Synthesis and characterization of PLZT thin films obtained by pulsed laser deposition

Thin films of Pb_1-xLa_x(Zr_0.65Ti_0.35)_1-x/4O₃ with x=0.09 (PLZT 9/65/35) have been grown by pulsed laser deposition (PLD) and by PLD assisted by radio frequency (RF) discharge in oxygen which increases the plasma reactivity and reduces the oxygen vacancies in films and at the film-bottom electrode interface. Significant compositional, structural and dielectric differences have been found among samples grown in the same deposition conditions excepting for RF power. Films grown by RF-assisted PLD have less pyrochlore and are more oriented. For these films dielectric permittivity vs. temperature variation was typical of relaxor ferroelectrics and the temperature of the dielectric maximum was close to that obtained in bulk, but the permittivity value was much lower. This was attributed mainly to the influence of a low permittivity interface layer and to the detrimental effect of pyrochlore phase, still present in small quantities even in the films obtained by RF-PLD. The dielectric behavior of films grown without RF discharge was very different: no dielectric anomaly was observed, only a step increase above 180 °C. Moreover much higher dielectric loss was measured for these films. PACS 84.15.Fg; 77.84.-s; 77.22.Gm     

Vibrational spectroscopy of SiC thin films deposited by excimer laser ablation

A large number of thin SiC films, prepared at different conditions by KrF excimer laser ablation of solid SiC targets and deposition onto Si substrates (some onto quartz glass (QG) and yttrium-stabilized zirconia (YSZ)) were characterized by infrared and Raman spectroscopy. The films consisted of nano- and microcrystalline SiC and contained nanocrystalline carbon in the case of QG or YSZ substrates. Raman spectra of nanocrystalline SiC (grains <30 nm) reflect the phonon density-of-state function of SiC by broad scattering effects at 220–600 and 650–950 cm⁻¹. Medium-size crystallites are represented by a relatively narrow asymmetric band at 790 cm⁻¹ and crystallites >200 nm by an additional asymmetric band at 960 cm⁻¹. Small satellite bands at 760 and 940 cm⁻¹, attributed to SiC surface layers, were resolved in some well-ordered samples. Optical modelling was needed to interpret the IR spectra. SiC films could be represented by an effective medium model containing a SiC host phase and embedded particles with free charge carriers. The crystalline order of SiC films can be estimated from the parameters of the SiC oscillators. Received: 5 October 1998 / Accepted: 8 January 1999 / Published online: 5 May 1999     

Dynamics of excimer laser ablation of thin tungsten films monitored by ultrafast photography

The time course of laser light induced transport of tungsten films from a glass support is followed by ultrafast photography using delayed dye laser pulses. The photographs provide unambiguous evidence that the material transport in the 40–200 mJ/cm² intensity domain takes place via removal of solid pieces from the film material. These results are consistent with heat flow calculations which predict the overall melting of the metal layer above 380 mJ/cm². The series of photographs presented give detailed insight into the melting process and have revealed an unexpected in-flight phase separation of solid fracture pieces and molten droplets throughout the 200–900 mJ/cm² domain. The faster propagating molten droplets form a condensed halo in front of the solid pieces, thereby providing an efficient shield between the processing laser light and the solid phase.     

Characterization of polycrystalline Ge thin films fabricated by short-pulse XeF excimer laser crystallization

XeF excimer laser-induced melting and recrystallization dynamics of amorphous germanium are investigated using time-resolved optical reflection and transmission measurements with a nanosecond time resolution, field-emission scanning electron microscopy, and micro-Raman spectroscopy. It is found that the disc-shaped grain with a diameter of approximately 0.8 μm is located in the complete melting regime with a melt phase duration of approximately 141–200 ns. The significant change of transmissivity is a key phenomenon revealing the excessive excimer laser fluence during excimer laser crystallization by in-situ optical measurements. Differences between the melting and recrystallization phenomenon for Si and Ge thin films are also discussed.     

Pulsed laser deposition process of PLZT thin films using an infrared Nd:YAG laser

Pulsed laser depositions of PLZT thin films were performed using an Nd:YAG (1064 nm) laser. The growths took place in vacuum or in an oxygen background. Room temperature and 500 °C were the used substrate temperatures. The X-ray diffraction analysis revealed a preferential crystallographic orientation in the films grown at room temperature in vacuum. Such result is discussed. The velocity distribution functions of the species in the plasma plume were obtained from a time of flight study using optical emission spectroscopy. The maximums of these distributions functions fall around 10⁶ cm/s, equivalent to an energy range of 18-344 eV. Ionic species of heavy elements (like lead) achieved higher velocities than other lighter species. This result is linked to the creation of an accelerating spatial charge and to the thermal nature of the target material extraction that allows some elements to be released first than others. Chemical state variations of the elements present in the films were analyzed. Under these different growing conditions, lead chemical states varied the most.     

Patterning of CIGS thin films induced by rear-side laser ablation of polyimide carrier foil

Laser patterning of thin films is essential for the future development of flexible electronic devices. The damage-free scribing of thermally sensitive thin films such as copper–indium–gallium diselenide (CIGS) that is required for solar module fabrication by integrated interconnections is still challenging. In this study a new approach for non-thermal, damage-free scribing of CIGS films on polyimide foil is proposed and demonstrated. In contrast to the usually used direct laser ablation of the thin-film stack, laser ablation of the polyimide carrier foil at laser fluences higher than 3 J/cm² is utilized to achieve CIGS film delamination and thus the patterning of the thin film. The edges of the patterned CIGS films do not show typical laser-ablation-induced modifications like melting, debris contamination, or crack formation. The mechanism of the thin-film removal is of non-thermal origin and is probably due to stress formation at the CIGS/Mo interface resulting from secondary processes of polyimide laser ablation like shock-wave formation or local sample deformation.     

Pulsed laser deposition of polyhydroxybutyrate biodegradable polymer thin films using ArF excimer laser

We demonstrated the pulsed laser deposition (PLD) of high quality films of a biodegradable polymer, the polyhydroxybutyrate (PHB). Thin films of PHB were deposited on KBr substrates and fused silica plates using an ArF (λ = 193 nm, FWHM = 30 ns) excimer laser with fluences between 0.05 and 1.5 J cm⁻². FTIR spectroscopic measurements proved that at the appropriate fluence (0.05, 0.09 and 0.12 J cm⁻²), the films exhibited similar functional groups with no significant laser-produced modifications present. Optical microscopic images showed that the layers were contiguous with embedded micrometer-sized grains. Ellipsometric results determined the wavelength dependence (λ ∼ 245-1000 nm) of the refractive index and absorption coefficient which were new information about the material and were not published in the scientific literature. We believe that our deposited PHB thin films would have more possible applications. For example to our supposal the thin layers would be applicable in laser induced forward transfer (LIFT) of biological materials using them as absorbing thin films.     

Crystallisation of TiO2 thin films induced by excimer laser irradiation

Titanium dioxide thin films have been deposited by reactive magnetron sputtering on glass substrate and subsequently irradiated by UV radiation using a KrF excimer laser. In this work, we have study the influence of the laser fluence (F) ranging between 0.05 and 0.40 mJ/cm² on the constitution and microstructure of the deposited films. Irradiated thin films are characterized by profilometry, scanning electron microscopy and X-ray diffraction. As deposited films are amorphous, while irradiated films present an anatase structure. The crystallinity of the films strongly varies as a function of F with maximum for F = 0.125 J/cm². In addition to the modification of their constitution, the irradiated areas present a strongly modified microstructure with appearance of nanoscale features. The physico-chemical mechanisms of these structural modifications are discussed based on the theory of nucleation.     

Evolution of microstructure in polycrystalline silicon thin films upon excimer laser crystallization

Polycrystalline silicon (poly-Si) films fabricated by pulsed excimer laser crystallization (ELC) have been investigated using time-resolved optical measurements, scanning-electron microscopy, and cross-sectional transmission-electron microscopy. Detailed crystallization mechanisms are proposed to interpret the microstructure evolution of poly-Si films for both frontside and backside ELC. It is found that the backside ELC is a good candidate for the manufacturing of low-temperature polycrystalline silicon because of the high laser efficiency and low surface roughness of the poly-Si films.     

Control of structure and electric properties of amorphous organic semiconductive thin films prepared by excimer laser ablation

Excimer laser ablation (ELA) of 3,4,9,10-perylene-tetracarboxylic dianhydride (PTCDA) with ArF (193 nm), KrF (248 nm), XeCl (308 nm), and XeF (351 nm) beams under optimized conditions enables us to obtain organic semiconductor thin films with various structures such as amorphous carbon, polyperinaphthalene (PPN), and PTCDA itself. Electric conductivity and carrier species of the films depend strongly on the ablation wavelength, fluence, substrate temperature, and ambient vapor species. It is found that electric conductivities of the films are controllable, ranging from 10^-6 to 10¹ S cm^-1 with the selection of appropriate ablation conditions. An organic pn junction is successfully constructed by the change of ablation conditions during ELA. Furthermore, ELA of PTCDA at 248 nm in iodine vapor leads to formation of tetraiodoallene in the film.     

In situ time-resolved optical measurements of a-Si thin films during excimer laser crystallization

An in situ time-resolved optical reflection and transmission (TRORT) monitoring system combining two He-Ne probe lasers, a digital oscilloscope and three fast photodetectors is developed to investigate the crystallization processes of Si thin films during excimer laser crystallization (ELC). The physical meaning of optical spectra obtained by TRORT measurements has been interpreted in detail. The melt duration and transient phase transformation dynamics of Si thin films can be determined and interpreted immediately. A high efficiency and non-destructive evaluation approach is proposed for determining the grain size of polycrystalline Si after ELC directly and immediacy under appropriate experimental conditions.     

Dynamical resolidification behavior of silicon thin films during frontside and backside excimer laser annealing

Excimer laser annealing (ELA) is frequently employed to fabricate low-temperature polycrystalline silicon films on glass substrate. The grain size and crystallinity of polycrystalline silicon films are significantly affected by the resolidification behavior during ELA. A real-time in situ time-resolved optical measurement system is developed to record the rapid phase transformation process during ELA. The average solidification velocity of liquid-Si is calculated from these optical spectra using MATLAB and Excel softwares. Field emission scanning electron microscopy images reveal maximum grain size of poly-Si films with a diameter of 1 μm, which is obtained in the complete melting regime of both frontside ELA and backside ELA. Recrystallization mechanisms of complete melting of Si thin films in frontside ELA and backside ELA are demonstrated. Resolidification scenarios of partial melting, near-complete melting and complete melting in frontside ELA and backside ELA are proposed.     

Measurement of optical and surface properties of PLZT thin films

Lanthanum-modified lead zirconate titanate (Pb_0.93La_0.07(Zr_0.3Ti_0.7)_0.93O₃, PLZT7/30/70) thin films with and without a seeding layer of PbTiO₃ (PT) were successfully deposited on indium-doped tin oxide (ITO) coated glass substrate via spin coating in conjunction with a sol–gel process, and a top transparent conducting thin film of SnO₂ was also prepared in the same way. The thicknesses of PLZT and PT layers are 0.5 μm and 24 nm, respectively. The retardance of PLZT film was measured by a new heterodyne interferometer and enhanced by application of a seeding layer of PT. The Pockels linear electro-optical coefficient of PLZT film with a PT layer was determined to be 3.17 × 10^?9 m/V when the refractive index is considered as 2.505, which is one order larger than 1.4 × 10^?10 m/V for PLZT12/40/60 doped with Dy reported in the literature. The root-mean-square (rms) roughness of PLZT thin film with a PT layer (R_rms = 6.867 nm) was larger than that of PLZT film (R_rms = 0.799 nm). From the comparisons, the average transmittance of PLZT film with a PT seeding layer was 77.01%, which was a little smaller than that of PLZT film (around 80.75%). Experimental results imply that the PT seeding layer plays a key role in the increase of retardance value, leading to a higher Pockels coefficient.     

Biomaterial immobilization on polyurethane films by XeCl excimer laser processing

The surface chemical modification of polyurethane (PU) films was performed by an UV laser-induced chemical reaction in a polysaccharide solution. This process may be applicable as hydrophilic packaging of implantable medical devices and in vivo sensors. When a PU film in contact with an aqueous alginic acid (AAC) solution was irradiated with a XeCl laser, the PU film turned hydrophilic. Contact angles of water on the film were reduced from 110° to 60°. Since light absorption of the AAC solution at 308 nm was negligibly small, reactive sites were generated solely on the PU surface. There, AAC could be immobilized by chemical bonds thus allowing for a nanometer-scaled grafting of this biomolecule. The mechanism was investigated by surface analyses with Fourier-transform infrared spectroscopy (FT-IR), dye staining, ultraviolet-visible (UV-VIS) spectroscopy, and scanning electron microscopy (SEM) techniques. A one-photon photochemical process could beidentified. Received: 30 June 2000 / Accepted: 4 July 2000 / Published online: 13 September 2000     

脉冲准分子激光淀积薄膜的实验研究

利用两种脉宽 (30ns,5 0 0fs)的KrF准分子激光展开了淀积类金刚石薄膜的实验研究 ,并且成功地制备了大面积不含氢成分的HF DLC薄膜 ,运用时空分辨的等离子体发射光谱诊断系统和离子探针系统研究了等离子体特性对薄膜性能的影响。尝试了利用准分子激光制备非晶硅薄膜 ,研究了实验参数对非晶硅薄膜制备的影响 ,并分析了制备具有良好电学和光学性能的非晶硅薄膜的条件     

Low-temperature fabrication of silicon nitride films by ArF excimer laser irradiation

The low-temperature fabrication of silicon nitride films by ArF excimer laser irradiation has been studied. Two fabrication methods are presented. One is photoenhanced direct nitridation of a silicon surface with NH₃ for very thin gate insulators, and the other is photo-enhanced deposition of silicon nitride films with Si₂H₆ and NH₃ gases for stable passivation films. The ArF excimer laser irradiation dissociates the NH3 gas producing NH and NH₂ radicals which proved effective in instigating the nitridation reaction. The quality of both films has been much improved and the growth temperature has been lowered by using laser irradiation. These photo-enhanced processes seem to be promising ULSI techniques because they do not depend on high temperatures and are free from possible reactor contamination.     

Patterning of Aluminium thin film on polyethylene terephthalate by multi-beam picosecond laser

High speed patterning of a 30 nm thick Aluminium thin film on a flexible Polyethylene Terephthalate substrate was demonstrated with the aid of Computer Generated Holograms (CGH׳s) applied to a phase only Spatial Light Modulator. Low fluence picosecond laser pulses minimise thermal damage to the sensitive substrate and thus clean, single and multi-beam, front side thin film removal is achieved with good edge quality. Interestingly, rear side ablation shows significant Al film delamination. Measured front and rear side ablation thresholds were F_th=0.20±0.01 J cm⁻² and F_th=0.15±0.01 J cm⁻² respectively. With laser repetition rate of 200 kHz and 8 diffractive spots, a film removal rate of R>0.5 cm² s⁻¹ was demonstrated during patterning with a fixed CGH and 5 W average laser power. The effective laser repetition rate was f_eff~1.3 MHz. The application of 30 stored CGH׳s switching up to 10 Hz was also synchronised with motion control, allowing dynamic large area multi-beam patterning which however, slows micro-fabrication.     

Preparation and characterization of La0.8Sr0.2MnO3 thin films by an excimer laser MOD process for a bolometer

La_0.8Sr_0.2MnO₃ (LSMO) films were prepared on LaAlO₃ substrates by excimer laser metal organic deposition (ELMOD) at 500 °C. The temperature dependence of resistance of the LSMO films was investigated by changing the laser fluence, irradiation time, and film thickness. It was found that the resistance of the LSMO films 80 nm in thickness that were irradiated by an ArF laser at a fluence of 100 mJ/cm² for 60 min showed a metallic temperature dependence, and the maximum temperature coefficient of resistance of the films (defined as 1/R×dR/dT) was 3.4% at 265 K. PACS 81.15.-z; 81.15.Fg; 81.15.Np; 73.61.-r; 71.30.+h     

Micro-Raman spectroscopy characterization of polycrystalline silicon films fabricated by excimer laser crystallization

The rapid recrystallization of amorphous silicon films utilizing excimer laser crystallization (ELC) is presented. The resulting poly-Si films are characterized by Raman spectroscopy. Polycrystalline silicon (poly-Si) films with higher crystallinity can be realized by a dehydrogenation process before ELC. Raman spectra as a function of various excimer laser energy densities are demonstrated. The crystallinity and residual stress of the poly-Si films are determined and discussed.