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.     

An investigation into the effects of high laser fluence on hydroxyapatite/calcium phosphate films deposited by pulsed laser deposition

Pulsed laser deposited mixed hydroxyapatite (HA)/calcium phosphate thin films were prepared at room temperature using KrF laser source with different laser fluence varying between 2.4 J/cm² and 29.2 J/cm². Samples deposited at 2.4 J/cm² were partially amorphous and had rough surfaces with a lot of droplets while higher laser fluences showed higher level of crytallinity and lower roughness of surfaces of obtained samples. Higher laser fluences also decreased ratio Ca/P of as-deposited samples. X-ray photoelectron spectroscopy (XPS) revealed traces of carbonate groups in obtained samples, which were removed after thermal annealing. The decomposition of HA into TCP was observed to start at about 400 °C. The formation of new crystalline phase of HA was found after annealing as well. The cracks observed on surface of sample deposited at 29.2 J/cm² after annealing indicated that the HA/ calcium phosphate films deposited at higher laser energy densities were probably more densed.     

Patterning of PLZT and PSZT thin films by excimer laser

The patterning of lanthanum-doped lead zirconate titanate (PLZT) and strontium-doped lead zirconate titanate (PSZT) thin films has been examined using a 5-ns pulsed excimer laser. Both types of film were deposited by rf magnetron sputtering with in situ heating and a controlled cooling rate in order to obtain the perovskite-structured films. The depth of laser ablation in both PSZT and PLZT films showed a logarithmic dependence on fluence. The ablation rate of PLZT films was slightly higher than that of PSZT films over the range of fluence (10–150 J/cm²) and increased linearly with number of pulses. The threshold fluence required to initiate ablation was ∼ 1.25 J/cm² for PLZT and ∼ 1.87 J/cm² for PSZT films. Individual squares were patterned with areas ranging from 10×10 μm² up to 30×30 μm² using single and multiple pulses. The morphology of the etched surfaces comprised globules which had diameters of 200–250 nm in PLZT and 1400 nm in PSZT films. The diameter of the globules has been shown to increase with fluence until reaching an approximately constant size at ≤ 20 J/cm² in both types of film. The composition of the films following ablation has been compared using X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy. PACS 79.20.Ds; 82.80.Pv; 82.80.Ej     

Growth process of nanostructured silver films pulsed laser ablated in high-pressure inert gas

The growth process of silver thin films deposited by pulsed laser ablation in a controlled inert gas atmosphere was investigated. A pure silver target was ablated in Ar atmosphere, at pressures ranging between 10 and 100 Pa, higher than usually adopted for thin film deposition, at different numbers of laser shots. All of the other experimental conditions such as the laser (KrF, wavelength 248 nm), the fluence of 2.0 J cm⁻², the target to substrate distance of 35 mm, and the temperature (295 K) of the substrates were kept fixed. The morphological properties of the films were investigated by transmission and scanning electron microscopies (TEM, SEM). Film formation results from coalescence on the substrate of near-spherical silver clusters landing as isolated particles with size in the few nanometers range. From a visual inspection of TEM pictures of the films deposited under different conditions, well-separated stages of film growth are identified.     

Effect of laser fluence on the deposition and hardnessof boron carbide thin films

We deposited amorphous thin films of boron carbide by pulsed laser deposition using a B₄C target at room temperature. As the laser fluence increased from 1 to 3 J/cm², the number of 0.25–5 μm particulates embedded in the films decreased, and the B/C atomic ratio of the films increased from 1.8 to 3.2. The arrival of melt droplets, atoms, and small molecular species depending on laser fluence appeared to be involved in the film formation. In addition, with increasing fluence the nanoindentation hardness of the films increased from 14 to 32 GPa. We believe that the dominant factor in the observed increase in the films’ hardness is the arrival of highly energetic ions and atoms that results in the formation of denser films. Received: 23 March 2001 / Accepted: 1 July 2001 / Published online: 2 October 2001     

Pulsed laser deposition of PbTe films on glass substrates

PbTe thin films were prepared by pulsed laser deposition from a Nd:YAG laser (532 nm). The films were deposited on glass substrates. The influence of deposition temperature (80-160 °C), fluence (5-13 J/cm²) and nominal composition of the target on the chemical composition of the films was studied. It was found that the tellurium content of the film is strongly dependent on both the laser fluence and the deposition temperature. Highly textured stoichiometric films can be obtained with suitable conditions.     

Investigation on upconversion photoluminescence of Bi3TiNbO9:Er:Yb thin films

Bi₃TiNbO₉:Er³⁺:Yb³⁺ (BTNEY) thin films were fabricated on fused silica by pulsed laser deposition. It was demonstrated that different laser fluence and substrate temperature during growth of BTNEY upconversion photoluminescence (UC-PL) samples control the film’s grain size and hence influences the UC-PL properties. The average grain size of BTNEY thin films deposited on fused silica substrates with laser fluence 4, 5, 6, and 7 J/cm² are 30.8, 35.9, 40.6, and 43.4 nm, respectively. The 525 nm emission intensities increase with the deposition laser fluence and the emission intensities of BTNEY thin film deposited under 700 and 600 °C are almost 24 and 4 times, respectively, as strong as those of samples under 500 °C. The grain size of BTNEY thin film increases with the increasing temperature. UC-PL of BTNEY films is enhanced by increasing grain size of the films.     

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.     

Structural characterization of AlN films synthesized by pulsed laser deposition

We obtained AlN thin films by pulsed laser deposition (PLD) from a polycrystalline AlN target using a pulsed KrF* excimer laser source (248 nm, 25 ns, intensity of ∼4 × 10⁸ W/cm², repetition rate 3 Hz, 10 J/cm² laser fluence). The target-Si substrate distance was 5 cm. Films were grown either in vacuum (10⁻⁴ Pa residual pressure) or in nitrogen at a dynamic pressure of 0.1 and 10 Pa, using a total of 20,000 subsequent pulses. The films structure was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and spectral ellipsometry (SE). Our TEM and XRD studies showed a strong dependence of the film structure on the nitrogen content in the ambient gas. The films deposited in vacuum exhibited a high quality polycrystalline structure with a hexagonal phase. The crystallite growth proceeds along the c-axis, perpendicular to the substrate surface, resulting in a columnar and strongly textured structure. The films grown at low nitrogen pressure (0.1 Pa) were amorphous as seen by TEM and XRD, but SE data analysis revealed ∼1.7 vol.% crystallites embedded in the amorphous AlN matrix. Increasing the nitrogen pressure to 10 Pa promotes the formation of cubic (≤10 nm) crystallites as seen by TEM but their density was still low to be detected by XRD. SE data analysis confirmed the results obtained from the TEM and XRD observations.     

Effect of temperature on pulsed laser deposition of HgCdTe films

HgCdTe thin films have been deposited on Si(1 1 1) substrates at different substrate temperatures by pulsed laser deposition (PLD). An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the substrate temperature on the crystalline quality, surface morphology and composition of HgCdTe thin films were characterized by X-ray diffraction (XRD), selected area electron diffraction (SAED), atomic force microscopy (AFM) and energy dispersive X-ray spectroscopy (EDS). The results show that in our experimental conditions, the HgCdTe thin films deposited at 200 °C have the best quality. When the substrate temperature is over 250 °C, the HgCdTe film becomes thermodynamically unstable and the quality of the film is degraded.     

Pulsed laser ablation and deposition of silicon

A KrF laser was used to ablate a polycrystalline Si target for deposition of Si on MgO and GaAs substrates at room temperature. The deposition was performed in 10⁻⁸ mbar, with two types of laser beams: a homogeneous beam being imaged onto the target (2.9 J/cm²), and a non-homogeneous which is nearly focused (2 J/cm², 6.5 J/cm²). In both cases, the beam was scanned over an area of 1 cm². For the homogenous beam, we observed only a limited number of droplets (<0.1 μm). A high number of micron-sized (<5 μm) droplets were observed on the film by the higher fluence nonhomogeneous laser beam. Raman spectroscopy showed that the micron-sized droplets are crystalline while the film is amorphous. The generation of the large droplets is most likely related to the cone structures formed on the ablated target. We also compared cone formation on a polycrystalline Si target and a single crystalline Si wafer, using multiple laser pulses onto a single spot.     

High fluence deposition of polyethylene glycol films at 1064 nm by matrix assisted pulsed laser evaporation (MAPLE)

Matrix assisted pulsed laser evaporation (MAPLE) has been applied for deposition of thin polyethylene glycol (PEG) films with infrared laser light at 1064 nm. We have irradiated frozen targets (of 1 wt.% PEG dissolved in water) and measured the deposition rate in situ with a quartz crystal microbalance. The laser fluence needed to produce PEG films turned out to be unexpectedly high with a threshold of 9 J/cm², and the deposition rate was much lower than that with laser light at 355 nm. Results from matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis demonstrate that the chemistry, molecular weight and polydispersity of the PEG films were identical to the starting material. Studies of the film surface with scanning electron microscopy (SEM) indicate that the Si-substrate is covered by a relatively homogenous PEG film with few bare spots.     

Preparation of super-hard coatings by pulsed laser deposition

Amorphous diamond-like carbon (DLC) films and nanocrystalline cubic boron nitride (c-BN) films were prepared by pulsed laser deposition. DLC films with 80 to 85% sp³ bonds prepared at a laser fluence above 6 J/cm² and a substrate temperature below 100 °C show high compressive stresses in the range of 8 to 10 GPa. Those stresses can be completely removed by means of pulsed laser annealing, allowing the preparation of DLC films with several-micrometre thickness. c-BN films were prepared with additional ion-beam bombardment at a substrate temperature of 250 °C. The properties of DLC and c-BN films deposited at high growth rates up to 100 nm/min are presented . PACS 81.15.Fg; 68.60.Bs: 62.40.+i     

Effects of oxygen pressures on pulsed laser deposition of ZnO films

Zinc oxide (ZnO) thin films on Si (1 1 1) substrates were deposited by pulsed laser ablation of ZnO target at different oxygen pressures. A pulsed Nd:YAG laser with wavelength of 1064 nm was used as laser source. The deposited thin films have been characterized by X-ray diffraction (XRD), Atomic force microscopy (AFM), and Raman spectroscopy. XRD measurements indicate that the ZnO thin films deposited at the oxygen pressure of 1.3 Pa have the best crystalline quality. AFM results show that the surface roughness of ZnO film increases with the increase of oxygen pressure. The Raman results indicate that oxygen ambient plays an important role in removing defects due to excess zinc.     

Matrix-assisted pulsed laser evaporation of polyfluorene thin films

Poly(9,9-dioctylfluorene) (PF8) thin films have been deposited by matrix-assisted pulsed laser evaporation (MAPLE) using a KrF excimer laser. The influence of the laser fluence (50-500 mJ/cm²) and the nature of the solvent (chloroform, toluene, tetrahydrofuran) on the films properties have been studied. The chemical composition of the deposited films was investigated by Fourier transform infrared (FTIR) spectroscopy and compared with the one of spin coated films. To investigate the effect of the deposition parameters on the optical properties of the films, photoluminescence (PL) measurements were performed. Poor structural and optical properties were observed for films deposited starting from chloroform solutions. When using toluene as solvent, the spectra characteristics improved with increasing laser fluence, while wide PL spectra were observed. The characteristic emission bands of the PF8 polymer were nicely detected for films deposited starting from a tetrahydrofuran (THF) solution. Moreover, in this last case, the PF8 structure is preserved at high laser fluences, too.     

Radiation effects and pulsed laser deposition of titanium by Nd:Yag laser

A study of Ti laser irradiation and thin film deposition produced by an Nd:Yag pulsed laser is presented. The laser pulse, 9?ns width, has a power density of the order of 10¹⁰?W/cm². The titanium etching rate is of the order of 1?µg/pulse, it increases with the laser fluence and shows a threshold value at about 30?J/cm² laser fluence. The angular distribution of ejected atoms (neutrals and ions) is peaked along the normal of the target surface. At high fluence, the fractional ionization of the plasma produced by the laser is of the order of 10%. Time-of-flight measurements demonstrate that the titanium ions, at high laser fluence, may reach kinetic energies of about 1?keV. Obtained results can be employed to produce energetic titanium ions, to produce coverage of thin films of titanium and to realize high adherent titanium-substrate interfaces. The obtained results can be employed to produce energetic titanium ions, to produce a coverage of thin titanium films on polymers, and to realize highly adherent titanium–substrate interfaces.     

Pulsed laser treatment of gold and black gold thin films fabricated by thermal evaporation

The effect of pulsed laser treatment of metal, and metal blacks, was studied. Gold and black gold thin films were fabricated by thermal evaporation of gold in a vacuum and nitrogen atmosphere respectively. Black gold films were grown in a nitrogen atmosphere at pressures of 200 Pa and 300 Pa. UV pulsed laser radiation (λ = 266 nm, τ = 4 ns), with fluence ranging from 1 mJ·cm⁻² to 250 mJ·cm⁻² was used for the film treatment in a vacuum and nitrogen atmosphere. The nitrogen pressure was varied up to 100 kPa. Surface structure modifications were analyzed by optical microscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Energy dispersive X-ray spectroscopy (EDX) was used for chemical characterization of the samples. A significant dependence of the film optical and structural properties on laser treatment conditions (laser fluence, ambient pressure and number of applied pulses) was found. The threshold for observable damage and initiation of changes of morphology for gold and black gold surfaces was determined. Distinct modifications were observed for fluences greater than 106 mJ·cm⁻² and 3.5 mJ·cm⁻² for the gold and black gold films respectively. Absorbtivity of the black gold film is found to decrease with an increase in the number of laser pulses. Microstructural and nanostructural modifications after laser treatment of the black gold film were observed. EDX analysis revealed that no impurities were introduced into the samples during both the deposition and laser treatment.      

Matrix assisted pulsed laser deposition of light emitting polymer thin films

Matrix assisted laser processing allows for the deposition of functional and fragile materials with a minimum of breakdown and decomposition. In this communication we report on light emitting thin films of ruthenium tris(bipyridine)-centered star-shaped poly(methyl methacrylate), Ru(bpyPMMA₂)₃(PF₆)₂, grown by matrix assisted pulsed laser deposition. A pulsed excimer laser (KrF) operating at 248 nm was used for all experiments. Due to the absorption at 248 nm and the solubility characteristics of [Ru(bpyPMMA₂)₃](PF₆)₂, dimethoxy-ethane (DME) was used as a solvent [1]. Dilute solutions (2 wt.%) of [Ru(bpyPMMA₂)₃](PF₆)₂ and DME were flash frozen in liquid nitrogen producing a solid target. Thin films ranging from 20 to 100 nm were grown on Si in an Ar atmosphere at 200 mTorr at a laser fluence of 0.04 J/cm². The deposited materials were characterized by proton nuclear magnetic resonance (¹H NMR) and gel permeation chromatography (GPC) equipped with refractive index (RI), and ultraviolet/visible (UV/vis) detection. PACS 81.15.Fg; 79.20.Ds; 78.66.Qn; 42.70.Jk     

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.     

Fabrication and characterization of freestanding ultrathin diamond-like carbon targets for high-intensity laser applications

Here, we report the fabrication of diamond-like carbon (DLC) thin films using pulsed laser deposition (PLD). PLD is a well-established technique for deposition of high-quality DLC thin films. Carbon tape target was ablated using a KrF (248 nm, 25 ns, 20 Hz) excimer laser to deposit DLC films on soap-coated substrates. A laser fluence between 8.5 and 14 J/cm² and a target to substrate distance of 10 cm was used. These films were then released from substrates to obtain freestanding DLC thin foils. Foil thicknesses from 20 to 200 nm were deposited using this technique to obtain freestanding targets of up to 1-inch square area. Typically, 100-nm-thick freestanding DLC films were characterized using different techniques such as AFM, XPS, and nano-indentation. AFM was used to obtain the film surface roughness of 9 nm rms of the released film. XPS was utilized to obtain 74 % sp², 23 % sp³, and 3 % C–O bond components. Nano-indentation was used to characterize the film hardness of 10 GPa and Young’s modulus of 110 GPa. Damage threshold properties of the DLC foils were studied (1,064 nm, 6 ns) and found to be 7 × 10¹⁰ W/cm² peak intensity for our best ultrathin DLC foils.