Physical reasons of emission transformation in infrared CdSeTe/ZnS quantum dots at bioconjugation

The core/shell CdSeTe/ZnS quantum dots (QDs) with emission at 780–800 nm (1.55–1.60 eV) have been studied by means of photoluminescence (PL) and Raman scattering methods in the nonconjugated state and after conjugation to different antibodies (Ab): (i) mouse monoclonal [8C9] human papilloma virus Ab, anti-HPV 16-E7 Ab, (ii) mouse monoclonal [C1P5] human papilloma virus HPV16 E6+HPV18 E6 Ab, and (iii) pseudo rabies virus (PRV) Ab. The transformations of PL and Raman scattering spectra of QDs, stimulated by conjugated antibodies, have been revealed and discussed.The energy band diagram of core/shell CdSeTe/ZnS QDs has been designed that helps to analyze the PL spectra and their transformations at the bioconjugation. It is shown that the core in CdSeTe/ZnS QDs is complex and including the type II quantum well. The last fact permits to explain the nature of infrared (IR) optical transitions (1.55–1.60 eV) and the high energy PL band (1.88–1.94 eV) in the nonconjugated and bioconjugated QDs. A set of physical reasons has been analyzed with the aim to explain the transformation of PL spectra in bioconjugated QDs. Finally it is shown that two factors are responsible for the PL spectrum transformation at bioconjugation to charged antibodies: (i) the change of energy band profile in QDs and (ii) the shift of QD energy levels in the strong quantum confinement case. The effect of PL spectrum transformation is useful for the study of QD bioconjugation to specific antibodies and can be a powerful technique for early medical diagnostics.     

Re-charging the luminescence states in CdSe/ZnS quantum dots at the conjugation to Osteopontin antibodies

The paper presents the original study of photoluminescence (PL) and Raman scattering spectra of core–shell CdSe/ZnS quantum dots (QDs) covered by the amine-derivatized polyethylene glycol (PEG) with luminescence interface states. First commercially available CdSe/ZnS QDs with emission at 640 nm (1.94 eV) covered by PEG polymer have been studied in nonconjugated states. PL spectra of nonconjugated QDs are characterized by a superposition of PL bands related to exciton emission in a CdSe core and to the hot electron–hole recombination via high energy luminescence states. The study of high energy PL bands in QDs at different temperatures has shown that these PL bands are related to luminescence interface states at the CdSe/ZnS or ZnS/polymer interface. Then CdSe/ZnS QDs have been conjugated with biomolecules—the Osteopontin antibodies. It is revealed that the PL spectrum of bioconjugated QDs changed essentially with decreasing hot electron–hole recombination flow via luminescence interface states. It is shown that the QD bioconjugation process to Osteopontin antibodies is complex and includes the covalent and electrostatic interactions between them. The variation of PL spectra due to the bioconjugation is explained on the basis of electrostatic interaction between the QDs and biomolecule dipoles that stimulates re-charging QD interface states. The study of Raman scattering of bioconjugated CdSe/ZnS QDs has confirmed that the antibody molecules have the electric dipoles. It is shown that CdSe/ZnS QDs with luminescence interface states are promising for the study of bioconjugation effects with specific antibodies and can be a powerful technique in biology and medicine.     

Copper- or manganese-doped ZnS quantum dots as fluorescent probes for detecting folic acid in aqueous media

3-Mercaptopropionic acid-capped core/shell ZnS:Cu/ZnS and ZnS:Mn/ZnS doped quantum dots (QDs) prepared through hydrothermal methods exhibit high photoluminescence intensity as well as good photostability. These water-dispersible nanoparticles exhibit high fluorescence sensitivity to folic acid due to the high affinity of the carboxylate groups and nitrogen atoms of folic acid towards the Zn surface atoms of the doped dots. Quenching of the fluorescence intensity of the QDs allows the detection of folic acid concentrations as low as 11 μM, thus affording a very sensitive system for the sensing of this biologically active molecule in aqueous solution. The possible quenching mechanism is discussed.     

Near-infrared photoluminescence and thermally stimulated current in Cu3Ga5Se9 layered crystals: A comparative study

Near-infrared photoluminescence (PL) and thermally stimulated current (TSC) spectra of Cu₃Ga₅Se₉ layered crystals grown by Bridgman method have been studied in the photon energy region of 1.35–1.46 eV and the temperature range of 15–115 K (PL) and 10–170 K (TSC). An infrared PL band centered at 1.42 eV was revealed at T = 15 K. Radiative transitions from shallow donor level placed at 20 meV to moderately deep acceptor level at 310 meV were suggested to be the reason of the observed PL band. TSC curve of Cu₃Ga₅Se₉ crystal exhibited one broad peak at nearly 88 K. The thermal activation energy of traps was found to be 22 meV. An energy level diagram demonstrating the transitions in the crystal band gap was plotted taking account of results of PL and TSC experiments conducted below room temperature.     

Two and four photon absorption and nonlinear refraction in undoped,chromium doped and copper doped ZnS quantum dots

The ZnS quantum dots (QDs) with Cr and Cu doping were synthesized by chemical co-precipitation method. The nanostructures of the prepared undoped and doped ZnS QDs were characterized by UV–vis spectroscopy, Transmission electron microscopy (TEM) and X-ray diffraction (XRD). The sizes of QDs were found to be within 3–5 nm range. The nonlinear parameters viz. Two photon absorption coefficient (β₂), nonlinear refractive index (n₂), third order nonlinear susceptibility (χ³) at wavelength 532 nm and Four photon absorption coefficient (β₄) at wavelength 1064 nm have been calculated by Z-scan technique using nanosecond Nd:YAG laser in undoped, Cr doped and Cu doped ZnS QDs. Higher values of nonlinear parameters for doped ZnS infer that they are potential material for the development of photonics devices and sensor protection applications.     

Tapping the potential of trioctylphosphine (TOP) in the realization of highly luminescent blue-emitting colloidal indium phosphide (InP) quantum dots

In this work, extremely small blue emitting colloidal InP-based quantum dots (size ~ 2–5 nm) have been synthesized using trioctylphosphine (TOP) as a source of phosphorus. The method reported here is unconventional, quite rapid (~90 min), more viable, less expensive and relatively greener as compared to other conventional methods that employ tristrimethylsilyylphosphine(P(SiMe₃)₃) which is scarce, expensive, flammable, highly toxic and even banned in a few countries. Highly luminescent InP QDs having bluish-green emission (λ~ 490 nm) can be synthesized using this method without resorting to any post-synthesis etching to tune the emission to the blue region. Besides being the source of phosphorus and the particle size regulating agent, the efficacy of TOP is further realized during synthesis via its reduction of indium salt, which aids in the formation of indium metal and then subsequently in the development of InP QDs. The PL intensity of as-synthesized InP QDs is further enhanced by growing a shell of wide band gap material, i.e. ZnS resulting in a concurrent increment in quantum yield from ~25% to ~38% respectively.     

Determination of rifampicin based on fluorescence quenching of GSH capped CdTe/ZnS QDs

Aqueous glutathione (GSH)-capped CdTe/ZnS QDs with the diameter of 3–4 nm were synthesized. The fluorescence of CdTe/ZnS QDs at 577 nm was quenched in the presence of rifampicin (Rfp), with excitation wavelength at 350 nm. The mechanism of the interaction of CdTe/ZnS QDs with Rfp was investigated. Under the optimal conditions, the calibration plot of ln(F₀/F) was linear in the range 0.83–56 μg mL^?1 with concentration of Rfp, and the detection limit was 0.25 μg mL^?1. The proposed method was successfully applied to the determination of Rfp in its commercial capsules, and satisfactory results were obtained. The recovery of the method was in the range 98.6–103.2%.     

Growth conditions effects on optical properties of InAs quantum dots grown by molecular beam epitaxy on GaAs (1 1 3)A substrate

We have investigated the optical properties of InAs/GaAs (1 1 3)A quantum dots grown by molecular beam epitaxy (MBE) with different growth rates by photoluminescence spectroscopy (PL) as a function of the excitation density and the sample temperature (10–300 K). Reflection high-energy electron diffraction (RHEED) is used to investigate the formation process of InAs quantum dots (QDs). A redshift of the InAs QDs PL band emission was observed when the growth rate was increased. This result was explained by the increase of the InAs quantum dot size with increasing growth rate. A significant redshift was observed when the arsenic flux was decreased. The evolution of the PL peak energy with increasing temperature has showed an S-shaped form due to the localization effects and is attributed to the efficient relaxation process of carriers in different InAs quantum dots and to the exciton transfer localized at the wetting layer.     

White-light emission from annealed ZnO:Si nanocomposite thin films

As grown ZnO:Si nanocomposites of different compositional ratios were fabricated by thermal evaporation techniques. These films were subjected to post-deposition annealing under high vacuum at a temperature of 250 °C for 90 min. The photoluminescence (PL) spectra of annealed samples have shown marked improvements both in terms of intensity and broadening. Structural and Raman analyses show formation of a Zn–Si–O shell around ZnO nanoclusters wherein on heating Zn₂SiO₄ compound forms resulting in huge UV, orange and red peaks at 310, 570 and 640 nm in PL. The new emissions due to Zn₂SiO₄ completes white light spectrum. The study not only suggests that 1:2 ratio is the best suited for material manipulation but also shows process at the interface of ZnO nanoclusters and silicon matrix leads to new PL emissions.     

Thermal annealing of GaSb quantum dots in GaAs formed by droplet epitaxy

We investigate effects of annealing on GaSb quantum dots (QDs) formed by droplet epitaxy. Ga droplets grown on GaAs are exposed to Sb molecular beam and then annealed at T_a=340–450 °C for 1 min to form GaSb QDs. An atomic force microscope study shows that with the increase of T_a, the average diameter of dots increases by about 60%, while their density decreases to about 1/3. The photoluminescence (PL) of GaSb QDs is observed at around 1 eV only for those samples annealed above T_a=380 °C, which indicates that the annealing process plays an important role in forming high quality GaSb QDs.     

Temperature dependent photoluminescence processes in ZnO thin films grown on sapphire by pulsed laser deposition

Temperature dependence of the photoluminescence (PL) transitions in the range of 10–300 K was studied for ZnO thin films grown on sapphire by pulsed laser deposition. The low temperature PL spectra were dominated by recombination of donor bound excitons (B_X) and their phonon replicas. With increasing temperature, free exciton (F_X) PL and the associated LO phonon replicas increased in intensity at the expense of their bound counterparts. The B_X peak with line width of ∼6 meV at 10 K exhibited thermal activation energy of ∼17 meV, consistent with the exciton-defect binding energy. The separation between the F_X and B_X peak positions was found to reduce with increasing temperature, which was attributed to the transformation of B_X into the shallower donor bound exciton complexes at consecutive lower energy states with increasing temperature, which are possible in ZnO. The energy separation between F_X peak and its corresponding 1-LO phonon replica showed stronger dependence on temperature than that of 2-LO phonon replica. However, their bound counterparts did not exhibit this behavior. The observed temperature dependence of the energy separation between the free exciton and it is LO phonon replicas are explained by considering the kinetic energy of free exciton. The observed PL transitions and their temperature dependence are consistent with observations made with bulk ZnO crystals implying high crystalline and optical quality of the grown films.     

Cadmium sulfide quantum dots stabilized by castor oil and ricinoleic acid

Castor oil and ricinoleic acid (an isolate of castor oil) are environmentally friendly bio-based organic surfactants that have been used as capping agents to prepare nearly spherical cadmium sulfide quantum dots (QDs) at 230, 250 and 280 °C. The prepared quantum dots were characterized by Ultra violet–visible (UV–vis), Photoluminescence (PL), Transmission Electron Microscopy (TEM), High Resolution Transmission Electron Microscopy (HRTEM) and X-ray diffraction (XRD) giving an overall CdS QDs average size of 5.14±0.39 nm. The broad XRD pattern and crystal lattice fringes in the HRTEM images showed a hexagonal phase composition of the CdS QDs. The calculated/estimated average size of the prepared castor oil capped CdS QDs for various techniques were 4.64 nm (TEM), 4.65 nm (EMA), 5.35 nm (UV–vis) and 6.46 nm (XRD). For ricinoleic acid capped CdS QDs, the average sizes were 5.56 nm (TEM), 4.78 nm (EMA), 5.52 nm (UV–vis) and 8.21 nm (XRD). Optical properties of CdS QDs showed a change of band gap energy from its bulk band gap of 2.42–2.82 eV due to quantum size confinement effect for temperature range of 230–280 °C. Similarly, a blue shift was observed in the photoluminescence spectra. Scanning electron microscope (SEM) observations show that the as-synthesized CdS QDs structures are spherical in shape. Fourier transform infra-red (FTIR) studies confirms the formation of castor oil and ricinoleic acid capped CdS QDs.     

The annealing effect on structural,optical and photoelectrical properties of CuInS2/In2S3 films

Successive Ionic Layer Adsorption and Reaction (SILAR) technique was used to deposit the CuInS₂/In₂S₃ multilayer thin film structure at room temperature. The as-deposited film was annealed at 100, 200, 300, 400 and 500 °C for 30 min in nitrogen atmosphere and the annealing effect on structural, optical and photoelectrical properties of the film was investigated. X-ray diffraction (XRD) and optical absorption spectroscopy were used for structural and optical studies. Current–Voltage (I–V) measurements were performed in dark environment and under 15, 30 and 50 mW/cm² light intensity to investigate the photosensitivity of the structure. Also, the electrical resistivity of the film was determined in the temperature range of 300–470 K. It was found that annealing temperature drastically affects the structural, optical and photoelectrical properties of the CuInS₂/In₂S₃ films.     

Improvement of the optical property and uniformity of self-assembled InAs/InGaAs quantum dots by layer-by-layer temperature and substrate rotation

The influence of layer-by-layer temperature and substrate rotation on the optical property and uniformity of self-assembled InAs/In_0.2Ga_0.8As/GaAs quantum dots (QDs) gown with an As₂ source was investigated. An improvement in the optical property of QDs was obtained by the precise control and optimization of growth temperature utilized for each layer, i.e., InAs QDs, InGaAs quantum wells, GaAs barriers and AlGaAs layers, respectively. By using a substrate rotation, the QD density increased from ∼1.4×10¹⁰ to ∼3.2×10¹⁰ cm⁻² and its size also slightly increased, indicating a good quality of QDs. It is found that the use of an appropriate substrate rotation during growth improves the room-temperature (RT) optical property and uniformity of QDs across the wafer. For the QD sample with a substrate rotation of 6 rpm, the RT photoluminescence (PL) intensity is much higher and the standard deviation of RT-PL full-width at half-maximum is decreased by 35% compared to that grown without substrate rotation.     

Influence of argon ambience on the structural,morphological and optical properties of pulsed laser ablated zinc sulfide thin films

Nanostructured zinc suplhide thin films are successfully deposited on quartz substrates using pulsed laser deposition (PLD) under different argon pressures (0, 5, 10, 15 and 20 Pa). The influence of argon ambience on the microstructural, optical and luminescence properties of zinc sulfide (ZnS) thin films is systematically investigated. The GIXRD data suggests rhombohedral structure for ZnS films prepared under different argon ambience. Self-assembly of grains into well-defined patterns along the y direction is observed in the AFM image of the film deposited under argon pressure 20 Pa. All the films show a blue shift in optical band gap. This can be due to the quantum confinement effect and less widening of conduction and valence band for the films with less thickness and smaller grain size. The PL spectra of the different films are recorded at excitation wavelengths 250 nm and 325 nm and the spectra are interpreted. The PL spectra of the films recorded at excitation wavelength 325 nm show intense yellow emission. The film deposited under an argon pressure of 15 Pa shows the highest PL intensity for excitation wavelength 325 nm. For the PL spectra (excitation at 250 nm), the highest PL intensity is observed for the film prepared under argon free ambience. In our study, 15 Pa is the optimum argon pressure for better crystallinity and intense yellow emission when excited at 325 nm.     

Growth and characterization of strain-compensated InGaAs/GaAsSb type II multiple quantum wells on InP substrate

Strain-compensated InGaAs/GaAsSb type II multiple quantum wells (MQWs) were grown by molecular beam epitaxy (MBE) and their optical and electrical properties were studied. High-quality strain-compensated type II MQWs were successfully grown, which have longer emission wavelength than that of lattice-matched type II MQWs. PL peak energy at 300 K of the strain-compensated type II MQWs, where the InGaAs layer has 0.6% tensile strain and GaAsSb layer has 0.6% compressive strain, shows a red-shift of 43 meV, which is 12 meV larger than the calculated energy shift of 31 meV. In addition, the PL intensity and the electron mobility of the strain-compensated MQWs are comparable to those of the lattice-matched MQWs, suggesting that the crystal quality of the strain-compensated MQWs is good and are very promising for low dark current photodiodes in the 2 μm wavelength region.     

Facile synthesis of mercaptosuccinic acid-capped CdTe/CdS/ZnS core/double shell quantum dots with improved cell viability on different cancer cells and normal cells

Water-soluble, mercaptosuccinic acid (MSA)-capped CdTe/CdS/ZnS core/double shell quantum dots (QDs) were prepared by successive growth of CdS and ZnS shells on the as-synthesized CdTe/CdS_thin core/shell quantum dots. The formation of core/double shell structured QDs was investigated by ultraviolet-visible (UV–Vis) absorption and photoluminescence (PL) spectroscopy, PL decay studies, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The core/double shell QDs exhibited good photoluminescence quantum yield (PLQY) which is 70% higher than that of the parent core/shell QDs, and they are stable for months. The average particle size of the core/double shell QDs was ～3 nm as calculated from the transmission electron microscope (TEM) images. The cytotoxicity of the QDs was evaluated on a variety of cancer cells such as HeLa, MCF-7, A549, and normal Vero cells by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) cell viability assay. The results showed that core/double shell QDs were less toxic to the cells when compared to the parent core/shell QDs. MCF-7 cells showed proliferation on incubation with QDs, and this is attributed to the metalloestrogenic activity of cadmium ions released from QDs. The core/double shell CdTe/CdS/ZnS (CSS) QDs were conjugated with transferrin and successfully employed for the biolabeling and fluorescent imaging of HeLa cells. These core/double shell QDs are highly promising fluorescent probe for cancer cell labeling and imaging applications.     

Luminescence enhancement by the reduction–oxidation synthesis in monoclinic RE2O3 (RE=Eu,Gd) phosphors containing Eu3+ activator

A novel synthesis was developed for enhanced luminescence in sesquioxide phosphors containing Eu³⁺ activator. It consisted of two annealing steps: reduction under vacuum with gaseous H₂ at 10 Torr and 1300 °C and re-oxidation at 300–1500 °C in air. The integrated luminescence intensity of the monoclinic Eu₂O₃ phosphor was enhanced ca. 21 times by this method compared with conventional processing. The photoluminescence (PL) intensity was maximized at re-oxidation temperatures of 500–1100 °C. The PL characteristics of monoclinic Eu₂O₃ and Gd₂O₃:0.06Eu samples were compared with a commercial cubic Y₂O₃:Eu phosphor. The evolution of physical characteristics during the two-step annealing was studied by Raman spectroscopy, XPS, XRD, PL decay analysis, and SEM. PL decay lifetime increased proportionally to the PL intensity over the range 0.5–100 μs. Additional vibrational modes appeared at 490, 497, and 512 cm^?1 after the two-step annealing. The increase in PL intensity was ascribed to the formation of excess oxygen vacancies and their redistribution during annealing. Resonance crossovers between the charge transfer state and the emitting ⁵D_J states are discussed in relation to reported luminescence saturation mechanisms for oxysulfides Ln₂O₂S:Eu³⁺ (Ln=Y, La).     

Thermo,Iono and photoluminescence properties of 100 MeV Si7+ ions bombarded CaSiO3:Eu3+ nanophosphor

This paper reports on the thermo (TL), iono (IL) and photoluminescence (PL) properties of nanocrystalline CaSiO₃:Eu³⁺ (1–5 mol %) bombarded with 100 MeV Si⁷⁺ ions for the first time. The effect of different dopant concentrations and influence of ion fluence has been discussed. The characteristic emission peaks ⁵D₀→⁷F_J (J=0, 1, 2, 3, 4) of Eu³⁺ ions was recorded in both PL (1×10¹¹–1×10¹³ ions cm^?2) and IL (4.16×10¹²–6.77×10¹² ions cm^?2) spectra. It is observed that PL intensity increases with ion fluence, whereas in IL the peaks intensity increases up to fluence 5.20×10¹² ions cm^?2, then it decreases. A well resolved TL glow peak at ～304 °C was recorded in all the ion bombarded samples at a warming rate of 5 °C s^?1. The TL intensity is found to be maximum at 5 mol% Eu³⁺ concentration. Further, TL intensity increases sub linearly with shifting of glow peak towards lower temperature with ion fluence.     

Luminescence properties of InAs quantum dots formed by a modified self-assembled method

The luminescence properties of self-assembled InAs quantum dots (QDs) on GaAs (1 0 0) substrates grown by molecular beam epitaxy have been investigated using temperature-dependent photoluminescence (PL) and time-resolved PL (TRPL). InAs QDs were grown using an In-interruption growth technique, in which the indium flux was periodically interrupted. InAs QDs grown using In-interruption showed reduced PL linewidth, redshifted PL emission energy, increased energy level spacing between the ground state and the first excited state, and reduced decay time, indicating an improvement in the size distribution and size/shape of QDs.