In this work are presented the results obtained with solar cells sensitized with quantum dots of cadmium sulphide (CdS) incorporating luminescent materials (NaYF4:Yb/Er). The study revealed that through using a bifunctional layer of NaYF4:Yb/Er submicron rods, the infrared radiation is absorbed in 980nm to generate luminescence in the visible region to 530nm, under the UP-conversion process, in the same way simultaneously, NaYF4:Yb/Er layer causes scattering toward the quantum dots, the emission and scattering generated by this material is reabsorbed by the QD-CdS, and these in turn are absorbing in its range of solar radiation absorption, Thus generates an increase in the electron injection into the semiconductor of TiO2. The results of a cell incorporating NaYF4: Yb/Er at 0.07M shown photoconversion efficiencies of 3.39% improving efficiency with respect to the reference solar cell without using NaYF4: Yb/Er of 1.99%. The obtained values of current and voltage showed a strong dependence of the percentage of NaYF4 Yb/Er, and the mechanism of incorporation of this material.
A technique to fabricate dye (rhodamine B) sensitized solar cells based on Titanium Oxide (TiO2) and Zinc Oxide (ZnO) nanoparticles are reported. The TiO2 was synthesized using the sol-gel method and the ZnO was synthesized by hydrolysis method to obtain nanoparticles of ~ 5 nm and 150 nm respectively. ZnO was doped with Al3+ in order to enhance the photovoltaic efficiency to promote the electrons mobility. The photovoltaic conversion characterization of films of TiO2, ZnO and ZnO:Al3+ nanoparticles is also reported. The generated photocurrent was measured by two methods; one of those uses a three electrode electrochemical cell and the other use an electronic array where the cells were exposed to UV lamp and the sun light. The role of the TiO2, ZnO and Al3+ doped ZnO nanoparticles is discussed to obtain a better efficiency in the generation of photocurrent (PC). The results exhibited by the electrochemical cell method, efficiencies of 0.55 (PC=187 μA/cm2) and 0.22 (PC=149 μA/cm2) for TiO2 and undoped ZnO respectively. However, when ZnO is doped with Al3+ at the higher concentration the efficiency was 0.44. While using the electronic array the results exhibited efficiencies of 0.31 (PC=45 μA/cm2) and 0.09 (PC=16 μA/cm2) for TiO2 and undoped ZnO respectively. However, when ZnO is doped with Al3+ at the higher concentration the efficiency was 0.44 and 0.48 for electrochemical cell and electronic array respectively. This shows that Al3+ enhances the photogenerated charge carriers increasing the mobility of electrons.
In recent years the use of nanoparticles in medical applications has boomed. This is because the various applications that provide these materials like drug delivery, cancer cell diagnostics and therapeutics [1-5]. Biomedical applications of Quantum Dots (QDs) are focused on molecular imaging and biological sensing due to its optical properties. The size of QDs can be continuously tuned from 2 to 10 nm in diameter, which, after polymer encapsulation, generally increases to 5 – 20 nm diminishing the toxicity. The QDs prepared in our lab have a diameter between 2 to 7 nm. Particles smaller than 5 nm can interact with the cells [2]. Some of the characteristics that distinguish QDs from the commonly used fluorophores are wider range of emission, narrow and more sharply defined emission peak, brighter emission and a higher signal to noise ratio compared with organic dyes [6]. In this paper we will show our progress in the study of the interaction of quantum dots in live cells for image and Raman spectroscopy applications. We will also show the results of the interaction of quantum dots with genomic DNA for diagnostic purposes.
This work reports the synthesis, structural characterization, and optical properties of ZrO2:Yb3+-Er3+ (2–1 mol%) nanocrystals. The nanoparticles were coated with 3-aminopropyl triethoxysilane (APTES) and further modified with biomolecules, such as Biotin-Anti-rabbit (mouse IgG) and rabbit antibody-AntiKi-67, through a conjugation method. The conjugation was successfully confirmed by Fourier transform infrared, zeta potential, and dynamic light scattering. The internalization of the conjugated nanoparticles in human cervical cancer (HeLa) cells was followed by two-photon confocal microscopy. The ZrO2:Yb3+-Er3+ nanocrystals exhibited strong red emission under 970-nm excitation. Moreover, the luminescence change due to the addition of APTES molecules and biomolecules on the nanocrystals was also studied. These results demonstrate that ZrO2:Yb3+-Er3+ nanocrystals can be successfully functionalized with biomolecules to develop platforms for biolabeling and bioimaging.
In this work, it is presented the synthesis of ZrO2:Yb3+, Er3+ nanocrystals by precipitation method with a hydrothermal
process and annealing at 1000 °C. Samples were prepared with 2 mol% of Yb3+ and 1mol% of Er3+, and sensitized with
different concentration of Gd3+ and S2+. The ceramic powders were characterized with different techniques to determine
their chemical composition, crystalline structure, crystallite size, morphology and upconversion emission. All samples
present the tetragonal crystalline phase with crystallite size lower than 70 nm with cubic shape. Experimental results
suggest the presence of SO4 on the surface of nanocrystals reducing the OH's and then improving the signal emitted. The
nanocrystals presented strong upconversion emission enhanced by the presence of both sensitizer Gd3+ and S2+. A
synergistic effect was observed with the combination of both sensitizers, improving the upconverted visible emission.
The red emission peak centered at 655 nm dominates the signal emitted but the red/green intensity ratio can be changed
by controlling the dopant composition.
This work presents the structural, morphological and luminescent properties of Y3Al5O12:Ce3+(0.1%)-Pr3+(0.1%)
nanophosphors synthesized by a hydrothermal precipitation method. It was observed that the incorporation of Amonium
hydroxide (NH4OH, Ammonia) increases the YAG (%)/YAM(%) ratio, leading to an increase of 83% in the overall
emission under 460 nm excitation. The nanophosphor with the highest content of YAM, presented the best broad green-yellow-
red emission band corresponding to Ce3+ and Pr3+ emissions under 340 nm excitation. The average
nanocrystallite size was 50 and 55 nm for the samples with and without Ammonia respectively. Quenching of the overall
emission after an annealing treatment at 1100°C is observed in spite of reaching single YAG crystalline phase. That
suggests Pr4+ and/or color centers formation due to the estequiometric unbalance as a consequence of the YAM to YAG
transformation. By taking advantage of the broad emission under 340 nm and using a blue dye, we produced white light
with CIE coordinates of (0.30, 0.36).
In this work, the preparation and photovoltaic conversion characterization of 10 μm films of sensitized TiO2 is
reported. The 13 nm TiO2 nanocrystals with anatase crystalline phase were deposited on an FTO substrate
and decorated with Au nanocrystals and sensitized with CdSe Quantum dots (QD) and poly(3-octylthiophene)
(P3OT) in different configurations. The photocurrent was measured in a three electrode electrochemical cell. The
results exhibited that TiO2/Au/QD/P3OT films have the largest photocurrent, giving approximately fivefold
the photocurrent of TiO2 films sensitized only with QD and near sevenfold the photocurrent of Au decorated
TiO2 films. These results are attributed to the ability of the Au nanocrystals to extract electrons from QD and
the photogeneration and hole transport of P3OT. Both phenomena combined with the QD's photogeneration
give a great amount of electrons that increase the photocurrent generation.
Er doped and Yb-Er-Tm codoped ZrO2 nanocrystals of average 80 nm in size were prepared by a sol-gel
process with the presence of nonionic (PLURONIC F-127) surfactant, and the up-conversion emission
was characterized under IR (980 nm) excitation. The effect of the codoped conditions on the crystalline
structure and photoluminescence properties were studied. A strong green emission was produced with 5
mol %, 0.2 mol %, 0.01 mol % of Yb3+-Er3+-Tm3+ codoped ZrO2 respectively. It was prepared Er doped
ZrO2 -SiO2 core-shell and SiO2 coated Er doped ZrO2 in 2-propanol and water, respectively. The presence
of the silica shell of average of 15 nm in thickness has been confirmed by transmition electron
microscopy. Photolumineiscence studies show that the silica shell does not affect the emission when the
nanoparticles are excited with 980 nm. The up-converting Yb3+-Er3+-Tm3+ codoped ZrO2 nanocrystal has
showed to be a powerful tool to future detection techniques. The viability of the nanoparticles of codoped
ZrO2 for biological imaging was confirmed by multiphotonic microscope imaging of cervix tissue with inserted codoped ZrO2 nanoparticles. The cervix tissue has a moderate dysplasia. The nanoparticles were
introduced at 80 % of the tissue depth (5 μm) without being functionalized.
Although the general properties of the rare earths' electronic states and transitions are well understood, much less is
known regarding the relationships between them and the electronic band states of a crystal lattice. These interactions can
enhance or inhibit performance and provide mechanisms for manipulating the material's optical properties. Up-conversion
ZrO2:Tm3+, Yb3+, Er3+, Ho3+ nano-crystalline samples were synthesized by sol-gel method and emission
properties were analyzed as function of different concentrations of rare earth ions. The samples were pumped at 970 nm
with a semiconductor laser source. The introduction of different ion concentrations affects the shape and peak intensities
of the measured blue, green and red bands. Results showed in this work tend to demonstrate a feasible control of the
chromaticity coordinates of emission and present an approximation to the equipotential white chromaticity coordinates.
The Photoluminescence (PL), FFTIR, Raman characterization, XRD and TEM of Er doped nanocrystals (Y3Al5O12:Er)
prepared by glycolate method modified with PVA and UREA is reported. Irregular morphology was observed but for
some concentration of PVA and UREA nanorods was observed, being PVA dominant in final morphology. XRD patterns
show the presence of hexagonal phase of YAG (YAH) when the UREA was used but pure YAG crystalline structure was
obtained with only PVA. Raman spectroscopy confirms the crystalline phase and in combination with infrared
spectroscopy the presence of oxygen deficiency was observed. Strong green emission was observed as a result of the
upconversion mechanism due to the two photon process. Luminescence results show that both PVA and UREA do not
modify the emission properties but control the morphology.
The thermoluminescence (TL) characterization of undoped and Lu3+ doped nanocrystalline ZrO2 under β-ray irradiation
is presented. The average crystallite size was 40 nm and the crystalline structure was monoclinic although for doped
samples 5 wt% of tetragonal was observed. The TL results show a typical second order kinetic with four TL peaks
centered around 120, 170, 240 and 280 °C when the sample is exposed to β-ray irradiation. The presence of dopant ion
induces changes in the trapping process and recombination efficiency in the TL response. The result is that dominant
peak typically centered at 120 °C was quenched while the peak centered at 240 °C was enhanced. This shifting to higher
temperature of the dominant peak induces important changes in the dosimetric properties of nanocrystals. The dosimetric
behavior for TL method and the TL fading of the samples under β-irradiation was systematically characterized as
function of the dopant concentration. The high efficiency of the TL suggest a good potential of this nanophosphor as β-
irradiation dosimeter.
Au/Ag and Ag/Ag alloy surface roughened consisting of various mole fractions of gold and silver have been synthesized in aqueous solution by the co-reduction of chlorauric acid (HAuCl) and silver nitrate (AgNO3) with trisodium citrate. For the metallic alloys it was found that the maximum of the plasmon band shifts linearly towards the blue with increasing silver content. Metal nanoparticles could be used in applications such specificity sensors and substrates for Enhanced Raman Spectroscopy (ERS). A goal in the emerging field of nanotechnology is to make nanostructures or nanoarrays with a very large surface area. Crystalline SnO2 and Sc2O3 were also used for ERS experiments. Tin (IV) oxide is widely applied as a sensor component as a consequence of the high sensitivity of its conductivity to the surrounding atmosphere. Scandium oxide has been used for high reflectance coatings for UV applications. Nanoparticles were characterization by UV-VIS Spectroscopy and Scanning Electron-Microscopy (SEM). The SEM has been used to provide microstructural information of coverage used. Nanoparticle structure and spectral and electronic properties of these systems may allow for applications in sensors development for the use in nitroaromatic explosive detection at the subpicograms range.
A method to prepare metallic nanoparticles films in the presence of a hydrophilic copolymer with the aim of inhibiting the formation of clusters in the nanoparticles has been developed. Thin films prepared could be used in applications such as sensors development and substrates for surface-enhanced Raman spectroscopy. The synthesis of colloidal solutions of silver nanoparticles was achieved by the reduction AgNO3 using sodium citrate with thermal treatment which results in a robust fabrication of gold and silver films. The polymeric films were prepared by polymerization 2-hydroxyethyl methacrylate with methacrylic acid (method 1). The other procedure employed (method 2) incorporated the use of polyvinyl pyrrolidone and polyethylene glycol as copolymers. A scanning electron microscope was used to provide microstructural information of coverage achieved. The ability to tune the nanocoating structure and spectral and electronic properties can be used for applications such as sensors used in the detection of explosives. Silver nanoparticles were also characterized by surface-enhanced Raman scattering (SERS), which integrates high chemical sensitivity with spectroscopic identification and has enormous potential for applications involving ultra-sensitive chemical detection. Spectra were obtained using a Renishaw RM2000 Raman
Microspectrometer system operating in the visible region excitation (532 nm).
Silver colloids have been used for detecting single molecules in solution with high sensitivity and molecular specificity. Single particle detection is of great scientific and practical interest in many fields such as chemistry, biology, medicine and environmental science. We report the Surface Enhanced Resonance Raman Scattering (SERRS) spectrum of derivatized dye-TNT and DNT at a concentration level of 1x10-9 M in silver colloids at pH 9 at 532 nm for three 10 second intervals at different power intensities by suppressing the solvent of the colloid and obtaining nanoparticle to be diluted in another solvent or for mixing with another compound that has affinity for DNT. The azo structures obtained by derivatizing the TNT and DNT are highly colored derivatives, which contain a functionality that will enable a strong bond with the metal surface. The objective of this study is to modify silver colloids by using compounds such as adenine and the modified compounds are structurally similar to the ones that are going to be further studied in the colloid systems and were utilized for SERRS to increase the Raman signal from TNT and DNT.
Surface Enhanced Raman Scattering (SERS) is normally obtained from nanoactive surfaces or colloids of group II-B metals, in particular of silver and gold. In this study another type of nanosurface has been explored seeking more reproducible Raman spectra than those obtained from metallic substrates. Compounds of elements of the fourth transition period were tested for SERS analysis of nitroexplosives. Titanium (IV) oxides were found to give good Raman Enhanced signals of target molecules. TNT and DNT increased their signal intensities for this technique and were evaluated for the increase in different excitation sources. Laser lines at 785, 532 and 514.5 nm were evaluated to determine relative SERS cross sections for various vibrational bands of the target nitroexplosives. Polymorphism seems to play an important role in the Raman signal enhancement when using metal oxides: high rutile percent mixtures with anatase gave higher Raman scattered signal enhancement.
Chemical oxidation doping effect produced by 3000 ppm of NO2 with N2 balance on spin coated regioregular head-to-tail poly(3-octylthiophene) (P3OT) thin films is reported. Undoped and doped states mechanisms are discussed based on changes in optical absorptiometry, surface analysis and refractive index. The two midgaps created for few minutes in the P3OT under NO2 doping effect by the polarons and bipolarons for mobility capabilities and its final doped state has been optically monitored and discussed. A significant change on the surface of undoped and doped P3OT thin films was inspected by atomic force microscopy (AFM). A P3OT refractive index transition from 1.69 (undoped) to 1.55 (doped) has been observed and discussed. Finally, the electrostatic attraction between the polaron and its counter ion (NO2-) has been analyzed for the possibility to diffuse the counter ion from the P3OT thin films and make possible its backward state (reversibility). The theoretical and experimental data results presented are part of a fiber optic chemical sensor (FOCS) project for NO2 particles detection.
Nanocrystalline yttrium aluminum garnet doped with Cerium (YAG:Ce3+), was synthesized by means of a modified sol-gel method that consists of a mixture of salts in an aqueous media. Structure and morphology were characterized by X-ray diffraction and Transmission Electron Microscopy. Single crystalline phase were obtained and the crystallite size range from 26 nm to 96 nm depending on the annealing temperature (from 800 to 1150 °C, respectively). The photoluminescence dependence on the crystallite size and ion concentration was performed. The experimental results show that the best ion concentration where the highest luminescence was obtained correspond to 0.1 mol% and that increases as the crystallite size increases. The feasibility of the modified sol-gel method for the preparation of nanocrystalline YAG is discussed.
Nanocrystalline ZrO2:Sm3+ doped at 2 mol% was prepared by sol-gel process and the structure and photoluminescence characterization as function of the annealing temperature were performed. Strong visible fluorescence emission produced by transitions 4G5/2→4H5/2,7/2,9/2 of Sm3+ was obtained by energy transfer process exciting the host at 320 nm and by direct excitation at 408 nm. The experimental results show a quenching of the emission bands by reducing the annealing temperature that is associated with a high content of tetragonal structure. Furthermore, an important change in the structure of the signal emitted was observed when ion was excited directly and the annealing temperature was reduced. These results suggest the possibility to tune the emission of ZrO2:Sm3+ nanophosphor.
The photoluminescence and crystalline structure characterization of undoped and several samarium and erbium doped ZrO2 samples are reported. Strong visible fluorescence emission produced by the transitions 4G5/2→6H5/2,7/2,9/2 of Sm3+ was obtained by the excitation of the host at 320 nm (downconversion). Green (545 nm) and red (680 nm) emissions bands were observed under 962 nm excitation (upconversion). Experimental results showed that the emission bands could be tuned by controlling the Er3+ concentration. In particular, for the highest Er3+ concentration, the red band is enhanced under 962 nm excitation. The nature of this behavior is discussed taking into account the concentration dependent non-radiative energy transfer (4I13/2 + 4I11/2) → (4F9/2 + 4I15/2) and cross-relaxation (2H11/2 + 4I15/2) → (4I9/2 + 4I13/2) process.
The photoluminescence (PL) and thermoluminescence (TL) characterization of undoped and cerium and terbium doped nanocrystalline Y3Al5O12 (YAG) prepared by the sol-gel method is reported. The experimental results of the PL show the typical emission bands centered at 490, 543 and 590 nm for YAG:Tb3+ and 530 nm for YAG:Ce3+ when excited with 325 and 345 nm light, respectively. The TL signal was obtained after exposure to UV-, X- and β- irradiation. The thermoluminescence results indicate that YAG:Tb3+ sample is very sensitive to all type of irradiation used, being highly sensitive for UV-irradiation. The high efficiency of the TL and PL suggests a good potential of this material as radiation dosimeter as well as active optical windows and new generation television screen.
Polystyrene dye doped plastic optical fiber was prepared and used to detect gamma and beta radiation from I151 and TeO4 gamma tracers typically used to get images of tumor areas within the human body. Absorption and fluorescence emission of TMQ, PBDBD365, POPOP styrene doped was performed under gamma and UV-irradiation. The fluorescence efficiency of the binary system PBDBD365-POPOP and the ternary TMQ- PBDBD365-POPOP was compared and according to the experimental results it was shown that the presence of the TMQ dye enhance the fluoresce obtained under I151 radiation. Systematic characterization of the binary system was performed as function of primary dye concentration .
Spectroscopic properties of Nd3+ in barium fluoroborophosphate and barium fluorosulphatephosphate glassy matrices have been analyzed by fitting the experimental data with the standard Judd-Ofelt theory. Various spectroscopic parameters viz. Radiative transition probabilities, radiative decay time, stimulated emission cross sections and quantum efficiency of the principal fluorescence transition from the 4F3/2 metastable level are obtained. Results show that addition of borate content to the fluorophosphate matrix will reduce the fluorescence spectral properties of Nd3+, whereas the influence of sulphate content is to improve the fluorescence spectral properties over a considerable extent. A comparison of the radiative properties of two hosts with that of fluorophosphate shows that the performance of the fluorosulphatephosphate matrix is superior and hence can be considered as possible candidate for solid state laser amplifiers.
Photoluminescence (PL) of pure and 0.2 mol percent Sm3+ doped zirconium oxide prepared by the Sol-Gel process and annealed at 1000 degrees C to stabilize the monoclinic phase were performed. The experimental spectra suggest the presence of energy transfer pro9cesses between the host and the dopant when the host was excited with a signal centered at 320 nm. The Sm3+ doped monoclinic zirconium oxide shows strong emission at the green and red bands, corresponding to the 4G5/2 yields 6H5/2 and 4G5/2 yields 6H7/2 samarium transition, respectively; whereas the undoped sample only shows a broad band emission centered at 495 nm. The main mechanism that allows the samarium emission under UV-excitation appears to be non-radiative energy transfer from the ZoO2 host to the Sm3+ ions.
We present side induced fluorescence (SIF) results on laser dye doped unclad plastic optical fibers. The SIF data can be used to obtain optical loss spectra for the low loss region of the absorption tail of the laser dye that has been doped into the fiber. Dyes which have been examined include derivatives of rhodamine and pyromethene. SIF deduced loss results in combination with cutback loss measurements on undoped fibers suggest that the electronic absorption of the laser dye dominates the loss far (> 200 nm) from the peak of the dye absorption (the order of 0.5 cm-1 at 750 nm). Loss measurements of unclad undoped fibers suggest that loss is dominated by scattering and defect mechanisms. In fact these losses are quite high compared to literature measurements of analogous clad fibers. Thus intrinsic loss of the polymer (PMMA in most cases) is minor compared to scattering and defect losses when dealing with unclad fibers. We also present the fit of our dye-doped fiber loss data to homogeneous and inhomogeneous broadening equations and show that broadening is dominated by inhomogeneous mechanisms as is expected.
The mechanism of non-radiative energy transfer between Tb3+ and Nd3+ ions in fluorophosphate glass has been analyzed with the Forster-Dexter theory. Several/transfer parameters such as the transfer probability, transfer efficiency, critical transfer distance, and critical concentration have been evaluated by fitting the experimental fluorescence spectrum of those ions with that theory. The recorded emission spectrum of Tb3+ with different Nd3+ ion concentrations shows that the transfer process from the 5D4 state of Tb3+ to the 4G5/2 state of Nd3+ is driven predominantly by a dipole-dipole interaction. The effect of this energy transfer is to considerably enhance the optical gain of the 4F3/2 to 4I11/2 emission band of Nd3+ ions. The reduction in optical gain at high activator concentrations is attributed to the concentration quenching in Nd3+ ion pairs. In addition to this, the dependence of the J-O parameters, several radiative properties of Nd3+ ions in the phosphate content as well as the nature of alkali content were also studied.
We report on a procedure to prepare plastic optical fibers with in-line indium electrodes alongside a wave-guiding core. The goal is the realization of an electro-optic modulator device structure entirely contained with the cladding of the fiber. This work is analogous to that of Kuzyk and others at Washington State University, though we report on a different procedure to manufacture the preform from which the fiber is drawn.
Acrylic plastic optical fibers containing the laser dye Rhodamine B chloride have been drawn from unclad doped acrylic preforms. The fibers strongly emit waveguided fluorescence light produced form ambient side illumination along the length of the fiber. We have characterized the loss in the wavelength region of strong absorption by measuring the attenuation of the side induced fluorescence (SIF) produced by He-Ne (green) and He-Cd (blue) laser lines. We can accurately quantify the loss in the high loss spectral region using SIF. Attenuation data and the associated SIF analysis will be discussed.
We discuss plastic optical fiber technology in the context of its relationship to glass optical fiber technology. POF technology serves as a low cost way to investigate innovative optical fiber material structures. POFs offer some application advantages, especially in low cost broad bandwidth easily interconnected local area networks. Applications to space technology include scintillation sensing and other specialty sensing fibers.
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