Pulsed Laser Evaporation Research Articles

In vitro evaluation of poly(ethylene glycol)-block-poly(ɛ-caprolactone) methyl ether copolymer coating effects on cells adhesion and proliferation

Understanding and controlling natural and synthetic biointerfaces is known to be the key to a wide variety of application within cell culture and tissue engineering field. As both material characteristics and methods are important in tailoring biointerfaces characteristics, in this work we explore the feasibility of using Matrix Assisted Pulsed Laser Evaporation technique for obtaining synthetic copolymeric biocoatings (i.e. poly(ethylene glycol)-block-poly(ɛ-caprolactone) methyl ether) for evaluating in vitro Vero and MC3T3-E1 pre-osteoblasts cell response. Characterization and evaluation of the coated substrates were carried out using different techniques. The Fourier transform infrared spectroscopy data demonstrated that the main functional groups in the MAPLE-deposited films remained intact. Atomic Force Microscopy images showed the coatings to be continuous, with the surface roughness depending on the deposition parameters. Moreover, the behaviour of the coatings in medium mimicking the pH and temperature of the human body was studied and corelated to degradation. Spectro-ellipsometry (SE) and AFM measurements revealed the degradation trend during immersion time by the changes in coating thickness and roughness. In vitro biocompatibility was studied by indirect contact tests on Vero cells in accordance with ISO 10993-5/2009. The results obtained in terms of cell morphology (phase contrast microscopy) and cytotoxicity (LDH and MTT assays) proved biocompatibility. Furthermore, direct contact assays on MC3T3-E1 pre-osteoblasts demonstrated the capacity of all analyzed specimens to support cell adhesion, normal cellular morphology and growth.

Activated complex model and surfactant reorganization during SWCNT separations on hydrogels

Hydrogels can efficiently separate metallic and semiconducting single-wall carbon nanotube (SWCNT) species at high rates by selective adsorption in a column configuration, but mechanistic details remain unclear. We examined the temperature dependence of SWCNT adsorption in an operating column using a model that considers the formation of an activated complex. The enthalpy and entropy changes associated with formation of the activated complex were determined. Due to a high sensitivity to protonation doping, large diameter pulsed laser vaporization tubes provided an opportunity to probe details of the adsorption mechanism. In contrast to the prevailing view in the literature, we conclude that the surfactant environment surrounding the nanotube is substantially reorganized upon adsorption and that adsorption also occurs within gel pores. Our findings provide new mechanistic insights that should assist in the development of improved separation methods.

M-DOPA addition in MAPLE immobilization of lipase for biosensor applications

Matrix Assisted Pulsed Laser Evaporation (MAPLE) is a thin film deposition technique which uses a pulsed laser beam impinging, inside a high vacuum chamber, on a frozen target containing the guest molecules in a volatile matrix to induce fast “evaporation” of the matrix, and ejection of the guest molecules. Lipase, an enzyme acting as a catalyst in hydrolysis of lipids, is widely used in biosensors for detection of triglycerides in blood serum. A key action to this purpose is lipase immobilization on a substrate. In a recent paper, we have shown that MAPLE technique is able to deposit lipase on a substrate in an active form. Here we show that addition to the guest/matrix target of a small amount of m-DOPA (3-(3,4-dihydroxyphenyl)-2-methyl-l-alanine) in order to improve adhesion and protect lipase secondary structure, also allows the lowering the laser pulse energy required for matrix evaporation and therefore the risk of damaging the enzyme.

Composite biodegradable biopolymer coatings of silk fibroin – Poly(3-hydroxybutyric-acid-co-3-hydroxyvaleric-acid) for biomedical applications

Composite silk fibroin–poly(3-hydroxybutyric-acid-co-3-hydroxyvaleric-acid) (SF–PHBV) biodegradable coatings were grown by Matrix Assisted Pulsed Laser Evaporation on titanium substrates. Their physico-chemical properties and particularly the degradation behavior in simulated body fluid at 37°C were studied as first step of applicability in local controlled release for tissue regeneration applications.SF and PHBV, natural biopolymers with excellent biocompatibility, but different biodegradability and tensile strength properties, were combined in a composite to improve their properties as coatings for biomedical uses.FTIR analyses showed the stoichiometric transfer from targets to coatings by the presence in the spectra of the main absorption maxima characteristic of both polymers. XRD investigations confirmed the FTIR results showing differences in crystallization behavior with respect to the SF and PHBV content. Contact angle values obtained through wettability measurements indicated the MAPLE deposited coatings were highly hydrophilic; surfaces turning hydrophobic with the increase of the PHBV component. Degradation assays proved that higher PHBV contents resulted in enhanced resistance and a slower degradation rate of composite coatings in SBF. Distinct drug-release schemes could be obtained by adjusting the SF:PHBV ratio to controllably tuning the coatings degradation rate, from rapid-release formulas, where SF predominates, to prolonged sustained ones, for larger PHBV content.

Patterned arrays of lateral heterojunctions within monolayer two-dimensional semiconductors.

The formation of semiconductor heterojunctions and their high-density integration are foundations of modern electronics and optoelectronics. To enable two-dimensional crystalline semiconductors as building blocks in next-generation electronics, developing methods to deterministically form lateral heterojunctions is crucial. Here we demonstrate an approach for the formation of lithographically patterned arrays of lateral semiconducting heterojunctions within a single two-dimensional crystal. Electron beam lithography is used to pattern MoSe2 monolayer crystals with SiO2, and the exposed locations are selectively and totally converted to MoS2 using pulsed laser vaporization of sulfur to form MoSe2/MoS2 heterojunctions in predefined patterns. The junctions and conversion process are studied by Raman and photoluminescence spectroscopy, atomically resolved scanning transmission electron microscopy and device characterization. This demonstration of lateral heterojunction arrays within a monolayer crystal is an essential step for the integration of two-dimensional semiconductor building blocks with different electronic and optoelectronic properties for high-density, ultrathin devices.

Time-Resolved Imaging Study of Jetting Dynamics during Laser Printing of Viscoelastic Alginate Solutions.

Matrix-assisted pulsed-laser evaporation direct-write (MAPLE DW) has been successfully implemented as a promising laser printing technology for various fabrication applications, in particular, three-dimensional bioprinting. Since most bioinks used in bioprinting are viscoelastic, it is of importance to understand the jetting dynamics during the laser printing of viscoelastic fluids in order to control and optimize the laser printing performance. In this study, MAPLE DW was implemented to study the jetting dynamics during the laser printing of representative viscoelastic alginate bioinks and evaluate the effects of operating conditions (e.g., laser fluence) and material properties (e.g., alginate concentration) on the jet formation performance. Through a time-resolved imaging approach, it is found that when the laser fluence increases or the alginate concentration decreases, the jetting behavior changes from no material transferring to well-defined jetting to well-defined jetting with an initial bulgy shape to jetting with a bulgy shape to pluming/splashing. For the desirable well-defined jetting regimes, as the laser fluence increases, the jet velocity and breakup length increase while the breakup time and primary droplet size decrease. As the alginate concentration increases, the jet velocity and breakup length decrease while the breakup time and primary droplet size increase. In addition, Ohnesorge, elasto-capillary, and Weber number based phase diagrams are presented to better appreciate the dependence of jetting regimes on the laser fluence and alginate concentration.

Stainless steel surface biofunctionalization with PMMA-bioglass coatings: compositional, electrochemical corrosion studies and microbiological assay

A solution is proposed to surpass the inconvenience caused by the corrosion of stainless steel implants in human body fluids by protection with thin films of bioactive glasses or with composite polymer-bioactive glass nanostructures. Our option was to apply thin film deposition by matrix-assisted pulsed laser evaporation (MAPLE) which, to the difference to other laser or plasma techniques insures the protection of a more delicate material (a polymer in our case) against degradation or irreversible damage. The coatings composition, modification and corrosion resistance were investigated by FTIR and electrochemical techniques, under conditions which simulate their biological interaction with the human body. Mechanical testing demonstrates the adhesion, durability and resistance to fracture of the coatings. The coatings biocompatibility was assessed by in vitro studies and by flow cytometry. Our results support the unrestricted usage of coated stainless steel as a cheap alternative for human implants manufacture. They will be more accessible for lower prices in comparison with the majority present day fabrication of implants using Ti or Ti alloys.

Electrically stimulated osteogenesis on Ti-PPy/PLGA constructs prepared by laser-assisted processes.

This work describes a versatile laser-based protocol for fabricating micro-patterned, electrically conductive titanium-polypyrrole/poly(lactic-co-glycolic)acid (Ti-PPy/PLGA) constructs for electrically stimulated (ES) osteogenesis. Ti supports were patterned using fs laser ablation in order to create high spatial resolution microstructures meant to provide mechanical resistance and physical cues for cell growth. Matrix Assisted Pulsed Laser Evaporation (MAPLE) was used to coat the patterned Ti supports with PPy/PLGA layers acting as biocompatible surfaces having chemical and electrical properties suitable for cell differentiation and mineralization. In vitro biological assays on osteoblast-like MG63 cells showed that the constructs maintained cell viability without cytotoxicity. At 24 h after cell seeding, electrical stimulation with currents of 200 μA was applied for 4 h. This treatment was shown to promote earlier onset of osteogenesis. More specifically, the alkaline phosphatase activity of the stimulated cultures reached the maximum before that of the non-stimulated ones, i.e. controls, indicating faster cell differentiation. Moreover, mineralization was found to occur at an earlier stage in the stimulated cultures, as compared to the controls, starting with Day 6 of cell culture. At later stages, calcium levels in the stimulated cultures were higher than those in control samples by about 70%, with Ca/P ratios similar to those of natural bone. In all, the laser-based protocol emerges as an efficient alternative to existing fabrication technologies.

Octahydroacridine thin films grown by matrix-assisted pulsed laser evaporation for non linear optical applications

We report on the thin film growth of 1,2,3,4,5,6,7,8-octahydroacridine (OHA) by matrix-assisted pulsed laser evaporation (MAPLE), starting from a frozen solution of 1% OHA dissolved in methanol and using a Nd:YAG laser emitting at 266nm wavelength with fluences in the range 0.1–1J/cm2. The optical properties were studied by spectroscopic-ellipsometry (SE), while Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), and scanning electron microscopy (SEM) were performed for structure and surface morphology investigation. Second harmonic generation (SHG) capabilities of the thin films were investigated by using a tunable Ti:sapphire laser with maximum emission centred in near infra-red. The peak of emitted photons is located at 388nm, therefore half the wavelength of the initial photons (776nm). The semi logarithmic dependence of SHG intensity on incident power is almost linear, except the value obtained at highest power of incident photons. This value indicates a local changing of sample due to the heating produced by the high-power incident beam.

Hybrid nanocomposite thin films deposited by emulsion-based resonant infrared matrix-assisted pulsed laser evaporation for photovoltaic applications

Emulsion-based, resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) was used to deposit CdSe nanoparticle films and hybrid nanocomposite films comprising colloidal CdSe nanoparticles embedded in a low band gap polymer, poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT). We show that, in contrast to traditional MAPLE deposition, the CdSe nanoparticle film deposited by emulsion based RIR-MAPLE is contiguous and uniform, and it maintains the optical properties of the nanoparticle solution. Moreover, we show that the RIR-MAPLE deposited PCPDTBT/CdSe hybrid nanocomposite film exhibits a relatively random and uniform distribution of CdSe nanoparticles without the significant phase segregation that is observed in hybrid nanocomposite films deposited by spin-casting. Finally, hybrid organic solar cells based on nanocomposite films deposited by the RIR-MAPLE technique were fabricated and characterized, showing 0.4% power conversion efficiency. This is the first demonstration of a polymer–nanoparticle hybrid organic solar cell fabricated by a MAPLE-related technique.

Analytical formula for interpretation of time-of-flight distributions for neutral particles under pulsed laser evaporation in vacuum

A theoretical study of the time-of-flight (TOF) distributions of neutral species produced by low-fluence pulsed laser evaporation in a vacuum has been performed. A database of TOF distributions has been calculated by the direct simulation Monte Carlo method. The calculated TOF signals have been fitted by a modification of the shifted Maxwell–Boltzmann distribution function with the only parameter being the shift velocity. The dependence of the shift velocity on the number of evaporated monolayers has been described by an analytical expression, derived based on the gas-dynamic analysis of pulsed gas expansion into a vacuum. This expression allows the derivation of a new formula for TOF distributions for neutral particles with the only parameter being the surface temperature. This new formula has been used for the analysis of experimental data on pulsed laser ablation of niobium, copper, graphite and gold. The evaluated surface temperature agrees well with the results of the thermal model calculations and available experimental data with an error of 10% instead of 50–150% for commonly used formulas.

MAPLE-deposited PFO films: influence of the laser fluence and repetition rate on the film emission and morphology

The Matrix-Assisted Pulsed Laser Evaporation (MAPLE) technique is emerging as an alternative route to the conventional methods for depositing organic materials, although the MAPLE-deposited films very often present high surface roughness and characteristic morphological features. Films of the blue-emitting polymer, poly(9,9-dioctylfluorene)—PFO, have been deposited by MAPLE to investigate the influence of the laser fluence and repetition rate on both their topography and emission properties. The laser fluence has been changed from 150 up to 450 mJ/cm2, while laser repetition rates of 2 and 10 Hz have been considered. The interplay/relationship between the topography and the emission properties of the MAPLE-deposited films has been studied by confocal microscopy, photoluminescence spectrometry and atomic force microscopy. It has been found that under high irradiation (fluence of 450 mJ/cm2) conditions, the sample surface is characterized by bubbles presenting the intrinsic PFO blue emission. Instead, while improvements in the film morphology can be observed for lowered fluence and laser repetition rate, green emission becomes predominant in such conditions. Such result is very interesting to better understand the MAPLE ablation mechanism, which is discussed in this study.

Very low roughness MAPLE-deposited films of a light emitting polymer: an alternative to spin coating

The matrix assisted pulsed laser evaporation (MAPLE) technique is emerging as an alternative route to conventional deposition methods of organic materials (solution-phase and thermal evaporation approaches). However, the high surface roughness of the films deposited by MAPLE makes this technique not compatible with applications in electronics and photonics. In this paper we report the deposition of MAPLE-films of a green light emitting polymer, commercially named ADS125GE, with remarkable low roughness values, down to about 10 nm at the thickness conventionally used in photonic devices (~40 nm). This issue is discussed as a function of polymer concentration, target-substrate distance and substrate rotation based on AFM topography images, roughness estimation and optical (absorption and luminescent) measurements. In addition we have fabricated an organic light emitting diode with this technique using the best deposition parameters which guarantee the lowest roughness. These results open the way to MAPLE applications in organic photonics and opto-electronics.

Patchy Janus particles with tunable roughness and composition via vapor-assisted deposition of macromolecules

Here, we present a technique for the fabrication of patchy Janus particles utilizing a vapor-assisted macromolecular deposition technique, termed Matrix Assisted Pulsed Laser Evaporation (MAPLE). Using this technique, both inorganic and organic precursor particles, immobilized on a surface, are functionalized on one hemisphere with nanodroplets of a desired polymer, thus forming particles with a patchy Janus morphology and textured surface topology. This fabrication method is flexible with respect to the chemical identity of the precursor particle and the selection of the deposited polymer. By tuning MAPLE deposition parameters, e.g., target composition or deposition time, the Janus anisotropy and roughness (i.e., patchiness) can be tuned, thus enabling greater control over the particles' behavior for applications as nanoparticle surfactants for stabilization of emulsions and foams.

Fabrication of magnetite-based core–shell coated nanoparticles with antibacterial properties

We report the fabrication of biofunctionalized magnetite core/sodium lauryl sulfate shell/antibiotic adsorption-shell nanoparticles assembled thin coatings by matrix assisted pulsed laser evaporation for antibacterial drug-targeted delivery. Magnetite nanoparticles have been synthesized and subsequently characterized by transmission electron microscopy and x-ray diffraction. The obtained thin coatings have been investigated by FTIR and scanning electron microscope, and tested by in vitro biological assays, for their influence on in vitro bacterial biofilm development and cytotoxicity on human epidermoid carcinoma (HEp2) cells.

Corrigendum to “Biomimetic nanocrystalline apatite coatings synthesized by Matrix Assisted Pulsed Laser Evaporation for medical applications” [Mater. Sci. Eng. B (2014) 56–63

Corrigendum to “Biomimetic nanocrystalline apatite coatings synthesized by Matrix Assisted Pulsed Laser Evaporation for medical applications” [Mater. Sci. Eng. B (2014) 56–63

Poly(lactic-co-glycolic) acid/chitosan microsphere thin films functionalized with Cinnamomi aetheroleum and magnetite nanoparticles for preventing the microbial colonization of medical surfaces

Poly(lactic-co-glycolic) acid/chitosan micro- sphere coatings containing Cinnamomi aetheroleum-func- tionalized magnetite nanoparticles (Fe3O4@CA) were deposited by matrix-assisted pulsed laser evaporation in order to improve the surface resistance to microbial colonization. The obtained surface proved a very good biocompatibility and demonstrates that bacterial colonization is impaired on the nanomodified bioactive surfaces and also Staphylococcus aureus biofilm formation is significantly altered. Graphical Abstract

Pulsed laser processing of poly(3,3‴-didodecyl quarter thiophene) semiconductor for organic thin film transistors

We report on the growth of thin solid layers of poly(3,3‴ didodecyl quater thiophene) (PQT-12) by matrix-assisted pulsed laser evaporation (MAPLE), on silicon and quartz substrates. The effects of PQT-12 solubilization in toluene, anisole, 1,2-dichlorobenzene, and a mixture of chlorobenzene and 1,2-dichlorobenzene, are discussed with respect to the MAPLE technique. Different film thicknesses have been grown, and their morphology and optical properties are presented. Thermal analysis studies have been realized to understand and explain the laser-induced photo-thermal effects on the organic semiconductor. Subsequently, micrometric-sized pixels of PQT-12 have been printed by laser-induced forward transfer (LIFT), with the goal to fabricate organic thin-film transistors (OTFT) devices. The influence of the donor films thickness and morphology, in LIFT experiments, is discussed. Electrical characterizations supplement this study, the resulting printed transistors are fully functional and provide field-effect mobility up to 5×10−3cm2·V−1·s−1 together with current modulation of 106.

Evidence of chromium-cobalt binary cluster formation by pulsed laser evaporation

We report on the use of time of flight mass spectrometry to investigate the cluster spectrum resulting from Nd-YAG ablation of a Co-Cr target. Cr+ clusters dominated the spectrum, with Co+ clusters as the second most intense peak, and we found a clearly resolved Cr-Co binary cluster that could be suitable for co-doping during the growth of laser crystals. Significant contributions from elemental dimers as well as some oxide clusters were also observed. Density functional calculations confirmed that formation of the observed intermetallic clusters was thermodynamically favorable.

Strontium and zoledronate hydroxyapatites graded composite coatings for bone prostheses

Both strontium and zoledronate (ZOL) are known to be useful for the treatment of bone diseases associated to the loss of bone substance. In this work, we applied an innovative technique, Combinatorial Matrix-Assisted Pulsed Laser Evaporation (C-MAPLE), to deposit gradient thin films with variable compositions of Sr-substituted hydroxyapatite (SrHA) and ZOL modified hydroxyapatite (ZOLHA) on Titanium substrates. Compositional gradients were obtained by simultaneous laser vaporization of the two distinct material targets. The coatings display good crystallinity and granular morphology, which do not vary with composition. Osteoblast-like MG63 cells and human osteoclasts were co-cultured on the thin films up to 21days. The results show that Sr counteracts the negative effect of relatively high concentration of ZOL on osteoblast viability, whereas both Sr and ZOL enhance extracellular matrix deposition. In particular, ZOL promotes type I collagen production, whereas Sr increases the production of alkaline phosphatase. Moreover, ZOL exerts a greater effect than Sr on osteoprotegerin/RANKL ratio and, as a consequence, on the reduction of osteoclast proliferation and activity. The deposition method allows to modulate the composition of the thin films and hence the promotion of bone growth and the inhibition of bone resorption.