Pulsed Laser Evaporation Research Articles

Tunable internal quantum well alignment in rationally designed oligomer-based perovskite films deposited by resonant infrared matrix-assisted pulsed laser evaporation

RIR-MAPLE enables thin-film deposition of organic–inorganic materials with tunable synergistic photophysics.

Enhancement of the supercapacitive properties of laser deposited graphene-based electrodes through carbon nanotube loading and nitrogen doping.

Several technological routes are being investigated for improving the energy storage capability and power delivery of electrochemical capacitors. In this work, ternary hybrid electrodes composed of conducting graphene/reduced graphene oxide (rGO), which store charge mainly through electric double-layer mechanisms, covered by NiO nanostructures, for adding pseudocapacitance, were fabricated through a matrix assisted pulsed laser evaporation technique. The incorporation of multiwall carbon nanotubes (MWCNTs) provokes an increase of the porosity and thus, a substantial enhancement of the electrodes' capacitance (from 4 to 20 F cm-3 at 10 mV s-1). Volumetric capacitances of 34 F cm-3 were also obtained with electrodes containing just carbon nanotubes coated with NiO nanostructures. Moreover, the use of nitrogen containing precursors (ammonia, urea) for laser-induced N-doping of the nanocarbons also provokes a notable increase of the capacitance. Remarkably, N-containing groups in rGO-MWCNTs mainly add electric double layer charge storage, pointing to an increase of electrode porosity, whereas redox reactions contribute with a minor diffusion fraction. It was also observed that the loading of carbon nanotubes leads to an increase of diffusion-controlled charge storage mechanisms versus capacitive ones in rGO-based electrodes, the opposite effect being observed in graphene electrodes.

Tunable internal quantum well alignment in rationally designed oligomer-based perovskite films deposited by resonant infrared matrix-assisted pulsed laser evaporation

Tunable internal quantum well alignment in rationally designed oligomer-based perovskite films deposited by resonant infrared matrix-assisted pulsed laser evaporation

Biocompatible pure ZnO nanoparticles-3D bacterial cellulose biointerfaces with antibacterial properties

In this paper, we present for the first time the obtaining and characterization of new antibacterial and biocompatible nano-ZnO–bacterial cellulose (BC) material with controlled interfaces for studying in vitro microorganisms (Escherichia Coli (ATCC 8737), B. subtilis Spizizenii Nakamura (ATCC 6633), Candida albicans (ATCC10231)) and mammalian cells (human dermal fibroblast cells) response. The use of BC based material with controlled characteristics in terms of quantity and distribution of ZnO onto BC membrane (with 2D and 3D fibers arrangement) is directly correlated with the surface chemical and topographical properties, the method of preparation, and also with the type of cells implied for the specific application within the bioengineering fields. In our study, the uniform distribution and the control on the quantity of ZnO nanoparticles onto 3D BC were obtained using matrix assisted pulsed laser evaporation (MAPLE) method. The influence on particle distribution onto 3D bio cellulose were investigated based on two types of solvents (water and chloroform) involved in target preparation within MAPLE deposition. The attachment of the nanoparticles to the bacterial cellulose surface and fibrils was demonstrated by SEM and FT-IR studies. The BC-ZnO showed both resistance to bacteria-sticking and non-cytotoxic effect on the human dermal fibroblasts cells at a mass distribution onto surface of 1.68 µg ZnO NPS/mm2. These results represent a good premise in terms of tailoring BC substrates with ZnO particles that could determine or enhance both the biocompatibility and antibacterial properties of BC-composite materials.

Mass-analyzed threshold ionization spectroscopy of lanthanide imide LnNH (Ln = La and Ce) radicals from N-H bond activation of ammonia.

Ln (Ln = La and Ce) atom reactions with ammonia are carried out in a pulsed laser vaporization supersonic molecular beam source. Lanthanide-containing species are observed with time-of-flight mass spectrometry, and LnNH molecules are characterized by mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. The theoretical calculations include density functional theory for both Ln species and a scalar relativity correction, electron correlation, and spin-orbit coupling for the Ce species. The MATI spectrum of LaNH exhibits a single vibronic band system with a strong origin band and two weak vibronic progressions, whereas the spectrum of CeNH displays two band systems separated by 75 cm-1 with each being like the LaNH spectrum. By comparing with the theoretical calculations, both LaNH and CeNH are identified as linear molecules with C∞v symmetry, and the two vibronic progressions are attributed to the excitations of Ln-N stretching and Ln-N-H bending modes in the ions. The additional band system observed for CeNH is due to the spin-orbit splitting from the interactions of triplet and singlet states. The ground valence electron configurations of LaNH and CeNH are La 6s1 and Ce 4f16s1, and the ionization of each species removes the Ln 6s1 electron. The remaining two electrons that are associated with the isolated Ln atoms or ions are in a doubly degenerate molecular orbital that is a bonding combination between Ln 5dπ and N pπ orbitals.

Highly selective surface acoustic wave e-nose implemented by laser direct writing

In this paper, we present an e-nose for the detection of volatile compounds based on an array of six surface acoustic wave (SAW) resonators coated with five different polymers (i.e. polyepichlorohydrin, polyisobutylene, polyethylenimine, (hydroxypropyl)methyl cellulose, and poly(styrene-co-maleic acid) partial isobutyl/methyl mixed ester, plus an uncoated SAW device used as reference. In particular, matrix assisted pulsed laser evaporation was used to deposit thin polymer layers which were subsequently used as donor films in the laser induced forward transfer process to selectively cover each SAW resonators of the array. The SAW e-nose was tested upon exposure to vapors of ethyl acetate, dimethyl methylphosphonate, dichloromethane, dichloropentane, and water. The frequency responses showed, for each of the sensors, a different sensitivity to the selected chemical agents and a good agreement with the theoretical sensitivities derived from the linear-solvation-energy-relationship between vapors and polymers. Specifically, the implemented SAW e-nose allowed the discrimination between all the considered vapors in the tested concentrations ranges as highlighted by the results of principal component analysis. Finally, the obtained results indicated that laser deposition of polymers onto SAW resonators is possible without significant modifications of their functionality and with a good reliability and reproducibility.

MAPLE Assembled Acetylcholinesterase⁻Polyethylenimine Hybrid and Multilayered Interfaces for Toxic Gases Detection.

Developing a controlled method for obtaining hybrid enzymatic-based interfaces for sensing application require the use of a multiuse, reusable sensor. By controlling the interface characteristics in terms of the surface chemistry, thickness, and roughness, a tailored response toward various toxic compounds can be obtained, regarding both materials used as active surfaces and fabrication methods. Herein, we report a preliminary study on using a laser-based method (i.e., matrix-assisted pulsed laser evaporation, or MAPLE) for obtaining active polymeric–enzymatic interfaces as hybrid or layered coatings for detecting toxic vapors. The MAPLE fabrication consisted of the simultaneous alternating evaporation of layers of polyethylenimine (PEI) and acetylcholinesterase (AchE) in order to obtain active surfaces as both hybrid PEI-AchE and a PEI/AchE layered coating, respectively. The deposition processes of the polymer and enzyme were carried out using a double-target system and a Nd:YAG pulsed laser, operating at 0.45 J/cm2 fluences with a wavelength of 266 nm and a repetition rate of 10 Hz. Fourier transform infrared spectroscopy revealed no significant changes in the functional groups of both hybrid and layered coatings compared with the initial material. The thickness and roughness, as well as the morphologies of the coatings revealed by atomic force microscopy and scanning electron microscopy showed coatings thicker than two μm that had smooth surfaces and average roughness values below six nm. The sensors were tested with simulants for nerve gases and pesticides containing phosphonate ester groups, namely dimethyl methylphosphonate (DMMP) and diisopropyl methylphosphonate (DIMP), and a different sensitivity was shown to the selected chemical agents for each of the sensors. The best sensitivities for DMMP and DIMP obtained by using a PEI-AchE coated sensor are 65 kHz and 200 kHz, respectively, whereas the best sensitivity when using multilayered interfaces is 30 kHz and 10 KHz for DIMP and DMMP, respectively.

Dynamics of gas cloud expansion under pulsed laser evaporation into vacuum

Two-dimensional direct Monte Carlo simulation of neutral gas expansion under pulsed evaporation into vacuum has been performed. Analysis of temporal evolution of the spatially-averaged characteristics of the plume has been carried out for a wide range of the problem parameters: the spot radius and the evaporation depth. Special attention has been paid to determination of the limits of applicability of one-dimensional approach for gas dynamic simulation.

Specific Features of the Magnetic Anisotropy of Thin Yttrium Iron Garnet Films Prepared by Pulsed Laser Deposition

The specific features of dependences of the magnetic anisotropy constants on the thickness of yttrium iron garnet films prepared by pulsed laser deposition were studied. Films with thicknesses of 96–333 nm were produced by pulsed laser evaporation of the target material and deposition onto gadolinium-gallium-garnet substrates with the (111) orientation. The results of an investigation into static magnetic properties showed that the saturation magnetization decreases as the films get thinner. The high-frequency properties were studied by ferromagnetic resonance (FMR). The uniaxial and cubic anisotropy fields and the relaxation parameter were determined by analyzing the angular dependences of the resonance field and the FMR line width. It was found that as the thickness decreases, the strength of the uniaxial anisotropy field increases monotonically, while the cubic anisotropy field decreases and reverses its sign.

Exploiting physical vapor deposition for morphological control in semi‐crystalline polymer films

Research in semi-crystalline polymer thin films has seen significant growth due to their fascinating thermal, mechanical, and electronic properties. In all applications, acquiring precise control over the film morphology atop various substrates or in the free-standing film geometry is key to advancing product performance. This article reviews the crystallization of polymer thin films processed via physical vapor deposition (PVD). Classical PVD techniques are briefly reviewed, highlighting their working principles as well as successes and challenges to achieving morphological control of polymer films. Subsequently, the recent development of a unique PVD technique termed Matrix Assisted Pulsed Laser Evaporation (MAPLE) is highlighted. The non-destructive technology overcomes the major drawback of polymer degradation by classical PVD. Recent advances highlighting how MAPLE can be exploited to control polymer film morphology in ways not achievable by other methods are presented. Challenges and future scope of PVD for polymer film deposition concludes the review.

Gradient multifunctional biopolymer thin film assemblies synthesized by combinatorial MAPLE

Combinatorial Matrix-Assisted Pulsed Laser Evaporation (C-MAPLE) was recently introduced to the fast generation of compositional libraries of two biopolymers in a single-step process, for tissue engineering and regenerative medicine applications.Synchronized laser irradiation of two distinct cryogenic targets, one consisting of Sulfated Halomonas Levan and the other of quaternized low molecular weight Chitosan was used to fabricate compositional gradient coatings for surface functionalization. Synthesized coatings preserved the base material composition as confirmed by Fourier Transform Infrared Spectroscopy. Morphological study by Scanning Electron Microscopy, Atomic Force Microscopy and profilometry correlated with water contact angles measurements demonstrated that the obtained thin coatings have improved surface properties with respect to pure material coatings. Fluorescence microscopy validated the compositional gradient, while in vitro assays evidenced characteristic responses of mouse fibroblasts (L929 cell line) by distinct deposition surface regions. The coagulation test pointed out good properties for Sulfated Halomonas Levan coatings as compared to the case of an increased amount of quaternized low molecular weight Chitosan biopolymer or the control.The antimicrobial effect of the coatings was demonstrated against Escherichia coli and Staphylococcus aureus strains, representative for both Gram negative and Gram positive bacterial species, respectively, mainly involved in implant and nosocomial infections. The assembled nanostructures possess variable anti-biofilm activity along the compositional gradient, with a stronger inhibitory effect on the initial adherence phase of both tested microbial strains, but also against mature Escherichia coli biofilms.It was shown that C-MAPLE can generate discrete areas of blended polymeric composition exhibiting improved surface properties for a broad range of biomedicine applications, e.g. the fabrication of thin bioactive and cell-instructive coatings with anti-adherence properties.

Deposition of YBCO nanoparticles on graphene nanosheets by using matrix-assisted pulsed laser evaporation

Matrix-assisted pulsed laser evaporation (MAPLE) process demonstrates a versatile and contamination free deposition. Compared to conventional laser ablation deposition, MAPLE technique can realize the retention of the properties and structures of deposited biomaterials and hybrid nanocomposites without damaging the backbone of organic macromolecules. Here, MAPLE process is applied to deposit yttrium barium copper oxide (YBCO) superconductor particles on graphene sheets. The microstructures and elemental composition of YBCO nanoparticle deposited on graphene sheet by the MAPLE process were studied as a function of the irradiation time (t). The amount of YBCO nanoparticles deposited on graphene is increased with increasing t. The average particle size of the spherical YBCO nanoparticles deposited on graphene sheets is decreased from 70 ± 25 nm to 50 ± 15 nm when t increases from 0.5 h to 2.0 h. This study demonstrates that MAPLE is a suitable process for depositing superconductor nanoparticles on graphene sheets.

Antibiofilm Coatings Based on PLGA and Nanostructured Cefepime-Functionalized Magnetite.

The aim of our study was to obtain and evaluate the properties of polymeric coatings based on poly(lactic-co-glycolic) acid (PLGA) embedded with magnetite nanoparticles functionalized with commercial antimicrobial drugs. In this respect, we firstly synthesized the iron oxide particles functionalized (@) with the antibiotic Cefepime (Fe3O4@CEF). In terms of composition and microstructure, the as-obtained powdery sample was investigated by means of grazing incidence X-ray diffraction (GIXRD), thermogravimetric analysis (TGA), scanning and transmission electron microscopy (SEM and TEM, respectively). Crystalline and nanosized particles (~5 nm mean particle size) with spherical morphology, consisting in magnetite core and coated with a uniform and reduced amount of antibiotic shell, were thus obtained. In vivo biodistribution studies revealed the obtained nanoparticles have a very low affinity for innate immune-related vital organs. Composite uniform and thin coatings based on poly(lactide-co-glycolide) (PLGA) and antibiotic-functionalized magnetite nanoparticles (PLGA/Fe3O4@CEF) were subsequently obtained by using the matrix assisted pulsed laser evaporation (MAPLE) technique. Relevant compositional and structural features regarding the composite coatings were obtained by performing infrared microscopy (IRM) and SEM investigations. The efficiency of the biocompatible composite coatings against biofilm development was assessed for both Gram-negative and Gram-positive pathogens. The PLGA/Fe3O4@CEF materials proved significant and sustained anti-biofilm activity against staphylococcal and Escherichia coli colonisation.

Flexible organic heterostructures obtained by MAPLE

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 (ISC) 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.

Shellac Thin Films Obtained by Matrix-Assisted Pulsed Laser Evaporation (MAPLE)

We report on the fabrication of shellac thin films on silicon substrates by matrix-assisted pulsed laser evaporation (MAPLE) using methanol as matrix. Very adherent, dense, and smooth films were obtained by MAPLE with optimized deposition parameters, such as laser wavelength and laser fluence. Films with a root mean square (RMS) roughness of 11 nm measured on 40 × 40 µm2 were obtained for a 2000-nm-thick shellac film deposited with 0.6 J/cm2 fluence at a laser wavelength of 266 nm. The MAPLE films were tested in simulated gastric fluid in order to assess their capabilities as an enteric coating. The chemical, morphological, and optical properties of shellac samples were investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and atomic force microscopy (AFM).

Lincomycin–embedded PANI–based coatings for biomedical applications

We report on the successful laser transfer of biocompatible composite coatings based on polyaniline (PANI) embedded with magnetite (PANI-Fe3O4) and Lincomycin hydrochloride (PANI-Lincomycin) or Lincomycin-functionalized magnetite (PANI-Fe3O4@Lincomycin) by matrix assisted pulsed laser evaporation (MAPLE) technique.The physico-chemical investigations revealed relevant data regarding the stoichiometric deposition, morphology and topography of the as-deposited coatings. Regarding the MAPLE coatings, the FTIR studies evidenced the vibrational bands characteristic to pristine PANI material, while the SEM investigations unveiled a preferential particulate morphology (with aggregates shape and size depending on the deposited material). Additionally, the AFM measurements indicated variations of RMS value, following the Lincomycin and magnetite incorporation. The wettability measurements displayed a hydrophilic behavior of the synthesized coatings, while the electrochemical studies emphasized an enhanced resistance against corrosion in simulated body fluid when compared with bare Ti.Cellular viability, immunofluorescence and SEM results proved that the MAPLE coatings were suitable materials for beneficial adhesion, spreading and proliferation of osteoblast-like cells (MG-63). Moreover, an increased efficiency was evidenced against Staphylococcus aureus biofilm development.The multifunctional properties of the laser processed composite coatings – confirmed by cumulative biocompatible, antimicrobial and anticorrosive behaviors – recommend them as promising solutions for biomedical applications.

MAPLE deposition of Nigella sativa functionalized Fe3O4 nanoparticles for antimicrobial coatings

Implant- related infections are a consequence of microbial’ adhesion to an implant surface followed by biofilm development on the implanted device. Chemical and biological functionalization of medical surfaces represents topical tactic of enhancing biocompatibility, together with the prevention of bacterial contamination and biofilm inhibition. For this purpose, we focused our work on laser surface modification of medical devices. We prepared nanoparticles of Fe3O4 loaded with Nigella sativa oil by a modified co-precipitation method in aqueous solution of NH4OH by oil-in-water emulsion. For further studies, we mixed them with poly(lactic-co-glycolic acid) spheres. The functionalized nanoparticles were deposited on glass and silicone surfaces by Matrix Assisted Pulsed Laser Evaporation technique. The influence of experimental factors, such as laser fluences was studied. The obtained thin coatings were analyzed by high resolution transmission electron microscopy, scanning electron microscopy and infrared microscopy. The most suitable coatings were selected and tested against a broad spectrum of pathogens found in the most implant rejection issues, such as S. aureus, E. coli and C. albicans, at different time intervals and proved to limit microbial colonization and biofilm formation. In addition, biocompatibility studies using MG-63 cells adopting MTS assay confirmed the possible use of the obtained thin coatings to safely modify medical surfaces.

MAPLE fabricated coatings based on magnetite nanoparticles embedded into biopolymeric spheres resistant to microbial colonization

The aim of this study was to obtain improved coatings for advanced surfaces with increased biocompatibility and resistance to microbial colonization and biofilm formation. The prepared magnetite nanoparticles functionalized with gentamicin (Fe3O4@G) have been embedded into poly(lactic-co-glycolic acid) (PLGA) spheres by oil-in-water emulsion. The PLGA-Fe3O4@G spheres were deposited on glass and silicone surfaces by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique. The obtained thin coatings were analyzed by Scanning Electron Microscopy (SEM) and Infrared Microscopy (IRM). The antimicrobial and antibiofilm efficiency of coatings was tested with respect to Gram-positive (Staphylococcus aureus) and Gram-negative (Pseudomonas aeruginosa) clinical strains by viable cells counts assay, performed at different time intervals. The obtained results proved that coatings based on PLGA-Fe3O4@G spheres exhibited an efficient antimicrobial activity against both adherent and sessile bacterial cells. Besides their excellent anti-adherence and antibiofilm effect, the obtained MAPLE-deposited coatings were highly biocompatible, allowing the normal development and growth of cultured human amniotic fluid stem cells. This approach could be successfully applied for the optimization of medical surfaces in order to control and prevent microbial colonization and further development of biofilm associated infections.

Gradient coatings of strontium hydroxyapatite/zinc β-tricalcium phosphate as a tool to modulate osteoblast/osteoclast response

The chemistry, structure and morphology of the implant surface have a great influence on the integration of an implant material with bone tissue. In this work, we applied Combinatorial Matrix-Assisted Pulsed Laser Evaporation (C-MAPLE) to deposit gradient thin films with variable compositions of Sr-substituted hydroxyapatite (SrHA) and Zn-substituted β-tricalcium phosphate (ZnTCP) on Titanium substrates. Five samples with different SrHA/ZnTCP composition ratios were fabricated by a single step laser procedure. SrHA was synthesized in aqueous medium, whereas ZnTCP was obtained by reaction at high temperature. Both powders were separately suspended in deionized water, frozen at liquid nitrogen temperature and used as targets for C-MAPLE experiments, which proceed via simultaneous laser vaporization of two distinct material targets. X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy analyses confirmed that the coatings contain the same crystalline phases as the as-prepared powder samples, with a homogeneous distribution of the two phosphates along deposited thin films. Human osteoclast precursor 2T-110 and human osteoblast-like cells MG63 were co-cultured on the coatings. The results indicate that osteoblast viability and production of osteocalcin were promoted by the presence of ZnTCP. On the other hand, SrHA inhibited osteoclastogenesis and osteoclast differentiation, as demonstrated by the observed increase of the osteoprotegerin/RANKL ratio and decrease of the number of TRAP-positive multinucleated cells when increasing SrHA amount in the coatings. The results indicate that the possibility to tailor the composition of the coatings provides materials able to modulate bone growth and bone resorption.

In vitro behavior of human mesenchymal stem cells on poly(N-isopropylacrylamide) based biointerfaces obtained by matrix assisted pulsed laser evaporation

The use of smart coatings with tunable characteristics in bioengineering fields is directly correlated with the surface chemical and topographical properties, the method of preparation, and also with the type of cells implied for the specific application. In this work, a versatile surface modification technique based on the use of lasers (Matrix-Assisted Pulsed Laser Evaporation (MAPLE)) was used to yield poly(N-isopropylacrylamide) (pNIPAM) and its derivatives (amine, azide and amide terminated pNIPAM) functional and termoresponsive thin films. Surface properties of pNIPAM and its derivative films such as morphology, roughness and hydrophobic/hydrophilic character, as well as the thermoresponsive capacity were investigated by atomic force microscopy and contact angle measurements. The chemical characteristics of the pNIPAM based thin films were analysed by Fourier Transform Infrared Spectroscopy (FTIR). The chemical functionality was kept for all the samples obtained by MAPLE and the thermoresponse was demonstrated by the change in the contact angle and thickness values when the temperature was shifted from 37 °C to 24 °C for all the materials tested, with a smaller change for maleimide terminated pNIPAM. Biological assays performed in vitro (fluorescence microscopy and Scanning Electron Microscopy (SEM)) confirmed the conditioning of the early mesenchymal stem cell (MSC) growth by specific chemistry of the coatings. The cell imaging analysis revealed no cytotoxic effect of pNIPAM surfaces irrespective of type of functionalization. An increased proliferation rate of the cells grown on pNIPAM-azide surfaces and a lower cell density on pNIPAM-maleimide surfaces compared to the pNIPAM surfaces was observed, which can direct their use to potential surfaces in regenerative medicine approaches.