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Thin films of transition metal oxides and oxynitrides have proven highly effective in protecting stainless steels against corrosion in both chemically aggressive environments and biological fluids. In the present work, cerium zirconium oxynitride thin films were deposited to enhance the corrosion resistance of surgical-grade stainless steel to be used in osteosynthesis processes. Two techniques were employed: co-sputtering and radiofrequency (RF) sputtering, and the morphology and corrosion efficiency of the coatings deposited by each technique were evaluated. X-ray diffraction, X-ray photoelectron spectroscopy and field emission transmission electron microscopy were used to characterize the morphological and chemical structure, respectively. Additionally, the corrosion resistance of the oxynitride-coated surgical grade stainless steel system (ZrCeOxNy-AISI 316L) was assessed using Hank's solution as the corrosive electrolyte, to determine its resistance to corrosion in biological media. The results show that ZrCeOxNy coatings increase the corrosion resistance of surgical grade stainless steel by two orders of magnitude and that the Ce(III)/Ce(IV) equilibrium decreases the corrosion rate, thereby increasing the durability of the steel in a biological environment. The results show that Ce coatings increase the corrosion resistance of surgical grade stainless steel by two orders of magnitude and that the Ce(III)/Ce(IV) equilibrium decreases the corrosion rate, thereby increasing the durability of the steel in a biological environment.

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Biological signaling correlates with the interrelation between ion and nanofluidic transportation pathways. However, artificial embodies with reconfigurable ion-fluid transport interaction aspects remain largely elusive. Herein, we unveiled an intimate interplay between nanopore-driven advancing flow and ion carriage for the spontaneous imbibition of aqueous solutions at the nanoporous thin film level. Ionic factors dominate transport phenomena processing and integration (ions influence fluid motion, which in turn governs the self-regulated ion traveling). We show an ion-induced translation effect that finely converts a chemical input, the nature of ions, into a related fluidic output: modulation of the extent of imbibition. We further find complex imbibition dynamics induced by the ion type and population. We peculiarly pinpoint a stop-and-go effective transport process with a programmable delay time triggered by selective guest-host interactions. The ion-fluid transport interplay is captured by a simple model that considers the counterbalance between the capillary infiltration and solution concentration, owing to water loss at the nanoporous film-air interface. Our results demonstrate that nanopore networks present fresh scenarios for understanding and controlling autonomous macroscopic liquid locomotion and offer a distinctive working principle for smart ion operation.

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Perovskite nanocrystals hold significant promise for a wide range of applications, including solar cells, LEDs, photocatalysts, humidity and temperature sensors, memory devices, and low-cost photodetectors. Such technological potential stems from their exceptional quantum efficiency and charge carrier conduction capability. Nevertheless, the underlying mechanisms of photoexcitation, such as phase segregation, annealing, and ionic diffusion, remain insufficiently understood. In this context, we harnessed hyperspectral fluorescence microspectroscopy to advance our comprehension of fluorescence enhancement triggered by UV continuous-wave (cw) laser irradiation of CsPbBr3 colloidal nanocrystal thin films. Initially, we explored the kinetics of fluorescence enhancement and observed that its efficiency (φph) correlates with the laser power (P), following the relationship φph = 7.7⟨P⟩0.47±0.02. Subsequently, we estimated the local temperature induced by the laser, utilizing the finite-difference method framework, and calculated the activation energy (Ea) required for fluorescence enhancement to occur. Our findings revealed a very low activation energy, Ea ∼ 9 kJ/mol. Moreover, we mapped the fluorescence photoenhancement by spatial scanning and real-time static mode to determine its microscale length. Below a laser power of 60 µW, the photothermal diffusion length exhibited nearly constant values of approximately (22 ± 5) µm, while a significant increase was observed at higher laser power levels. These results were ascribed to the formation of nanocrystal superclusters within the film, which involves the interparticle spacing reduction, creating the so-called quantum dot solid configuration along with laser-induced annealing for higher laser powers.

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Simultaneous interrogation of pump and probe beams interacting in ZnO nanostructures of a two-wave mixing is proposed for dual-path data processing of optical signals by nonlinear optical effects. An enhancement in third-order nonlinear optical properties was exhibited by Al-doped ZnO thin films. Multiphoton absorption and nonlinear refraction were explored by the z-scan technique at 532 nm with nanosecond pulses. The evolution of the optical Kerr effect in the ZnO thin films was analyzed as a function of the incorporation of Al in the sample by a vectorial two-wave mixing method. Electrical and photoconductive effects were evaluated to further characterize the influence of Al in the ZnO solid samples. Potential applications of nonlinear optical parameters for encoding and encrypting information in light can be envisioned.

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In this paper, we outline the development of stoichiometric chalcostibite, CuSbS2 thin films, from a single bath by pulse electrodeposition for its application as a photocathode in photoelectrochemical cells (PEC). The Cu/Sb precursor molar ratio of the deposition bath was varied to obtain stoichiometric CuSbS2 thin films. The optimized deposition and dissolution potentials were -0.72 V and -0.1 V vs saturated calomel electrode, respectively. The formation of CuSbS2 was analyzed using different characterization tools. X-ray diffraction and Raman results showed the formation of the pure chalcostibite phase from a precursor bath with molar ratio Cu/Sb = 0.41. The heterostructure CuSbS2/CdS/Pt was tested as a photocathode in the PEC. The energy positions of the conduction and valence bands were estimated from the Mott Schottky plots. The conduction band and valence band offset of CuSbS2/CdS heterojunction were 0.1 eV and 1.04 eV, respectively. The electric field created in the junction reduced the recombination of the electron/hole pairs and improved charge transfer in the interface. The heterostructure CuSbS2/CdS/Pt demonstrated an improved photocurrent density of 3.4 mA cm-2 at 0 V vs reversible hydrogen electrode. The PEC efficiency obtained from the CuSbS2/CdS heterojunction was 0.56 %. Therefore, we demonstrated the feasibility of an inexpensive technique like electrodeposition for the development of an efficient earth-abundant photocathode.

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In the herein report, we synthesized ZnO thin films doped with manganese (Mn). We studied the impact of Mn doping loads (1 %, 3 %, 5 % wt.) on physicochemical properties of the compounds. Furthermore, we presented the photocatalytic efficiency in removal of methylene blue dye. The structural assay indicated ZnO conserve the wurtzite crystalline structure after dopant insertion. Furthermore, the crystalline size of catalysts was reduced after dopant incorporation. The SEM analysis showed a change in surface morphology after modification of ZnO thin films. Furthermore, Raman spectroscopy verified the Mn insertion inside the ZnO lattice. After the doping process, band gap was reduced by 16 %, in comparison to bare ZnO. After the photocatalytic test, the doped catalysts showed better performance than bare ZnO in removing MB. The best test showed a kinetics constant value of 2.9 × 10-3 min-1 after 120 min of visible irradiation. Finally, the Mn(5 %):ZnO thin film was suitable after five degradation cycles, and the degradation process efficiency was reduced by 32%.

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Using the SILAR method Zinc sulfide coatings were deposited on glass slices. The physical properties and the chemical mechanism throughout the variation in concentration of tri-sodium citrate (TSC) as a chelating agent in the synthesis of thin films were investigated. Results shows that ZnS thin films exhibit an average transmittance of 16% in visible light spectra region and a zinc blende structure. The ZnS films synthesized using TSC as a complexing agent, present a smaller average particle size, an average transmittance of 85%, and an adsorption edge at 300-340 nm. Based on our experimental data and analysis, we conclude that the contribution of the oxychloride species, a subproduct in the chemical deposition, is suggested to be related as an impurity level former in the synthesis of ZnS thin films. TSC as a complexing agent in the SILAR technique is a non-toxic option to reduce the generation of the oxychloride species and synthesize a wide band gap semiconductor. Moreover, the use of complexing agents could be extended to other types of semiconductors deposited by SILAR.

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In this work, we fabricated and characterized ZnO and TiO2 thin films, determining their structural, optical, and morphological properties. Furthermore, we studied the thermodynamics and kinetics of methylene blue (MB) adsorption onto both semiconductors. Characterization techniques were used to verify thin film deposition. The semiconductor oxides reached different removal values, 6.5 mg/g (ZnO) and 10.5 mg/g (TiO2), after 50 min of contact. The pseudo-second-order model was suitable for fitting the adsorption data. ZnO had a greater rate constant (45.4 × 10-3) than that of TiO2 (16.8 × 10-3). The removal of MB by adsorption onto both semiconductors was an endothermic and spontaneous process. Finally, the stability of the thin films showed that both semiconductors maintained their adsorption capacity after five consecutive removal tests.

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Chalcogenides semiconductors are currently being studied as active layers in the development of electronic devices in the field of applied technology. In the present paper, cadmium sulfide (CdS) thin films containing nanoparticles of the same material as the active layer were produced and analyzed for their application in fabricating optoelectronic devices. CdS thin films and CdS nanoparticles were obtained via soft chemistry at low temperatures. The CdS thin film was deposited via chemical bath deposition (CBD); the CdS nanoparticles were synthesized via the precipitation method. The construction of a homojunction was completed by incorporating CdS nanoparticles on CdS thin films deposited via CBD. CdS nanoparticles were deposited using the spin coating technique, and the effect of thermal annealing on the deposited films was investigated. In the modified thin films with nanoparticles, a transmittance of about 70% and a band gap between 2.12 eV and 2.35 eV were obtained. The two characteristic phonons of the CdS were observed via Raman spectroscopy, and the CdS thin films/CdS nanoparticles showed a hexagonal and cubic crystalline structure with average crystallite size of 21.3-28.4 nm, where hexagonal is the most stable for optoelectronic applications, with roughness less than 5 nm, indicating that CdS is relatively smooth, uniform and highly compact. In addition, the characteristic curves of current-voltage for as-deposited and annealed thin films showed that the metal-CdS with the CdS nanoparticle interface exhibits ohmic behavior.

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This work presents a post-cured treatment alternative for photopolymer substrates considering the plasma produced via the sputtering process. The sputtering plasma effect was discussed, analyzing the properties of zinc/zinc oxide (Zn/ZnO) thin films deposited on photopolymer substrates, with and without ultraviolet (UV) treatment as a post-treatment process, after manufacturing. The polymer substrates were produced from a standard Industrial Blend resin and manufactured using stereolithography (SLA) technology. After that, the UV treatment followed the manufacturer's instructions. The influence of the sputtering plasma as an extra treatment during the deposition of the films was analyzed. Characterization was performed to determine the microstructural and adhesion properties of the films. The results showed the effect of plasma as a post-cured treatment alternative: fractures were found in thin films deposited on polymers with previous UV treatment. In the same way, the films showed a repetitive printing pattern due to the phenomenon of polymer shrinkage caused by the sputtering plasma. The plasma treatment also showed an effect on the thicknesses and roughness values of the films. Finally, according to VDI-3198 standards, coatings with acceptable adhesion failures were found. The results provide attractive properties of Zn/ZnO coatings on polymeric substrates produced by additive manufacturing.

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Recently, rare-earth elements (REEs) have attracted great interest due to their importance in several fields, such as the high-technology and medicine industries. Due to the recent intensification of the use of REEs in the world and the resulting potential impact on the environment, new analytical approaches for their determination, fractionation and speciation are needed. Diffusive gradients in thin films are a passive technique already used for sampling labile REEs, providing in situ analyte concentration, fractionation and, consequently, remarkable information on REE geochemistry. However, data based on DGT measurements until now have been based exclusively on the use of a single binding phase (Chelex-100, immobilized in APA gel). The present work proposes a new method for the determination of rare earth elements using an inductively coupled plasma‒mass spectrometry technique and a diffusive gradients in thin films (DGT) technique for application in aquatic environments. New binding gels were tested for DGT using carminic acid as the binding agent. It was concluded that acid dispersion directly in agarose gel presented the best performance, offering a simpler, faster, and greener method for measuring labile REEs compared to the existing DGT binding phase. Deployment curves obtained by immersion tests in the laboratory show that 13 REEs had linearity in their retention by the developed binding agent (retention x time), confirming the main premise of the DGT technique obeying the first Fick's diffusion law. For the first time, the diffusion coefficients were obtained in agarose gels (diffusion medium) and carminic acid immobilized in agarose as the binding phase for La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu, which were 3.94 × 10-6, 3.87 × 10-6, 3.90 × 10-6, 3.79 × 10-6, 3.71 × 10-6, 4.13 × 10-6, 3.75 × 10-6, 3.94 × 10-6, 3.45 × 10-6, 3.97 × 10-6, 3.25 × 10-6, 4.06 × 10-6, and 3.50 × 10-6 cm2 s-1, respectively. Furthermore, the proposed DGT devices were tested in solutions with different pH values (3.5, 5.0, 6.5 and 8) and ionic strengths (I = 0.005 mol L-1, 0.01 mol L-1, 0.05 mol L-1 and 0.1 mol L-1 - NaNO3). The results of these studies showed an average variation in the analyte retention for all elements at a maximum of approximately 20% in the pH tests. This variation is considerably lower than those previously reported when using Chelex resin as a binding agent, particularly for lower pH values. For the ionic strength, the maximum average variation was approximately 20% for all elements (except for I = 0.005 mol L-1). These results indicate the possibility of a wide range of the proposed approach to be used for in situ deployment without the use of correction based on apparent diffusion coefficients (as required for using the conventional approach). In laboratory deployments using acid mine drainage water samples (treated and untreated), it was shown that the proposed approach presents excellent accuracy compared with data obtained from Chelex resin as a binding agent.

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In this study, the impact of pH on the production of ZnO nanostructured thin films using chemical bath deposition was investigated for the purpose of enhancing the efficiency of solar cells. The ZnO films were directly deposited onto glass substrates at various pH levels during the synthesis process. The results indicate that the crystallinity and overall quality of the material were not affected by the pH solution, as observed through X-ray diffraction patterns. However, scanning electron microscopy revealed that surface morphology improved with increasing pH values, leading to changes in the size of the nanoflowers between pH 9 and 11 values. Furthermore, the ZnO nanostructured thin films synthesized at pH levels of 9, 10, and 11 were utilized in the fabrication of dye-sensitized solar cells. The ZnO films synthesized at pH 11 exhibited superior characteristics in short-circuit current density and open-circuit photo-voltage compared with those produced at lower pH values.

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TiO2-SiO2 thin films were created on Corning glass substrates using a simple method. Nine layers of SiO2 were deposited; later, several layers of TiO2 were deposited, and their influence was studied. Raman spectroscopy, high resolution transmission electron spectroscopy (HRTEM), an X-ray diffractometer (XRD), ultraviolet-visible spectroscopy (UV-Vis), a scanning electron microscope (SEM), and atomic force microscopy (AFM) were used to describe the sample's shape, size, composition, and optical characteristics. Photocatalysis was realized through an experiment involving the deterioration of methylene blue (MB) solution exposed to UV-Vis radiation. With the increase of TiO2 layers, the photocatalytic activity (PA) of the thin films showed an increasing trend, and the maximum degradation efficiency of MB by TiO2-SiO2 was 98%, which was significantly higher than that obtained by SiO2 thin films. It was found that an anatase structure was formed at a calcination temperature of 550 °C; phases of brookite or rutile were not observed. Each nanoparticle's size was 13-18 nm. Due to photo-excitation occurring in both the SiO2 and the TiO2, deep UV light (λ = 232 nm) had to be used as a light source to increase photocatalytic activity.

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Bismuth telluride thin films were grown by pulsed laser deposition by implementing a novel method that combines both Te and Bi plasmas resulting from the laser ablation of individual Bi and Te targets. Furthermore, the mean kinetic ion energy and density of the plasmas, as estimated by TOF curves obtained from Langmuir probe measurements, were used as control parameters for the deposition process. The obtained thin films exhibit a metallic mirror-like appearance and present good adhesion to the substrate. Morphology of the thin films was observed by SEM, yielding smooth surfaces where particulates were also observed (splashing). Chemical composition analysis obtained by EDS showed that apparently the films have a Te-rich composition (ratio of Te/Bi of 3); however, Te excess arises from the splashing as revealed by the structural characterization (XRD and Raman spectroscopy). The XRD pattern indicated that depositions have the rhombohedral (D3d5 (R3¯m)) structure of Bi2Te3. Likewise, Raman spectra exhibited the presence of signals that correspond to Eg2, A1u2 and A1g2(LO) vibrational modes of the same rhombohedral phase of Bi2Te3. Additionally, oxidation states, analyzed by XPS, resulted in signals associated to Bi3+ and Te2- that correspond to the Bi2Te3 compound. Finally, surface topology and thickness profiles were obtained from AFM measurements, confirming a combination of a smooth surface with particulates on top of it and a film thickness of 400 nm.

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This work aims to evaluate the size and lability of Cu and Zn bound to proteins in the cytosol of fish liver of Oreochromis niloticus by employing solid-phase extraction (SPE), diffusive gradients in thin films (DGT), and ultrafiltration (UF). SPE was carried out using Chelex-100. DGT containing Chelex-100 as binding agent was employed. Analyte concentrations were determined by ICP-MS. Total Cu and Zn concentrations in cytosol (1 g of fish liver in 5 ml of Tris-HCl) ranged from 39.6 to 44.3 ng ml-1 and 1498 to 2106 ng ml-1, respectively. Data from UF (10-30 kDa) suggested that Cu and Zn in cytosol were associated with ∼70% and 95%, respectively, with high-molecular-weight proteins. Cu-metallothionein was not selectively detected (although 28% of Cu was associated with low-molecular-weight proteins). However, information about the specific proteins in the cytosol will require coupling UF with organic mass spectrometry. Data from SPE showed the presence of labile Cu species of ∼17%, while the fraction of labile Zn species was >55%. However, data from DGT suggested a fraction of labile Cu species only of 7% and a labile Zn fraction of 5%. This data, as compared with previous data from literature, suggests that the DGT technique gave a more plausible estimation of the labile pool of Zn and Cu in cytosol. The combination of results from UF and DGT is capable of contributing to the knowledge about the labile and low-molecular pool of Cu and Zn.

Assuntos

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The development of biobased antioxidant active packaging has been valued by the food industry for complying with environmental and food waste concerns. In this work, physicochemical properties for chitosan composite films as a potential active food packaging were investigated. Chitosan films were prepared by solution casting, plasticized with a 1:2 choline chloride: glycerol mixture as a deep eutectic solvent (DES) and incorporated with 0-10% of optimized açaí oil polyelectrolyte complexes (PECs). Scanning electron microscopy and confocal laser scanning microscopy revealed that the chitosan composite films were continuous and contained well-dispersed PECs. The increased PECs content had significant influence on the thickness, water vapor permeability, crystallinity (CrD) and mechanical and dynamic behavior of the films, as well as their antioxidant properties. The tensile strength was reduced in the following order: 11.0 MPa (control film) > 0.74 MPa (5% DES) > 0.63 MPa (5% DES and 5% PECs). Films containing 2% of PECs had an increased CrD, ~6%, and the highest elongation at break, ~104%. Films with 1% of PECs displayed the highest antioxidant properties against the ABTS and DPPH radicals, ~6 and ~17 mg TE g-1, respectively, and highest equivalent polyphenols content (>0.5 mg GAE g-1). Films with 2% of particles were not significantly different. These results suggested that the chitosan films that incorporated 1-2% of microparticles had the best combined mechanical and antioxidant properties as a potential material for food packaging.

Assuntos

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The fabrication of NiO films by different routes is important to extend and improve their applications as hole-transporting layers in organic and inorganic optoelectronic devices. Here, an automated ultrasonic pyrolysis spray method was used to fabricate NiO and Li-doped NiO thin films using nickel acetylacetonate and lithium acetate dihydrate as metal precursor and dimethylformamide as solvent. The effect of the amount of lithium in the precursor solution on the structural, morphological, optical, and electrical properties were studied. XRD results reveal that all the samples are polycrystalline with cubic structure and crystallite sizes in the range of 21 to 25 nm, without any clear trend with the Li doping level. AFM analysis shows that the crystallites form round-shaped aggregates and all the films have low roughness. The optical transmittance of the films reaches values of 60% to 77% with tendency upward as Li content is increased. The electrical study shows that the films are p-type, with the carrier concentration, resistivity, and carrier mobility depending on the lithium doping. NiO:Li (10%) films were successfully incorporated into inorganic light emitting diodes together with Mn-doped ZnS and ZnO:Al films, all deposited on ITO by the same ultrasonic spray pyrolysis technique.

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Memristors are expected to be one of the key building blocks for the development of new bio-inspired nanoelectronics. Memristive effects in transition metal oxides are usually linked to the electromigration at the nanoscale of charged oxygen vacancies (OV). In this paper we address, for Pt/TiOx/TaOy/Pt devices, the exchange of OV between the device and the environment upon the application of electrical stress. From a combination of experiments and theoretical simulations we determine that both TiOxand TaOylayers oxidize, via environmental oxygen uptake, during the electroforming process. Once the memristive effect is stabilized (post-forming behavior) our results suggest that oxygen exchange with the environment is suppressed and the OV dynamics that drives the memristive behavior is restricted to an internal electromigration between TiOxand TaOylayers. Our work provides relevant information for the design of reliable binary oxide memristive devices.

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Thin films of BiFeO3, VO2, and BiFeO3/VO2 were grown on SrTiO3(100) and Al2O3(0001) monocrystalline substrates using radio frequency and direct current sputtering techniques. To observe the effect of the coupling between these materials, the surface of the films was characterized by profilometry, atomic force microscopy, and X-ray photoelectron spectroscopy. The heterostructures, monolayers, and bilayers based on BiFeO3 and VO2 grew with good adhesion and without delamination or signs of incompatibility between the layers. A good granular arrangement and RMS roughness between 1 and 5 nm for the individual layers (VO2 and BiFeO3) and between 6 and 18 nm for the bilayers (BiFeO3/VO2) were observed. Their grain size is between 20 nm and 26 nm for the individual layers and between 63 nm and 67 nm for the bilayers. X-ray photoelectron spectroscopy measurements show a higher proportion of V4+, Bi3+, and Fe3+ in the films obtained. The homogeneous ordering, low roughness, and oxidation states on the obtained surface show a good coupling in these films. The I-V curves show ohmic behavior at room temperature and change with increasing temperature. The effect of coupling these materials in a thin film shows the appearance of hysteresis cycles, I-V and R-T, which is typical of materials with high potential in applications, such as resistive memories and solar cells.

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TiO2 time-dependent electrodeposited thin films were synthesized using an electrophoretic apparatus. The XRD analysis revealed that the films could exhibit a crystalline structure composed of ~81% anatase and ~6% rutile after 10 s of deposition, with crystallite size of 15 nm. AFM 3D maps showed that the surfaces obtained between 2 and 10 s of deposition exhibit strong topographical irregularities with long-range and short-range correlations being observed in different surface regions, a trend also observed by the Minkowski functionals. The height-based ISO, as well as specific surface microtexture parameters, showed an overall decrease from 2 to 10 s of deposition, showing a subtle decrease in the vertical growth of the films. The surfaces were also mapped to have low spatial dominant frequencies, which is associated with the similar roughness profile of the films, despite the overall difference in vertical growth observed. The electrical conductivity measurements showed that despite the decrease in topographical roughness, the films acquired a thickness capable of making them increasingly insulating from 2 to 10 s of deposition. Thus, our results prove that the deposition time used during the electrophoretic experiment consistently affects the films' structure, morphology, and electrical conductivity.