Solvent-related effects in MAPLE mechanism

To study the role of the solvent and of the laser fluence in the matrix-assisted pulsed laser evaporation (MAPLE) process, we used a soft polymer (polydimethylsiloxane—PDMS) as “sensing surface” and toluene as solvent. Thin films of the PDMS polymer were placed in the position of the growing film, while a frozen toluene target was irradiated with an ArF laser at the conventional fluences used in MAPLE depositions (60–250 mJ/cm²). Apart the absence of solute, the MAPLE typical experimental conditions for the deposition of thin organic layers were tested. The effects on the PDMS films of the toluene target ablation, at different fluences, were studied using atomic force microscopy and contact angles measurements. The results were compared with the effects produced on similar PDMS films by four different treatments (exposure to a drop of the solvent, to saturated toluene vapors and to plasma sources of two different powers). From this comparative study, it appears that depending on the MAPLE experimental conditions: (1) the MAPLE process may be “semidry” rather than purely dry (namely the solvent is likely to be present in the deposition environment near the growing film), (2) the solvent, if sufficiently volatile, is in form of vapor molecules (neutral, ionized and probably dissociated) rather than in liquid phase near the substrate and (3) at relatively high laser fluences (>150 mJ/cm²), the formation of an intense plasma plume results which can damage/affect a soft substrate as well as a growing polymer film.     

Impact of the lasr wavelength and fluence on the ablation rate of aluminium

The dependence of the ablation rate of aluminium on the fluence of nanosecond laser pulses with wavelengths of 532 nm and respectively 1064 nm is investigated in atmospheric air. The fluence of the pulses is varied by changing the diameter of the irradiated area at the target surface, and the wavelength is varied by using the fundamental and the second harmonic of a Q-switched Nd-YAG laser system. The results indicate an approximately logarithmic increase of the ablation rate with the fluence for ablation rates smaller than ∼6 μm/pulse at 532 nm, and 0.3 μm/pulse at 1064 nm wavelength. The significantly smaller ablation rate at 1064 nm is due to the small optical absorptivity, the strong oxidation of the aluminium target, and to the strong attenuation of the pulses into the plasma plume at this wavelength. A jump of the ablation rate is observed at the fluence threshold value, which is ∼50 J/cm² for the second harmonic, and ∼15 J/cm² for the fundamental pulses. Further increasing the fluence leads to a steep increase of the ablation rate at both wavelengths, the increase of the ablation rate being approximately exponential in the case of visible pulses. The jump of the ablation rate at the threshold fluence value is due to the transition from a normal vaporization regime to a phase explosion regime, and to the change of the dimensionality of the hydrodynamics of the plasma-plume.      

Effects of phase explosion in pulsed laser deposition of nickel thin film and sub-micron droplets

Nickel (Ni) thin films were deposited on glass substrates in high vacuum and at room temperature with third-harmonic or 355-nm output from a nanosecond Nd:YAG laser. At low laser fluence of 1 J/cm², the deposition rate was about 0.0016 nm/shot which increased linearly until 4 J/cm². Above 4 J/cm², the onset of phase explosion in the ablation abruptly increased the optical emission intensity from laser-produced Ni plume as well as thin-film deposition rate by about 6×. The phase explosion also shifted the size distribution and number density of Ni droplets on its thin-film surface. On the other hand, the surface structures of the ablated Ni targets were compared between the scan-mode and the fixed-mode ablations, which may suggest that droplets observed on the thin-film surface were caused by direct laser-induced splashing of molten Ni rather than vapour-to-cluster condensation during the plume propagation.     

Resonant infrared laser deposition of polymer-nanocomposite materials for optoelectronic applications

Polymers find a number of potentially useful applications in optoelectronic devices. These include both active layers, such as light-emitting polymers and hole-transport layers, and passive layers, such as polymer barrier coatings and light-management films. This paper reports the experimental results for polymer films deposited by resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) and resonant infrared pulsed laser deposition (RIR-PLD) for commercial optoelectronic device applications. In particular, light-management films, such as anti-reflection coatings, require refractive-index engineering of a material. However, refractive indices of polymers fall within a relatively narrow range, leading to major efforts to develop both low- and high-refractive-index polymers. Polymer nanocomposites can expand the range of refractive indices by incorporating low- or high-refractive-index nanoscale materials. RIR-MAPLE is an excellent technique for depositing polymer-nanocomposite films in multilayer structures, which are essential to light-management coatings. In this paper, we report our efforts to engineer the refractive index of a barrier polymer by combining RIR-MAPLE of nanomaterials (for example, high refractive-index TiO₂ nanoparticles) and RIR-PLD of host polymer. In addition, we report on the properties of organic and polymer films deposited by RIR-MAPLE and/or RIR-PLD, such as Alq₃ [tris(8-hydroxyquinoline) aluminum] and PEDOT:PSS [poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate)]. Finally, the challenges and potential for commercializing RIR-MAPLE/PLD, such as industrial scale-up issues, are discussed.     

RIR-MAPLE deposition of conjugated polymers for application to optoelectronic devices

Resonant-infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) is a promising deposition technology for the fabrication of conjugated polymer-based optoelectronic devices for two primary reasons: (i) the ability to control film morphology, and (ii) the ability to deposit multi-layered heterostructures. This article reviews a variation of RIR-MAPLE that uses emulsified targets of organic solvents and water such that the incident laser wavelength (Er:YAG at 2.9 μm) is resonant with hydroxyl (O–H) bonds in the host matrix, which are absent from the guest material. The novelty of the approach lies in the fact that while most polymers of interest and many compatible solvents do not resonantly absorb the laser energy at 2.9 μm, the emulsion with water enables high-quality, thin-film deposition with minimal photochemical and structural degradation for almost any polymer of interest. In addition, the advantages of emulsion-based RIR-MAPLE for conjugated polymer-based optoelectronic devices are demonstrated by two important studies. First, conjugated polymer films deposited by RIR-MAPLE are shown to have higher hole drift mobilities than films deposited using traditional drop-casting and spin-casting techniques. Second, the unique capability of RIR-MAPLE to enable conjugated polymer-based optical heterostructures is demonstrated by the fabrication and characterization of a multi-layer, polymer distributed Bragg reflector.     

Applications of the matrix-assisted pulsed laser evaporation method for the deposition of organic,biological and nanoparticle thin films: a review

The matrix-assisted pulsed laser evaporation (MAPLE) technique offers an efficient mechanism to transfer soft materials from the condensed to the vapor phase, preserving the versatility, ease of use and high deposition rates of the pulsed laser deposition (PLD) technique. The materials of interest (polymers, biological cells, proteins, …) are diluted in a volatile solvent. Then the solution is frozen and irradiated with a pulsed laser beam. Here, important results of MAPLE deposition of polymer, biomaterials and nanoparticle films are summarized. Finally, the MAPLE mechanism is discussed. A review of experimental and theoretical works points out that the simple model of individual molecule evaporation must be abandoned. Solute concentration, solubility, evaporation temperature of solvents, laser pulse power density and laser penetration depth emerge as important parameters to explain the morphology of the MAPLE-deposited films.     

Interface kinetics during pulsed laser ablation

This work investigates evaporation kinetics -- the relation between the surface temperature and pressure during excimer laser ablation. Nickel targets are ablated by excimer laser pulses in a laser fluence range between 1 and 6 J/cm², with the upper limit exceeding the threshold of phase explosion (5 J/cm²). The surface pressure is determined with a polyvinylidene fluoride (PVDF) piezoelectric transducer. When phase explosion occurs, the surface temperature is known to be near the thermodynamic critical temperature, therefore, by measuring the surface pressure, the surface temperature-pressure relation is determined at the threshold fluence of phase explosion. The surface temperature and the threshold fluence of phase explosion are also estimated from the measured velocity of the vapor plume and gas dynamics calculations. It is shown that, during excimer laser ablation, the temperature and pressure relation deviates significantly from the equilibrium kinetic relation.     

Strong emission of particulates towards the incident beam direction in pulsed-laser ablation experiments

Theoretical predictions suggested that particulates (large clusters and droplets) in pulsed-laser ablation deposition (PLD) move towards the surface normal and constitute a small fraction of the total plume mass. Contrary to expectations, here we report that, independently of the laser beam direction, large clusters are ejected towards the laser direction of incidence, which generally differs from the surface normal. Moreover, fragments and droplets constitute the major fraction of the ablated mass. Cross-sectional SEM investigations performed on the Si targets show that the direction of growth of the columns follows the laser beam direction. These observations have been explained by the change of the microscopic ablation mechanism from monomer evaporation at low local laser fluences to phase explosion at higher local fluences.     

Pulsed laser deposition vs. matrix assisted pulsed laser evaporation for growth of biodegradable polymer thin films

Thin films of poly (lactide-co-glycolide) (PLGA), a biodegradable polymer, were deposited on Si wafers by both conventional pulsed laser deposition (PLD) and matrix assisted pulsed laser evaporation (MAPLE) using chloroform (CHCl₃) as a matrix solvent. This research represents an initial study to investigate the deposition characteristics of each technique at comparable conditions to gain insight into the transport and degradation mechanisms of each approach. The deposited materials were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H NMR), and gel permeation chromatography (GPC) with refractive index (RI) detection. While FTIR and NMR results do not show a measurable departure from the native, in sharp contrast GPC results show a significant change (up to 95%) in molecular weight for both deposition methods. This result makes it clear that it is possible to overlook substantial degradation when incomplete chemical analysis is conducted.Optical transmission measurements of the starting MAPLE targets yielded laser penetration depths on the order of 0.362 cm and 0.209 cm for pure CHCl₃ and 1 wt. % PLGA in CHCl₃, respectively. Straightforward application of the Beer–Lambert law for laser energy deposition predicts a negligible temperature rise of less than 1 K at the target surface, which is in clear contradiction with ablation rates of 1.85 μm/pulse experimentally measured for polymer loaded samples. With an ablation process of this magnitude, the material ejection is likely due to contributions of nonlinear or non-homogeneous laser light absorption rather than evaporation. Severe non-uniformity of the final surface morphologies of the MAPLE films, similar to solvent wicking artifacts found in spin casting supports the spallation scenario in MAPLE. PACS 81.15.Fg; 79.20.Ds; 78.66.Qn; 42.70Jk     

Studying condensed phase formed upon interaction between a high-power laser pulse and crystal aluminum oxide

Forms of the condensed phase created under the action of a high-power CO₂ laser pulse (power, 4 J/pulse; λ = 10.6 μm; pulse duration, 1.5 μs) on optical sapphire (Al₂O₃) solid targets are investigated. The ablation products emitted from the laser crater and the particles formed in the space above the surface of the target are collected using witness samples oriented in a predetermined manner with respect to the laser crater. Forms of the condensed phase are studied via electron microscopy and atomic force microscopy. Conclusions are drawn as to the mechanisms of formation of particles with different shapes and structures, including Al₂O₃ vacuum hollow microspheres (hollow bubbles).     

Identification of non-thermal and thermal processes in femtosecond laser-ablated aluminum

Non-thermal and thermal processes due to femtosecond laser ablation of aluminum (Al) at low, moderate, and high-fluence regimes are identified by Atomic Force Microscope (AFM) surface topography investigations. For this purpose, surface modifications of Al by employing 25 fs Ti: sapphire laser pulses at the central wavelength of 800 nm have been performed to explore different nano- and microscale features such as hillocks, bumps, pores, and craters. The mechanism for the formation of these diverse kinds of structures is discussed in the scenario of three ablation regimes. Ultrafast electronic and non-thermal processes are dominant in the lower fluence regime, whereas slow thermal processes are dominant at the higher fluence regime. Therefore, by starting from the ablation threshold three different fluence regimes have been chosen: a lower fluence regime (0.06–0.5 J cm^?2 single-shot irradiation under ultrahigh vacuum condition and 0.25–2.5 J cm^?2 single-shot irradiation in ambient condition), a moderate-fluence regime (0.25–1.5 J cm^?2 multiple-shot irradiation), and a high-fluence regime 2.5–3.5 J cm^?2 multiple-shot irradiation. For the lower fluence (gentle ablation) regime, around the ablation threshold, the unique appearance of individual, localized Nano hillocks typically a few nanometers in height and less than 100 nm in diameter are identified. These Nano hillock-like features can be regarded as a nonthermal, electronically induced phase transition process due to localized energy deposition as a result of Coulomb explosion or field ion emission by surface optical rectification. At a moderate-fluence regime, slightly higher than ablation threshold multiple-pulse irradiation produces bump-formation and is attributed to ultrafast melting (plasma formation). The high-fluence regime results in greater rates of material removal with highly disturbed and chaotic surface of Al with an appearance of larger protrusions at laser fluence well above the ablation threshold. These nonsymmetrical shapes due to inhomogeneous nucleation, cluster formation, and resolidification of a metallic surface after melting are attributable to slow thermal processes (ps time scale).     

Double-peak droplet mass distribution observed during sub-ps laser ablation of Si targets

The angular distribution of the ablated material was studied during sub-ps Si laser ablation deposition using a special hemicylindrical substrate holder and different laser fluences ranging between 0.4 and 1.7 J/cm². Scanning electron microscopy analysis of the deposited films showed that, independent of the fluence, the distribution of the deposited droplets presents two maxima. The first maximum corresponds to the average plume deflection angle value due to the local surface orientation produced by the preferential etching process. The second maximum is observed approximately at 45° with respect to the normal of the target surface, and is related to the phase explosion products that expand along the incident laser beam direction. The investigation of the twofold distribution of the sub-μm size deposited droplets is important to improve the quality of the deposited coatings. PACS 81.15.Fg; 68.55.Jk; 79.20.Ds     

TEA CO2 laser ablation of coronary artery

Summary One of the prerequisites for successful laser angioplasty is the ablation of the atherosclerotic lesions, without thermal or shock-wave damage of the healthy tissue. In this study was evaluated the effectiveness of a TEA CO₂ laser, emitting pulses of the lower TEM mode, 100 ns duration, at a repetition rate of 2.4 Hz, for the ablation of cardiovascular tissue. Normal and atherosclerotic human arteries (post mortem) were irradiated for a range of fluences up to 10J pulse⁻¹ cm⁻². After irradiation, the samples were prepared for histologic examination. The results showed that controlled ablation of normal and atherosclerotic coronary artery can be accomplished with the TEA CO₂ laser, with minimal thermal damage.     

Characterization of polymer thin films obtained by pulsed laser deposition

The development of laser techniques for the deposition of polymer and biomaterial thin films on solid surfaces in a controlled manner has attracted great attention during the last few years. Here we report the deposition of thin polymer films, namely Polyepichlorhydrin by pulsed laser deposition. Polyepichlorhydrin polymer was deposited on flat substrate (i.e. silicon) using an NdYAG laser (266 nm, 5 ns pulse duration and 10 Hz repetition rate).The obtained thin films have been characterized by atomic force microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy and spectroscopic ellipsometry.It was found that for laser fluences up to 1.5 J/cm² the chemical structure of the deposited polyepichlorhydrin polymer thin layers resembles to the native polymer, whilst by increasing the laser fluence above 1.5 J/cm² the polyepichlorohydrin films present deviations from the bulk polymer.Morphological investigations (atomic force microscopy and scanning electron microscopy) reveal continuous polyepichlorhydrin thin films for a relatively narrow range of fluences (1-1.5 J/cm²).The wavelength dependence of the refractive index and extinction coefficient was determined by ellipsometry studies which lead to new insights about the material.The obtained results indicate that pulsed laser deposition method is potentially useful for the fabrication of polymer thin films to be used in applications including electronics, microsensor or bioengineering industries.     

Latex film formation induced by solvent vapor: A photon transmission study

A photon transmission method was used to study latex film formation induced by organic solvent vapor. Various films with the same latex content were prepared separately from the poly(methyl methacrylate) (PMMA) particles and exposed to vapor of chloroform-heptane mixture in various percentage volumes of chloroform. Transmitted photon intensities, I _tr, from these films increased in time under vapor exposure. The increase in I _tr is attributed to the increase in 'crossing density' at the junction surface. The Prager-Tirrell model was employed to obtained back-and-forth frequency, ν of the reptating polymer chain during film formation induced by solvent vapor. ν values were obtained and found to be strongly correlated with the percent of chloroform in the solvent mixture. At high and low chloroform contents, polymer chains diffuse according to t ^1/2 and t ^1/4 laws respectively.     

高强度二倍频激光辐照银薄膜靶的烧蚀和X光辐射实验研究

激光聚变物理实验中,背光透视照相是靶丸内爆动力学过程观测的重要方法. Ag是一种重要的背光材料, 激光辐照产生的等离子体可以产生强L线辐射, 研究其烧蚀和辐射特性, 对提高内爆靶丸背光透视照相的图像质量具有十分重要的意义.在神光II装置上, 采用第九路输出的2 ns, ～ 5× 10¹⁴ W/cm², 526.5 nm激光均匀辐照Ag薄膜靶, 实验研究了其烧蚀特性, 获得了银薄膜靶在激光烧蚀驱动下的飞行轨迹和飞行速度的数据. 实验结果与一维辐射流体力学模拟结果相符. 火箭模型对实验数据进行拟合, 得到了Ag材料的质量烧蚀速率和烧蚀压的数据. 采用平面晶体谱仪和X射线二极管探测器阵列观测等离子体的辐射特性, 获得了Ag等离子体辐射光谱和L线转换效率, 实验结果对激光聚变内爆靶丸背光照相的实验设计具有重要的参考价值.     

Resonant infrared matrix-assisted pulsed laser evaporation of TiO2 nanoparticle films

The successful development of flexible, high performance thin films that are competitive with silicon-based technology will likely require fabricating films of hybrid materials that incorporate nanomaterials, glasses, ceramics, polymers, and thin films. Resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) is an ideal method for depositing organic materials and nanoparticles with minimal photochemical or photothermal damage to the deposited material. Furthermore, there are many nonhazardous solvents containing chemical functional groups with infrared absorption bands that are accessible using IR lasers. We report here results of recent work in which RIR-MAPLE has been employed successfully to deposit thin films of TiO₂ nanoparticles on Si substrates. Using an Er:YAG laser (λ=2.94 μm), we investigated a variety of MAPLE matrices containing –OH moieties, including water and all four isomers of butyl alcohol. The alcohol isomers are shown to provide effective and relatively nontoxic solvents for use in the RIR-MAPLE process. In addition, we examine the effects of varying concentration and laser fluence on film roughness and surface coverage.     

Dynamics of radiation scattering by particles of condensed phase in quasicontinuous laser irradiation of metals

Radiation scattering by particles of condensed phase in an ablation plasma plume has been experimentally studied during quasicontinuous laser irradiation (λ = 1.06 μm, q = 0.1–9 MW/cm², τ ∼ 1.5 msec) of duraluminum D16T, aluminum A99, and bismuth. The particle size distribution and the nature of their dispersal during irradiation was studied in scattered light (λ = 0.69 μm) from individual particles that could be visually observed on photographs. It was found that under the pressure developed in the plume, large particles ejected from the irradiated zone can move backward and return to the target (D16T). The plume (Bi) becomes brighter due to ablation of particles in the path of the laser beam. The directional scattering coefficients for scattering from the local zone on the axis of the plume, measured during the laser pulse, were used to study the relationship between the dynamics of entry of condensed phase into the plume, shielding of the target by the particles, and brightening of the plume under the action of the incident laser radiation. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 210–219, March–April, 2006.     

Pulsed laser ablation of solids: transition from normal vaporization to phase explosion

We present experimental data on mass removal during 1064-nm pulsed laser ablation of graphite, niobium and YBa₂Cu₃O_7-δ superconductor. Evidence for the transition from normal vaporization to phase explosion has been obtained for these materials, showing a dramatic increase in the ablation rate at the threshold fluences of 22, 15 and 17.5 J/cm², respectively. A numerical model is used to evaluate the ablation rate and temperature distribution within the targets under near-threshold ablation conditions. The results are analyzed from the viewpoint of the vaporized matter approaching the critical point with increasing laser fluence. A possible means of the estimating the thermodynamic critical temperature from the data for nanosecond laser ablation is discussed. It is suggested that the critical temperature of refractory metals is higher than that estimated with the traditional methods due to plasma effects. An analogy with the boiling crisis (the transition from nucleate to film boiling) is drawn to explain the formation of ablation craters with spallated edges. Received: 18 May 2000 / Accepted: 14 July 2000 / Published online: 22 November 2000     

Comparison of the laser ablation process on Zn and Ti using pulsed digital holographic interferometry

Pulsed digital holographic interferometry has been used to compare the laser ablation process of a Q-switched Nd-YAG laser pulse (wavelength 1064 nm, pulse duration 12 ns) on two different metals (Zn and Ti) under atmospheric air pressure. Digital holograms were recorded for different time delays using collimated laser light (532 nm) passed through the volume along the target. Numerical data of the integrated refractive index field were calculated and presented as phase maps. Intensity maps were calculated from the recorded digital holograms and are used to calculate the attenuation of the probing laser beam by the ablated plume. The different structures of the plume, namely streaks normal to the surface for Zn in contrast to absorbing regions for Ti, indicates that different mechanisms of laser ablation could happen for different metals for the same laser settings and surrounding gas. At a laser fluence of 5 J/cm², phase explosion appears to be the ablation mechanism in case of Zn, while for Ti normal vaporization seems to be the dominant mechanism.