Evolution of luminescence properties of CdTe quantum dots in liquid/solid environment

We studied the luminescence behavior of different sized CdTe quantum dots (QDs) dispersed in liquid solution, close-packed films and layer-by-layer assembled films respectively. The changes of emission color from CdTe QDs in water droplets during the evaporation of solvent have been observed. The quenching of the emission from small dots accompanied by the enhancement of the emission from large dots indicate that Forster resonance energy transfer processes occur from donors (small dots) to acceptors (large dot) for CdTe QDs system. Excitation (PLE) spectra confirm that the changes of the luminescence were attributed to the resonance energy transfer between small and larger dots in a mixed QD system.     

New insights in high-energy electron emission and underlying transport physics of nanocrystalline Si

This paper presents quantitative analysis of electron emission from nanocrystalline Si dots, and discusses its mechanism based on the calculations of electronic and phononic states. Analysis of emission energy distribution measured from the vacuum level shows that the energy at the peak of the distribution increases linearly with increasing voltage applied across the nanocrystalline Si system. The slope of the linear law is unity, regardless of process conditions. Increasing voltage significantly changes the shape of the distribution at the energies smaller than the peak, while it has minimal impact at the energies larger than the peak. Both the conventional field emission model and the metal-oxide-semiconductor model fail to explain those behaviors. Calculations of electronic and phononic states in a chain of the nanocrystalline Si dots indicate a possibility of strong suppression of electron energy relaxation, which may be a possible mechanism of the high-energy electron emission phenomena.     

Ultrafast excited state deactivation of doped porous anodic alumina membranes

Free-standing, bi-directionally permeable and ultra-thin anodic aluminum oxide (AAO) membranes establish attractive templates (host) for the synthesis of nano-dots and rods of various materials (guest). This is due to their chemical and structural integrity and high periodicity on length scales of 5-150 nm which are often used to host photoactive nano-materials for various device applications including dye-sensitized solar cells. In the present study, AAO membranes are synthesized by using electrochemical methods and a detailed structural characterization using FEG-SEM, XRD and TGA confirms the porosity and purity of the material. Defect-mediated photoluminescence quenching of the porous AAO membrane in the presence of an electron accepting guest organic molecule (benzoquinone) is studied by means of steady-state and picosecond/femtosecond-resolved luminescence measurements. Using time-resolved luminescence transients, we have also revealed light harvesting of complexes of porous alumina impregnated with inorganic quantum dots (Maple Red) or gold nanowires. Both the F?rster resonance energy transfer and the nano-surface energy transfer techniques are employed to examine the observed quenching behavior as a function of the characteristic donor-acceptor distances. The experimental results will find their relevance in light harvesting devices based on AAOs combined with other materials involving a decisive energy/charge transfer dynamics.     

Super‐Efficient Exciton Funneling in Layer‐by‐Layer Semiconductor Nanocrystal Structures

In semiconductor nanocrystals the electronic energy gap is determined not only by the material but also by the size of the nanocrystals. This allows the construction of an energy‐gap gradient normal to multiple layers of nanocrystals where the diameters of the nanocrystals are monotonically increasing or decreasing in subsequent layers. In such devices we observe a highly efficient funneling of excitation energy from layers comprising smaller nanocrystals towards the layer with the largest nanocrystals in the center of the funnel. Most importantly, not only are excitons in radiative states transferred, but also excitons from trapped states, usually lost for luminescence, can be effectively recycled, hence increasing the overall luminescence yield.     

Enhanced emissions of Eu(3+) by energy transfer from ZnO quantum dots embedded in SiO(2) glass

SiO(2):Eu(3+) based bulk composites containing ZnO quantum dots were synthesized by an in situ sol-gel process. The quantum dots homogeneously distributed among the SiO(2) glass matrix exhibited a broad ultraviolet emission band centered at 385?nm. The ZnO ultraviolet luminescence intensity decreased monotonically with increasing Eu(3+) doping concentration, while the Eu(3+) visible emission was intensified significantly by the precipitation of ZnO quantum dots, ascribed to the energy transfer from ZnO to Eu(3+). The Eu(3+) luminescence at 612?nm for the sample with 20?mol% ZnO was about ten times stronger than that for the sample without ZnO. The influence of ZnO or Eu(3+) concentration on the energy transfer process is discussed.     

Exciton storage by Mn(2+) in colloidal Mn(2+)-doped CdSe quantum dots

Colloidal Mn (2+)-doped CdSe quantum dots showing long excitonic photoluminescence decay times of up to tau exc = 15 mus at temperatures over 100 K are described. These decay times exceed those of undoped CdSe quantum dots by approximately 10 (3) and are shown to arise from the creation of excitons by back energy transfer from excited Mn (2+) dopant ions. A kinetic model describing thermal equilibrium between Mn (2+ 4)T 1 and CdSe excitonic excited states reproduces the experimental observations and reveals that, for some quantum dots, excitons can emit with near unity probability despite being approximately 100 meV above the Mn (2+ 4)T 1 state. The effect of Mn (2+) doping on CdSe quantum dot luminescence at high temperatures is thus completely opposite from that at low temperatures described previously.     

DNA-based programming of quantum dot valency, self-assembly and luminescence

The electronic and optical properties of colloidal quantum dots, including the wavelengths of light that they can absorb and emit, depend on the size of the quantum dots. These properties have been exploited in a number of applications including optical detection, solar energy harvesting and biological research. Here, we report the self-assembly of quantum dot complexes using cadmium telluride nanocrystals capped with specific sequences of DNA. Quantum dots with between one and five DNA-based binding sites are synthesized and then used as building blocks to create a variety of rationally designed assemblies, including cross-shaped complexes containing three different types of dots. The structure of the complexes is confirmed with transmission electron microscopy, and photophysical studies are used to quantify energy transfer among the constituent components. Through changes in pH, the conformation of the complexes can also be reversibly switched, turning on and off the transfer of energy between the constituent quantum dots.     

Organic–inorganic nanostructures for luminescent indication in the near-infrared range

Amplifying and quenching of IR luminescence of colloidal Ag₂S quantum dots were revealed to take place when they couple to organic dye molecules of 3,3′-di-(γ-sulfopropyl)-9-ethyl-4,5,4′,5′-dibenzothiacarbocyanine betaine and erytrosine pyridinium salts, respectively. The observed effects are explained as due to the formation of organic–inorganic heterostructures with different mutual arrangement of electronic states of the dyes and the quantum dots.     

Electronic excited states in bilayer graphene double quantum dots

We report tunneling spectroscopy experiments on a bilayer graphene double quantum dot device that can be tuned by all-graphene lateral gates. The diameter of the two quantum dots are around 50 nm and the constrictions acting as tunneling barriers are 30 nm in width. The double quantum dot features additional energies on the order of 20 meV. Charge stability diagrams allow us to study the tunable interdot coupling energy as well as the spectrum of the electronic excited states on a number of individual triple points over a large energy range. The obtained constant level spacing of 1.75 meV over a wide energy range is in good agreement with the expected single-particle energy spacing in bilayer graphene quantum dots. Finally, we investigate the evolution of the electronic excited states in a parallel magnetic field.     

Nonradiative resonance energy transfer between two semiconductor quantum dots

We consider the nonradiative resonance energy transfer between two semiconductor quantum dots (donor and acceptor), taking into account the nonparabolicity of the electron dispersion law, and the energy transfer due to the Coulomb interaction between charge carriers of the donor and acceptor. We show that, when nonparabolicity of the dispersion law is taken into account, a new term enters the matrix element of the energy transfer, which enhances the probability of the resonance energy transfer.     

Level structure of InAs quantum dots in two-dimensional assemblies

The electronic level structure of colloidal InAs quantum dots (QDs) in two-dimensional arrays, forming a QD-solid system, was probed using scanning tunneling spectroscopy. The band gap is found to reduce compared to that of the corresponding isolated QDs. Typically, the electron (conduction-band) ground state red shifts more than the hole (valence-band) ground state. This is assigned to the much smaller effective mass of the electrons, resulting in stronger electron delocalization and larger coupling between electron states of neighboring QDs compared to the holes. This is corroborated by comparing these results with those for InAs and CdSe nanorod assemblies, manifesting the effects of the electron effective mass and arrangement of nearest neighbors on the band gap reduction. In addition, in InAs QD arrays, the levels are broadened, and in some cases their discrete level structure was nearly washed out completely and the tunneling spectra exhibited a signature of two-dimensional density of states.     

Energy Offset Between Silicon Quantum Structures: Interface Impact of Embedding Dielectrics as Doping Alternative

Ultrasmall silicon (Si) nanoelectronic devices require an energy shift of electronic states for n‐ and p‐conductivity. Nanocrystal self‐purification and out‐diffusion in field effect transistors cause doping to fail. Here, it is shown that silicon dioxide (SiO₂) and silicon nitride (Si₃N₄) create energy offsets of electronic states in embedded Si quantum dots (QDs) in analogy to doping. Density functional theory (DFT), interface charge transfer (ICT), and experimental verifications arrive at the same size of QDs below which the dielectric dominates their electronic properties. Large positive energy offsets of electronic states and an energy gap increase exist for Si QDs in Si₃N₄ versus SiO₂. Using DFT results, the SiO₂/QD interface coverage is estimated with nitrogen (N) to be 0.1 to 0.5 monolayers (ML) for samples annealed in N₂ versus argon (Ar). The interface impact is described as nanoscopic field effect and propose the energy offset as robust and controllable alternative to impurity doping of Si nanostructures.     

Protein‐Directed Synthesis of NIR‐Emitting,Tunable HgS Quantum Dots and their Applications in Metal‐Ion Sensing

The development of luminescent mercury sulfide quantum dots (HgS QDs) through the bio‐mineralization process has remained unexplored. Herein, a simple, two‐step route for the synthesis of HgS quantum dots in bovine serum albumin (BSA) is reported. The QDs are characterized by UV–vis spectroscopy, Fourier transform infrared (FT‐IR) spectroscopy, luminescence, Raman spectroscopy, transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), circular dichroism (CD), energy dispersive X‐ray analysis (EDX), and picosecond‐resolved optical spectroscopy. Formation of various sizes of QDs is observed by modifying the conditions suitably. The QDs also show tunable luminescence over the 680–800 nm spectral regions, with a quantum yield of 4–5%. The as‐prepared QDs can serve as selective sensor materials for Hg(II) and Cu(II), based on selective luminescence quenching. The quenching mechanism is found to be based on Dexter energy transfer and photoinduced electron transfer for Hg(II) and Cu(II), respectively. The simple synthesis route of protein‐capped HgS QDs would provide additional impetus to explore applications for these materials.     

Electronic structure and optical property of semiconductor nanocrystallites

Semiconductor nanostructures show many special physical properties associated with quantum confinement effects, and have many applications in the opto-electronic and microelectronic fields. However, it is difficult to calculate their electronic states by the ordinary plane wave or linear combination of atomic orbital methods. In this paper, we review some of our works in this field, including semiconductor clusters, self-assembled quantum dots, and diluted magnetic semiconductor quantum dots. In semiconductor clusters we introduce energy bands and effective-mass Hamiltonian of wurtzite structure semiconductors, electronic structures and optical properties of spherical clusters, ellipsoidal clusters, and nanowires. In self-assembled quantum dots we introduce electronic structures and transport properties of quantum rings and quantum dots, and resonant tunneling of 3-dimensional quantum dots. In diluted magnetic semiconductor quantum dots we introduce magnetic-optical properties, and magnetic field tuning of the effective g factor in a diluted magnetic semiconductor quantum dot.     

Luminescence of CdSe quantum dots near a layer of silver nanoparticles ion-synthesized in sapphire

We study the characteristics of the luminescence of composite films based on polymethyl methacrylate with CdSe quantum dots deposited from solution onto the surface of a sapphire substrate containing a preliminarily formed layer with ion-synthesized silver nanoparticles. The sapphire layer with silver nanoparticles exhibits selective plasmon absorption in the visible spectral range with a peak at 463 nm. Enhancement in the exciton luminescence intensity of quantum dots with a peak at 590 nm is observed upon excitation at wavelengths lying in the region of plasmon resonance of metal nanoparticles, as well as luminescence quenching for quantum dots located in the vicinity of silver nanoparticles.     

Ultrafast dynamics of excitons in semiconductor quantum dots on a plasmonically active nano-structured silver film

The excited state dynamics of core-shell type semiconductor quantum dots (QDs) of various sizes in close contact with a plasmonically active silver thin film has been demonstrated by using picosecond resolved fluorescence spectroscopy. The non-radiative energy transfer from the QDs to the metal surface is found to be of F?rster resonance energy transfer (FRET) type rather than the widely expected nano-surface energy transfer (NSET) type. The slower rate of energy transfer processes compared to that of the electron transfer from the excited QDs to an organic molecule benzoquinone reveals an insignificant possibility of charge migration from the QDs to the metallic film.     

Luminescence centers in CaS:Er3+

The diffuse reflectance, photoexcitation, and luminescence spectra and luminescence decay time of CaS:Er³⁺ have been measured at 77 and 300 K and different activator contents. The absorption and luminescence bands due to Er³⁺ centers and native defects have been revealed, and the radiative electronic transitions between excited and ground Er³⁺ states have been identified. The characteristic decay times of the Er^{3+ 2} H _11/2 and ⁴ F _9/2 states in CaS have been determined, and radiative energy transfer from excited states of native defects to erbium ions in CaS:Er³⁺ has been revealed.     

Nanoparticle fluorescence based technology for biological applications

Fluorescence is widely used in biological detection and imaging. The emerging luminescent nanoparticles or quantum dots provide a new type of biological agents that can improve these applications. The advantages of luminescent nanoparticles for biological applications include their high quantum yield, color availability, good photo-stability, large surface-to-volume ratio, surface functionality, and small size. In this review article, we first introduce quantum size confinement, photoluminescence and upconversion luminescence of nanoparticles, then describe the preparation and conjugation of water soluble nanoparticles and introduce the applications of luminescence nanoparticles for in vitro and in vivo imaging, fluorescence resonance energy based detection, and the applications of luminescence nanoparticles for photodynamic activation.     

On the quenching of semiconductor quantum dot photoluminescence by proximal gold nanoparticles

Luminescent quantum dots (QDs) were proven to be very effective fluorescence resonance energy transfer donors with an array of organic dye acceptors, and several fluorescence resonance energy transfer based biosensing assemblies utilizing QDs have been demonstrated in the past few years. Conversely, gold nanoparticles (Au-NPs) are known for their capacity to induce strong fluorescence quenching of conventional dye donors. Using a rigid variable-length polypeptide as a bifunctional biological linker, we monitor the photoluminescence quenching of CdSe-ZnS QDs by Au-NP acceptors arrayed around the QD surface, where the center-to-center separation distance was varied over a broad range of values (approximately 50-200 Angstrom). We measure the Au-NP-induced quenching rates for such QD conjugates using steady-state and time-resolved fluorescence measurements and examine the results within the context of theoretical treatments based on the F?rster dipole-dipole resonance energy transfer, dipole-metal particle energy transfer, and nanosurface energy transfer. Our results indicate that nonradiative quenching of the QD emission by proximal Au-NPs is due to long-distance dipole-metal interactions that extend significantly beyond the classical F?rster range, in agreement with previous studies using organic dye-Au-NP donor-acceptor pairs.     

Optoelectronic and nonlinear optical processes in low dimensional semiconductors

Spatial confinement of quantum excitations on their characteristic wavelength scale in low dimensional materials offers unique possibilities to engineer the electronic structure and thereby control their physical properties by way of simple manipulation of geometrical parameters. This has led to an overwhelming interest in quasi-zero dimensional semiconductors or quantum dots as tunable materials for multitude of exciting applications in optoelectronic and nonlinear optical devices and quantum information processing. Large nonlinear optical response and high luminescence quantum yield expected in these systems is a consequence of huge enhancement of transition probabilities ensuing from quantum confinement. High quantum efficiency of photoluminescence, however, is not usually realized in the case of bare semiconductor nanoparticles owing to the presence of surface states. In this talk, I will focus on the role of quantum confinement and surface states in ascertaining nonlinear optical and optoelectronic properties of II–VI semiconductor quantum dots and their nanocomposites. I will also discuss the influence of nonlinear optical processes on their optoelectronic characteristics.