis are studied. The average nanocrystal size and the mean nanocrystal concentration are derived from the optical spectra and their changes during the synthesis are investigated. It is found that synthesis at lower temperature (150 °C) favors the continuous nucleation and leads to the formation of relatively smaller nanocrystals (~3 nm in size), whereas the nanocrystal concentration is relatively constant during synthesis at higher temperature (250 °C) thus leading to the formation of larger nanocrystals (~5 nm in size).     

Fe掺杂ZnS半导体纳米晶的微乳液法制备及其性能研究

采用Span 80/Tween 80/cyclohexane/wa-ter微乳液体系合成了ZnS∶Fe纳米晶,分别利用XRD、TEM、荧光光谱对其相结构、形貌及光学性能进行了研究。结果表明合成的ZnS∶Fe纳米晶为球形,平均粒度约3nm。随着Fe离子掺杂浓度的增加,发光峰强度先增大后减小,浓度为1%的时候发光峰强最大。对ZnS∶Fe纳米晶的荧光衰减曲线进行测试并计算得到其荧光寿命为3.07ns。     

Spatially indirect emission in a luminescent nanocrystal molecule

Recent advances in the synthesis of multicomponent nanocrystals have enabled the design of nanocrystal molecules with unique photophysical behavior and functionality. Here we demonstrate a highly luminescent nanocrystal molecule, the CdSe/CdS core/shell tetrapod, which is designed to have weak vibronic coupling between excited states and thereby violates Kasha's rule via emission from multiple excited levels. Using single particle photoluminescence spectroscopy, we show that in addition to the expected LUMO to HOMO radiative transition, a higher energy transition is allowed via spatially indirect recombination. The oscillator strength of this transition can be experimentally controlled, enabling control over carrier behavior and localization at the nanoscale.     

Size-dependent absolute quantum yields for size-separated colloidally-stable silicon nanocrystals

Size-selective precipitation was used to successfully separate colloidally stable allylbenzene-capped silicon nanocrystals into several visible emitting monodisperse fractions traversing the quantum size effect range of 1-5 nm. This enabled the measurement of the absolute quantum yield and lifetime of photoluminescence of allylbenzene-capped silicon nanocrystals as a function of size. The absolute quantum yield and lifetime are found to monotonically decrease with decreasing nanocrystal size, which implies that nonradiative vibrational and surface defect effects overwhelm spatial confinement effects that favor radiative relaxation. Visible emission absolute quantum yields as high as 43% speak well for the development of "green" silicon nanocrystal color-tunable light emitting diodes that can potentially match the performance of their toxic heavy metal chalcogenide counterparts.     

Second‐Harmonic Generation from a Single Core/Shell Quantum Dot

Nanoparticles emitting two‐photon luminescence are broadly used as photostable emitters for nonlinear microscopy. Second‐harmonic generation (SHG) as another two‐photon mechanism offers complementary optical properties but the reported sizes of nanoparticles are still large, of a few tens of nanometers. Herein, coherent SHG from single core/shell CdTe/CdS nanocrystals with a diameter of 10 to 15 nm is reported. The nanocrystal excitation spectrum reveals resonances in the nonlinear efficiency with an overall maximum at about 970 nm. Polarization analysis of the second‐harmonic emission confirms the expected zinc blende symmetry, and allows extraction of the three‐dimensional nanocrystal orientation. The small size of these nonlinearly active quantum dots, together with the intrinsic coherence and orientation sensitivity of the SHG process, are well adapted for ultrafast probing of optical near‐fields with high resolution as well as for orientation tracking for bioimaging applications.     

Synthesis of CuS and PbS nanocrystals on the basis of PE/NBR polymer/elastomeric composites for their applications

In this research work, we have presented a chemical method to elaborate the PbS, CuS nanocrystals embedded in a polymer composites matrix. We have used polyethylene and nitrile butadiene rubber PE/NBR as a support for synthesis of lead sulfide (PbS) and copper sulfide (CuS) nanocrystals. The size control and morphology of these (PbS and CuS) nanoparticles have been applied by the method of “layer by layer”. The obtained nanoparticles were characterized by X-ray diffraction (XRD), UV–Vis and Atomic Force Microscopy (AFM). UV–Vis spectroscopy was used to determine simple optical responses, getting the biggest transmittances of CuS and PbS nanoparticles. Measured size of CuS nanoparticles is approximately 5.5–90 nm in different dose. X-ray diffraction (XRD) study confirmed the formation of cubic phase of PbS nanocrystals into the composite matrix. The size of PbS was estimated ∼9 nm. The surface morphology and crystallite sizes were determined by Atomic Force Microscopy measurements.