Morphological characterization of ZnS thin films for photovoltaic applications

Le celle solari a film sottile sono tra le alternative più promettenti nel campo fotovoltaico. La ricerca di materiali non tossici ed economici per la passivazione delle superfici è di fondamentale importanza. Il presente è uno studio sulla morfologia di film sottili di ZnS. I campioni analizzati sono stati cresciuti tramite DC sputtering a diversa potenza (range 50-150W) per studiare le connessioni tra condizioni di deposizione e proprietà strutturali. Lo studio è stato condotto mediante acquisizione di mappe AFM. E' stata effettuata un'analisi dei buchi (dips) in funzione della potenza di sputtering, per individuare il campione con la minore densità di dips in vista di applicazioni in celle solari a film sottile. I parametri strutturali, quali la rugosità superficiale e la lunghezza di correlazione laterale sono stati determinati con un'analisi statistica delle immagini. La densità e dimensione media dei grani sono state ricavate da una segmentazione delle immagini. Le analisi sono state svolte su due campioni di ZnO per fini comparativi. Tramite EFM sono state ottenute mappe di potenziale di contatto. Tramite KPFM si è valutata la differenza di potenziale tra ZnS e un layer di Al depositato sulla superficie. La sheet resistance è stata misurata con metodo a quattro punte. Dai risultati la potenza di sputtering influenza la struttura superficiale, ma in maniera non lineare. E' stato individuato il campione con la minore rugosità e densità di dips alla potenza di 75 W. Si è concluso che potenze troppo grandi o piccole in fase di deposizione promuovono il fenomeno di clustering dei grani e di aumentano la rugosità e densità di dips. E' emersa una corrispondenza diretta tra morfologia e potenziale di contatto alla superficie. La differenza di potenziale tra Al e ZnS è risultata inferiore al valore noto, ciò può essere dovuto a stati superficiali indotti da ossidi. Il campione risulta totalmente isolante.

Deposição de A/N por sputtering não reativo

In this work we deposit via non-reactive magnetron sputtering of radio-frequency nanofilmes of nitreto of aluminum(AlN). The nanofilms aluminum nitride are semiconductors materials with high thermal conductivity, high melting point, piezoelectricity and wide band gap (6, 2 eV) with hexagonal wurtzite crystal structure, belonging to the group of new materials called III-V nitrides in which together with the gallium nitride and indium nitride have attracted much interest because they have physical and chemical properties relevant to new technological applications, mainly in microelectronic and optoelectronic devices. Three groups were deposited with thicknesses nanofilms time dependent on two substrates (glass and silicon) at a temperature of 25 ° C. The nanofilms AlN were characterized using three techniques, X-ray diffraction, Raman spectroscopy and atomic force microscopy (AFM), examined the morphology of these. Through the analysis of X-rays get the thickness of each sample with its corresponding deposition rate. The analysis of X-rays also revealed that nanofilms are not crystalline, showing the amorphous character of the samples. The results obtained by the technique, atomic force microscopy (AFM) agree with those obtained using the technique of X-rays. Characterization by Raman spectroscopy revealed the existence of active modes characteristic of AlN in the samples

Preparation of films from aluminum acetylacetonate by plasma sputtering

Aluminum acetylacetonate has been reported as a precursor for the deposition of alumina films using different approaches. In this work, alumina-containing films were prepared by plasma sputtering this compound, spread directly on the powered lowermost electrode of a reactor, while grounding the substrates mounted on the topmost electrode. Radiofrequency power (13.56 MHz) was used to excite the plasma from argon atmosphere at a working pressure of 11 Pa. The effect of the plasma excitation power on the properties of the resulting films was studied. Film thickness and hardness were measured by profilometry and nanoindentation, respectively. The molecular structure and chemical composition of the layers were analyzed by Fourier transform infrared spectroscopy and energy dispersive spectroscopy. Surface micrographs, obtained by scanning electron microscopy, allowed the determination of the sample morphology. Grazing incidence X-ray diffraction was employed to determine the structure of the films. Amorphous organic layers were deposited with thicknesses of up to 7 μm and hardness of around 1.0 GPa. The films were composed by aluminum, carbon, oxygen and hydrogen, their proportions being strongly dependent on the power used to excite the plasma. A uniform surface was obtained for low-power depositions, but particulates and cracks appeared in the high-power prepared materials. The presence of different proportions of aluminum oxide in the coatings is ascribed to the different activations promoted in the metalorganic molecule once in the plasma phase. Copyright © 2013 John Wiley & Sons, Ltd. Copyright © 2013 John Wiley & Sons, Ltd.

Polydispersity of ethylene sequence length in metallocene ethylene/alpha-olefin copolymers. I. Characterized by thermal-fractionation technique

In this article, the polydispersity of the ethylene sequence length (ESL) in ethylene/alpha-olefin copolymers was studied by atomic force microscopy (AFM) and the thermal-fractionation technique. The crystal morphology observation by AFM showed that morphology changed gradually with decreasing average ESL from complete lamellae over shorter and more curved lamellae to a granular-like morphology, and the mixed morphology was observed after stepwise crystallization from phase-separated melt. This result indicated that the ethylene sequence with different lengths crystallized into a crystalline phase with a different size and stability at the copolymer systems. The thermal-fractionation technique was used to characterize the polydispersity of ESL. Three of the following statistical terms were introduced to describe the distribution of ESL and the lamellar thickness: the arithmetic mean (L) over bar (n), the weight mean (L) over bar (w), and the broadness index I = (L) over bar (w)/(L) over bar (n). It was concluded that the polydispersity of ESL could be quantitatively characterized by the thermal-fractionation technique. The effects of temperature range, temperature-dependent specific heat capacity C-p of copolymer, and the molecular weight on the results of thermal fractionation were discussed,

Morphology controlled synthesis of wurtzite ZnS nanostructures through simple hydrothermal method and observation of white light emission from ZnO obtained by annealing the synthesized ZnS nanostructures

A controllable synthesis of phase pure wurtzite (WZ) ZnS nanostructures has been reported in this work at a low temperature of similar to 220 degrees C using ethylenediamine as the soft template and by varying the molar concentration of zinc to sulphur precursors as well as by using different precursors. A significant reduction in the formation temperature required for the synthesis of phase pure WZ ZnS has been observed. A strong correlation has been observed between the morphology of the synthesized ZnS nanostructures and the precursors used during synthesis. It has been found from Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) image analyses that the morphology of the ZnS nanocrystals changes from a block-like to a belt-like structure having an average length of similar to 450 nm when the molar ratio of zinc to sulphur source is increased from 1 : 1 to 1 : 3. An oriented attachment (OA) growth mechanism has been used to explain the observed shape evolution of the synthesized nanostructures. The synthesized nanostructures have been characterized by the X-ray diffraction technique as well as by UV-Vis absorption and photoluminescence (PL) emission spectroscopy. The as-synthesized nanobelts exhibit defect related visible PL emission. On isochronal annealing of the nanobelts in air in the temperature range of 100-600 degrees C, it has been found that white light emission with a Commission Internationale de I'Eclairage 1931 (CIE) chromaticity coordinate of (0.30, 0.34), close to that of white light (0.33, 0.33), can be obtained from the ZnO nanostructures obtained at an annealing temperature of 600 degrees C. UV light driven degradation of methylene blue (MB) dye aqueous solution has also been demonstrated using as-synthesized nanobelts and similar to 98% dye degradation has been observed within only 40 min of light irradiation. The synthesized nanobelts with visible light emission and having dye degradation activity can be used effectively in future optoelectronic devices and in water purification for cleaning of dyes.

IN-SITU AFM STUDY OF THE SURFACE-MORPHOLOGY OF POLYPYRROLE FILM

In this paper we focus on the surface morphology of polypyrrole film by using in situ atomic force microscopy (AFM). The formation process of polypyrrole film and the transformation process of the film from the oxidized to reduced state were clearly observed.

Growth evolution of ZnO thin films deposited by RF magnetron sputtering

We study the surface morphology evolution of ZnO thin films grown on glass substrates as a function of thickness by RF magnetron sputtering technique. The surface topography of the samples is measured by atomic force microscopy (AFM). All AFM images of the films are analyzed using scaling concepts. The results show that the surface morphology is initially formed by a small grains structure. The grains increase in size and height with growth time resulting in the formation of a mounds-like structure. The growth exponent, beta, and the exponent defining the evolution of the characteristic wavelength of the surface, p, amounted to beta = 0.76 +/- 0.08 and p = 0.3 +/- 0.05. From these exponents, the surface morphology is determined by the nonlocal shadowing effects, that is the dominant mechanism, due to the incident deposition particles during film growth.

Structural transition of ZnO thin films produced by RF magnetron sputtering at low temperatures

Zinc oxide (ZnO) thin films were prepared using reactive radio-frequency magnetron sputtering of a pure metallic zinc target onto glass substrates. The evolution of the surface morphology and the optical properties of the films were studied as a function of the substrate temperature, which was varied from 50 to 250 C. The surface topography of the samples was examined using atomic force microscopy (AFM), and their optical properties were studied via transmittance measurements in the UV-Vis-NIR region. DRX and AFM analyses showed that the surface morphology undergoes a structural transition at substrate temperatures of around 150 C. Actually, at 50 C the formation of small grains was observed while at 250 C the grains observed were larger and had more irregular shapes. The optical gap remained constant at ∼3.3 eV for all films. In the visible region, the average optical transmittance was 80 %. From these results, one can conclude that the morphological properties of the ZnO thin films were more greatly affected by the substrate temperature, due to mis-orientation of polycrystalline grains, than were the optical properties. © 2013 Springer Science+Business Media New York.

Influence of solvent on the morphology and photocatalytic properties of ZnS decorated CeO2 nanoparticles

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Growth evolution of self-textured ZnO films deposited by magnetron sputtering at low temperatures

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Al-doping effect on the surface morphology of zno films grown by reactive rf magnetron sputtering

Zinc oxide (ZnO) and aluminum-doped zinc oxide (ZnO:Al) thin films were deposited onto glass and silicon substrates by RF magnetron sputtering using a zinc-aluminum target. Both films were deposited at a growth rate of 12.5 nm/min to a thickness of around 750 nm. In the visible region, the films exhibit optical transmittances which are greater than 80%. The optical energy gap of ZnO films increased from 3.28 eV to 3.36 eV upon doping with Al. This increase is related to the increase in carrier density from 5.9 × 1018 cm−3 to 2.6 × 1019 cm−3 . The RMS surface roughness of ZnO films grown on glass increased from 14 to 28 nm even with only 0.9% at Al content. XRD analysis revealed that the ZnO films are polycrystalline with preferential growth parallel to the (002) plane, which corresponds to the wurtzite structure of ZnO.

AFM study of morphological changes associated with electrochemical solid--solid transformation of three-dimensional crystals of TCNQ to metal derivatives (metal= Cu, Co, Ni; TCNQ= tetracyanoquinodimethane)

In situ atomic force microscopy (AFM) allows images from the upper face and sides of TCNQ crystals to be monitored during the course of the electrochemical solid–solid state conversion of 50 × 50 μm2 three-dimensional drop cast crystals of TCNQ to CuTCNQ or M[TCNQ]2(H2O)2 (M = Co, Ni). Ex situ images obtained by scanning electron microscopy (SEM) also allow the bottom face of the TCNQ crystals, in contact with the indium tin oxide or gold electrode surface and aqueous metal electrolyte solution, to be examined. Results show that by carefully controlling the reaction conditions, nearly mono-dispersed, rod-like phase I CuTCNQ or M[TCNQ]2(H2O)2 can be achieved on all faces. However, CuTCNQ has two different phases, and the transformation of rod-like phase 1 to rhombic-like phase 2 achieved under conditions of cyclic voltammetry was monitored in situ by AFM. The similarity of in situ AFM results with ex situ SEM studies accomplished previously implies that the morphology of the samples remains unchanged when the solvent environment is removed. In the process of crystal transformation, the triple phase solid∣electrode∣electrolyte junction is confirmed to be the initial nucleation site. Raman spectra and AFM images suggest that 100% interconversion is not always achieved, even after extended electrolysis of large 50 × 50 μm2 TCNQ crystals.

Nanocrystalline vanadium oxide films synthesized by plasma-assisted reactive rf sputtering deposition

Plasma-assisted reactive rf magnetron sputtering deposition is used to fabricate vanadium oxide films on glass, silica and silicon substrates. The process conditions are optimized to synthesize phase-pure vanadium pentoxide (V2O5) featuring a nanocrystalline structure with the predominant (0 0 1) crystallographic orientation, surface morphology with rod-like nanosized grains and very uniform (the non-uniformity does not exceed 4%) coating thickness over large surface areas. The V2O5 films also show excellent and temperature-independent optical transmittance in a broad temperature range (20-95 °C). The results are relevant to the development of smart functional coatings with temperature-tunable properties. © 2007 IOP Publishing Ltd.

Stoichiometry, crystallinity, and nano-scale surface morphology of the graded calcium phosphate-based bio-ceramic interlayer on Ti-Al-V

A plasma-assisted concurrent Rf sputtering technique for fabrication of biocompatible, functionally graded CaP-based interlayer on Ti-6Al-4V orthopedic alloy is reported. Each layer in the coating is designed to meet a specific functionality. The adherent to the metal layer features elevated content of Ti and supports excellent ceramic-metal interfacial stability. The middle layer features nanocrystalline structure and mimics natural bone apatites. The technique allows one to reproduce Ca/P ratios intrinsic to major natural calcium phosphates. Surface morphology of the outer, a few to few tens of nanometers thick, layer, has been tailored to fit the requirements for the bio-molecule/protein attachment factors. Various material and surface characterization techniques confirm that the optimal surface morphology of the outer layer is achieved for the process conditions yielding nanocrystalline structure of the middle layer. Preliminary cell culturing tests confirm the link between the tailored nano-scale surface morphology, parameters of the middle nanostructured layer, and overall biocompatibility of the coating.

Amino group positions dependent morphology and coverage of electropolymerized metallophthalocyanine (M = Ni and Co) films on electrode surfaces

Electropolymerized films of teraaminometallophthalocyanines (MTAPc; M = Ni and Co) with amino groups at α- (4α-MTAPc) and β- (4β-MTAPc) positions were prepared on glassy carbon (GC) and indium tin oxide (ITO) electrodes. It was found that the electropolymerization growth rate of 4α-MTAPc was less than that of 4β-MTAPc prepared under identical conditions. Further, the surface coverage of the polymerized 4β-MTAPc film was greater than that of 4α-MTAPc polymerized film. Atomic force microscopy (AFM), X-ray diffraction (XRD) and UV–visible spectroscopic studies were carried out for the polymerized films of 4α-NiIITAPc (p-4α-NiIITAPc) and 4β-NiIITAPc (p-4β-NiIITAPc) alone because both Ni(II) and Co(II) polymerized films show similar trend in electropolymerization and surface coverage values. AFM images show that p-4α-NiIITAPc film contains islands and the thickness of this film was nearly three times less than that of p-4β-NiIITAPc. XRD patterns for the two polymerized films reveal that p-4β-NiIITAPc film was relatively more crystalline than p-4α-NiIITAPc film. Further, the compactness of these films was scrutinized from their barrier properties toward [Fe(CN)6]3−/4− redox couple. The differences in the polymerization growth rate of 4α-MTAPc and 4β-MTAPc, and the thicknesses of the resultant polymerized films suggest that unlike 4β-MTAPc one or two amino groups might have not involved in electropolymerization in the case of 4α-MTAPc. Further, the influence of surface coverage on the electrocatalytic properties of the polymerized films was studied by taking p-4β-CoIITAPc and p-4α-CoIITAPc films as examples. The electrocatalytic oxygen reduction current was almost same at both the electrodes suggesting that only the surface species were involved in the electrocatalytic reduction of oxygen.