Influence of laser repetition rate on ferroelectric properties of pulsed laser deposited BaTiO3 films on platinized silicon substrate

BaTiO₃ thin films were deposited by pulsed laser deposition on Pt–Si at different laser pulse repetition frequencies. X-ray diffraction spectra show that preferred oriented films can be grown by adjusting the pulse repetition frequency. Enhanced dielectric and ferroelectric properties obtained in films deposited at 1 Hz is attributed to preferred orientation, low strain and homogeneous grain distribution. The films deposited at 1 Hz show an impressive remanent polarization of 21.4 μC/cm² with a coercive field of 70.0 kV/cm. The shift in Curie temperature, which stems from changing the laser pulse repetition frequency, is associated with the strain state in the film.     

Improvement of corrosion resistance of carbon steel using chemical vapor deposition from Cr(CO)6 with an ArF excimer laser

Corrosion resistance of carbon steel coated with thin film deposited from Cr(CO)₆ using an ArF excimer laser (193 nm) has been evaluated by an electrochemical method as a function of laser beam intensity. The carbon steel coated with the film formed at higher beam intensity shows higher corrosion resistance. Microstructure, composition, and thickness of the films have also been investigated. SEM micrographs show that the films consist of small grains which decrease in size with increasing beam intensity. Auger electron spectroscopy (AES) combined with Ar⁺ beam sputtering reveals that the films deposited at higher beam intensity give higher chromium content, and that the thickness at a fixed total irradiation energy increases up to the intensity of 10 MW cm^–2, falling above this intensity. In addition, the change of film thickness by addition of buffer gases (Ar, CO, and H₂O) has been investigated. The thickness is 10 times smaller under the addition of H₂O, and twice smaller under the addition of Ar or CO than without the addition of gases. A deposition mechanism based on photolysis of Cr(CO)₆ in the gas phase is proposed related to the experimental data after the discussion of several possible mechanisms.     

Improvement of corrosion resistance of carbon steel using chemical vapor deposition from the mixture of Mo(CO)6 and Cr(CO)6 with an ArF-excimer laser

The corrosion resistance of carbon steel has been improved by the deposition from the mixture of Mo(CO)₆ and Cr(CO)₆ as well as from each carbonyl alone with an ArF-excimer laser (193 nm). The corrosion resistance attained by coating with the films from the mixture is higher than from Mo(CO)₆ alone, while lower than from Cr(CO)₆ alone. While the corrosion resistance increases with beam intensity monotonically over the range 4–25 MW cm^–2 for the deposition from Cr(CO)₆ alone, it tends to decrease slightly above 15 MW cm^–2 for the deposition from Mo(CO)₆ alone and from the mixture. SEM (Scanning Electron Microscope) photographs show that the films from each carbonyl and their mixture consist of small grains that are more densely packed at higher beam intensities. The comparison of the film thickness evaluated from sputtering time to remove the films with that from direct observation with SEM suggests that the density of the film increases with beam intensity. In the films deposited from the mixture, molybdenum is preferentially incorporated from the gas phase. Present name: Department of Quantum Engineering and Systems Science     

Low-temperature growth of SnO2 film prepared by XeCl excimer laser MOD process

A SnO₂ film has been prepared by an excimer laser metal organic deposition (ELMOD) process using an XeCl laser. The effects of the laser fluence, shot number, and the pretreatment temperature of the Sn acetylacetonate (Sn-acac) on the crystallization of the SnO₂ film were investigated by X-ray diffraction and infrared spectroscopy. When the MO spin-coated film preheated at room temperature on a Si substrate was irradiated by the laser at a fluence of 100 mJ/cm² and at a repetition rate of 10 Hz for 5 min, a crystallized SnO₂ film was successfully obtained without heat treatment. At a fluence of 260 mJ/cm², the highest crystalline film was formed. On the other hand, when the amorphous SnO₂ film was irradiated by the laser at 260 mJ/cm², the crystallinity of the SnO₂ film was improved. SnO₂ films were also prepared by conventional thermal MOD in a temperature range from 300 to 900 °C. The crystallinity of the SnO₂ films prepared by the ELMOD process at room temperature was higher than that of the films prepared by heating at 900 °C for 60 min. PACS 81.15.Fg; 81.15.-z; 81.16.Mk; 82.50.Hp; 73.61.Le     

Excimer laser processing of ZnO thin films prepared by the sol-gel process

ZnO thin films were prepared on soda-lime glass from a single spin-coating deposition of a sol-gel prepared with anhydrous zinc acetate [Zn(C₂H₃O₂)₂], monoethanolamine [H₂NC₂H₄OH] and isopropanol. The deposited films were dried at 50 and 300 °C. X-ray analysis showed that the films were amorphous. Laser annealing was performed using an excimer laser. The laser pulse repetition rate was 25 Hz with a pulse energy of 5.9 mJ, giving a fluence of 225 mJ cm⁻² on the ZnO film. Typically, five laser pulses per unit area of the film were used. After laser processing, the hexagonal wurtzite phase of zinc oxide was observed from X-ray diffraction pattern analysis. The thin films had a transparency of greater than 70% in the visible region. The optical band-gap energy was 3.454 eV. Scanning electron microscopy and profilometry analysis highlighted the change in morphology that occurred as a result of laser processing. This comparative study shows that our sol-gel processing route differs significantly from ZnO sol-gel films prepared by conventional furnace annealing which requires temperatures above 450 °C for the formation of crystalline ZnO.     

Laser-assisted etching of gallium arsenide in chlorine at 308 nm

Xenon chloride (308 nm) excimer laser-assisted etching of GaAs (100) in Cl₂ was demonstrated and characterized with respect to laser and gas parameters. The etch rate increased linearly with laser fluence from thresholds in the range of 50 to 75 mJ/cm² to the highest fluence studied, 650 mJ/cm². For a laser fluence of 370 mJ/cm², the etch rate varied with Cl₂ pressure reaching a maximum at a Cl₂ pressure of about 2 Torr. The etch rate decreased monotonically with Ar buffer gas pressure because of redeposition of GaCl₃ products into the etched channel. The redeposited GaCl₃ affected the etch rate and the etch morphology. The etch rate and morphology also varied with laser repetition rate. The mobility of chlorine on the surface also plays an important role in the etching mechanism.     

Structural characterization and optoelectronic properties of GaN thin films on Si(111) substrates using pulsed laser deposition assisted by gas discharge

GaN films have been grown on Si(111) substrates with a thin AlN buffer layer using pulsed laser deposition (PLD) assisted by gas discharge. The crystalline quality, surface morphology and optoelectronic properties of the deposited films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL) spectroscopy, and room-temperature Van der Pauw–Hall measurements. The influence of the deposition temperature in the range 637–1037 K on the crystallinity of GaN films, the laser incident energy in the range 150–250 mJ/pulse on the surface morphology and the optoelectronic properties were systematically studied. The XRD analysis shows that the crystalline quality of the GaN films improves with increasing deposition temperature to 937 K, but further increase of the deposition temperature to 1037 K leads to the degradation of the crystalline quality. AFM results show that the surface roughness of the GaN films can be decreased with increasing laser incident energy to 220 mJ/pulse. Further increase of the laser incident energy to 250 mJ/pulse leads to an increase in the surface roughness. The optoelectronic properties of GaN films were also improved by increasing the laser incident energy to 220 mJ/pulse. GaN films which have a n-type carrier concentration of 1.26×10¹⁷ cm^-3 and a mobility of 158.1 cm²/Vs can be deposited at a substrate temperature of 937 K, a deposition pressure of 20 Pa and a laser incident energy of 220 mJ/pulse. Their room-temperature PL spectra exhibit a strong band-edge emission at 365 nm. PACS 81.15.Fg; 81.05.Ea; 78.20.-e; 73.61.Ey; 78.66.Fd     

Multiwatt optically pumped ammonia laser operation in the 12–13 μm

Design and operating caracteristics of high pulse repetition rate NH₃ laser producing up to 20 W of average output power are described. The NH₃ laser, operating in the 12–13 μm region was optically pumped with a high pulse repetition rate TEA CO₂ laser. Dependences of the NH₃ laser output on the pump energy, ammonia and buffer gas pressures and pulse repetition rate have been studied. The conversion efficiency of up to 16% has been received.     

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.     

Control of electrical resistance of TiO2 films by short-pulse laser irradiation

Titanium dioxide (TiO₂) films were irradiated with a femtosecond laser beam to alter their electrical resistances. The TiO₂ film was produced by aerosol beam deposition. The wavelength, pulse duration, and repetition rate of the femtosecond laser scanned across the sample surface were 800 nm, 100 fs, and 1 kHz, respectively. By attenuating the laser fluence on the TiO₂ film, a range was found in which the electrical resistance of the TiO₂ film was varied even though the morphology of the film surface was not changed.     

Effect of buffer layers on the property of Pb(Zr,Ti)O3-Pb(Mn,W,Sb,Nb)O3 thin films grown by pulsed laser deposition

New ferroelectric Pb(Zr,Ti)O₃-Pb(Mn,W,Sb,Nb)O₃ (PZT-PMWSN) thin film has been deposited on a Pt/Ti/SiO₂/Si substrate by pulsed laser deposition. Buffer layer was adopted between film and substrate to improve the ferroelectric properties of PZT-PMWSN films. Effect of a Pb(Zr_0.52Ti_0.48)O₃ (PZT) and (Pb_0.72La_0.28)Ti_0.93O₃ (PLT) buffer layers on the stabilization of perovskite phase and the suppression of pyrochlore phase has been examined. Role of buffer layers was investigated depending on different types of buffer layer and thickness. The PZT-PMWSN thin films with buffer layer have higher remnant polarization and switching polarization values by suppressing pyrochlore phase formation. The remnant polarization, saturation polarization, coercive field and relative dielectric constant of 10-nm-thick PLT buffered PZT-PMWSN thin film with no pyrochlore phase were observed to be about 18.523 μC/cm², 47.538 μC/cm², 63.901 kV/cm and 854, respectively.     

Crystal growth of phosphor perovskite titanate thin films under excimer laser irradiation

Ca_0.997Pr_0.002TiO₃ (CPTO) thin films that show strong red luminescence were successfully prepared by means of an excimer laser assisted metal organic deposition (ELAMOD) process with a KrF laser at a fluence of 100 mJ/cm², a pulse duration of 26 ns, and a repetition rate of 20 Hz at 100°C in air. The CPTO films grew on the silica, borosilicate, and indium-tin-oxide (ITO) glasses. The crystallinity of the CPTO films depended on the substrates; the films were well grown on the borosilicate and ITO glasses compared to the silica glass. To elucidate the key factors for the crystallization of the CPTO films in this process, we carried out numerical simulations for the temperature variation at the laser irradiation, using a heat diffusion equation, and compared the experimental data with thermal simulations. According to the results, we have shown that a large optical absorbance of the film and a small thermal conductivity of the substrate provide effective annealing time and temperature for the crystallization of the CPTO films, and polycrystalline intermediate layer which has a large optical absorption such as the ITO also plays a key role for the nucleation of the CPTO crystals in the ELAMOD process.     

Effect of the laser fluence on the surface characterization of β-FeSi2 films prepared by pulsed laser deposition

Single-phase β-FeSi₂ films on silicon (1 0 0) were fabricated by pulse laser deposition. The structure and crystal quality of the samples were characterized by X-ray diffraction and Fourier transform infrared spectroscopy. The field scanning electron microscopy showed that the film thickness increases with the increasing of the laser fluence. Moreover, atomic force microscopy observations revealed the changes of surface properties with different laser fluence. Based upon all experimental results, it is found that 7 J/cm² is the most favorable for the formation of β-FeSi₂ thin films.     

Deposition of aluminum nitride thin film on Si(1 1 1) by KrF excimer laser and its characterizations

We present the deposition of aluminum nitride (AlN) thin film by KrF excimer laser sputtering and the study of the effects of substrate temperature and laser fluences. Deposition rate of AlN thin film at 0.3 Å/pulse has been achieved with laser fluence of 1500 mJ/cm² and at substrate temperature of 250 K, and this shows the enhancement of the deposition rate at low substrate temperature. Surface morphology of the deposited films is characterized by atomic force microscopy (AFM). In addition, the electrical performance of the MIS devices with AlN thin films prepared in this experiment has been characterized.     

Synthesis of chromium silicide with laser pulses

Thin chromium films, 60 nm thick, were deposited onto single-crystal silicon wafers. The samples were irradiated with 30 ns single pulses from a Nd: glass laser at fluences ranging from 0.4 to 2.25 J/cm². Rutherford backscattering spectrometry, transmission electron microscopy and electron diffraction measurements evidence the formation of CrSi₂ layers at the Cr/Si interface. The silicide thickness depends on the laser fluence.     

Double-pulse laser ablation applied to reactive PLD method for synthesis of carbon nitride film: A second laser shot delay

Carbon nitride films were deposited using ablation of graphite target by second harmonic radiation of Nd:YAG laser in nitrogen atmosphere. To produce high hardness films, the deposited particles should have sufficient kinetic energy to provide their efficient diffusion on a substrate surface for formation of crystal structure. However, a shock wave is arisen in ambient gas as a consequence of laser plasma explosive formation. This shock wave reflected from the substrate interacts with plume particles produced by the first laser pulse and decreases their kinetic energy. This results in decrease of film crystallinity. To improve film quality, two successive laser pulses was proposed to be used. At adjusting time delay, the particles induced by the second pulse wilt serve as a piston, which will push forward both stopped particles ablated by the first pulse and arisen from chemical reactions in ambient gas. An X-ray photoelectron spectroscopy (XPS) analysis of deposited films has shown an increase of content of sp ³ carbon atoms corresponding to crystalline phase, if double-pulse configuration is employed. The luminescence of excited C₂ and CN molecules in laser plume at different distances from the target was studied to optimize the delay between laser pulses.     

衬底温度对PLD制备的Mo薄膜结构及表面形貌的影响

 运用脉冲激光沉积(PLD)技术在Si(100)基片上沉积了金属Mo薄膜。在激光重复频率2 Hz,能量密度5.2 J/cm²,本底真空10^－6 Pa的条件下,研究Mo薄膜的结构和表面形貌,讨论了衬底温度对薄膜形貌与结构的影响。原子力显微镜(AFM)图像和X射线小角衍射(XRD)分析表明,薄膜表面平整、光滑,均方根粗糙度小于2 nm。沉积温度对Mo薄膜结构和表面形貌影响较大,在373~573 K范围内随着温度升高,薄膜粗糙度变小,结晶程度变好。     

Variety of nanostructures induced by femtosecond laser pulses on surface of Au/Cr film stack

Several nanostructures were obtained after irradiation with femtosecond laser pulse (130 fs, 800 nm, 1 kHz pulse repetition frequency) on Au/Cr film stack. The influence of laser parameters such as fluence (0.5 J/cm², 1.5 J/cm², 3 J/cm²) and the number of pulse were investigated. With single pulse irradiation, the nanoline and nonoparticle were obtained for the pulse fluence of 0.5 J/cm² and 3 J/cm², respectively. The formation mechanism of those nanostructures was discussed. The results of this experiment demonstrate that different kinds of nanostructures could be formed by varying the laser parameters such as fluence and the number of pulse.     

Pulsed reactive crossed beam laser ablation of La0.6Ca0.4CoO3 using O: Where does the oxygen come from?

The composition of thin perovskite films, especially the oxygen content, is a crucial parameter which influences many physical properties, such as conductivity and catalytic activity. Films produced by pulsed laser deposition are normally annealed in an oxygen atmosphere after deposition to achieve a desired oxygen content. In pulsed reactive crossed beam laser ablation, no annealing step is necessary, but a fundamental question regarding this deposition technique is still open: where does the oxygen in the films come from?There are three possibilities, i.e. from the target, from the gas background, or from the gas pulse. To answer this question two experiments were performed: ¹⁸O₂ was used during the deposition process as background gas with ¹⁶O anions in the target and ¹⁶O₂ gas pulse, and a ¹⁸O₂ gas pulse with ¹⁶O from the target and background. These experiments revealed that the quantification of the oxygen origin is only possible, when no oxygen exchange occurs at the deposition temperature. The films are characterized after deposition by elastic recoil detection analysis (ERDA) to determine the ¹⁶O/¹⁸O ratio. Experiments with different oxidizing species in the gas pulse (N₂O and O₂) confirm that the oxidizing potential (N₂O > O₂) as well as the number of molecules are important.     

High repetition rate femtosecond laser nano-machining of thin films

Thin film laser micromachining has been utilized for repairing semiconductor masks, creating solar cells and fabricating MEMS devices. A unique high repetition rate femtosecond fiber laser system capable of variable repetition rates from 200 KHz to 25 MHz along with helium gas assist was used to study the effect of pulse repetition rate and pulse energy on femtosecond laser machining of gold-coated silicon wafer. It was seen that high repetition rates lead to smaller craters with uniform line width. Craters created at 13 MHz pulse repetition rate with 2.042 J/cm² beam energy fluence measured 110 nm in width and had a heat affected zone of 0.79 μm. It was found that pulse repetition rate only played a significant role in the size of the heat affected zone in the lower pulse energy ranges. In the future, a 1 W laser system will be acquired to find the optimal repetition rate that would create the minimal feature size with the least heat affected zone. Using this kind of setup along with techniques such as radial polarization and a different gas assist may enable us to create sub 100 nm feature size with good quality.