Dr. Nicoleta PREDA

Today, flexible and lightweight electronics are regarded as a viable alternative to conventional rigid and heavy devices in various application fields. In the optoelectronic area, organic semiconductors offer advantages such as high absorption coefficients, low processing temperatures, mechanical flexibility and compatibility with plastic substrates, while inorganic nanostructures provide good electronic properties and high thermal stability. Thus, composite films with enhanced properties can be achieved by inserting inorganic nanostructures within organic layers. In this research work, CuS nanoparticles were prepared by wet chemical precipitation and then added to an organic mixture containing poly(3-hexylthiophene) (P3HT) and N,N-bis-(1-dodecyl)perylene-3,4,9,10 tetracarboxylic diimide (AMC14), a chemically synthesized semiconductor, for fabricating hybrid composite films by matrix assisted pulsed laser evaporation (MAPLE) on indium tin oxide/poly(ethylene terephthalate) (ITO/PET) flexible substrates. A comparative assessment of the morphological, compositional, optical and electrical properties of the composite (P3HT:AMC14:CuS) and organic (P3HT:AMC14) layers was performed to evaluate their applicability in the photovoltaic cells. The transmission and emission spectra of the composite films are dominated by the optical features of AMC14, a perylene diimide derivative compound used as acceptor. In the case of devices based on MAPLE deposited composite layer fabricated on ITO/PET substrates, the electrical measurements carried under illumination revealed an improvement in the open circuit voltage parameter emphasizing their potential applications in the flexible device area.

Laser thin layer deposition technologies were applied to develop organic heterostructures on flexible transparent conductive electrode (TCE). Flexible substrates such as flexible glass (FG), polyethersulfone (PES), amorphous polyethylene terephthalate (PET-A) and biaxially-oriented polyethylene terephthalate (PET-B) were employed to assess the influence of the substrate type on the optical and electrical characteristics of the organic devices. For comparison reason, the organic heterostructures were fabricated on rigid glass substrate and commercially available indium tin oxide (ITO)-coated PET. Hence, flexible and rigid glass substrates were coated with ITO film by pulsed laser deposition (PLD) at low fluence, subsequently a blend layer based on zinc phthalocyanine (ZnPc) and N, N '-bis-(1-dodecyl)perylene-3,4,9,10 tetracarboxylic diimide (AMC14) being deposited by matrix assisted pulsed laser evaporation (MAPLE) on the TCE film. The investigations evidenced that the roughness and the substrate type can strongly influence the properties of the ITO layer deposited by PLD as well as the optical and electrical characteristics of the organic heterostructures based on the blend layer deposited by MAPLE. Thus, the lowest roughness (0.8 nm) and the best Hall mobility (41.9 cm2/V center dot s) were achieved for ITO coatings deposited on flexible glass substrate. Also, the highest current density value (9.3 x 10- 4 A/cm2 at 0.5 V) was reached for the organic heterostructures fabricated on this type of flexible substrate.

Due to the importance of buffer layers in interface engineering, the development of more variants and the rational design of materials have a significant influence on the performance of optoelectronic devices. This study provides a strategy to increase device performance by facilitating efficient charge transfer and defect passivation by combining the properties of eco-friendly materials (adenine, cytosine, guanine, thymine, and uracil) with the physicochemical properties of metal oxides. The aim of this paper was to investigate the interaction of zinc oxide (ZnO) nanostructures (seed, nanoparticles, and nanowires) with nucleobase layers and to discuss their potential applications as organic-inorganic interfacial bilayers. The impact is analyzed from structural, morphological, optical, and electrical points of view. Nucleobase-ZnO nanostructure layers present high optical transparency in the visible range. Electrical measurements confirmed that the high surface area of nanowires can enhance interactions with nucleobases, leading to better charge transfer. The results showed that these nucleobase-ZnO nanostructure layers are promising interface materials for enhancing optoelectronic device performance through interfacial charge transport and light management, while enabling the design of environmentally friendly devices.

Photoanodes based Ce-doped ZnO nanorods arrays were prepared by hydrothermal method in order to improve photoelectrochemical efficiency of ZnO photoanodes in water splitting process. Scanning electron microscopy investigation showed ZnO based nanorods with length of around 500 nm and different thicknesses and growth directions. Some morphological changes were noted following the thermal treatment. Energy-dispersive X-ray analysis and X-ray photoelectron spectroscopy measurements proved the presence of cerium species both in bulk and on the surface of ZnO nanorods. A current density of 2.44 mA/cm(2) at 1.23 V against the reversible hydrogen electrode (0.265 V vs. Ag/AgCl) was obtained for Ce-doped ZnO sample, which is >162% increase over that of ZnO sample. The increased photocurrent value obtained for this sample was correlated with the passivation of surface defects evidenced by photoluminescence study and the increased concentration of Ce3+ on the surface. Also, the electrochemical impedance spectroscopy measurements suggested that Ce doping improves the charge transfer in bulk.

In this work, we investigated the influence of reduced graphene oxide (RGO) on the electrical performances of ZnO/Ag multilayer transparent conductive electrodes. RGO flakes were successfully laser transferred by matrix assisted pulsed laser evaporation (MAPLE) using frozen targets obtained from suspensions of commercially chemically RGO powder dispersed in dimethyl sulfoxide (DMSO). The main deposition parameters such as RGO concentration, laser fluence, number of the laser pulses and deposition pressure were varied to identify the optimal morphological and optical characteristics. The laser transfer conditions for the RGO structures with the best transmittance were further employed in preparation of RGO/Ag/ZnO multilayer transparent conductive electrodes (MTCE). Thus, the MAPLE deposited RGO structures were covered with metal (Ag) by vacuum thermal evaporation (VTE) and subsequently with metal oxide (ZnO) by radio frequency magnetron sputtering (RF-MS). In comparison to the optical and electrical properties of a ZnO/Ag/ZnO reference structure, the results emphasize that the RGO/Ag/ZnO are featured by a similar transmittance (similar to 82-85 %) and improved sheet resistance (similar to 10.6 Omega/square, meaning up to 2-fold smaller).

Recently, much research has focused on the search for new mixed donor-acceptor layers for applications in organic electronics. Organic heterostructures with layers based on the generation 1 poly(propylene thiophenoimine) (G1PPT) dendrimer, N,N '-diisopropylnaphthalene diimide (MNDI), and a combination of the two were prepared and their electrical properties were investigated. Single layers of G1PPT and MNDI and a mixed layer (G1PPT:MNDI) were obtained via spin coating on quartz glass, silicon, and glass/ITO substrates, using chloroform as a solvent. The absorption mechanism was investigated, the degree of disorder was estimated, and the emission properties of the layers were highlighted using spectroscopic methods (UV-Vis transmission and photoluminescence). The effects of the concentration and surface topographical particularities on the properties of the layers were analyzed via atomic force microscopy. All of the heterostructures realized with ITO and Au electrodes showed good conduction, with currents of the order of mA. Additionally, the heterostructure with a mixed layer exhibited asymmetry in the current-voltage curve between forward and reverse polarization in the lower range of the applied voltages, which was more significant at increased concentrations and could be correlated with rectifier diode behavior. Consequently, the mixed-layer generation 1 poly(propylene thiophenoimine) dendrimer with N,N '-diisopropylnaphthalene diimide can be considered promising for electronic applications.

Nowadays, the development of devices based on organic materials is an interesting research challenge. The performance of such devices is strongly influenced by material selection, material properties, design, and the manufacturing process. Usually, buckminsterfullerene (C60) is employed as electron transport material in organic photovoltaic (OPV) devices due to its high mobility. However, considering its low solubility, there have been many attempts to replace it with more soluble non-fullerene compounds. In this study, bulk heterojunction thin films with various compositions of zinc phthalocyanine (ZnPc), a perylene diimide derivative, or C60 were prepared by matrix-assisted pulsed laser evaporation (MAPLE) technique to assess the influence of C60 replacement on fabricated heterostructure properties. The investigations revealed that the optical features and the electrical parameters of the organic heterostructures based on this perylene diimide derivative used as an organic acceptor were improved. An increase in the JSC value (4.3 x 10-4 A/cm2) was obtained for the structures where the perylene diimide derivative acceptor entirely replaced C60 compared to the JSC value (7.5 x 10-8 A/cm2) for the heterostructure fabricated only with fullerene. These results are encouraging, demonstrating the potential of non-fullerene compounds as electron transport material in OPV devices.

A metallic phthalocyanine (zinc phthalocyanine - ZnPc) and a non-metallic porphyrin (10,15,20-tetra(4-pyridyl) 21H,23H-porphyne -TPyP) were used to deposit mixed and stacked organic thin films by vacuum thermal evaporation method. The obtained layers were analyzed in a comparative manner from optical, structural, morphological and electrical point of view. The ultraviolet-visible spectra of the deposited layers showed that both organic components have absorption bands in the visible part of the solar spectrum, which means that the acceptor TPyP also contributes to absorption together with the donor. The photoluminescence spectra revealed only the emission bands associated to the porphyrin, especially in the single and stacked layers, while a quenching effect of the photoluminescence was noted in the mixed ones. The X-ray diffraction showed that the prepared layers are in general amorphous. The constituent materials in the single layers and the ratio between the two organic components in the mixed layers affect the morphology of the deposited films as was emphasized by scanning electron microscopy and atomic force microscopy analysis. The current density-voltage characteristics plotted under illumination revealed that the highest short-circuit current value was achieved in the case of the structure based on the layer showing the lowest roughness and thickness emphasizing the significant role played by these parameters of the layers considered for possible applications in the optoelectronic device area.

Nanocomposite films based on macrocyclic compounds (zinc phthalocyanine (ZnPc) and 5,10,15,20-tetra(4-pyridyl) 21H,23H-porphyrin (TPyP)) and metal oxide nanoparticles (ZnO or CuO) were deposited by matrix-assisted pulsed laser evaporation (MAPLE). 1,4-dioxane was used as a solvent in the preparation of MAPLE targets that favor the deposition of films with a low roughness, which is a key feature for their integration in structures for optoelectronic applications. The influence of the addition of ZnO nanoparticles (similar to 20 nm in size) or CuO nanoparticles (similar to 5 nm in size) in the ZnPc:TPyP mixture and the impact of the added metal oxide amount on the properties of the obtained composite films were evaluated in comparison to a reference layer based only on an organic blend. Thus, in the case of nanocomposite films, the vibrational fingerprints of both organic compounds were identified in the infrared spectra, their specific strong absorption bands were observed in the UV-Vis spectra, and a quenching of the TPyP emission band was visible in the photoluminescence spectra. The morphological analysis evidenced agglomerated particles on the composite film surface, but their presence has no significant impact on the roughness of the MAPLE deposited layers. The current density-voltage (J-V) characteristics of the structures based on the nanocomposite films deposited by MAPLE revealed the critical role played by the layer composition and component ratio, an improvement in the electrical parameters values being achieved only for the films with a certain type and optimum amount of metal oxide nanoparticles.

Thick tungsten oxide layers were prepared electrophoretically in order to be used as photoanodes in photoelectrochemical water oxidation applications. The highest photocurrent density was obtained for a WO3 layer with thickness of similar to 900 nm. Additionally, WO3/BiVO4 and WO3/BiVO4/MIL-101(Fe) heterojunctions have been fabricated using WO3 layer as substrate. WO3/BiVO4 shows an increased value of the electrochemical active surface area indicating that more sites of this photoanode are activated through the formation of the heterojunction. The small V5+ signals observed in the V 2p XPS spectra of these heterojunctions were attributed to the substitution of V5+ atoms with W6+ atoms on the surface of BiVO4. Excessive W doping of the BiVO4 film determined the decrease of the photoelectrochemical performance of WO3/BiVO4 photoanode. The significant improvement of the photoconversion efficiency of the sample decorated with MIL-101(Fe) indicated that this cocatalyst provides sites more efficiently in the photoelectrochemical process. This performance was correlated with the reduced value of the charge transfer resistance at electrode/electrolyte interface obtained from electrochemical impedance spectroscopy investigation.

Nanostructured surfaces based on silver nanoparticles decorated ZnO-CuO core-shell nanowire arrays, which can assure protection against various environmental factors such as water and bacteria were developed by combining dry preparation techniques namely thermal oxidation in air, radio frequency (RF) magnetron sputtering and thermal vacuum evaporation. Thus, high-aspect-ratio ZnO nanowire arrays were grown directly on zinc foils by thermal oxidation in air. Further ZnO nanowires were coated with a CuO layer by RF magnetron sputtering, the obtained ZnO-CuO core-shell nanowires being decorated with Ag nanoparticles by thermal vacuum evaporation. The prepared samples were comprehensively assessed from morphological, compositional, structural, optical, surface chemistry, wetting and antibacterial activity point of view. The wettability studies show that native Zn foil and ZnO nanowire arrays grown on it are featured by a high water droplet adhesion while ZnO-CuO core-shell nanowire arrays (before and after decoration with Ag nanoparticles) reveal a low water droplet adhesion. The antibacterial tests carried on Escherichia coli (a Gram-negative bacterium) and Staphylococcus aureus (a Gram-positive bacterium) emphasize that the nanostructured surfaces based on nanowire arrays present excellent antibacterial activity against both type of bacteria. This study proves that functional surfaces obtained by relatively simple and highly reproducible preparation techniques that can be easily scaled to large area are very attractive in the field of water repellent coatings with enhanced antibacterial function.

Lately, there is a growing interest in organic photovoltaic (OPV) cells due to the organic materials' properties and compatibility with various types of substrates. However, their efficiencies are low relative to the silicon ones; therefore, other ways (i.e., electrode micron/nanostructuring, synthesis of new organic materials, use of additives) to improve their performances are still being sought. In this context, we studied the behavior of the common organic bulk heterojunction (P3HT:PC70BM) deposited by matrix-assisted pulsed laser evaporation (MAPLE) with/without 0.3% of 1,8-diiodooctane (DIO) additive on flat and micro-patterned ITO substrates. The obtained results showed that in the MAPLE process, a small quantity of additive can modify the morphology of the organic films and decrease their roughness. Besides the use of the additive, the micro-patterning of the electrode leads to a greater increase in the absorption of the studied photovoltaic structures. The inferred values of the filling factors for the measured cells in ambient conditions range from 19% for the photovoltaic structures with no additive and without substrate patterning to 27% for the counterpart structures with patterning and a small quantity of additive.

Single-doped [Ag, Na, iodine, naphthalene (Naph), meta-dintrobenzene (m-DNB)] and double-doped, organic-inorganic (Naph + iodine; m-DNB + iodine) benzil (Bz) crystals have been grown from melt in a Bridgman-Stockbarger configuration. All crystals have been grown in the same experimental conditions, temperature variation at the growth interface = 30 K and moving speed of the growth ampoule = 1 mm/h. These conditions have been estimated from the theoretical analysis involving the solution of the classical (conventional) Stefan problem for flat solid-liquid interface in the boundary conditions imposed by our growth system. The effect of doping on the disorder degree, photoluminescence and dielectric constant of the Bz matrix has been investigated. The disorder in the crystals increased with the increase of dopant concentration. The highest disorder was induced by the organic dopant m-DNB, whose molecules does not show an adequate geometrical similarity with Bz molecules. The position of the photoluminescence peak, both at excitation with 335 nm and 435 nm, has not been affected by the presence of dopant(s). All doped samples show Second Harmonic Generation, even those with a significant degree of disorder. The effect of the single and double-doping on the second-order ONL co-efficient was analyzed by comparison with the second-order ONL coefficient of pure Bz crystals. In the case of the double-doping, the highest second-order optical nonlinear coefficient has been evidenced in the Bz crystals simultaneously doped with m-DNB and iodine in the same concentration (1%).

An original photodetector system based on self-connected CuO-ZnO radial core-shell heterojunction nanowire arrays grown on metallic interdigitated electrodes, operating as visible-light photodetector was developed by combining simple preparation approaches. Metallic interdigitated electrodes were fabricated on Si/SiO2 substrates using a conventional photolithography process. Subsequently, a Cu layer was electrodeposited on top of the metallic interdigitated electrodes. The CuO nanowire arrays (core) were obtained by thermal oxidation in air of the Cu layer. Afterwards, a ZnO thin film (shell) was deposited by RF magnetron sputtering covering the surface of the CuO nanowires. The morphological, structural, compositional, optical, electrical and photoelectrical properties of the CuO nanowire arrays and CuO-ZnO core-shell nanowire arrays grown on metallic interdigitated electrodes were investigated. The performances of the devices were evaluated by assessing the figures of merit of the photodetectors based on self-connected CuO-ZnO core-shell heterojunction nanowire arrays grown on the metallic interdigitated electrodes. The radial p-n heterojunction formed between CuO and ZnO generates a type II band alignment that favors an efficient charge separation of photogenerated electron-hole pairs at the CuO-ZnO interface, suppressing their recombination and consequently enhancing the photoresponse and the photoresponsivity of the photodetectors. The electrical connections in the fabricated photodetector devices are made without any additional complex and time-consuming lithographic step through a self-connecting approach for CuO-ZnO core-shell heterojunction nanowire arrays grown directly onto the Ti/Pt metallic interdigitated electrodes. Therefore, the present study provides an accessible path for employing low dimensional complex structures in functional optoelectronic devices such as photodetectors.

Herein, the properties of the organic heterostructures with triple-layer ZnO/Ag/ZnO as a replacement for ITO and mixed layer containing arylenevinylene oligomer (based on triphenylamine or carbazole) donor and nonfullerene (perylene diimide) acceptor mixed in the ratio 1:2 and the effect of a buffer layer of PEDOT-PSS intercalated between triple layer and mixed organic layer are discussed. The UV-vis transmission and photoluminescence (PL) properties are investigated in correlation with the surface topography and reveal a good match between the absorption and emission domain, which can favor the generation of the charge carriers. The heterostructure with the mixed layer based on triphenylamine oligomer shows the widest absorption domain, and the PL spectra of the heterostructures realized with either triphenylamine or carbazole oligomer show peaks corresponding to the radiative decay of the donor and acceptor. The I-V characteristics in the dark indicate a slightly nonlinear behavior and the current is affected by the charge carriers recombination on the defects present in the thick mixed layer deposited by matrix-assisted pulsed laser evaporation. The effect of the PEDOT-PSS buffer layer on the electrical properties of the organic heterostructure with ZnO/Ag/ZnO electrode is also investigated.

The properties of organic heterostructures with mixed layers made of arylenevinylene-based polymer donor and non-fullerene perylene diimide acceptor, deposited using Matrix Assisted Pulsed Laser Evaporation on flat Al and nano-patterned Al electrodes, were investigated. The Al layer electrode deposited on the 2D array of cylindrical nanostructures with a periodicity of 1.1 mu m, developed in a polymeric layer using UV-Nanoimprint Lithography, is characterized by an inflorescence-like morphology. The effect of the nanostructuring on the optical and electrical properties was studied by comparison with those of the heterostructures based on a mixed layer with fullerene derivative acceptor. The low roughness of the mixed layer deposited on flat Al was associated with high reflectance. The nano-patterning, which was preserved in the mixed layer, determining the light trapping by multiple scattering, correlated with the high roughness and led to lower reflectance. A decrease was also revealed in photoluminescence emission both at UV and Vis excitation of the mixed layer, with the non-fullerene acceptor deposited on nano-patterned Al. An injector contact behavior was highlighted for all Al/mixed layer/ITO heterostructures by I-V characteristics in dark. The current increased, independently of acceptor (fullerene or non-fullerene), in the heterostructures with nano-patterned Al electrodes for shorter conjugation length polymer donors.

Hierarchical functionalization of flax fibers with ZnO nanostructures was achieved by electroless deposition to improve the interfacial adhesion between the natural fibers and synthetic matrix in composite materials. The structural, morphological, thermal and wetting properties of the pristine and ZnO-coated flax fibers were investigated. Thus, the ZnO-coated flax fabric discloses an apparent contact angle of similar to 140 degrees immediately after the placement of a water droplet on its surface. An assessment of the interfacial adhesion at the yarn scale was also carried out on the flax yarns coated with ZnO nanostructures. Thus, after the ZnO functionalization process, no significant degradation of the tensile properties of the flax yarns occurs. Furthermore, the single yarn fragmentation tests revealed a notable increase in the interfacial adhesion with an epoxy matrix, reductions of 36% and 9% in debonding and critical length values being measured compared to those of the pristine flax yarns, respectively. The analysis of the fracture morphology by scanning electron microscopy and X-ray microtomography highlighted the positive role of ZnO nanostructures in restraining debonding phenomena at the flax fibers/epoxyresin matrix interphase.

Basalt fibers were functionalized by ZnO electroless deposition for obtaining a nanostructured interphase for enhancing the interfacial strength with an epoxy resin matrix. The structural, morphological and wetting properties of the pristine basalt fabrics and ZnO-coated basalt fabrics were evaluated. The fabrics were uniformly coated with ZnO nanostructures featuring a wurtzite structure and a twin hexagonal prism morphology. The contact angle measurements revealed that ZnO prisms transformed the hydrophilic basalt fabric into a hydrophobic one (similar to 130 degrees). ZnOs were also grown on the basalt fibers as yarns to evaluate their interfacial adhesion by single fiber pull-out tests. The results emphasize significant improvement in the apparent interfacial shear strength (similar to 42%) with limited degradation of the pristine basalt fiber tensile strength (a reduction of similar to 17%). Therefore, ZnO electroless deposition can be regarded as an effective mute to improve the mechanical performance of basalt/epoxy composites expanding their potential range of applications as structural materials.

In this paper we report the results of a photoelectrochemical study performed on photoanodes based on hematite nanowire arrays and films prepared on fluoride-doped tin oxide coated glass (FTO) and FTO/TiO2 substrates, respectively by hydrothermal and spray pyrolysis methods. The hematite nanowires grown on FTO/TiO2 substrate are more stable mechanically, longer (1 ?m) and their density on substrate is higher. Hematite film obtained on FTO substrate has a thickness of 92 nm covering uniformly the substrate. X-ray photoelectron spectroscopy measurements showed that hematite samples synthesized on FTO/TiO2 substrate have lower content of oxygen vacancies. The photoelectrochemical performances of the prepared photoanodes are in close connection with the presence or absence of the TiO2 underlayer, with oxygen vacancies content and with their morphological characteristics. Electrochemical impedace spectroscopy was used to investigate the charge transfer kinetics at electrode/electrolyte interface and Mott-Schottky analysis was performed to estimate the flatband potential and the carrier density. TiO2 underlayer led to the formation of defects on the samples surface which induced a positive shift of the flatband potentials compared to that of the bare hematite film. The results showed that the best density photocurrent was obtained with a photoanode of hematite nanowires grown on FTO/TiO2 substrate.

Ferroelectric alpha-Fe2O3/BaTiO3 photoanodes (hematite/BT) were fabricated on FTO and FTO/TiO2 substrates using a hydrothermal process and spin coating along with thermal treatments. The prepared hematite nanowires had length under 1 mu m and the BT film was about 18 nm thick. SEM, TEM and XPS investigations prove the formation of alpha-Fe2O3/BaTiO3 heterojunction structure. The ferroelectric poling of hematite/BT heterojunction was conducted both in propylene carbonate and in air. The photoelectrochemical performance of hematite/BT photoanodes is strongly influenced by the direction of ferroelectric polarization. The positive poling of the hematite/BT prepared on FTO/TiO2 substrate produces a 40.4% photocurrent density enhancement, in comparison with not poled version of the sample. Electrochemical impedance spectroscopy measurements provided usefull information regarding the effect of ferroelectric polarization on the charge transfer kinetics at the photoanode/electrolyte interface. (C) 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Environmentally-friendly bio-organic materials have become the centre of recent developments in organic electronics, while a suitable interfacial modification is a prerequisite for future applications. In the context of researches on low cost and biodegradable resource for optoelectronics applications, the influence of a 2D nanostructured transparent conductive electrode on the morphological, structural, optical and electrical properties of nucleobases (adenine, guanine, cytosine, thymine and uracil) thin films obtained by thermal evaporation was analysed. The 2D array of nanostructures has been developed in a polymeric layer on glass substrate using a high throughput and low cost technique, UV-Nanoimprint Lithography. The indium tin oxide electrode was grown on both nanostructured and flat substrate and the properties of the heterostructures built on these two types of electrodes were analysed by comparison. We report that the organic-electrode interface modification by nano-patterning affects both the optical (transmission and emission) properties by multiple reflections on the walls of nanostructures and the electrical properties by the effect on the organic/electrode contact area and charge carrier pathway through electrodes. These results encourage the potential application of the nucleobases thin films deposited on nanostructured conductive electrode in green optoelectronic devices.

Continuing growth in global energy consumption and the growing concerns regarding climate change and environmental pollution are the strongest drivers of renewable energy deployment. Solar energy is the most abundant and cleanest renewable energy source available. Nowadays, photovoltaic technologies can be regarded as viable pathways to provide sustainable energy generation, the achievement attained in designing nanomaterials with tunable properties and the progress made in the production processes having a major impact in their development. Solar cells involving hybrid nanocomposite layers have, lately, received extensive research attention due to the possibility to combine the advantages derived from the properties of both components: flexibility and processability from the organic part and stability and optoelectronics features from the inorganic part. Thus, this review provides a synopsis on hybrid solar cells developed in the last decade which involve composite layers deposited by spin-coating, the most used deposition method, and matrix-assisted pulsed laser evaporation, a relatively new deposition technique. The overview is focused on the hybrid nanocomposite films that can use conducting polymers and metal phthalocyanines as p-type materials, fullerene derivatives and non-fullerene compounds as n-type materials, and semiconductor nanostructures based on metal oxide, chalcogenides, and silicon. A survey regarding the influence of various factors on the hybrid solar cell efficiency is given in order to identify new strategies for enhancing the device performance in the upcoming years.

Human society's demand for energy has increased faster in the last few decades due to the world's population growth and economy development. Solar power can be a part of a sustainable solution to this world's energy need, taking into account that the cost of the renewable energy recently dropped owed to the remarkable progress achieved in the solar panels field. Thus, this inexhaustible source of energy can produce cheap and clean energy with a beneficial impact on the climate change. The considerable potential of the organic photovoltaic (OPV) cells was recently emphasized, with efficiencies exceeding 18% being achieved for OPV devices with various architectures. The challenges regarding the improvement in the OPV performance consist of the selection of the adequate raw organic compounds and manufacturing techniques, both strongly influencing the electrical parameters of the fabricated OPV devices. At the laboratory level, the solution-based techniques are used in the preparation of the active films based on polymers, while the vacuum evaporation is usually involved in the deposition of small molecule organic compounds. The major breakthrough in the OPV field was the implementation of the bulk heterojunction concept but the deposition of mixed films from the same solvent is not always possible. Therefore, this review provides a survey on the development attained in the deposition of organic layers based on small molecules compounds, oligomers and polymers using matrix-assisted pulsed laser evaporation (MAPLE)-based deposition techniques (MAPLE, RIR-MAPLE and emulsion-based RIR-MAPLE). An overview of the influence of various experimental parameters involved in these laser deposition methods on the properties of the fabricated layers is given in order to identify, in the forthcoming years, new strategies for enhancing the OPV cells performance.

We investigated the optical and electrical properties of flexible single and bi-layer organic heterostructures prepared by vacuum evaporation with a p-type layer of arylenevinylene oligomers, based on carbazole, 3,3 ' bis(N hexylcarbazole)vinylbenzene = L13, or triphenylamine, 1,4 bis [4 (N,N' diphenylamino)phenylvinyl] benzene = L78, and an n-type layer of 5,10,15,20-tetra(4-pyrydil)21H,23H-porphyne = TPyP. Transparent conductor films of Al-doped ZnO (AZO) with high transparency, >90% for wavelengths > 400 nm, and low resistivity, between 6.9 x 10(-4) ohm center dot cm and 23 x 10(-4) ohm center dot cm, were deposited by pulsed laser deposition on flexible substrates of polyethylene terephthalate (PET). The properties of the heterostructures based on oligomers and zinc phthalocyanine (ZnPc) were compared, emphasizing the effect of the surface morphology. The measurements revealed a good absorption in the visible range of the PET/AZO/arylenevinylene oligomer/TPyP heterostructures and a typical injection contact behavior with linear (ZnPc, L78) or non-linear (L13) J-V characteristics in the dark, at voltages < 0.4 V. The heterostructure PET/AZO/L78/TPyP/Al showed a current density of similar to 1 mA/cm(2) at a voltage of 0.3 V. The correlation between the roughness exponent, evaluated from the height-height correlation function, grain shape, and electrical behavior was analyzed. Consequently, the oligomer based on triphenylamine could be a promising replacement of donor ZnPc in flexible electronic applications.

Hybrid organic-inorganic thin films based on zinc phthalocyanine (ZnPc) and ZnO nanoparticles were deposited by Matrix Assisted Pulsed Laser Evaporation (MAPLE). Synthesized by a simple wet chemical precipitation method, the ZnO nanoparticles were featured by a hexagonal wurtzite structure, a band-gap value of similar to 3.3 eV and emission bands typical for this semiconductor. The hybrid films containing ZnPc and various amounts of ZnO nanoparticles were evaluated from morphological, compositional, structural, optical and electrical point of view. No chemical decomposition of the organic compound was observed in the FTIR spectra of the deposited layers. The transmittance and photoluminescence spectra recorded on hybrid films disclose the optical signature of both organic (ZnPc) and inorganic (ZnO) components. The electrical measurements carried out under illumination emphasized the importance of the quantity of the inorganic component on the performance parameters of the structures prepared with the hybrid films. Our study provides new insight in the MAPLE deposition of the organic-inorganic hybrid films with potential applications in the photovoltaic cells area.

Matrix-assisted pulsed laser evaporation (MAPLE) was used to deposit hybrid nanocomposite thin films based on cobalt phthalocyanine (CoPc), C60 fullerene and ZnO nanoparticles. The inorganic nanoparticles, with a size of about 20 nm, having the structural and optical properties characteristic of ZnO, were chemically synthesized by a simple precipitation method. Furthermore, ZnO nanoparticles were dispersed in a dimethyl sulfoxide solution in which CoPc and C60 had been dissolved, ready for the freezing MAPLE target. The effect of the concentration of ZnO nanoparticles on the structural, morphological, optical and electrical properties of the CoPc:C60:ZnO hybrid nanocomposite layers deposited by MAPLE was evaluated. The infrared spectra of the hybrid nanocomposite films confirm that the CoPc and C60 preserve their chemical structure during the laser deposition process. The CoPc optical signature is recognized in the ultraviolet-visible (UV-Vis) spectra of the obtained layers, these being dominated by the absorption bands associated to this organic compound while the ZnO optical fingerprint is identified in the photoluminescence spectra of the prepared layers, these disclosing the emission bands linked to this inorganic semiconductor. The hybrid nanocomposite layers exhibit globular morphology, which is typical for the thin films deposited by MAPLE. Current-voltage (J-V) characteristics of the structures developed on CoPc:C60:ZnO layers reveal that the addition of an appropriate amount of ZnO nanoparticles in the CoPc:C60 mixture leads to a more efficient charge transfer between the organic and inorganic components. Due to their photovoltaic effect, structures featuring such hybrid nanocomposite thin films deposited by MAPLE can have potential applications in the field of photovoltaic devices.

In this work, ZnO-CdS composite powders synthesized by a simple chemical precipitation method were thoroughly characterized. The morphological, structural, compositional, photocatalytical, and biological properties of the prepared composites were investigated in comparison with those of the pristine components and correlated with the CdS concentration. ZnO-CdS composites contain flower-like structures, their size being tuned by the CdS amount added during the chemical synthesis. The photocatalytic activity of the composites was analyzed under UV irradiation using powders impregnated with methylene blue; the tests confirming that the presence of CdS along the ZnO in composites can improve the dye discoloration. The biological properties such as antioxidant capacity, antibacterial activity, and cytotoxicity of the ZnO, CdS, and ZnO-CdS composites were evaluated. Thus, the obtained composites presented medium antioxidant effect, biocidal activity against Escherichia coli, and no toxicity (at concentrations less than 0.05 mg/mL for composites with a low CdS amount) for human fibroblast cells. Based on these results, such composites can be used as photocatalytic and/or biocidal additives for photoactive coatings, paints, or epoxy floors, which in their turn can provide a cleaner and healthier environment.

Three-dimensional (3D) fibrous networks based on metal oxides were obtained by a bio-inspired approach: the replication of an ecological daily-waste, the eggshell membrane (ESM). The biomorphic process consists in the immersion of the ESM into aqueous solutions containing the metal salt precursors followed by the calcination of the metal ions impregnated ESM. Biomorphic ZnO, CuO and ZnO-CuO composite networks were obtained, their morphological, structural, compositional, optical, photocatalytical and electrical properties being evaluated. The scanning electron microscopy investigations proved that the hierarchical structure of the original organic template is perfectly replicated into inorganic architectures consisting of interconnected fibers containing metal oxide nanoparticles as building blocks. The photocatalytical properties of the metal oxide networks under solar simulator irradiation were tested through the degradation of methylene blue. Using Si/SiO2 patterned with interdigitated metallic electrodes as substrates during the calcination step, the electrical properties of the selfcontacted metal oxide networks were investigated. Thus, by replicating the unique architecture of the ESM, 3D metal oxide interwoven meshwork can be easily developed for various applications in fields such as photocatalysis, sensing, optoelectronic devices, etc.

The matrix-assisted pulsed laser evaporation (MAPLE) technique was used for depositing thin films based on a recently developed conjugated polymer, poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)] (DPP-DTT) and fullerene C60 blends. The targets used in the MAPLE process were obtained by freezing chloroform solutions with different DPP-DTT:C60 weight ratios, with the MAPLE deposition being carried at a low laser fluence, varying the number of laser pulses. The structural, morphological, optical, and electrical properties of the DPP-DTT:C60 blend layers deposited by MAPLE were investigated in order to emphasize the influence of the DPP-DTT:C60 weight ratio and the number of laser pulses on these features. The preservation of the chemical structure of both DPP-DTT and C60 during the MAPLE deposition process is confirmed by the presence of their vibrational fingerprints in the FTIR spectra of the organic thin films. The UV-VIS and photoluminescence spectra of the obtained organic layers reveal the absorption bands attributed to DPP-DTT and the emission bands associated with C60, respectively. The morphology of the DPP-DTT:C60 blend films consists of aggregates and fibril-like structures. Regardless the DPP-DTT:C60 weight ratio and the number of laser pulses used during the MAPLE process, the current-voltage characteristics recorded, under illumination, of all structures developed on the MAPLE deposited layers evidenced a photovoltaic cell behavior. The results proved that the MAPLE emerges as a viable technique for depositing thin films based on conjugated polymers featured by a complex structure that can be further used to develop devices for applications in the solar cell area.

Organic bulk heterojunctions (BHJ) based on zinc phthalocyanine (ZnPc), fullerene compounds (C60 fullerene and [6,6]-phenyl C71 butyric acid methyl ester (PC70BM)), and 5,6,11,12-tetraphenylnaphthacene (rubrene) were fabricated through the matrix-assisted pulsed-laser evaporation (MAPLE) technique. Thus, ZnPc:C60 and ZnPc:PC70BM binary BHJ and ZnPc:rubrene:PC70BM ternary BHJ were deposited as thin films on various substrates. The preservation of the chemical structure of the organic compounds during the MAPLE deposition was confirmed by infrared spectroscopy. The structural, optical, and morphological properties of the deposited layers were investigated by X-ray diffraction (XRD), UV-Vis spectroscopy, photoluminescence (PL), field emission scanning electron microscopy (FESEM), and atomic force microscopy (AFM), respectively. Further, the electrical properties of the developed structures based on ZnPc:C60, ZnPc:PC70BM, and ZnPc:rubrene:PC70BM were evaluated. The J-V characteristics of the organic structures, recorded under illumination, show that an increase in the open-circuit voltage (V-OC) is achieved in the case of the ternary blend in comparison with that obtained for the binary blends. The results evidenced that MAPLE-deposited thin films containing binary and ternary organic bulk heterojunctions can find applications in the field of photovoltaic devices.

Biopolymers provide versatile platforms for designing naturally-derived wound care dressings through eco-friendly pathways. Eggshell membrane (ESM), a widely available, biocompatible biopolymer based structure features a unique 3D porous interwoven fibrous protein network. The ESM was functionalized with inorganic compounds (Ag, ZnO, CuO used either separately or combined) using a straightforward deposition technique namely radio frequency magnetron sputtering. The functionalized ESMs were characterized from morphological, structural, compositional, surface chemistry, optical, cytotoxicity and antibacterial point of view. It was emphasized that functionalization with a combination of metal oxides and exposure to visible light results in a highly efficient antibacterial activity against Escherichia coli when compared to the activity of individual metal oxide components. It is assumed that this is possible due to the fact that an axial p-n junction is created by joining the two metal oxides. This structure separates into components the charge carrier pairs promoted by visible light irradiation that further can influence the generation of reactive oxygen species which ultimately are responsible for the bactericide effect. This study proves that, by employing inexpensive and environmentally friendly materials (ESM and metal oxides) and fabrication techniques (radio frequency magnetron sputtering), affordable antibacterial materials can be developed for potential applications in chronic wound healing device area.

Core-double shell nylon-ZnO/polypyrrole electrospun nanofibers were fabricated by combining three straightforward methods (electrospinning, sol-gel synthesis and electrodeposition). The hybrid fibrous organic-inorganic nanocomposite was obtained starting from freestanding nylon 6/6 nanofibers obtained through electrospinning. Nylon meshes were functionalized with a very thin, continuous ZnO film by a sol-gel process and thermally treated in order to increase its crystallinity. Further, the ZnO coated networks were used as a working electrode for the electrochemical deposition of a very thin, homogenous polypyrrole layer. X-ray diffraction measurements were employed for characterizing the ZnO structures while spectroscopic techniques such as FTIR and Raman were employed for describing the polypyrrole layer. An elemental analysis was performed through X-ray microanalysis, confirming the expected double shell structure. A detailed micromorphological characterization through FESEM and TEM assays evidenced the deposition of both organic and inorganic layers. Highly transparent, flexible due to the presence of the polymer core and embedding a semiconducting heterojunction, such materials can be easily tailored and integrated in functional platforms with a wide range of applications.

CuO-ZnO core-shell radial heterojunction nanowire arrays were obtained by a simple route which implies two cost-effective methods: thermal oxidation in air for preparing CuO nanowire arrays, acting as a p-type core and RF magnetron sputtering for coating the surface of the CuO nanowires with a ZnO thin film, acting as a n-type shell. The morphological, structural, optical and compositional properties of the CuO-ZnO core-shell nanowire arrays were investigated. In order to analyse the electrical and photoelectrical properties of the metal oxide nanowires, single CuO and CuO-ZnO core-shell nanowires were contacted by employing electron beam lithography (EBL) and focused ion beam induced deposition (FIBID). The photoelectrical properties emphasize that the p-n radial heterojunction diodes based on single CuO-ZnO core-shell nanowires behave as photodetectors, evidencing a time-depending photoresponse under illumination at 520 nm and 405 nm wavelengths. The performance of the photodetector device was evaluated by assessing its key parameters: responsivity, external quantum efficiency and detectivity. The results highlighted that the obtained CuO-ZnO core-shell nanowires are emerging as potential building blocks for a next generation of photodetector devices.

This paper presents some studies on the organic heterostructures realized by Matrix Assisted Pulsed Laser Evaporation in both bi-layer and mixed layer configurations on glass substrates covered by flat or nano-patterned ITO. The donor, a star-shaped arylenevinylene compound, 4,4',4 ''-tris[(4'-diphenylamino) styryl] triphenylamine, and acceptor, a non-fullerene compound, N,N'-bis-(1-dodecyl)perylene-3,4,9,10 tetracarboxylic diimide, were blended in three weight ratios: 1:2, 1:3 and 1:4. A grating of cylindrical pillars with a periodicity of 1.1 mu m has been developed by UV-Nanoimprint Lithography in a polymer layer. The shape of the nanostructures changed to cone trunk by the Pulsed Laser Deposition of ITO on this nanostructured surface. The effect of the nanostructures and composition on the optical and electrical properties of the heterostructures was analyzed. The nano-patterning affected both the UV-Vis transmission and photoluminescence through the multiple reflections inside the cavities and at interfaces and the particularities of the molecular arrangement. The patterning was preserved independently of composition, but the roughness increased with increasing acceptor amount. The I-V characteristics drawn at room temperature in dark revealed an ohmic contact behavior for all heterostructures. The nano-patterning had a similar effect on the current in the heterostructures with mixed layer (1:2) and stacked bi-layer.

The present work describes a new simple procedure for the direct immobilization of biomolecules on Ni electrodes using magnetic Ni nanoparticles (NiNPs) as biomolecule carriers. Ni electrodes were fabricated by electroplating, and NiNPs were chemically synthesized. The chemical composition, crystallinity, and granular size of Ni electrodes, NiNP, and NiNP-modified Ni electrodes (NiNP/Ni) were determined by X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS). The electrochemical characterization of Ni electrodes by cyclic voltammetry and electrochemical impedance spectroscopy confirmed the existence of nickel oxides, hydroxides, and oxohydroxide films at the surface of Ni. Magnetic characterization and micromagnetic simulations were performed in order to prove that the magnetic force is responsible for the immobilization process. Further, Ni electrodes were employed as amperometric sensors for the detection of hydrogen peroxide because it is an important performance indicator for a material to be applied in biosensing. The working principle for magnetic immobilization of the enzyme-functionalized NiNP, without the use of external magnetic sources, was demonstrated for glucose oxidase (GOx) as a model enzyme. XPS results enabled to identify the presence of GOx attached to the NiNP (GOx-NiNP) on Ni electrodes. Finally, glucose detection and quantification were evaluated with the newly developed GOx-NiNP/Ni biosensor by amperometry at different potentials, and control experiments at different electrode materials in the presence and absence of NiNP demonstrated their importance in the biosensor architecture.

Staggered gap radial heterojunctions based on ZnO-CuxO core-shell nanowires are used as water stable photocatalysts to harvest solar energy for pollutants removal. ZnO nanowires with a wurtzite crystalline structure and a band gap of approximately 3.3 eV are obtained by thermal oxidation in air. These are covered with an amorphous CuxO layer having a band gap of 1.74 eV and subsequently form core-shell heterojunctions. The electrical characterization of the ZnO pristine and ZnO-CuxO core-shell nanowires emphasizes the charge transfer phenomena at the junction and at the interface between the nanowires and water based solutions. The methylene blue degradation mechanism is discussed taking into consideration the dissolution of ZnO in water based solutions for ZnO nanowires and ZnO-CuxO core-shell nanowires with different shell thicknesses. An optimum thickness of the CuxO layer is used to obtain water stable photocatalysts, where the ZnO-CuxO radial heterojunction enhances the separation and transport of the photogenerated charge carriers when irradiating with UV-light, leading to swift pollutant degradation.

ZnO-CuxO core-shell radial heterojunction nanowire arrays were fabricated by a straightforward approach which combine two simple, cost effective and large-scale preparation methods: (i) thermal oxidation in air of a zinc foil for obtaining ZnO nanowire arrays and (ii) radio frequency magnetron sputtering for covering the surface of the ZnO nanowires with a CuxO thin film. The structural, compositional, morphological and optical properties of the high aspect ratio ZnO-CuxO core-shell nanowire arrays were investigated. Individual ZnO-CuxO core-shell nanowires were contacted with Pt electrodes by means of electron beam lithography technique, diode behaviour being demonstrated. Further it was found that these n-p radial heterojunction diodes based on single ZnO-CuxO nanowires exhibit a change in the current under UV light illumination and therefore behaving as photodetectors.

Indium tin oxide (ITO) thin films were grown on nanopatterned glass substrates by the pulsed laser deposition (PLD) technique. The deposition was carried out at 1.2 J/cm(2) laser fluence, low oxygen pressure (1.5 Pa) and on unheated substrate. Arrays of periodic pillars with widths of similar to 350 nm, heights of similar to 250 nm, and separation pitches of similar to 1100 nm were fabricated on glass substrates using UV nanoimprint lithography (UV-NIL), a simple, cost-effective, and high throughput technique used to fabricate nanopatterns on large areas. In order to emphasize the influence of the periodic patterns on the properties of the nanostructured ITO films, this transparent conductive oxide (TCO) was also grown on flat glass substrates. Therefore, the structural, compositional, morphological, optical, and electrical properties of both non-patterned and patterned ITO films were investigated in a comparative manner. The energy dispersive X-ray analysis (EDX) confirms that the ITO films preserve the In2O3:SnO2 weight ratio from the solid ITO target. The SEM and atomic force microscopy (AFM) images prove that the deposited ITO films retain the pattern of the glass substrates. The optical investigations reveal that patterned ITO films present a good optical transmittance. The electrical measurements show that both the non-patterned and patterned ITO films are characterized by a low electrical resistivity (<2.8 x 10(-4)). However, an improvement in the Hall mobility was achieved in the case of the nanopatterned ITO films, evidencing the potential applications of such nanopatterned TCO films obtained by PLD in photovoltaic and light emitting devices.

Controlled deposition of g-C3N4 films, used as photoelectrodes in PEC water splitting is still considered a challenge. In this paper, nanosheets of g-C3N4 were deposited on FTO and FTO/TiO2 substrates via spray coating method. This method allows the preparation of g-C3N4 films with a better exposure of nanosheet edges to the solution and light, favoring the photocatalytic process. The morphology, chemical composition and optical properties of these films were investigated, their behavior as photoanodes in photoelectrochemical water splitting being also evaluated. The results evidenced the formation of g-C3N4 films with an enhanced visible light absorption and improved photocatalytic activity. The interaction of these films with TiO2 substrate consists in the insertion of nitrogen species in the TiO2 lattice. A significant increase in bulk donor densities value correlated with a longer lifetime of photogenerated electrons was observed for TiO2/g-C3N4 photoanode. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

The work demonstrates growth by the Verneuil method of SrTiO3 single crystals of 30 mm in diameter. Experiments are performed under an industrial environment. Growth was for 4.75 h, i.e., within one production shift. The optimum growth conditions for which the length of the region with bubbles D is zero and the effective length EL (i.e., the crystal length of commercial value) is maximized are for the amount of SrCO3 additive of similar to 3 wt % and for H-2 outer flow rate of similar to 35 L/min. These two parameters show the strongest influence on the bubble-free growth, but other growth parameters (H-2 inner flow rate, O-2 flow rate increase, rotation speed) were also optimized. Selected crystals are characterized from the structural, microstructural, optical, and THz spectroscopy viewpoints, and they are compared with a commercial substrate and with crystals reported in the literature. This work opens the possibility for the industrial growth of large SrTiO3 single crystals and commercialization of large area substrates.

The present investigation deals with the development, characterization and application of nano-structured Pd doped Ni electrodes (Pd@Ni), which uses the electrochemical properties of Pd in synergy with the magnetic properties of Ni for biosensors development. The Pd@Ni electrodes have been characterized by X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. It has been shown that palladium presented spherical assemblies ranging 150-200 nm medium diameter size that covers large areas of the electrode surface while metallic nickel, which confers magnetic properties, showed a uniform granular structure with sizes between 20 and 50 nm. Cyclic voltammetry and electrochemical impedance spectroscopy were performed to understand the electrochemical process at the Pd@Ni electrodes in neutral media. The Pd@Ni electrodes were applied for the electrochemical detection of H2O2. Finally, Ni nanoparticles (NiNP) functionalized with the model enzyme glucose oxidase (GOx-NiNP) have been attached to the Pd@Ni electrode solely through magnetic interactions, and the obtained GOx-NiNP/Pd@Ni biosensor applied for glucose determination in aqueous solutions by fixed potential amperometry at -0.05 V (vs Ag/AgCl) with reduced interferences. (C) 2019 Elsevier Ltd. All rights reserved.

The paper is focused on the investigation of the properties of some organic heterostructures deposited on patterned AZO electrodes. In the first step, 2D patterned arrays based on commercially photoresist were fabricated on glass substrates using nanoimprint litography. Next, on these periodic nanostructures, the transparent AZO layers were deposited by pulsed laser deposition. Further, heterostructures consisting in organic thin films such as 4,7 diphenyl-1,10-phenanthroline (BPhen) (electron transport layer), N,N'-di(1-naftalenil)-N,N'-diafenil-(1,1'-bifenil)-4,4'-diamina (alpha-NPD) (hole transport layer) and arylenevinylene oligomers (3,3-bis (N-hexylcarbazole)vinylbenzene (P13) and 1,4-bis [4-(N,N-diphenylamino)phenylvinyl] benzene (P78)) were obtained by matrix assisted pulsed laser evaporation. The fabricated multilayer organic structures have been investigated from optical (UV-VIS spectroscopy), morphological (scanning electron microscopy and atomic force microscopy) and electrical (I-V characteristics) point of view. An improvement in the current value recorded on the samples prepared on nanostructured electrode was recorded. The results evidence the possibility to integrate these heterostructures in organic electronic devices.

The present study is focused on the wet chemical synthesis and the characterization of ZnO-CdS composites. The X-ray diffraction shows that the composites contain ZnO in hexagonal wurtzite structure and CdS in cubic phase. The scanning/transmission electron microscopy images reveal flower-like structures with different sizes depending on the CdS content. The optical investigations on composites reveal that the reflectance spectra disclose two thresholds of similar to 370 nm and similar to 460 nm associated with the ZnO and CdS, respectively. The photocatalytic activity measurements evidenced that the degradation efficiency of RhB in the presence of composites is higher comparatively with pristine ZnO, depending on the catalyst morphology, which varies with CdS content and the pH value of RhB solution. The electron paramagnetic resonance revealed the presence of the paramagnetic point defects in the samples. Thus, the wet chemical approaches are suitable for a large scale production of such ZnO-CdS composites having enhanced photocatalytic activity.

Organic heterostructures based on zinc phthalocyanine (ZnPc) and perylene tetracarboxylic dianhydride (PTCDA) were deposited by matrix-assisted pulsed laser evaporation (MAPLE) technique on conductive flexible substrate (ITO/PET) in three configurations: ZnPc/PTCDA (stacked layers), ZnPc:PTCDA (blend) and ZnPc/ZnPc:PTCDA/PTCDA. The effect of the configuration on the optical and electrical properties of the obtained heterostructures was investigated. For all heterostructures was observed an improved optical absorption in visible domain. The I-V characteristics recorded under illumination, revealed higher short circuit current (I (SC)) values for the ZnPc:PTCDA and ZnPc/ZnPc:PTCDA/PTCDA structures in comparison with that of the ZnPc/PTCDA structure. The results proved that by MAPLE can be obtained flexible organic heterostructures (in different configurations) with properties adequate for applications in flexible electronics and solar cell fields.

This paper presents a comparative study between the properties of the heterostructures realized with single/multi layer organic (zinc phthalocyanine or/and fullerene) prepared on Si substrate between flat or patterned aluminum (Al) layer metallic electrode and multi layer ZnO/Au/ZnO transparent conductor electrode (TCE). The UV-Nanoimprint Lithography was used for the realization of a 2D array of nanostructures (holes/pillars) characterized by a periodicity of 1.1 mu m and cylindrical shape: diameter = 400 nm and depth/height = 300 nm. The effect of the electrode patterning on the properties of the organic heterostructures was analyzed. For the samples with patterned Al electrode was remarked a slight red shift of the peaks in the reflection spectra determined by an increased interaction between the organic molecules in the delimited region of the patterned holes. The shape of the emission spectra at excitation with UV light showed a narrow intense peak around 500 nm associated with the intense resonance phenomena between the energy of the incident light and the surface plasmons in the patterned Al layer. The TCE followed the morphology of the organic film on which it was deposited. The significant differences between the morphology of the top layer in the heterostructures realized on flat and patterned Al are correlated with the total thickness of the successively deposited layers and with the particularities of the molecular arrangement, leading to the preservation or deleting of patterning. An injection contact behavior was evidence for most heterostructures built on flat and patterned Al. The slight increase in current at an applied bias <1 V in the heterostructure Si/Al/ZnPc/TCE is attributed to the larger interfacial area between the patterned Al electrode and ZnPc layer compared to the interface area between flat Al and ZnPc. A buffer layer of 1,4,5,8-naphthalen-tetracarboxylic dianhydride (NTCDA), sandwiched between the flat metallic electrode and organic film in the heterostructure Si/Al/C60/ZnPc/TCE has determined an increase in the current at low applied voltages. (C) 2018 Elsevier B.V. All rights reserved.

This work is focused on the use of multilayer transparent conductive electrode (TCE) based on ZnO/Ag/ZnO in the fabrication of the organic heterostructures. The ZnO/Ag/ZnO obtained combining sputtering/thermal evaporation/sputtering techniques is featured by a good optical transmittance, a low electrical resistivity and a reduced roughness. All these characteristics recommend it as a viable alternative to indium tin oxide (ITO) for different applications. The organic materials, N,N' - diphenyl N,N' - bis (1 - aphthyl) 1,1' - biphenyl 4,4' - diamine (alpha-NPD), 5,12-Dihydro-5-12-dimethylquino [2,3-b]acridine-7,14dione (DMQA) and 4,7 diphenyl-1,10-phenanthroline (BPhen) were deposited by vacuum thermal evaporation (VTE) method, the properties of the obtained layers being investigated by FTIR, UV-VIS and PL) spectroscopy. The I-V characteristic (recorded in dark) of the organic heterostructure fabricated on the ZnO/Ag/ZriO electrode shows diode behavior, revealing its potential applications in the organic light emitting devices (OLED).

Eggshell membranes were employed as biological scaffolds for developing soft and versatile actuators. A particular architecture, consisting of eggshell membrane coated with polypyrrole, has been fabricated and has been found to be a green, inexpensive, lightweight, and easy to handle class of actuators. The polypyrrole-coated eggshell membrane devices were tested in liquid, ambient atmosphere and controlled humidity environment, with the recorded movements proving their versatility. In 1 M NaCl aqueous solution, by applying successive potential pulses, the actuator contracts/expands owing to the expulsion/insertion of the electrolyte ions out/into polypyrrole film, producing a displacement of similar to 0.1 cm. In air, upon application of voltages from 2 to 5 V on a V-shaped geometry actuator, it bends due to water desorption from its structure induced by Joule heating, generating a displacement which reaches similar to 0.4 cm at 5 V. In a chamber with controlled humidity, the decrease of humidity stimulates a bending/curling motion of the actuator, achieving a displacement of similar to 2.1 cm at 50% relative humidity. Upon modification of the humidity, these actuators move, hold, and release delicate and lightweight objects. Such polypyrrole-coated eggshell membrane actuators which operate in different environments and respond to multiple stimuli can have potential applications in biomimetic micromanipulators or artificial muscle fields.

Bio-waste eggshell membranes (ESM) present a unique micro-architecture consisting in an interwoven fibrous network which can be functionalized with metal oxides resulting in hybrid materials. ESM were covered with ZnO nanostructures by electroless deposition using Au as catalyst. The structural, optical, morphological and wetting properties of the pristine ESM and ESM/ZnO were evaluated. The ESM fibers were uniformly coated by ZnO hexagonal prisms, the hybrid ESM/ZnO preserving the water absorption characteristic of the pristine ESM. Combining an abundant bio-waste with a simple wet chemical synthesis method, flexible organic/inorganic hybrid networks based on ZnO-functionalized ESM can be designed for various applications. (C) 2018 Elsevier B.V. All rights reserved.

In: ZnO (IZO) thin films were deposited on flexible plastic substrates by pulsed laser deposition (PLD) method. The obtained layers present adequate optical and electrical properties competitive with those based on indium tin oxide (ITO). The figure of merit (9 X 10(-3) Omega(-1)) calculated for IZO layers demonstrates that high quality coatings can be prepared by this deposition technique. A thermal annealing (150 degrees C for 1 h) or an oxygen plasma etching (6 mbar for 10 min.) were applied to the IZO layers to evaluate the influence of these treatments on the properties of the transparent coatings. Using vacuum evaporation, organic heterostructures based on cooper phthalocyanine (CuPc) and 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) were deposited on the untreated and treated IZO layers. The optical and electrical properties of the heterostructures were investigated by UVVis, FTIR and current-voltage (I-V) measurements. For the heterostructure fabricated on IZO treated in oxygen plasma, an improvement in the current value with at least one order of magnitude was evidenced in the I-V characteristics recorded in dark conditions. Also, an increase in the current value for the heterostructure deposited on untreated IZO layer can be achieved by adding an organic layer such as tris-8-hydroxyquinoline aluminium (Alq(3)).

Mixed layers of azomethine oligomers containing 2,5-diamino-3,4-dicyanothiophene as central unit and triphenylamine (LV5) or carbazol (LV4) at both ends as donor and fullerene derivative, [6,6]-phenylC61 butyric acid butyl ester ([C60] PCB-C4) as acceptor, have been prepared by Matrix Assisted Pulsed Laser Evaporation (MAPLE) on glass/ITO and Si substrates. The effect of weight ratio between donor and acceptor (1: 1; 1: 2) and solvent type (chloroform, dimethylsulphoxide) on the optical (UV-vis transmission/absorption, photoluminescence) and morphological properties of LV4 (LV5): [C60] PCB-C4 mixed layers has been evidenced. Dark and under illumination I-V characteristics of the heterostructures realized with these mixed layers sandwiched between ITO and Al electrodes have revealed a solar cell behavior for the heterostructures prepared with both LV4 and LV5 using chloroform as matrix solvent. The solar cell structure realized with oligomer LV5, glass/ITO/LV5: [C60] PCB-C4 (1: 1) has shown the best parameters. (C) 2017 Elsevier B.V. All rights reserved.

Wetting properties of wool textiles were studied either for the raw samples or for those functionalized via covering them at low temperature with nanoparticles of titanium dioxide or zinc oxide. Oxygen plasma pretreatment was performed before deposition. Characterization used optical examination, scanning electron microscopy, infrared spectroscopy, thermogravimetry, X-ray diffraction. Wetting properties were tested under static conditions by estimating the water contact angle. The sessile drop method was applied. The deposited matter represents 3 to 8 wt%, covering rather uniformly the fiber surface. Treated samples show mostly lower values of contact angle than the pristine ones. Cassie-Baxter model is discussed in relation to the equilibrium contact angle of the support.

The aim of our study was to synthesize and evaluate the physicochemical and biological properties of composite films based on poly(lactic-co-glycolic acid) copolymer and quercetin (PLGA/Q) microspheres. During our experiments, we firstly synthesized the PLGA/Q microspheres by using an oil-in-water emulsion-diffusion-evaporation method. Subsequently, the as-prepared composite material was subjected to the matrix assisted pulsed laser evaporation (MAPLE) technique, in order to obtain the PLGA/Q coatings. Relevant compositional and microstructural features of the synthesized samples were obtained by means of Fourier transform infrared spectroscopy (FTIR) and AFM (atomic force microscopy). The long-term biocompatibility of the synthesized films was in vitro evaluated by cellular viability and immunofluorescence assays.

Organic heterostructures based on poly(3-hexylthiophene) (P3HT) and fullerene (C60) as blends or multilayer were deposited on Al:ZnO (AZO) by Matrix-Assisted Pulsed Laser Evaporation (MAPLE) technique. The AZO layers were obtained by Pulsed Laser Deposition (PLD) on glass substrate, the high quality of the films being reflected by the calculated figure of merit. The organic heterostructures were investigated from morphological, optical and electrical point of view by atomic force microscopy (AFM), UV-vis spectroscopy, photoluminescence (PL) and current-voltage (I-V) measurements, respectively. The increase of the C60 content in the blend heterostructure has as result a high roughness. Compared with the multilayer heterostructure, those based on blends present an improvement in the electrical properties. Under illumination, the highest current value was recorded for the heterostructure based on the blend with the higher C60 amount. The obtained results showed that MAPLE is a useful technique for the deposition of the organic heterostructures on AZO as transparent conductor electrode. (C) 2017 Elsevier B.V. All rights reserved.

Large scale ZnO nanowire arrays were grown directly on zinc foils using the thermal oxidation in air method. The X-ray diffraction and reflectance investigations confirm that the as-grown nanowires properties are typical for ZnO having a hexagonal wurtzite crystalline structure and band-gap values between 3.2 and 3.3 eV. The scanning electron microscopy images prove that the density and the dimensions (diameter and length) of the ZnO nanowires can be tuned by controlling the oxidation temperature. Wettability studies reveal in the case of Zn foils a hydrophilic behavior with high water droplet adhesion which is transformed into a superhydrophobic one with low water droplet adhesion after the foils' surfaces are covered with ZnO nanowires. Obtaining functional surfaces with such interesting wetting properties using a simple, inexpensive and highly reproducible thermal oxidation in air technique is very attractive for anticorrosion coatings and self-cleaning applications. (C) 2016 Elsevier B.V. All rights reserved.

This paper presents some investigations of the effect of nanopatterning on the properties of aluminum layer deposited by sputtering. UV-Nanoimprint Lithography technique has been used for the realization of a 2D array of nanostructures (pillars) in aluminum film characterized by cylindrical shape and the following structural parameters: diameter between 400 nm and 490 nm, depth between 320 nm and 420 nm and periodicity of 1.1 mu m, which have been revealed by SEM and AFM measurements. The UV-Vis transmission, reflection and photoluminescence measurements have evidenced the effect of the nanopatterning on the optical properties of the A1 layer.

Single ZnO nanowires prepared by wet and dry methods are used as channels in high performance back-gated field effect transistors working in low power operation mode, with on-off ratios up to 10(5) and mobilities up to 167 cm(2) V-1 s(-1). The nanowires' properties, generated by the growth techniques, influence the parameters of the transistors, therefore a throughout comparison is made.

Heterostructures based on zinc phthalocyanine (ZnPc), magnesium phthalocyanine (MgPc) and 5,10,15,20-tetra(4-pyrydil)21H,23H-porphine (TPyP) were deposited on ITO flexible substrates by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique. Organic heterostructures containing (TPyP/ZnPc(MgPc)) stacked or (ZnPc(MgPc):TPyP) mixed layers were characterized by X-ray diffraction-XRD, photoluminescence-PL, UV-vis and FTIR spectroscopy. No chemical decomposition of the initial materials was observed. The investigated structures present a large spectral absorption in the visible range making them suitable for organic photovoltaics applications (OPV). Scanning electron microscopy-SEM and atomic force microscopy-AFM revealed morphologies typical for the films prepared by MAPLE. The current-voltage characteristics of the investigated structures, measured in dark and under light, present an improvement in the current value (similar to 3 order of magnitude larger) for the structure based on the mixed layer (Al/MgPc:TPyP/ITO) in comparison with the stacked layer (Al/MgPc//TPyP/ITO). A photogeneration process was evidenced in the case of structures Al/ZnPc:TPyP/ITO with mixed layers. (C) 2015 Elsevier B.V. All rights reserved.

ZnO complex microstructures were deposited onto interdigitated metallic electrodes by electrospraying. Simple methods, such as wet chemical precipitation and optical lithography, were used for the synthesis of flower-like and snowflake-like ZnO structures and for the preparation of interdigitated metallic electrodes, respectively. The electrosprayed ZnO particles preserve the structural, optical and morphological properties of the chemically synthesized ZnO powders. During the electrospraying process, the ZnO microstructures form bridges between the interdigitated metallic electrodes leading to electrical contacting. Changes in the electron transport through the ZnO microstructures are evidenced by their exposure to ammonia or their passivation with poly(methyl methacrylate). Merging such easy-scalable and low-cost techniques, devices based on electrosprayed complex ZnO structures can be designed.

High aspect ratio CuO nanowires are synthesized by a simple and scalable method, thermal oxidation in air. The structural, morphological, optical, and electrical properties of the semiconducting nanowires were studied. Au-Ti/CuO nanowire and Pt/CuO nanowire electrical contacts were investigated. A dominant Schottky mechanism was evidenced in the Au-Ti/CuO nanowire junction and an ohmic behavior was observed for the Pt/CuO nanowire junction. The Pt/CuO nanowire/Pt structure allows the measurements of the intrinsic transport properties of the single CuO nanowires. It was found that an activation mechanism describes the behavior at higher temperatures, while a nearest neighbor hopping transport mechanism is characteristic at low temperatures. This was also confirmed by four-probe resistivity measurements on the single CuO nanowires. By changing the metal/semiconductor interface, devices such as Schottky diodes and field effect transistors based on single CuO p-type nanowire semiconductor channel are obtained. These devices are suitable for being used in various electronic circuits where their size related properties can be exploited. (c) 2015 AIP Publishing LLC.

Heterostructures with layers from small molecules organic compounds were deposited on ITO/glass substrate by thermal vacuum evaporation (TVE) technique. Structural, optical and morphological investigations were carried out on the realised layers (zinc phthalocyanine-ZnPc, fullerene-C60 and 1,4,5,8-naphthalene-tetracarboxylic dianhydride-NTCDA). The films are polycrystalline keeping the morphological features characteristic to these materials. The prepared heterostructures reveal a large absorption domain in the visible domain. The current-voltage (I-V) characteristics of the investigated structures, recorded in dark, present an improvement in the current value (similar to one order of magnitude) for the standard structure (ITO/PEDOT: PSS/ZnPc/C60/NTCDA/Al) with a supplimentary layer of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS). For the inverted structure (Al/NTCDA/C60/ZnPc/ITO) was also noticed an increased curent value in comparasion with that observed for the standard structure.

This paper presents some studies about the preparation by matrix-assisted pulsed laser evaporation (MAPLE) technique of heterostructures with single layer of arylene based polymer, poly[N-(2-ethylhexy1)2.7-carbazoly1 vinylene]/AMC16 and poly[N-(2-ethylhexy1)2.7-carbazolyl 1.4-phenylene ethynylene]/AMC22, and with layers of these polymers mixed with Buckminsterfullerene/C-60 in the weight ratio of 1:2 (AMC16: C60) and 1:3 (AMC22: C60). The deposited layers have been characterized by spectroscopic (UV-Vis-NIR, PL, FTIR) and microscopic (SEM, AFM) methods. The effect of the polymer particularities on the optical and electrical properties of the structures based on polymer and polymer: C-60 mixed layer has been analyzed. The study of the electrical properties has revealed typical solar cell behavior for the heterostructure prepared by MAPLE on glass/ITO/PEDOT-PSS with AMC16, AMC22 and AMC22: C-60 layer, confirming that this method is adequate for the preparation of polymeric and mixed active layers for solar cells applications. The highest photovoltaic effect was shown by the solar cell structure realized with single layer of AMC16 polymer: g1a55/ITO/PEDOT-PSSIA1VIC16/A1. (C) 2014 Elsevier B.V. All rights reserved.

ZnO crystallites were grown by electroless deposition on poly(methyl methacrylate) (PMMA) fiber mats prepared by an electrospinning technique. The electroless deposition involves three steps: sensitization, activation and deposition, which were performed by subsequently dipping the PMMA fiber mats in the appropriate solutions. After the deposition the PMMA fibers are uniformly coated with ZnO prisms which show hexagonal wurtzite structure and optical signatures (band-gap value and emission bands) typical for this semiconductor. By combining electroless deposition and electrospinning, different semiconductor coated polymer fibers can be obtained for a wide range of applications. Both methods are appropriate for large scale production, being scalable, cheap, efficient and suitable for large-area covering techniques. (C) 2014 Elsevier B.V. All rights reserved.

Bulk ceramics of Ga2S3 and rare-earth sulfides (EuS, Gd2S3, Er2S3) as well as combinations thereof have been prepared by spark plasma sintering (SPS). The disk-shaped ceramics were used as targets for pulsed laser deposition (PLD) experiments to obtain amorphous thin films. The properties of these new bulks and amorphous thin films have been investigated by x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX), optical transmission spectroscopy, and atomic force microscopy (AFM). In order to test the photoexpansion effect in Gd2S3 and the possibility to create planar arrays of microlenses, the film was irradiated with femtosecond laser pulses at different powers. For low laser power pulses (up to 100mW power per pulse) a photoexpansion effect was observed, which leads to formation of hillocks with a height of 40-50 nm. EuS doped Gd2S3 thin film shows luminescence properties, which recommend them for optoelectronic applications.

Low dimensional nanostructures represent a hot scientific field nowadays due mainly to the tremendous potential for applications. Low dimensions open the possibilities for both ultra-miniaturization and increase in functionality. Numerous procedures were developed for fabricating such nanostructures. Template replication represents a highly effective method in fabricating metallic nanowires and nanotubes. The approach is characterized by the excellent control in obtaining nano objects with the desired shape and dimensions. A large variety of templates are available ranging from viruses and proteins to nanoporous membranes fabricated by using swift heavy ion accelerators. In the following chapter the main steps involved in employing the method for fabricating metalic nanowires and nanotubes by replicating ion track nanoporous membranes were described. The steps include here membrane fabrication and replication and involve track etching and electrochemical metal deposition. The influence of the process parameters on the properties of the nanoobjects prepared by this approach was reviewed. It was found that simple experimental parameters can be chosen in such a way that the functionality of the nanowires or nanotubes can be finely tuned.

ZnO micro/nanostructures with complex morphology were synthesized by a simple chemical reaction between zinc nitrate and hexamethylenetetramine in the presence of polysaccharides. X-ray diffraction analysis showed that all obtained samples are of wurtzite structure. The reflectance and room temperature photoluminescence spectra have been used to investigate the optical properties of the ZnO structures. The scanning electron microscopy images reveal that the ZnO morphology (star, double-jellyfish, double-raspberry and edelweiss-flower) can be easily changed by varying the polysaccharides: sodium alginate, gum arabic and chitosan. The polysaccharide-assisted crystallization method could provide a facile approach to synthesize other desired compounds with controllable morphology. (C) 2013 Elsevier B.V. All rights reserved.

Organic heterostructures were fabricated by matrix assisted pulsed laser evaporation (MAPLE) method using arylenevinylene oligomers based on triphenylamine (P78)/carbazole (P13) group and tris(8-hydroxyquinolinato)aluminum salt (Alq3). Optical properties of the organic multilayer structures were characterized by spectroscopic techniques: FTIR, UV-vis and photoluminescence (PL). A good transparency (over 60%) was remarked for the structures with two organic layers in the 550-800 nm range. Photoluminescence (PL) spectra proved that the emission characteristics of the materials have been preserved. I-V characteristics of (ITO/oligomer/Alq3/Al and ITO/Alq3/Al) heterostructures were symmetrically while rectifying properties of these heterostructures have not been observed. A comparison between the heterostructures made of layers with different thickness reveals that the higher current (8 x 10(-6) A at 1 V) was obtained for the ITO/P78/Alq3/Al heterostructure, which is characterized by a larger thickness of the double organic layer. AFM measurements revealed a similar topography while RMS values of the reported structures depend on the organic material. (C) 2013 Elsevier B.V. All rights reserved.

Luminescent polymer fibers were obtained by electrospinning solutions of 8% (in ethanol) polyvinylpyrrolidone (PVP) doped with three different dyes (coumarin 6, rhodamine 6G and sulforhodamine 101). Using the same parameters for the electrospinning process, nanofibers with diameters between 200 and 800 nm and different sizes and distributions of the beads were obtained as proven by scanning electron microscopy (SEM). We assessed the dependence of their emissive properties (intensity and wavelength) on the type of dye using photoluminescence (PL) spectra for the same concentration of the dopand dye (10(-3)M). Moreover, employing 4 different concentrations for coumarin 6 and rhodamine 6G (from 10(-3) to 10(-6) M) we evaluated the dependence with the concentration of the dye on the emissive properties of the electrospun dye-doped PVP nanofibers.

Polyester fabrics modified with ZnO particles by electroless deposition were investigated by broadband dielectric spectroscopy in a parallel capacitor between 10(-2) and 10(7) Hz in a temperature interval from ca. 123 to 473 K. Textile samples were routinely characterized for the structure and interaction of the ZnO particles with the fiber surface. Since a textile fabric material is a mixture of air and fibers, the parameters taken into consideration should be called as effective ones. The deposition of ZnO particles lead to complex dielectric spectra and to the temperature dependence of the decomposed peaks following Arrhenius law.

ZnO structures were deposited using a simple chemical bath deposition technique onto interdigitated electrodes fabricated by a conventional photolithography method on SiO2/Si substrates. The X-ray diffraction studies show that the ZnO samples have a hexagonal wurtzite crystalline structure. The scanning electron microscopy observations prove that the substrates are uniformly covered by ZnO networks formed by monodisperse rods. The ZnO rod average diameter and length were tuned by controlling reactants' concentration and reaction time. Optical spectroscopy measurements demonstrate that all the samples display bandgap values and emission bands typical for ZnO. The electrical measurements reveal percolating networks which are highly sensitive when the samples are exposed to ammonia vapors, a variation in their resistance with the exposure time being evidenced. Other important characteristics are that the ZnO rod networks exhibit superhydrophobicity, with water contact angles exceeding 150 degrees and a high water droplet adhesion. Reproducible, easily scalable, and low-cost chemical bath deposition and photolithography techniques could provide a facile approach to fabricate such ZnO networks and devices based on them for a wide range of applications where multifunctionality, i.e., sensing and superhydrophobicity, properties are required.

Recently, ZnO and natural polysaccharides have received more and more attention as interesting components for designing complex functional nanomaterials, key elements being their high occurrence and low-cost. In this chapter are presented possibilities for tailoring the ZnO properties by using polysaccharides in the synthesis process as well as reports on the functionalization of cellulose-based natural fabrics with ZnO. In both cases, in the preparation step were used only simple and scalable wet chemical methods. The resulting materials with suitable characteristics, e.g. dependence of the ZnO nanostructures optical properties on their morphology or high-UV blocking and superhydrophobicity for ZnO-functionalized fabrics, can find applications in domains where such qualities are required.

Micropatterned ZnO was synthesized by an electroless deposition process using Au stripes as catalytic surfaces. The Au-patterned electrodes were prepared on SiO2/Si wafers using photolithography. The site-selective deposition of patterned ZnO hexagonal rod arrays is confirmed by scanning electron microscopy. The ZnO micropatterned surface revealed a conversion of wettability from hydrophilic to super-hydrophobic depending on the deposition reaction parameters. The electrical measurements carried out at room temperature before and after exposure to ammonia vapors of the patterned ZnO arrays show a resistance variation with exposure time. Highly reproducible, easy scalable and low-cost, photolithography and electroless deposition techniques could provide a facile approach to fabricate functionalized micropatterns, for a wide range of applications. (C) 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper presents some studies about the preparation by matrix-assisted pulsed laser evaporation (MAPLE) technique of organic bulk heterojunctions made from the mixture of a star-shaped arylenevinylene compound, 4,4',4aEuro(3)-tris[(4'-diphenylamino)styryl] triphenylamine as donor and fullerene derivative, [6, 6]-phenyl C61 butyric acid butyl ester, as acceptor, in the weight ratio 1:2. The mixed layer has been characterized by spectroscopic (UV-Vis, Fourier transform infrared) and microscopic (AFM) methods, and the effects of the deposition conditions (number of pulses) and of a buffer layer of poly(aniline-co-aniline propane sulfonic acid) or poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) have been analyzed. The study of the electrical properties has revealed a typical solar cell behavior for the heterostructure glass/ITO/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/4,4',4aEuro(3)-tris[(4'-diphenylamino)styryl] triphenylamine: [6, 6]-phenyl C61 butyric acid butyl ester/Al, confirming that MAPLE could be an adequate method for the preparation of active layer based on bulk heterojunction for solar cells.

This paper presents some studies about the bi-layer organic heterostructures realized with zinc phthalocyanine (ZnPc) as donor layer and 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) as acceptor layer, on substrate of glass covered by Al doped ZnO (AZO) layer. These heterostructures have been prepared using laser techniques: pulsed laser deposition (PLD) in an atmosphere of oxygen for AZO films deposition and matrix assisted pulsed laser evaporation (MAPLE) for organic films deposition. The influence of the deposition conditions on the transmission of the organic films has been analysed. The effect of the oxygen plasma treatment, with duration of 5 min and 10 min, on the surface topography, structural and optical properties of AZO layers deposited by PLD and, as consequence, on the optical and electrical properties of the single layer (ZnPc) and bi-layer (ZnPc/NTCDA) organic heterostructure, deposited by MAPLE, was investigated. (C) 2014 Elsevier B.V. All rights reserved.

We report the film deposition of Poly(D, L-lactide-co-glycolide) (PLGA) particle systems by matrix assisted pulsed laser evaporation (MAPLE) technique. PLGA+polyvinyl alcohol (PVA), PLGA+PVA+ bovine serum albumin (BSA) and PLGA+PVA+chitosan (CH) nanoparticles were prepared by an oil-in-water emulsion-diffusion-evaporation method. The average diameter of PLGA particles was between 180-250 nm. The coatings were obtained by laser evaporation of frozen targets prepared by mixing appropriate PLGA aqueous suspensions and dimethyl sulfoxide (DMSO) in three ratios. Depending on the DMSO content, we deposited PLGA particles embedded into polymeric layer mainly obtained due to the entirely or partially dissolving of nanoparticles into the initial solution. In vitro results showed that the distribution and morphology of osteoblast-like SaOs-2 cells on some PLGA particle coatings were similar with that of the positive control. The purpose of this study was to develop layers of PLGA particles for local controlled drug delivery.

A complex structure of four double layers of Ag / As2S3 has been deposited by Pulsed Laser Deposition method on a glass substrate. The effects of thermal annealing on the structural and optical properties were investigated. An effect of layer mixing has been evidenced.

Electroless deposition was successfully applied in developing crystalline particles of zinc oxide onto polyester textile materials; this deposition is here presented in comparison with other materials made from poly(lactic acid), polyamide or hemp. Structural and spectroscopic characterization of the raw and deposited samples has been performed. The structure of zinc oxide particles was that of wurtzite type as indicated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Crystallites were 20-500 nm in diameter and up to 1 mu m in length. The grown particles cover the fibers not only on the fabric surface but in the textile depth. Contact angle measurement by the sessile drop method was used to study the wettability behavior of the investigated composite systems. The hierarchical roughness structure generates superhydrophobic properties onto polyester fabrics, for which water contact angles exceed 150 degrees. The other functionalized samples also become more hydrophobic after deposition. Cassie-Baxter model was found suitable to describe the behavior, though the fraction of surface occupied by the water-solid interface is high enough. The electroless deposition technique applied previously for cotton fabrics was once more proven to be highly reproducible, easy scalable, and cheap, allowing a wide range of applications. (c) 2013 Wiley Periodicals, Inc.

ZnO uniform films were deposited on polymer sphere arrays by an electroless technique. The low-dimensional ZnO particles were grown from an aqueous solution of zinc nitrate and dimethylamineborane. The X-ray diffraction studies demonstrate that the ZnO crystallites have a hexagonal wurtzite structure. The scanning electron microscopy images prove that ZnO hexagonal prisms are synthesized with a fairly uniform diameter of around 200 nm. From the contact angle measurements it was found that the electroless deposition on polymer sphere arrays of semiconductor hexagonal prisms leads to an improvement of ZnO hydrophobic properties.

Zinc oxide particles were synthesized by a simple wet chemical method. Using zinc nitrate and various precipitating agents, like KOH, NaOH and (CH2)(6)N-4, particles with different morphologies were obtained. Also, the addition of a structure-directing agent, like gum arabic - a highly branched biopolymer, leads to a decrease in the ZnO particles size (for KOH and NaOH) and to a dramatical change of the ZnO particle shape in the case of (CH2)(6)N-4. The X-ray diffraction analysis showed that all obtained samples are of wurtzite structure. The reflectance and photoluminescence spectra have been used to investigate the optical properties of the ZnO structures. The morphologies observed by scanning electron microscopy reveal snowflake-like, flower-like, star-like and double-raspberry-like structures. A possible formation mechanism for ZnO micro/nanostructures with different morphologies was proposed. The biopolymer-assisted crystallization method could provide a facile approach to synthesize other desired compounds with controllable morphology.

Cotton fabrics were coated with arrays of ZnO hexagonal prisms using an electroless (catalytic/auto-catalytic) deposition process. A typical three step method, similar to those used for electroless deposition of metals on insulating substrates, consisting of pre-activation, activation and deposition steps was employed. The low-dimensional ZnO particles were grown from an aqueous solution containing zinc nitrate as source of zinc ions and dimethylamineborane as reducing agent. The as-obtained ZnO-coated cotton fabrics were characterized from the point of view of structure by X-ray diffraction (XRD) and morphology by scanning electron microscopy (SEM). The XRD studies demonstrate that the ZnO particles have a hexagonal wurtzite crystalline structure. The SEM observations prove that the cotton fibers are homogeneously covered by hexagonal prisms which have uniform base size of approximately 500 nm and height of 1 mu m. Optical spectroscopy measurements show that the functionalization with ZnO strongly decreases the transmittance in the UV vis region of the cotton fabrics. An important characteristic is that the ZnO-functionalized cotton fabrics exhibit superhydrophobicity, with water contact angles exceeding 150 degrees. The technique described is highly reproducible, easy scalable and cheap, allowing a wide range of applications. (C) 2012 Elsevier B.V. All rights reserved.

We synthesized by wet chemical route a novel europium-potassium phthalate complex Eu3+K+[(COO)(2)(C6H4)](2). The compound is a white powder insoluble in water. X-ray diffraction evaluation shows that we obtained a new crystalline compound with no traces of the starting materials (potassium hydrogen phthalate and europium chloride). Scanning electron microscopy reveals that the powder consists of fiber-shaped structures with sizes larger than 250 nm in diameter. Energy dispersive X-ray analysis proves that the compound has a 1:1 europium-potassium ratio. Fourier transform infrared spectroscopy confirms the presence of the phthalate in the new compound. Photoluminescence and cathodoluminescence measurements show that the fiber-shaped structures are intensely luminescent with emission bands corresponding to the D-5(0) -> F-7(J) (J = 1-4) Eu (III) ion's transitions in the region between 580 nm and 700 nm, the most intense maximum being observed around 615 nm. Up-converted luminescence with a maximum at 315 nm was recorded. (c) 2012 Elsevier B.V. All rights reserved.

Styrene, methyl methacrylate and glycidyl methacrylate vinyl monomers were grafted onto chitosan by surfactant-free emulsion copolymerization using potassium persulfate as initiator. The grafted compounds were characterized by X-ray diffraction, FTIR spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and zeta potential measurements. X-ray diffraction showed changes in the crystallinity pattern of chitosan after the copolymerization reaction. Evidence of grafting was confirmed by FTIR spectroscopy. From zeta potential measurements it is found that the surfaces of graft copolymers latex particles have positive charges resulting from the cationic chitosan molecules. The morphology evaluated by SEM, TEM and AFM proves that in the absence of chitosan, latexes of vinyl homopolymers contain quasi-monodispersed spheres with average diameter of about 400 nm or 250 nm while the graft copolymers latexes are formed by clustered irregular beads with average diameter around 100 nm.

Oxyfluoride glass-ceramics in the system SiO2-Al2O3-CaF2-EuF3 containing Eu3+-doped CaF2 nanocrystals were produced by using controlled crystallization of melt-quenched glass. X-ray diffraction and scanning electron microscopy data have revealed the formation of CaF2 nanocrystals of about 50 nm size. The Eu3+-dopant ions act as the nucleating agent necessary to initiate the crystallization process. The refractive index is higher in the glass ceramics than in the initial glass and varies as the annealing time increases. Two competitive processes are responsible for this behavior, the crystallization of the CaF2 phase and the decrease of the glass ceramic mass density. (C) 2012 Elsevier B.V. All rights reserved.

ZnO films were electrodeposited from an aqueous nitrate bath on ITO/glass substrates. The process was performed not by the usual potentiostatic approach but by using potential ramps with different sweep rates. We tested these ramps in both directions i.e. either towards electronegative (direct) or electropositive (inverse) potential. As expected, the samples prepared in different deposition conditions show different morphology, different quality of crystalline structure and different optical properties. By employing inverse ramps we prepared films with high quality structural and optical properties. We assume that in these conditions the growth is followed by an etching process which preferentially removes the areas with high defect concentration and leads to the formation of hollow hexagonal prisms. (c) 2012 Elsevier B.V. All rights reserved.

CdS micro- and nano-structures (micro/nanotubes and nanostructured films) were obtained by ammonia-free chemical bath deposition using polymer templates (ion track-etched polycarbonate membranes and poly(styrene-hydroxyethyl methacrylate) nanosphere arrays). The semiconductor structures were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), optical absorption, photoluminescence and electrical measurements. The diameters of CdS tubes are between 300 nm and few microns and the lengths are up to tens of micrometers. The SEM images prove that the CdS films are nanostructured due to the deposition on the polymer nanosphere arrays. For both CdS structures (tubes and films) the XRD patterns show a hexagonal phase. The optical studies reveal a band gap value of about 2.5 - 2.6 eV and a red luminescence at similar to 1.77 eV. A higher increase of conductivity is observed for illuminating the CdS nanostructured film when compared to the simple semiconductor film. This is a consequence of the periodic patterning induced by the polymer nanosphere array. (C) 2012 Elsevier Ltd. All rights reserved.

Surfactant-free emulsion copolymerization was used to prepare methyl methacrylate-hydroxyethyl methacrylate (MMA-HEA) and methyl methacrylate-hydroxypropyl methacrylate (MMA-HPMA) latex particles. Also, glycidyl methacrylate (GMA) was grafted onto the surface of the preformed MMA-HPMA latex particles by seeded surfactant-free emulsion copolymerization. The copolymerization reactions were conducted at 75 A degrees C using a water-soluble initiator, potassium persulfate (KPS). The morphologies of copolymer latex particles were observed using Scanning electron microscopy (SEM). The influence of different reactions parameters (the MMA saturation concentration (Sr), the KPS concentration and the aqueous solubility of the comonomers (HEA or HPMA)) on the particles average diameter and particles size dispersity was investigated. The experimental results showed that the increase of initiator concentration induces in all investigated cases the increase of particles average diameter, while the presence of HEA or HPMA as comonomers in the copolymerization reaction of MMA (1,000% Sr) lead to a decrease of particles average diameter. At small KPS concentration the latex is monodisperse, the increase of the initiator concentration leading to the formation of polydisperse latex. In the case of grafting reaction of GMA onto the monodisperse preformed MMA-HEA latex particles, although the average diameter of the final particles doubles the latex remains quasi-monodisperse.

PbS micro- and nanoparticles were synthesized by a simple precipitation reaction of lead nitrate with thioacetamide in hydrosoluble polymer water solutions. The effects of four water soluble polymers: polyacrylamide (PAM), polyvinyl alcohol (PVA), polyethylene glycol (PEG) and poly-N-vinyl pyrrolidone (PVP) on the PbS crystallites morphology and structural properties were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was found that for the PbS particles obtained in the PVA. PEG and PVP, the (2 0 0) diffraction peak of the nanocrystals becomes dominant. The highest texture in the [2 0 0] direction was observed for the crystallites obtained in the presence of PVP. Polydisperse PbS particles with cubic morphology and size ranging from 100 nm to several microns are obtained in the case of PAM and PEG. Monodisperse cubic PbS crystallites with an average size of 200 nm are formed in the presence of PVA and PVP. (C) 2011 Elsevier B.V. All rights reserved.

This paper discusses two arylenevinylene oligomers with optical nonlinear properties. Their trans molecular structure was confirmed by Fourier Transform Infrared Spectroscopy and Nuclear Magnetic Resonance. Second Harmonic Generation and two-photon fluorescence have been observed on Matrix Assisted Pulsed Laser Evaporation-deposited thin films. We have seen two local maxima in UV-Vis spectra and a red shift of the photoluminescence peak for carbazole-based oligomer, which can be correlated with a higher conformational flexibility and with strong polarization interactions in the solid state. Scanning Electron Microscopy and Atomic Force Microscopy images have revealed a grainy morphology of the film deposited on titanium and a higher roughness for carbazole-based oligomer. Second harmonic measurements have shown nearly equal values of the second-order nonlinear optical coefficient for the triphenylamine and carbazole-based oligomers for P-laser < 100 mW. z-Scan and x-scan representations of the carbazole-based oligomer film have shown strong two-photon fluorescence intensity inside the sample confirming a volume process, and a strong second harmonic at the surface of the sample determined by the surface morphology. (C) 2010 Elsevier B.V. All rights reserved.

This paper presents some investigations on the properties of guanine (G) and cytosine (C) based heterostructures deposited on flexible substrates. The effects of two types of maleic anhydride-aniline derivatives (maleic anhydride-cyano aniline or maleic anhydride-2,4 dinitroaniline) buffer layer, deposited between indium tin oxide and (G) or (C) layer, on the optical and electrical properties of the heterostructures have been identified. The heterostructures containing a film of maleic anhydride-2,4 dinitroaniline have shown a good transparency and low photoluminescence invisible range. This buffer layer has determined an increase in the conductance only in the heterostructures based on (G) and (C) deposited on biaxially-oriented polyethylene terephthalate substrate. (C) 2011 Elsevier B. V. All rights reserved.

Poly(styrene-hydroxyethyl methacrylate) [P(ST-HEMA)] latex particles were prepared by surfactant-free emulsion copolymerization. As water-soluble initiator was used potassium persulfate (KPS). The influence of different reactions parameters, such as the reaction temperature, the both monomers (ST and HEMA) concentrations and the KPS concentration on the particles average diameter and particles size dispersion was investigated. Generally monodisperse spherical particles are synthesized, but we also obtained stable large three-dimensional colloidal aggregates. These are formed by the agglomeration of monodispersed spheres in certain polymerization conditions. The P(ST-HEMA) monodispersed spheres with 350 nm average diameter were assembled into colloidal crystals using dip-coating technique. Colloidal crystals with different thickness were obtained by modifying two experimental factors, the colloidal concentration and the substrate lifting speed. The morphologies of copolymer latex particles and colloidal crystals were observed using scanning electron microscopy (SEM). The optical properties of colloidal crystals films were also investigated by transmission spectroscopy.

This paper presents a study of some thin monomer films deposited by MAPLE. These monomers have been synthesised from maleic anhydride and aniline derivatives and are characterized by a molecular structure adequate for the generation of optical non-linear phenomena. UV-VIS, FTIR, Raman and Photoluminescence spectroscopy have been used to investigate the influence of the experimental conditions on the properties of the films. X-Ray Diffraction has evidenced a certain degree of disorder in the thin films, which is correlated with the randomly orientated molecules and AFM images have revealed different roughness for different monomer layers and different substrates. Second harmonic measurements have shown a strong signal emitted by the thin film prepared from the monomer with one [-NH-NH-] donor and two [-NO(2)] acceptor groups. This thin film is characterized by good transparency and low photoluminescence emission at excitation with the wavelength of the second harmonic (lambda-400 nm).

In this study the Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique was used to prepare thin films from a low melting point (< 100 degrees C) organic compound (benzil). Optical properties of the films have been investigated by UV-VIS, FTIR and PL spectroscopy. Details about crystallinity were obtained by XRD measurements. FTIR spectra have confirmed the preservation of the chemical structure of the compound during the deposition process. SEM and AFM investigation have evidenced a topography of the MAPLE deposited films characterized by different grain size depending on the deposition conditions. Second harmonic generation measurements have revealed that the MAPLE deposited benzil films have preserved the optical nonliniar properties of the bulk crystalline benzil.

Intercalation, i.e. the insertion of guest species in a crystalline layered structure, is an efficient route for generating new materials with novel properties. Thin films and crystalline powder of BiI3 layered semiconductor were intercalated by exposure to ammonia vapors at room temperature. The intercalated compound was studied by thermo-gravimetric analysis, differential scanning calorimetry, X-ray diffraction, UV-vis optical absorption, FTIR spectroscopy and Raman scattering. After exposure of BiI3 to ammonia the formation of a new phase, BiI3(NH3)(3.83), was evidenced by thermal analysis. The intercalation process leads to a blue shift of the BiI3 Optical absorption edge by 0.5 eV. The appearance of new Raman lines at 135 and 353 cm(-1) in the Raman spectrum of intercalated BiI3 is considered as an evidence of the chemical interaction between the ammonia molecules and BiI3 lattice. (C) 2009 Elsevier Ltd. All rights reserved.

Electrochemical replication of nanoporous membranes represents a facile approach towards the fabrication of nanostructures with tailored properties. By the template method we prepared multisegment nanowires with tailored structure. The first step of the process was the fabrication of the nanoporous template by swift heavy ion irradiation and subsequent selective etching of the ion track. The next step was to fill the pores with the desired combination of materials. In this manner, by sequential electrodeposition steps of metal and semiconductor we prepared Ni - CdTe and Ni - ZnO - Ni nanowires.

The synthesis of a new hybrid composite based on PUS nanoparticles and poly( methyl methacrylate-2acrylamido-2-methylpropane sulfonic acid) [P(MMA-AMPSA)] copolymer is reported. The chemical synthesis consists in two steps: (i) a surfactant-free emulsion copolymerization between methyl methacrylate and 2-acrylamido-2-methylpropane sulfonic acid and (ii) the generation of PbS particles in the presence of the P( MMA-AMPSA) latex, from the reaction between lead nitrate and thiourea. The composite was studied by scanning electron microscopy (SEM), X-ray diffraction, FTIR spectroscopy, thermogravimetric analysis and differential scanning calorimetry. The microstructure observed using SEM proves that the PbS nanoparticles are well dispersed in the copolymer matrix. The X-ray diffraction measurements demonstrate that the PbS nanoparticles have a cubic rock salt structure. It was also found that the inorganic semiconductor nanoparticles improve the thermal stability of the copolymer matrix. (C) 2010 Elsevier Ltd. All rights reserved.

Electrochemical deposition was performed in order to prepare CdS nanowires. The method employed for preparation of such high aspect ratio nanostructures was template replication. Ion track polycarbonate membranes were used as templates. The nanowires were studied by scanning electron microscopy (morphology characterization), energy dispersive X ray analysis (composition) and optical spectroscopy. Optical reflection spectroscopy was performed in order to determine the band gap value while photoluminescence spectroscopy was used for getting information regarding the point defects in the material.

This paper presents a study of some functionalised copolymers thin films prepared on silicon and quartz substrates by matrix assisted pulsed laser evaporation ( MAPLE) method. Two polymeric structures have been synthesised by the copolymerisation of maleic anhydride and methyl methacrylate, respectively, maleic anhydride and vinyl benzyl chloride and their subsequent functionalisation with 2,4-dinitroaniline. UV-Vis, FTIR, Raman and photoluminescence spectroscopy have been used to investigate the influence on the properties of the films of different substrate temperature ( 150 degrees C and 250 degrees C), background N-2 pressure (5-30 Pa) and polymer concentration in target (2% and 3%). We have evidenced that this deposition process does not damage the chemical structure of the polymers. SEM investigations revealed the droplets type morphology of the polymeric films with thickness between 41 nm and 105 nm calculated from ellipsometric measurements. (C) 2008 Elsevier B. V. All rights reserved.

PbI2, BiI3, CdI2 and AgI crystalline samples intercalated with pyridine have been studied by Raman spectroscopy. Comparing the Raman spectra of pristine metal iodides with those of intercalated samples we have shown the coexistence, in the host crystalline lattice, of two adsorbed forms: a physisorbed one, featured by weak forces of van der Waals type and a chemisorbed one, involving stronger forces related to an electrostatic interaction. The physisorbed form is consistent with the molecules inserted into the interlayer spaces while the chemisorbed form is represented by the molecules forming coordination complexes with the crystalline lattice cations. The crucial role in the formation of such complexes is played by the lone pair of nitrogen atom belonging to the molecules.

This paper presents a study of two monomeric structures containing functional groups with different electronegativities [NH/NH-NH and NO2] and two different polymeric structures prepared by the copolymerisation of maleic anhydride and methylmethacrylate/maleic anhydride and vinyl benzyl chloride, and subsequent functionalization with 2,4 dinitroaniline. Thin films have been prepared by Matrix Assisted Pulsed Laser Evaporation (MAPLE) and UV-VIS, FTIR, Raman and Photoluminescence Spectroscopy have been used to comparatively investigate the properties of the synthesised compounds. We have evidenced the second harmonic emission (SHG), process sustained by the asymmetry of the chemical structure, which is correlated with the crystallization in non-centrosymmeric structures.

We report the formation of stable C-70 aggregate forms in o-dichlorobenzene/N-methyl-2-pyrrolidinone (DCB/NMP) and o-dichlorobenzene/acetonitrile (DCB/ACN) mixtures and their characterization by UV-VIS absorption spectroscopy and photoluminescence. As NMP acts on C-70 both as a solvent and reactant due to the unpaired electrons of the amidic nitrogen atom, molecular complexes (C-70/NMP) that aggregate slowly are formed by the binding of the NMP molecule to the fullerene cage. This interaction is seen in the UV-VIS absorption spectra of C-70 in DCB/NMP solvent mixtures by a gradual modification of the absorption spectra when increasing the NMP concentration. On the other hand, DCB and ACN combined form it typical solvent/non-solvent mixture favoring an intense aggregation of fullerenes. This yields to the C-70 clusters formations, having different size, similar to a precipitation process. Their characteristic is an abrupt variation in the absorbance appearing when the ACN is used in a greater extent. This different behavior of C-70 aggregation in DCB/NMP and DCB/ACN mixtures is also seen in their luminescence spectra recorded at different excitation wavelengths. While the PL spectra of C-70 solvated in DCB/NMP solution keeps almost the same modified shape irrespective the NMP concentration, the luminescence spectra Of C-70 in DCB/ACN mixture partially regains the powder C-70 PL signature as the ACN concentration is increased.

Hybrid material based on PbI2 intercalated with 2,2'-bypiridine (BIPY) was investigated by correlated studies of photoluminescence. infrared absorption and Raman spectroscopy. The PbI2(BIPY) intercalated compound has been synthesized by the chemical reaction of K1 and Pb(NO3)(2) in aqueous BIPY solution The optical studies reveal different properties for the hybrid material in comparison with those of pure PbI2 and BIPY. In the photoluminescence spectrum of the intercalated compound. recorded at liquid nitrogen temperature a new intense hand emission with maximum at 2 07 eV is observed. The excitation spectrum reveals it broad hand featured by several maxima at 2.77, 3.34 and 3 70 eV. New absorption bands at about 1589, 1489, 1435, 1312, 1009 cm(-1) are observed in the IR spectrum of PbI2(BIPY). The Raman spectrum of intercalated compound discloses new lines at 67, 83, 127 cm(-1) and the shift of two Raman lines from 994 cm(-1) to 1010 cm(-1) and from 1045 cm(-1) to 1060 cm(-1). A charge transfer process, leading to the formation of lead-BIPY coordination complexes. is considered its responsible for the strong host-guest interaction revealed by almost all experimental data

Crystals of potassium acid phthalate (KAP) doped with rhodamine 6G (Rh 6G) were grown by slow evaporation method from aqueous solutions. Crystals of good optical quality suitable for optical applications were obtained. Different concentrations of rhodamine 6G (10(-5) M, 2x10(-5) M, 5x10(-5) M and 10(-4) M in the growth solutions) were used in order to tune the optical properties of the crystals. Depending of the dye concentration, the absorption spectra of the dye-doped crystals show several bands in the range between 360 nm and 526 nm. The photoluminescence of the KAP crystals induced by the dye-doping reveals two emission bands peaking at 540 nm and 560 nm.

Functionalization of PbI2 with polyaniline-emeraldine base (PANI-EB) or polyaniline-emeraldine salt (PANI-ES) is demonstrated by Raman spectroscopy. Two functionalization methods were used: electrochemical polymerization of aniline onto the PbI2 modified Pt electrode and the mechanico-chemical reaction between PANI and PbI2. The functionalization induces changes in the Raman spectrum of PbI2 that consist in the appearance of new Raman lines with the peaks at 80, 144 and 170 cm(-1) The first line is the signature of the "stacking faults" that disrupt the stacking sequence of layers I-Pb-I atomic layers along the c crystalline axis by the intercalation of polymer molecules The bands at 144 and 170 cm(-1) are attributed to a vibrational mode associated to the Pb-NHR"(2) (R" = C6H4) bond.

Thin films and crystalline powder of PbI2 intercalated with ammonia or pyridine have been studied by optical absorption, Raman scattering, photoluminescence, FTIR spectroscopy and thermo-gravimetric analysis. Ammonia intercalated PbI2 shows an increased optical band gap, of about 0.6 eV, with an intense broad emission band peaking at about 2.3 eV as signature in the photoluminescence spectrum. The intercalation of PbI2 with ammonia is noticed in the Raman spectrum by the appearance of new lines situated in low frequency range. The D-3d coordination geometry of Pb2+ in the PbI2 crystal is reduced by compression to orthorhombic one, the distribution of the electronic states in valence band is also changed. Thus, the top of the valence band undergo a deformation inducing a weakness of the interaction between the lead and iodine ions within a layer. Also the PbI2 intercalated with pyridine is featured by optical and vibration properties different that of pure crystalline powder. Finally, the intercalation of PbI2 with different molecules changes the basic semiconducting properties of the crystal. Thermal analyses and infrared absorption spectra have been used to study the desorption of guests species from PbI2 in order to evaluate the stability range and morphological changes with temperature.

The effect of fullerene on the radical polymerization of N-vinylpyrrolidone with lauroyl peroxide in toluene was investigated kinetically. C-60 was found to act both as inhibitor and as retarder because the polymerization rate and the molecular weight of resulting poly(vinylpyrrolidone) is decreasing with the increase of the fullerene concentration (0-6.94 x 10(-4) mol l(-1)). The water-soluble poly(vinylpyrrolidone)-modified fullerene C-60 compound was characterized by differential scanning calorimetric, Infrared and Raman spectroscopy, UV absorption and photoluminescence. Based on the results obtained by optical measurements, it is argued that by the covalent attachment of the polymeric radicals to fullerene cage the extended electronic conjugation system of the C-60 is broken leading to the appearance of a polyene structure.

Photoluminescence (PL) properties of the composites based on zinc oxide (ZnO) and single-walled carbon nanotubes (SWNTs) prepared by hydrothermal synthesis are studied in this paper. The emission and excitation spectra of nanometric ZnO powder are dramatically influenced by the adsorption of different molecules coming from the environment. Therefore, a special attention is given to reveal the influences of adsorption/de-sorption process on photoluminescence properties of zinc oxide nanoparticles. A quenching effect of the intrinsic PL is observed regularly when the ZnO is synthesized in the presence of SWNTs, i.e. when a ZnO/SWNTs composite is formed. A distinct feature of the ZnO/SWNTs composite, is an emission band with a maximum at 405-450 nm.

Fullerene C-60 has attracted attention due to its special chemical and physical properties. However, its poor solubility and processability arise difficulties in practical applications. These problems may be surpassed by grafting C-60 on polymers. This study presents the synthesis of the polyethylene/maleic anhydride copolymers and C-60 structures and their characterization by photoluminescence. The synthesis of the material is based upon the reaction of fullerene C-60 with amino groups containing in the polymer chains. In the first step, some polyethylene (PE)/maleic anhydride (MA) copolymers having 1, 3, 6 and 10 wt.% anhydride groups were reacted with an amine compound. The following step consists in the reaction of C-60 with the amine groups. A proof that the structures synthesized contain C-60 is given by the photoluminescence spectra.

The fullerenated poly vinyl chloride was synthesized by the addition reaction of azido-substituted poly vinyl chloride with C-60. Structural characterization carried out using Raman and FTIR spectroscopy confirm the presence Of C-60 chemically bound in the new compound. Also, the photoluminescence properties of fullerenated poly vinyl chloride are considerably changed from those Of C-60.

Intercalated PbI2 compounds were prepared by exposing crystalline films and crystalline powders of lead iodide to pyridine or iodine vapor at room temperature. Correlated studies of optical absorption, Raman scattering and low temperature photoluminescence (PL) reveal different properties in comparison with those of pure crystalline PbI2 powder. Depending of the nature of intercalated molecules (organic or inorganic) the basic semiconducting properties of PbI2 are dramatically modified. The main signature of iodine intercalated PbI2 consists in a luminescence band peaking at 2.24 eV appearing at 77 K under 350 nm excitation light. In the case of pyridine intercalated PbI2 a new intense band at about 3.3 eV in the absorption spectrum is observed. The the PL spectra of pyridine intercalated PbI2 at 77 K change substantially when the excitation wavelength. The Raman spectra confirm the presence of pyridine between the PbI2 layers.

Carbon Nanotubes are exotic low-dimensional systems, and due to their remarkable properties, are promising components for technological applications. The electronic and vibrational signatures raising from their existence as individual entities or associated in bundles, is still a controversed subject. A careful analysis of the G (similar to 1600 cm(-1)) and RBM (100-200 cm(-1)) band features as: profile, peak position and intensity in the Raman spectra may be a valuable indication about their dispersion state. The UV-VIS-NIR absorption spectrum comes to support this assumption. Observing the absorption spectra associated to resonant excitation of semiconducting and metallic nanotubes, may reveal complementary informations concerning the individualization procedure efficiency.

Pbl(2) crystallite incorporated in optically transparent polyacrylamide and poly (vinyl alcohol) matrix have been studied by Raman scattering, photoluminescence (PL) at low temperature and Scanning Electron Microscopy (SEM). The small particles of Pbl(2) embedded in different host matrix were prepared by: i) cooling to the room temperature a boiling saturated aqueous Pbl(2) solution containing polyacrylamide or poly (vinyl alcohol) and ii) by chemical reaction of KI and Pb(NO3)2 in aqueous polyacrylamide solution. In all cases, were identified hexagonal platelets of Pbl(2) and rods like particles. The rods are featured by a similar Raman spectrum and a specific green emission (cca 550 nm). Modification of the Raman and PL spectra results from a compressing effect produced by the penetration between the Pbl(2) layers of different molecular species. By compression the hybridized electronic level situated at the top of valence band, formed by the contribution.of the 6s and 5p states of Pb2+ and l ions, undergo a deformation that induces a weakness of the interaction between the lead ion and iodine electron within a layer so that the photoluminescence of intercalated Pbl(2) acquires the characteristics of Pb2+ emission when it is dissolved in an alkali halide crystal.

Small particles of Pbl(2) embedded in transparent polymer matrix have been studied by Raman scattering, UV-VIS absorption spectroscopy, low temperature photoluminescence (PL) and Scanning Electron Microscopy (SEM). The Pbl(2) crystallites were prepared by two different methods: i) by cooling to the room temperature a boiling saturated aqueous Pbl(2) solution containing polyacrylamide and ii) by chemical reaction of Kl and Pb(NO3)(2) in aqueous polyacrylamide solution. In both cases, beside the hexagonal platelets of Pbl(2) Were identified rods whose luminescence and Raman signature is quite different than of Pbl(2) platelets. Regardless the rods nature, as distinct KPbl(3) particles or lead iodide low-dimensional particles embedded in the polymer matrix, their photoluminescence is featured by an intense green emission (550 nm) appearing at low temperature at excitation wavelengths less then 350 nm.

Through correlated studies using scanning electron microscopy (SEM), Raman spectroscopy and low-temperature photoluminescence (PL) we have demonstrated that the intercalated PbI2 with ammonia, poly (vinyl alcohol) and polyacrylamide are characterized by a distinctive signature in the Raman and photoluminescence spectra. After intercalation, the Raman spectrum of PbI2 reveals an orthorhombic structure, identical with that observed on the micrometric scale, of KPbI3 rod-like particles resulting from the reaction between Pb(NO3)(2) and KI, carried out in liquid media such as ethanol and acetonitrile. The rods and the intercalated PbI2 are characterized by a new and strong emission band at 2.23 eV (about 550 nm) that appears at 77 K under an excitation wavelength of about 340 nm. Modification of the Raman and PL spectra results from a compressing effect produced by the penetration between the PbI2 layers of different molecular species. The compression acting primarily on the iodine layers has the result of lowering the contribution of the 5p states of I- ions to the constitution of the electronic level situated at the top of valence band of PbI2, so that the photoluminescence of intercalated PbI2 acquires the characteristics of Pb2+ emission when it is dissolved in an alkali halide crystal.

Single-walled carbon nanotubes (SWNTs) under a moderate non-hydrostatic pressure, of 0.58 GPa, undergo a non-reversible transformation. Due to the plastic deformations, structural defects and carbon nanotube fragments of different size are produced. Short fragments of spherical or ellipsoidal form, behaving as closed-shell fullerenes are observed both by Raman spectroscopy and photoluminescence (PL). The main vibrational indicative of the fragments of shorter length is the band at similar to 1458 cm(-1) that is regularly observed in the Raman spectra of fullerene. Similar to fullerenes self assemblies, the interaction between the nanotube fragments is noticed in the Raman spectrum by the band at similar to 94 cm(-1) that reveals an inter-particle vibration mode. When the nanotubes are dispersed into host matrix, as aromatic hydrocarbons (AHs) with isolated or condensed phenyl rings, supplementary mechanico-chemical reactions take place. For AHs with isolated phenyl rings, like biphenyl or p-terphenyl, a chemical functionalization of SWNT fragments is demonstrated by the appearance of a new Raman band at 1160 cm(-1). In PL spectra, the interaction of SWNTs with AHs, is noticed by a detailed vibronic structure appearing in the high energy side of the emission spectrum, that increase with the weight of SWNTs in the AHs/SWNTs mixtures.

Electronic spin-lattice relaxation measurements performed in X and Q bands on electrons irradiated polyethylene, polycarbonate and polymethylmethacrylate have shown that at liquid helium temperatures and higher, up to 12K, the spin-lattice relaxation time of radiation induced free radicals does not depend on the magnetic. field but varies inverse proportionally with the square of absolute temperature and free radicals concentration. These peculiarities have been well explained by admitting that below 77 K there is a considerable amount of stable free radicals coupled in pairs that mediate the spin-lattice relaxation process of single radicals. Consequently, we have proposed an analytical equation that, within this hypothesis, quantitatively describes all these particularities.

Surface-enhanced Raman scattering (SERS) was used to investigate C-60 self-assembling in solvents like pyrrolidine (Py) and Nmethyl-2-pyrrolidinone (NMP) as well as in binary mixtures of o-dichlorobenzene (DCB)/acetonitrile (ACN) and DCB/NMP. For a correct evaluation of the modifications of Raman spectra induced by the C-60 aggregation, we have also presented the variations due to the measuring method, i.e., the signal dependence of the metallic support type and the surface roughness. The interaction between C-60 and the Au substrate, appearing as a chemical component in SERS generation, is mainly evidenced by a band at similar to342cm(-1). In the aggregated phase, the intermolecular interactions lead to a reduction in the parent I-h C-60 symmetry as observed by a modified phonon spectrum. As a general feature, the spectral range below 800cm(-1) is the most diagnostic for the aggregate assignment, the main indicative being the disappearance of the Raman bands associated to the radial vibration modes. SERS measurements have revealed two stages in the self-assembling of C-60 in NMP. In the beginning, charge-transfer molecular complexes that associate slowly in stable aggregates are formed by the binding of an NMP molecule to the C-60 cage. These complexes are noticed in the SERS spectrum by the replacement of the original H-g(l) band at similar to269cm(-1) with two others at similar to255 and similar to246cm(-1). In the aggregated phase, when using NMP and P as a solvent, the Raman spectrum reveals new bands that appear around 94 and 110-118cm(-1), which are associated with the interball interactions. In a DCB/ACN solvent mixture, the self-assembling process is driven by weak van der Waals type forces and resembles a precipitation, yielding C60 clusters of different size. (C) 2004 Published by Elsevier Ltd.

Correlated studies of Surface Enhanced Raman Scattering (SERS) spectroscopy, photoluminescence (PL) and viscosity on aggregation of C-60 fullerene in N-methyl-2-pyrrolidinone (NMP) solutions were performed. The aggregation is a result of storing of the solutions at the room temperature for different periods of time. The modified phonon spectrum in the aggregate phase is a consequence of the intermolecular interactions that lead to a large reduction in parent I-h C-60 symmetry. The Raman range below 800 cm(-1) is the most diagnostic for aggregate assignment. Substitution of the original of H, (1) band from similar to 269 cm(-1) with a new one at similar to 255 cm(-1) relates the formation of (C-60, NMP) complexes. In the second stage of aggregation, this band shifts at similar to 246 cm(-1) and a new band, associate to the interball interaction, is formed at similar to 94 cm(-1). PL emission of the C-60 solutes in NMP presents two components, one in red (1.92-2.00 eV) and another in green (2.18-2.3 eV), which originate in two successive processes. Their weights depend on C-60 concentration and on storage time. In the beginning are formed quickly molecular complexes (C-60, NMP) by charge transfer, which on associate slowly in stable aggregates. A dependence of specific viscosity on C-60 solution concentration is observed too.

At room temperature, soluted C-60 in pyrrolidine and N-methyl-2-pyrrolidinone associates slowly in stable aggregates. The process originates in the charge transfer from the solvent molecules as electron donors towards fullerene. In the aggregate phase the intermolecular interactions lead to a large reduction in parent I-h C-60 symmetry such that a modified phonon spectrum is observed. Using the surface-enhanced Raman scattering we demonstrate that the Raman range below 800 cm(-1) is most diagnostic for aggregate assignment. In particular, the strong decrease of the radial breathing mode and appearance of new bands at 110 and 93 cm(-1) due to the interball interactions must be noticed.

Photoluminescence (PL) spectra of C-60 solutions in N-methyl-2-pyrrolidinone (NMP) show a drastic increase of the PL intensity if the solutions are stored longer periods of time. Two distinct spectral components, one in the red (1.92-2.00 eV) and another in the green (2.18-2.3 eV) were identified in the whole PL emission. Their weights depend on C-60 concentration and on storage time. The two emissions come from two successive processes running with different kinetics. Charge transfer, leading to (C-60, NMP) loose molecular complexes and a slow aggregation process of these entities seems to originate the red and green emission, respectively. Similar PL properties are found when pyrrolidine (P) is used as solvent.

Scanning electron microscopy, Raman scattering, UV-VIS absorption spectroscopy and low temperature photoluminescence (PL) were used to examine small particles produced by the chemical reaction between Pb(NO3)(2) and KI in different liquid media: water, methanol, ethanol and acetonitrile. By stoichiometric changes in the synthesis reaction, platelets of PbI2 and rods probably of KPbI3 are produced. Regardless of shape and size, these particles exhibit almost the same PL, which consists of two intense bands centred around the 2.5 (E band) and 2.0 eV (G band), in turn similar to that of a crystalline slide or a micrometric powder, both prepared from a PbI2 single-crystal grown from the melt. Crystalline PbI2 platelets exhibit an E band with two components, at 2.49 (E-F band) and 2.47 eV (E-T band), originating in the recombination of the free and trapped excitons produced by inter-band irradiation. A close relation between the enhancement of the E-T and G band reveals that they are linked to the surface defects. For the rod-like particles, the PL spectrum is somewhat similar to that of a Pb2+ ion introduced into an alkaline halide lattice, which as for any ns(2) ion displays two emission bands, A(T) and A(X), whose correspondents are E and G bands.

Herein, the properties of the organic heterostructures with triple-layer ZnO/Ag/ZnO as a replacement for ITO and mixed layer containing arylenevinylene oligomer (based on triphenylamine or carbazole) donor and nonfullerene (perylene diimide) acceptor mixed in the ratio 1:2 and the effect of a buffer layer of PEDOT-PSS intercalated between triple layer and mixed organic layer are discussed. The UV-vis transmission and photoluminescence (PL) properties are investigated in correlation with the surface topography and reveal a good match between the absorption and emission domain, which can favor the generation of the charge carriers. The heterostructure with the mixed layer based on triphenylamine oligomer shows the widest absorption domain, and the PL spectra of the heterostructures realized with either triphenylamine or carbazole oligomer show peaks corresponding to the radiative decay of the donor and acceptor. The I-V characteristics in the dark indicate a slightly nonlinear behavior and the current is affected by the charge carriers recombination on the defects present in the thick mixed layer deposited by matrix-assisted pulsed laser evaporation. The effect of the PEDOT-PSS buffer layer on the electrical properties of the organic heterostructure with ZnO/Ag/ZnO electrode is also investigated.

Herein, the properties of the organic heterostructures with triple-layer ZnO/Ag/ZnO as a replacement for ITO and mixed layer containing arylenevinylene oligomer (based on triphenylamine or carbazole) donor and nonfullerene (perylene diimide) acceptor mixed in the ratio 1:2 and the effect of a buffer layer of PEDOT-PSS intercalated between triple layer and mixed organic layer are discussed. The UV-vis transmission and photoluminescence (PL) properties are investigated in correlation with the surface topography and reveal a good match between the absorption and emission domain, which can favor the generation of the charge carriers. The heterostructure with the mixed layer based on triphenylamine oligomer shows the widest absorption domain, and the PL spectra of the heterostructures realized with either triphenylamine or carbazole oligomer show peaks corresponding to the radiative decay of the donor and acceptor. The I-V characteristics in the dark indicate a slightly nonlinear behavior and the current is affected by the charge carriers recombination on the defects present in the thick mixed layer deposited by matrix-assisted pulsed laser evaporation. The effect of the PEDOT-PSS buffer layer on the electrical properties of the organic heterostructure with ZnO/Ag/ZnO electrode is also investigated.