Laser-induced ablation dynamics and flight of thin polymer films

We investigated the ejection dynamics of triazene polymer layers in the thickness range of 40 nm to 600 nm upon nanosecond laser ablation at a wavelength of 532 nm. The ablation is due to laser-induced thermal degradation of a small part of the polymer in contact with the silicon substrate. The subsequent dynamics of the flying polymer layer are measured with sub-nanosecond time resolution. The evaluation of the initial velocity for different film thicknesses gives insight into the energy transfer process during the acceleration of the films.     

Study on metal microparticle content of the material transferred with Absorbing Film Assisted Laser Induced Forward Transfer when using silver absorbing layer

Absorbing Film Assisted Laser Induced Forward Transfer (AFA-LIFT) is a modified LIFT method where a high absorption coefficient thin film coating of a transparent substrate is used to transform the laser energy into kinetic in order to transfer the “target” material spread on it. This method can be used for the transfer of biomaterials and living cells, which could be damaged by direct irradiation of the laser beam. In previous experiments, ∼50-100 nm thick metal films have been used as absorbing layer. The transferred material can also contain metal microparticles originating from the absorbing thin film and acting as non-desired impurities in some cases. The aim of our work was to study how the properties (number, size and covered area) of metal particles transferred during the AFA-LIFT process depend on film thickness and the applied fluence. Silver thin films with different thickness (50-400 nm) were used as absorbing layers and real experimental conditions were modeled by a 100 μm thick water layer. The particles transferred without the use of water layer were also studied. The threshold laser fluence for the complete removal of the absorber from the irradiated area was found to strongly increase with increasing film thickness. The deposited micrometer and submicrometer particles were observed with optical microscope and atomic force microscope. Their size ranged from 100 nm to 20 μm and depended on the laser fluence. The increase in fluence resulted in an increasing number of particles of smaller average size.     

Laser-induced forward transfer of focussed ion beam pre-machined donors

In this paper we report femtosecond laser-induced forward transfer (LIFT) of pre-machined donor films. 1 μm thick zinc oxide (ZnO) films were first machined using the focussed ion beam (FIB) technique up to a depth of 0.8 μm. Debris-free micro-pellets of ZnO with extremely smooth edges and surface uniformity were subsequently printed from these pre-machined donors using LIFT. Printing results of non-machined ZnO donor films and films deposited on top of a polymer dynamic release layer (DRL) are also presented for comparison, indicating the superior quality of transfer achievable and utility of this pre-machining technique.     

Hardening of smooth pulsed laser deposited PMMA films by heating

Smooth poly(methyl methacrylate) (PMMA) films without any droplets were pulsed laser deposited at a wavelength of 248 nm and a laser fluence of 125 mJ/cm². After deposition at room temperature, the films possess low universal hardness of only 3 N/mm². Thermal treatments up to 200°C, either during deposition or afterwards, lead to film hardening up to values of 200 N/mm². Using a combination of complementary methods, two main mechanisms could be made responsible for this temperature induced hardening effect well above the glass transition temperature of 102°C. The first process is induced by the evaporation of chain fragments and low molecular mass material, which are present in the film due to the ablation process, leading to an increase of the average molecular mass and thus to hardening. The second mechanism can be seen in partial cross-linking of the polymer film as soon as chain scission occurs at higher temperatures and the mobility and reactivity of the polymer material is high enough.     

Laser nano-fabrication of large-area plasmonic structures and surface plasmon resonance tuning by thermal effect

A simple and flexible technique aimed to generate large-area periodic nano-dot array features on metal thin films by laser interference lithography (LIL) has been demonstrated. In this paper, gold nano-dot arrays with a period of ∼450 nm and a dot diameter of ∼100 nm on quartz substrates coated with a gold film of 50 nm thick were fabricated. Multiple enhanced transmission peaks were observed in this patterned film. In addition to the characteristic peak of the gold surface plasmon resonance around 500 nm, multiple shoulder peaks that range from 550 to 700 nm were also observed in the nano-chain array structures. These shoulder peaks disappeared after thermal annealing. It was found that the nano-dots became smaller and well-separated nano-balls under the high temperature annealing process. These nano-structures have potential applications in solar cell, nano-lithography and biosensing.     

Controlled release of ketorolac through nanocomposite films of hydrogel and LDH nanoparticles

A novel nanocomposite film for sustained release of anionic ophthalmic drugs through a double-control process has been examined in this study. The film, made as a drug-loaded contact lens, consists principally of a polymer hydrogel of 2-hydroxyethyl methacrylate (HEMA), in whose matrix MgAl-layered double hydroxide (MgAl-LDH) nanoparticles intercalated with the anionic drug are well dispersed. Such nanocomposite films (hydrogel-LDH-drug) contained 0.6–0.8 mg of MgAl-LDH and 0.08–0.09 mg of the ophthalmic drug (ketorolac) in 1.0 g of hydrogel. MgAl-drug-LDH nanoparticles were prepared with the hydrodynamic particle size of 40–200 nm. TEM images show that these nanoparticles are evenly dispersed in the hydrogel matrix. In vitro release tests of hydrogel-LDH-drug in pH 7.4 PBS solution at 32 °C indicate a sustained release profile of the loaded drug for 1 week. The drug release undergoes a rapid initial burst and then a monotonically decreasing rate up to 168 h. The initial burst release is determined by the film thickness and the polymerization conditions, but the following release rate is very similar, with the effective diffusion coefficient being nearly constant (3.0 × 10⁻¹² m²/s). The drug release from the films is mechanistically attributed to anionic exchange and the subsequent diffusion in the hydrogel matrix.     

Influence of thermal diffusion on the laser ablation of thin polymer films

The laser ablation of a photosensitive triazene polymer was investigated with a ns XeCl excimer laser over a broad range of thicknesses (10–400 nm). We found that the ablation threshold fluence increased dramatically with decreasing film thickness for films thinner than 50 nm. Ablation on substrates with different thermal properties (sapphire, fused silica, PMMA) was investigated as well, and a clear influence of the substrate material was obtained. A mathematical model combining thermal diffusion and absorption effects was used to explain the experimental data. The model is in good agreement with the experimental data and shows that heat diffusion into the substrate plays a crucial role for the ablation process of very thin films. PACS 52.38.Mf; 44.05.+e; 81.05.Lg     

A point source analytical model of inverse pulsed laser deposition

A simple analytical model for inverse pulsed laser deposition is proposed. In the model the motion of the evaporated material is assumed to emerge as from a point source located above the surface of evaporation at some distance. The obtained thickness profiles of inverse deposited films agree well with those calculated by the test particle Monte Carlo method. The proposed approach has been applied for analysis of experimental data on inverse pulsed laser deposition of graphite in nitrogen atmosphere with nanosecond pulses of laser fluences between 1 and 7 J/cm². The model describes well the thickness profiles and pressure dependence of film growth rate for inverse deposition.     

Study of temperature dependence and angular distribution of poly(9,9-dioctylfluorene) polymer films deposited by matrix-assisted pulsed laser evaporation (MAPLE)

Poly(9,9-dioctylfluorene) (PFO) polymer films were deposited by matrix-assisted pulsed laser evaporation (MAPLE) technique. The polymer was diluted (0.5 wt%) in tetrahydrofuran and, once cooled to liquid nitrogen temperature, it was irradiated with a KrF excimer laser. 10,000 laser pulses were used to deposit PFO films on 〈1 0 0〉 Si substrates at different temperatures (−16, 30, 50 and 70 °C). One PFO film was deposited with 16,000 laser pulses at a substrate temperature of 50 °C. The morphology, optical and structural properties of the films were investigated by SEM, AFM, PL and FTIR spectroscopy. SEM inspection showed different characteristic features on the film surface, like deflated balloons, droplets and entangled polymer filaments. The roughness of the films was, at least partially, controlled by substrate heating, which however had the effect to reduce the deposition rate. The increase of the laser pulse number modified the target composition and increased the surface roughness. The angular distribution of the material ejected from the target confirmed the forward ejection of the target material. PFO films presented negligible modification of the chemical structure respect to the bulk material.     

Thickness-dependent tunable characteristics of (Ba0.5Sr0.5)0.925K0.075TiO3 thin films prepared by pulsed laser deposition

The thickness-dependent dielectric properties and tunability of pulsed laser deposited (Ba_0.5Sr_0.5)_0.925K_0.075TiO₃ (BSKT) thin films with different thickness ranging from 80 to 300 nm has been investigated. Dielectric properties of the BSKT thin films are substantially improved as the BSKT film thickness increases, which can be explained by the model of a low-permittivity dead layer that is connected in series with the bulk region of the film. The estimated values of thickness and the average dielectric constant for the dead layer are 2.4 nm and 23.5, respectively, in a Pt/BSKT/Pt capacitor structure. The tunability and figure of merit increased with increasing film thickness, which are attributed to the change in lattice parameter and the dead layer effect.     

Strain relaxation of CdTe films growing on lattice-mismatched substrates

We have deposited CdTe films by laser-assisted epitaxy approach and investigated the influence of substrate and film thickness on the film properties. Grown on Si(001), GaAs(001), and quartz substrates; the CdTe films exhibit preferential orientation along the cubic CdTe(111) direction. When the films are thin (<500 nm), a blueshift of the band gap and splitting of valence bands were observed. These results are attributed to the existence of residual strains induced by mismatch of the film lattice constant with that of the substrate, and by their difference in thermal expansion coefficients. The bulk band-gap energy of 1.5 eV was achieved on the surface of thick CdTe films grown on Si(001) substrate, indicating that strain was almost completely relaxed in this case. Our results demonstrate that by a proper selection of substrate and film thickness it is possible to grow film semiconductors with band gap approaching those of bulk crystals.     

Electromechanical properties of lanthanum-doped lead hafnate titanate thin films for integrated piezoelectric MEMS applications

This paper focuses on the deposition and electromechanical characterization of lanthanum-doped lead hafnate titanate (PLHT) thin films as key material in piezoelectric microelectromechanical systems (pMEMS). PLHT (x/30/70) and PLHT(x/45/55) films with a thickness between 150 nm and 250 nm were deposited by chemical solution deposition (CSD). Thereby x varies between 0 and 10% La content. The electrical characterization shows that undoped (x=0) PLHT exhibit ferroelectric behavior similar to PZT of the same composition. La doping results in reduced ferroelectric properties and also affects the electromechanical properties. Measurements using a double beam laser interferometer yield a piezoelectric coefficient d ₃₃ of 60 pm/V, which stays constant with an increasing electric field. This leads to a linear displacement compared to undoped PLHT or conventional PZT films used for MEMS applications.     

Optimization of F-doped SnO2 electrodes for organic photovoltaic devices

Fluorine-doped tin oxide (FTO) thin films have been investigated as an alternative to indium tin oxide anodes in organic photovoltaic devices. The structural, electrical, and optical properties of the FTO films grown by pulsed laser deposition were studied as a function of oxygen deposition pressure. For 400 nm thick FTO films deposited at 300°C and 6.7 Pa of oxygen, an electrical resistivity of 5×10⁻⁴ Ω-cm, sheet resistance of 12.5 Ω/□, average transmittance of 87% in the visible range, and optical band gap of 4.25 eV were obtained. Organic photovoltaic (OPV) cells based on poly(3-hexylthiophene)/[6,6]-phenyl-C₆₁-butyric acid methyl ester bulk heterojunctions were prepared on FTO/glass electrodes and the device performance was investigated as a function of FTO film thickness. OPV cells fabricated on the optimum FTO anodes (∼300–600 nm thick) exhibited power conversion efficiencies of ∼3%, which is comparable to the same device made on commercial ITO/glass electrodes (3.4%).     

Transparence and electrical properties of ZnO-based multilayer electrode

Three-layered ZnO/Ag–Ti/ZnO structures were prepared using both the sol-gel technique and DC magnetron sputtering. This study focuses on the electrical and optical properties of the ZnO/Ag–Ti/ZnO multilayers with various thicknesses of the Ag–Ti layer. The ZnO thin film prepared by the sol–gel method was dried at 300°C for 3 minutes, and a fixed thickness of 20 nm was obtained. The thickness of the Ag–Ti thin film was controlled by varying the sputtering time. The Ag–Ti layer substantially reduced the electrical resistivity of the sol–gel-sprayed ZnO thin films. The sheet resistance of the Ag–Ti layer decreased dramatically and then became steady beyond a sputtering time of 60 s. The sputtering time of Ag–Ti thin film deposition was determined to be 60 s, taking into account the optical transmittance. Consequently, the transmittance of the ZnO/Ag–Ti/ZnO multilayer films was 71% at 550 nm and 60% at 350 nm. The sheet resistance was 4.2 Ω/sq.     

Surface nano/micro functionalization of PMMA thin films by 157 nm irradiation for sensing applications

Laser irradiation at 157 nm of polymethylmethacrylate (PMMA) thin films induces major variations of polymer film thicknesses from sorption (absorption/desorption) of methanol and ethanol analytes in the gas phase as much as 400%, in comparison to the film thickness variation of the non-irradiated areas. The structural changes of irradiated areas involve scission of polymeric chains, cross-linking and formation of new bonds. In addition, 157 nm induces surface and volume morphological changes in the nano/micro domain, with different shapes, depending on the irradiation conditions. The reversibility of the sorption processes suggests that the polymer swelling has its origin at the tendency of the system to increase its volume during sorption. The internal forces from sorption are higher than the weak dipole interactions between the polymer and the analytes and they are amplified following 157 nm irradiation. A simple qualitative model explains adequately the experimental results. 157 nm laser treatment forms the basis to engineer a novel class of polymer sensor arrays with enhanced detection efficiency of liquid/gas analytes.     

Shadowgraphy investigation of laser-induced forward transfer: Front side and back side ablation of the triazene polymer sacrificial layer

Thin films of a photodecomposible triazene polymer are used as sacrificial layer for the micro-deposition of sensitive materials by laser-induced forward transfer. To understand the ablation process of this sacrificial layer, the ultraviolet laser ablation of triazene films was investigated by time-resolved shadowgraphy. Irradiation from the film side shows a complete decomposition into gaseous fragments, while ablation through the substrate causes ejection of a solid flyer of polymer. The occurence of the flyer depends on the film thickness as well as on the applied fluence, and a compact flyer is obtaind when these two parameters are optimized.     

The effects of thermal annealing on the structure and the electrical transport properties of ultrathin gadolinia-doped ceria films grown by pulsed laser deposition

Ultrathin crystalline films of 10 mol% gadolinia-doped ceria (CGO10) are grown on MgO (100) substrates by pulsed laser deposition at a moderate temperature of 400°C. As-deposited CGO10 layers of approximately 4 nm, 14 nm, and 22 nm thickness consist of fine grains with dimensions ≤∼11 nm. The films show high density within the thickness probed in the X-ray reflectivity experiments. Thermally activated grain growth, density decrease, and film surface roughening, which may result in the formation of incoherent CGO10 islands by dewetting below a critical film thickness, are observed upon heat treatment at 400°C and 800°C. The effect of the grain coarsening on the electrical characteristics of the layers is investigated and discussed in the context of a variation of the number density of grain boundaries. The results are evaluated with regard to the use of ultrathin CGO10 films as seeding templates for the moderate temperature growth of thick solid electrolyte films with improved oxygen transport properties.     

Thickness dependent phase transformation of magnetron-sputtered Ni–Mn–Sn ferromagnetic shape memory alloy thin films

In this study, the influence of film thickness on the first-order martensite–austenite phase transformation of Ni–Mn–Sn ferromagnetic shape memory alloy thin films has been systematically investigated. Different thicknesses of the Ni–Mn–Sn films (from ~100 to 2,500 nm) were deposited by DC magnetron sputtering on Si (100) substrates at 550 °C. X-ray analysis reveals that all the films exhibit austenitic phase with the L2₁ cubic crystal structure at room temperature. The grain size and crystallization extent increase with the increase in film thickness, but the films with thickness above ~1,400 nm show structural deterioration due to the formation of MnSn₂ and Ni₃Sn₄ precipitates. The improvement in the crystallinity of the film with thickness is attributed to the decrease in film–substrate interfacial strain resulting in preferred oriented growth of the films. Temperature-dependent magnetization measurements as well as electrical measurements demonstrate the complete absence of phase transformation for the film of thickness of ~120 nm. For thickness greater than 400 nm, film exhibits the structural transformation, and it occurs at higher temperature with better hysteresis as film thickness is increased up to ~1,400 nm, after which degradation of phase transformation phenomenon is observed. This degradation is attributed to the disorders present in the films at higher thicknesses. Film with thickness ~1,400 nm possesses the highest magnetization with the smallest thermal hysteresis among all the films and therefore best suited for the actuators based on first-order structural phase transformation. Nanoindentation measurements reveal that the higher values of hardness and elastic modulus of about 5.5 and 215.0 GPa obtained in film of 1,014 nm thickness can considerably improve the ductility of ferromagnetic shape memory alloys (FSMA) and their applicability for MEMS applications. The exchange bias phenomenon is also found to be present in the films of thickness 1014, 1412, and 2022 nm exhibiting prominent martensitic transformation. Film of thickness 2,022 nm exhibits maximum exchange bias of ~50 Oe and higher exchange bias blocking temperature of 70 K as compared to other films.     

Critical role of laser wavelength on carbon films grown by PLD of graphite

The structure of thin films deposited by pulsed laser ablation (PLD) is strongly dependent on experimental conditions, like laser wavelength and fluence, substrate temperature and pressure. Depending on these parameters we obtained various kinds of carbon materials varying from dense, mainly tetrahedral amorphous carbon (ta-C), to less compact vertically oriented graphene nano-particles. Thin carbon films were grown by PLD on n-Si 〈100〉 substrates, at temperatures ranging from RT to 800°C, from a rotating graphite target operating in vacuum. The laser ablation of the graphite target was performed by a UV pulsed ArF excimer laser (λ=193 nm) and a pulsed Nd:YAG laser, operating in the near IR (λ=1064 nm). The film structure and texturing, characterised by X-ray diffraction analysis, performed at grazing incidence (GI-XRD), and the film density, evaluated by X-ray reflectivity measurements, are strongly affected both by laser wavelength and fluence and by substrate temperature. Micro-Raman and GI-XRD analysis established the progressive formation of aromatic clusters and cluster condensation into vertically oriented nano-sized graphene structures as a direct function of increasing laser wavelength and deposition temperature. The film density, negatively affected by substrate temperature and laser wavelength and fluence, in turn, results in a porous bulk configuration and a high macroscopic surface roughness as shown by SEM characterisation. These structural property modifications induce a relevant variation also on the emission properties of carbon nano-structures, as evidenced by field emission measurements. This work is dedicated to our friend Giorgio who passed away 20th August.     

Microstructure and dielectric properties of La2O3 doped amorphous SiO2 films as gate dielectric material

As a potential gate dielectric material, the La₂O₃ doped SiO₂ (LSO, the mole ratio is about 1:5) films were fabricated on n-Si (0 0 1) substrates by using pulsed laser deposition technique. By virtue of several measurements, the microstructure and electrical properties of the LSO films were characterized. The LSO films keep the amorphous state up to a high annealing temperature of 800 °C. From HRTEM and XPS results, these La atoms of the LSO films do not react with silicon substrate to form any La-compound at interfacial layer. However, these O atoms of the LSO films diffuse from the film toward the silicon substrate so as to form a SiO₂ interfacial layer. The thickness of SiO₂ layer is only about two atomic layers. A possible explanation for interfacial reaction has been proposed. The scanning electron microscope image shows the surface of the amorphous LSO film very flat. The LSO film shows a dielectric constant of 12.8 at 1 MHz. For the LSO film with thickness of 3 nm, a small equivalent oxide thickness of 1.2 nm is obtained. The leakage current density of the LSO film is 1.54 × 10⁻⁴ A/cm² at a gate bias voltage of 1 V.