National Institute Of Materials Physics - Romania

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.

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.

Lanthanum orthophosphate (LaPO4) and La0.95-xCe0.05MnxPO4 (x = 0.00, 0.03, 0.10) phosphors were synthesized by a simple and cost-efficient co-precipitation method and the formation of LaPO4 nanorods with a monoclinic P21/n crystal structure was observed. X-ray diffraction pattern analysis indicated a slight distortion of the LaPO4 crystalline structure and an increase of the lattice strain as a consequence of the Mn2+ and Ce3+ dopants incorporation in the host matrix. Scanning electron microscopy revealed that the microstructure of all powders consists of agglomerations of nanorods, which are around 17 +/- 3 nm in diameter and length ranging from 100 nm to 300 nm. Electron paramagnetic resonance measurements have indicated the presence of Mn2+ in isolated species, but also as agglomerates. Ce3+ and Mn2+ doping of LaPO4 resulted also in a decrease of the band gap up to 4.70 eV compared to the un-doped sample. Because of an energy transfer effect from Ce3+ to Mn2+ ions, green emission of Mn2+ ions at around 550 nm was observed upon 275 nm excitation.

Photodegradation of the aqueous solutions of acetylsalicylic acid, in the absence (ASA) and the presence of excipients (ASE), is demonstrated by the photoluminescence (PL). A shift of the PL bands from 342 and 338 nm to 358 and 361-397 nm for ASA and ASE in solid state and as aqueous solutions was reported. By exposure of the solution of ASA 0.3 M to UV light, a decrease in the PL band intensity was highlighted. This behavior was revealed for ASA in the presence of phosphate buffer (PB) having the pH equal to 6.4, 7, and 8 or by the interaction with NaOH 0.3 M. A different behavior was reported in the case of ASE. In the presence of PB, an increase in the intensity of the PL band of ASE simultaneously with a change of the ratio between the intensities of the bands at 361-364 and 394-397 nm was highlighted. The differences between PL spectra of ASA and ASE have their origin in the presence of salicylic acid (SAL). The interaction of ASE with NaOH induces a shift of the PL band at 405-407 nm. Arguments for the reaction of ASA with NaOH are shown by Raman scattering and FTIR spectroscopy.

This work focuses on the investigation of the liquid crystalline behavior and luminescence properties of the lanthanide complexes of Eu(III), Sm(III) and Tb(III) with N-biphenyl-alkylated-4-pyridone ligands. The organic ligands having a biphenyl group attached via a long flexible spacer with either 9 or 10 carbon atoms were synthesized by the reaction between 4-hydroxypyridine and the corresponding bromide compounds. The chemical structures of the organic and lanthanide complexes were assigned based on elemental analysis, single-crystal X-ray diffraction, H-1, C-13 NMR and IR spectroscopies, and thermogravimetric analysis (TGA). The X-ray diffraction analysis of a parent compound shows that the lanthanide ions are surrounded by three monodentate pyridone ligands and three bidentate nitrate ions, giving a 9-coordinate environment. The mesogenic behavior and the type of liquid crystalline phases exhibited by the new complexes were analyzed by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM), and powder X-ray diffraction (XRD) studies. Only the lanthanide complexes with longer spacer (10) display a monotropic SmA phase, typically on a short thermal range (less than 10 degrees C). The complexes with shorter flexible chains (9) show no liquid crystalline properties with melting temperatures lower than their analogs with longer spacers. The emission spectra recorded in solid state at room temperatures show typical emission bands for each lanthanide ion employed (Eu(III), Tb(III) and Sm(III)).

In this paper, potassium based triple cation mixed-halide perovskite films were explored in order to enhance the stability and photovoltaic performance of perovskite based solar cells. It was found that adding potassium (K+) to a double cation mixed halide perovskite (FA(0.80)MA(0.20)PbI(2.8)Cl(0.2)), structural, morphological and optoelectronic properties of perovskites are improved. The perovskite films were prepared by one-step spin coating method with and without K+ and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). The results indicate that potassium incorporation reduces significantly the yellow non-perovskite delta-phase formation and improves the perovskite film quality, thus contributing to the reduction of hysteresis, improves the stability and increases the PCE up to 12.51%. Furthermore, the doped devices exhibit reduced hysteresis and provide remarkable shelf stability by retaining more than 70% of the initial efficiency with low humidity over 850 h. (C) 2020 Elsevier B.V. All rights reserved.

Phase-change memories have reached an advanced degree of maturity, although, to be able to meet the increasing storage demand, multilevel capability is needed. A GeTe memristor is obtained in an amorphous state and it is subjected to a specific thermal treatment which initiates the transition toward the crystalline state. It is found that this crystalline state initialization process is highly beneficial for subsequently obtaining a large number of intermediate resistive states between the high and low resistive states. Multiple resistance levels are achieved by operating the devices in both DC sweeps and rectangular pulse modes in the low-voltage subthreshold regime. The conduction is modeled using a space charge limited conduction model, showing three distinct conduction regions in the high resistive state which merge toward a single conduction region as the low resistive state is approached. The obtained memristors can be used as multilevel nonvolatile memories or as synapses in neuromorphic computing.

A new method to obtain poly(vinyl chloride) (PVC) spheres, which consists of an interaction between commercial PVC grains and hexyl ethyl cellulose and lauroyl peroxide at a temperature of 60 degrees C, is reported. The addition of the graphene oxide (GO) sheets dispersed in dimethylformamide to the reaction mixture leads to the generation of composites made of PVC spheres coated with GO sheets. Scanning electron microscopy studies have demonstrated that this method allows for the transformation of PVC grains with sizes between 75 and 227 mu m into spheres with sizes varying from 0.7 to 3.5 mu m when the GO concentration in the PVC/GO composite mass increases from 0.5 to 5 wt.%. Our studies of Raman scattering and FTIR spectroscopy highlight a series of changes that indicate the appearance of ClCH=CH-, CH2=CCl-, and/or -CH=CCl- units as a result of PVC partial dehydrogenation. New -COO- and C-OH bonds on the GO sheet surfaces are induced during the preparation of PVC spheres coated with GO sheets. A photoluminescence (PL) band with a maximum at 325 nm is reported to characterize the PVC spheres. A PVC PL quenching process is demonstrated to be induced by the increase in the concentration of the GO sheets in the PVC/GO composite mass. The perspectives regarding the use of this composite as a flame-retardant material are also reported.

Using Raman scattering and FTIR spectroscopy, new optical evidence for the assembly of sensors based on reduced graphene oxide (RGO) and polydiphenylamine (PDPA) for the electrochemical detection of the epidermal growth factor receptor (EGFR) are reported. The assembly process of the RGO sheets electrochemical functionalized with PDPA involves the chemical adsorption of 1,4-phenylene diisothiocyanate (PDITC), followed by an incubation with protein G in phosphate buffer (PB) solution and after that the interaction with EGFR antibodies solution. Taking into account the changes reported by Raman scattering and FTIR spectroscopy, a chemical mechanism of the assembling process for this sensor is proposed. The preliminary testing of the electrochemical activity of the sensors based on RGO and PDPA was reported by cyclic voltammetry.

In this work, new films containing composite materials based on blends of thermoplastic polymers of the polyurethane (TPU) and polyolefin (TPO) type, in the absence and presence of BaTiO3 nanoparticles (NPs) with the size smaller 100 nm, were prepared. The vibrational properties of the free films depending on the weight ratio of the two thermoplastic polymers were studied. Our results demonstrate that these films are optically active, with strong, broad, and adjustable photoluminescence by varying the amount of TPU. The crystalline structure of BaTiO3 and the influence of thermoplastic polymers on the crystallization process of these inorganic NPs were determined by X-ray diffraction (XRD) studies. The vibrational changes induced in the thermoplastic polymer's matrix of the BaTiO3 NPs were showcased by Raman scattering and FTIR spectroscopy. The incorporation of BaTiO3 NPs in the matrix of thermoplastic elastomers revealed the shift dependence of the photoluminescence (PL) band depending on the BaTiO3 NP concentration, which was capable of covering a wide visible spectral range. The dependencies of the dielectric relaxation phenomena with the weight of BaTiO3 NPs in thermoplastic polymers blends were also demonstrated.