Determining the properties of pulsed laser deposited thin films by controlling the kinetic energy of the film-forming particles

The deposition of Al₂O₃ thin films by pulsed KrF excimer laser radiation (248 nm) on fused silica substrates is investigated as a function of the processing variables: laser fluence, processing gas pressure and target-to-substrate distance. The kinetic energy of the Al species in the laser-generated plasma, as measured by time-of-flight optical emission spectroscopy and time-of-flight quadrupole mass spectrometry, is described as a function of the type and pressure of the processing gas, the distance from target, and the laser fluence. The influence of the kinetic energy of the film-forming particles on the density and the refractive index of the resulting films, determined by ellipsometry, is investigated. The densification of the Al₂O₃ thin films to 94% of the bulk value is achieved by film-forming Al particles impinging on the growing surface with mean kinetic energies of about 25 eV.     

Nanocrystalline growth and diagnostics of TiC and TiB2 hard coatings by pulsed laser deposition

Nanocrystalline coatings of TiC and TiB₂ were grown by pulsed laser deposition on Si(100) and on X155 steel at low substrate temperatures ranging from 40 °C to 650 °C. A pulsed KrF excimer laser was used with the deposition chamber at a base pressure of 10^-6 mbar. The morphology and structure of the films, studied with SEM, XRD, and TEM, showed that nanocrystalline films with a fine morphology of TiC and TiB₂ were deposited with a grain size of 10 nm-70 nm at all substrate temperatures. The growth of the polycrystalline coatings possessed a columnar morphology with a 𘜄¢ preferred orientation. The hardness of the coatings was determined to be 40 GPa and the elastic modulus, 240 GPa. The composition and the kinetics of the plume produced during the pulsed laser deposition of TiC and TiB₂ was studied under film growth conditions. The mass analysis of ions of the ejected material was performed by time-of-flight mass spectroscopy (TOF-MS) and showed the presence of Ti⁺ and C⁺ during TiC ablation and B⁺, B₂⁺, and Ti⁺ during TiB₂ ablation. The kinetic energies (KE) of the ions depended on the laser fluence which was between 0.5 eV and 340 eV. The kinetic energy and the evolution of the plasma was studied with a streak camera. The velocity of the plasma was of the order of 10⁶ cm/sec and was linearly dependent on the energy fluence of the laser. The emission spectroscopy of the plasma plume confirmed the atomic neutral and single excited species of Ti. These results show that coating growth basically occurs by the recombination of the ionic species at the surface of the substrate.     

Distinct orientation of AlN thin films deposited on sapphire substrates by laser ablation

We report the experimental characterization of the charged species produced in excimer laser ablation of a superconducting intermetallic compound (YNi₂B₂C). By using energy-selective time-of-flight mass spectrometry, we have obtained direct measurements of both mass spectra and kinetic energy distributions of ions. The investigation has been carried out in the laser fluence range 1-5 J cm^-2, which is typical of laser ablation thin film deposition. High kinetic energies of the charged component (up to 0.4 keV) have been observed even at moderate laser fluences.     

Growth of oriented Pb(ZrxTi1-x)O3 thin films on glass substrates by pulsed laser deposition

Oriented crystalline Pb(Zr_xTi_1-x)O₃ (x=0.53) (PZT) thin films were deposited on metallized glass substrates by pulsed laser deposition (1060-nm wavelength Nd:YAG laser light, 10-ns pulse duration, 10-Hz repetition rate, 0.35-J/pulse and 25-J/cm² laser fluence), from a commercial target at substrate temperatures in the range 380-400 °C. Thin films of 1-3 7m were grown on Au(111)/ Pt/NiCr/glass substrates with a rate of about 1 Å/pulse on an area of 1 cm². The deposited PZT films with perovskite structure were oriented along the (111) direction, as was revealed from X-ray diffraction spectra. Fourier transform infrared spectroscopy (FTIR) was performed on different PZT films so that their vibrational modes could be determined. Piezoelectric d₃₃ coefficients up to 30 pC/N were obtained on as-deposited films. Ferroelectric hysteresis loops at 100 Hz revealed a remanent polarization of 20 7C/cm² and a coercive field of 100 kV/cm.     

Time-resolved and integrated angular distributions of plume ions from silver at low and medium laser fluence

Laser impact on metals in the UV regime results in a significant number of ablated plume ions even at moderate fluence (0.7–2.4 J/cm²). The ablated particles are largely neutrals at the lowest fluence, but the fraction of ions increases strongly with fluence. The ion flow in different directions from a silver target irradiated by a laser beam at a wavelength of 355 nm in vacuum was measured with a hemispherical array of Langmuir probes. The time-of-flight spectra in all directions, as well as the total angular yield were determined. The angular distribution peaks strongly in forward direction with increasing fluence and can be well approximated by Anisimov’s model. Typically, the spectra of silver ions peak from 70 eV up to 145 eV in a direction close to the normal of the target surface with increasing fluence. With increasing observation angle, the time-of-flight spectra exhibit a peak at longer flight times, i.e., at a lower kinetic energy. At the highest fluence, the ionized fraction of the ablated particles in the plume increases up to 0.5.     

Emission of neutral molecules during UV laser ablation of a photolabile triazeno polymer

The neutral products of irradiating a photolabile triazeno-polymer with a pulsed laser at 248 nm (KrF excimer) were studied with time-of-flight (TOF) mass spectrometry. At fluences below 1.3 J/cm², N₂ is by far the most intense neutral product. Phenyl radical (mass 76) production was also observed. The leading edge of the N₂ TOF signal shows a shoulder corresponding to kinetic energies of about 1.1 eV, followed by a long tail that lasts hundreds of microseconds. The tail is attributed to delayed emission of reaction products from the polymer. The kinetic energy of the fast peak is attributed to direct ejection of products from surface sites undergoing exothermic decomposition. The fluence dependence of the N₂ signal is highly nonlinear and is shown to fit an Arrhenius equation.     

Dynamics of femtosecond laser-produced plasma ions

We investigated the ion laser-produced plasma plume generated during ultrafast laser ablation of copper and silicon targets in high vacuum. The ablation plasma was induced by ≈50 fs, 800 nm Ti:Sa laser pulses irradiating the target surface at an angle of 45°. An ion probe was used to investigate the time-of-flight profiles of the emitted ions in a laser fluence range from the ablation threshold up to ≈10 J/cm². The angular distribution of the ion flux and average velocity of the produced ions were studied by moving the ion probe on a circle around the ablation spot. The angular distribution of the ion flux is well described by an adiabatic and isentropic model of expansion of a plume produced by laser ablation of solid targets. The angular distribution of the ion flux narrows as the laser pulse fluence increases. Moreover, the ion average velocity reaches values of several tens of km/s, evidencing the presence of ions with kinetic energy of several hundred eV. Finally, the ion flux energy is confined in a narrow angular region around the target normal.     

Epitaxial growth of non-c-oriented ferroelectric SrBi2Ta2O9 thin films on Si(100) substrates

Epitaxial SrBi₂Ta₂O₉ (SBT) thin films with well-defined (116) orientation have been grown by pulsed laser deposition on Si(100) substrates covered with an yttria-stabilized ZrO₂ (YSZ) buffer layer and an epitaxial layer of electrically conductive SrRuO₃. Studies on the in-plane crystallographic relations between SrRuO₃ and YSZ revealed a rectangle-on-cube epitaxy with respect to the substrate. X-ray diffraction pole figure measurements revealed well-defined orientation relations, viz. SBT(116)SrRuO₃(110)YSZ(100)Si(100), SBT[110]SrRuO₃[001], and SrRuO₃[111]YSZ[110]Si[110].     

Growth of SiNx and SiCx thin films by pulsed reactive crossed-beam laser ablation

SiN_x and SiC_x films were grown on Si(001) and Si(111) using pulsed reactive crossed-beam laser ablation of Si with N₂ and CH₄. The scattering processes in the ablation plasma and the reactive gas pulse were investigated using time-of-flight quadrupole mass spectroscopy. The film crystallinity was determined by FTIR spectroscopy, X-ray diffraction, and reflection high-energy electron diffraction, while the stoichiometry and chemistry were investigated using XPS. SiN_x was amorphous over the investigated temperature range of 25-850 °C, and x increased monotonically with temperature from 0.67 to 0.94. SiC_x films grown at 850 °C consisted of oriented large #-SiC crystallites embedded in a Si matrix.     

Dielectric and piezoelectric properties of the Ba0.92Ca0.08Ti0.95Zr0.05O3 thin films grown on different substrate

Lead free Ba_0.92Ca_0.08Ti_0.95Zr_0.05O₃ (BCZT) thin films were deposited on Pt/Ti/SiO₂/Si and LaNiO₃(LNO)/Pt/Ti/SiO₂/Si substrates by a sol–gel processing technique, respectively. The effects of substrate on structure, dielectric and piezoelectric properties were investigated in detail. The BCZT thin films deposited on LNO/Pt/Ti/SiO₂/Si substrates exhibit (100) orientation, larger grain size and higher dielectric tunability (64%). The BCZT thin films deposited on Pt/Ti/SiO₂/Si exhibit (110) orientation, higher Curie temperature (75 °C), better piezoelectric property (d₃₃ of 50 pm/V) and lower dielectric loss (0.02). The differences in dielectric and piezoelectric properties in the two kinds of oriented BCZT films should be attributed to the difference of structure, in-plane stress and polarization rotation in orientation engineered BCZT films.     

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.     

Influence of laser-ablation plume dynamics on the room-temperature epitaxial growth of CeO2 on silicon

High-quality epitaxial CeO₂ thin films were obtained on Si(001) buffered with a yttria-stabilised zirconia layer by pulsed laser deposition. Although the best structural properties were achieved at high substrate temperature, high-quality epitaxy was obtained even at room temperature. Epitaxial growth at low temperature is promoted by the high kinetic energy of particles reaching the substrate. The oxygen pressure and target-substrate distance had a strong influence on the crystallographic structure and surface morphology in low-temperature deposition. This behaviour is attributed to a change in the kinetic energy of the particles, which was evaluated from the plasma expansion velocity determined by an intensified CCD camera. If a shock wave forms, a minimum substrate temperature of 550 °C is necessary for epitaxial growth.     

Laser induced mixing in multilayered Ti/Ta thin film structures

The possibility of interlayer mixing in a Ti/Ta multilayer system, induced by laser irradiation, was the main purpose of these experiments. Ti/Ta multilayer system, consisting of ten alternating Ti and Ta thin films and covered by slightly thicker Ti layer, was deposited on Si (100) wafers to a total thickness of 205 nm. Laser irradiation was performed in air by picoseconds Nd:YAG laser pulses in defocused regime with fluences of 0.057 and 0.11 J cm^?2. Laser beam was scanned over the 5?×?5 mm surface area with different steps along y-axes. Structural and compositional characterisation was done by auger electron spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy. Laser processing at lower fluence caused only oxidation of the top Ti layer, despite of the number of applied laser pulses. Interlayer mixing was not observed. Application of laser pulses at fluence of 0.11 J cm^?2 caused partial and/or complete ablation of deposited layers. In partially ablated regions considerable mixing between Ti and Ta films was registered.     

Fabrication of diamond-like carbon thin films by femtosecond laser ablation of frozen acetone

Diamond-like carbon (DLC) thin films were fabricated by the ablation of frozen acetone with a 790 nm, 130 fs Ti:sapphire laser. Compared to a solid carbon target, frozen acetone could significantly reduce the number of fragments mixed into the films. The optical and mechanical properties of the fabricated DLC films were determined when the laser fluence was varied from 3 to 470 J/cm². With the increase in laser fluence, the films tinged with brown and the optical bandgap of the films decreased from 2.0 to 1.2 eV. Also, the refractive index and hardness of the films increased from 1.75 to 1.99 and from 10 to 16 GPa, respectively. The sp³ content was not changed even if the laser fluence was varied. The change in properties resulted from the hydrogen content of the films. PACS 81.05.Uw; 81.15.Fg     

Structural and optical properties of Bi3.25Nd0.75Ti3O12 ferroelectric thin films

Ferroelectric Bi_3.25Nd_0.75Ti₃O₁₂ (BNT) thin films were grown on (111)Pt/Ti/SiO₂/Si substrates by a chemical solution method. The films were composed of large rod-like grains. XRD and Raman spectroscopy measurements showed they were polycrystalline perovskite structure with a good crystallinity. Pt/BNT/Pt capacitors had been fabricated and showed good ferroelectricity. The optical constants (n, k) of BNT thin films in the wavelength ranges of 0.2–1.7 μm and 2.5–11.4 μm were obtained by spectroscopic ellipsometry measurements. The dispersion of the refractive index in the interband transition region followed the single electronic oscillator model. The optical band gap was found to be about 3.61 eV. PACS 77.84.-s; 78.20.Ci; 77.80.-e     

Effects of texture on the dielectric properties of Ba(Zr0.2Ti0.8)O3 thin films prepared by pulsed laser deposition

Ba(Zr_0.2Ti_0.8)O₃ (BZT) thin films were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by a pulsed laser deposition process. The BZT thin films directly grown on annealed and un-annealed Pt/Ti/SiO₂/Si substrates exhibited random and high (100) orientations, respectively. The dielectric constant of a 400-nm-thick BZT film with (100) orientation was 331, which was higher than that of a BZT film with random orientation (∼236). This result is attributed to the fact that the polar axis of the (100)-oriented films was more tilted away from the normal to the film surface than that of the randomly oriented films. Also, the tunabilities of BZT thin films with random and (100) orientations were ∼50% and ∼59% at an applied field of 400 kV/cm, respectively. Improved tunability has been attributed to the (100) texture of the film leading to an enhancement of the in-plane-oriented polar axis. PACS 77.22.-d; 77.55.+f; 77.80.-e; 77.84.-s     

Structural and electrical properties of lithium manganese oxide thin films grown by pulsed laser deposition

LiMn₂O₄ thin films were deposited by reactive pulsed laser deposition technique and studied the microstructural and electrical properties of the films. The LiMn₂O₄ thin films deposited in an oxygen partial pressure of 100 mTorr and at a substrate temperature of 573 K from a lithium rich target were found to be nearly stoichiometric. The films exhibited predominantly (111) orientation representing the cubic spinel structure with Fd3m symmetry. The intensity of (111) peak increased and a slight shift in the peak position was observed with the increase of substrate temperature. The lattice parameter increased from 8.117 to 8.2417 Å with the increase of substrate temperature from 573 to 873 K. The electrical conductivity of the films is observed to be a strong function of temperature. The evaluated activation energy for the films deposited at 873 K is 0.64 eV.     

Structural and optical properties of nano-structured tungsten-doped ZnO thin films grown by pulsed laser deposition

Novel highly c-oriented tungsten-doped zinc oxide (WZO) thin films with 1 wt% were grown by pulsed laser deposition (PLD) technique on corning 1737F glass substrate. The effects of laser energy on the structural, morphological as well as optical transmission properties of the films were studied. The films were highly transparent with average transmittance exceeding 87% in the wavelength region lying between 400 and 2500 nm. X-ray diffraction analysis (XRD) results indicated that the WZO films had c-axis preferred orientation with wurtzite structure. Film thickness and the full width at half maximum (FWHM) of the (0 0 2) peaks of the films were found to be dependent on laser fluence. The composition determined through Rutherford backscattering spectroscopy (RBS) appeared to be independent of the laser fluence. By assuming a direct band gap transition, the band gap values of 3.36, 3.34 and 3.31 eV were obtained for corresponding laser fluence of 1, 1.7 and 2.7 J cm⁻², respectively. Compared with the reported undoped ZnO band gap value of 3.37 eV, it is conjectured that the observed low band gap values obtained in this study may be attributable to tungsten incorporation in the films as well as the increase in laser fluence. The high transparency makes the films useful as optical windows while the high band gap values support the idea that the films could be good candidates for optoelectronic applications.     

Identification of A- and B-site cation vacancy defects in perovskite oxide thin films

Cation vacancies on both sublattices (V(Ti), V(Sr)) have been identified in homoepitaxial pulsed laser deposited SrTiO3 films using high intensity variable energy positron annihilation lifetime spectroscopy (PALS) measurements. Film nonstoichiometry was varied by varying laser fluence. PALS showed that on increasing the fluence above the Ti/Sr～1 value, the concentration ratio [V(Sr)]/[V(Ti)] systematically increased. Reducing the fluence into the Ti-poor region below resulted in additional vacancy cluster defect formation. Vacancy concentrations greater than ～50 ppm were observed in all films.     

Optical Properties of Co-BaTiO3/Mg（100） Nano-Composite Films Grown by Pulsed Laser Deposition Method

Co nanoparticles embedded in a BaTiO3 matrix, namely Co-BaTiO3 nano-composite films are grown on Mg（100） single crystal substrates by the pulsed laser deposition （PLD） method at 650℃. Optical properties of the CoBaTiO3 nano-composite films are examined by absorption spectra （AS） and photoluminescence （PL） spectra. The results indicate that the concentration of Co nano-particles strongly influences the electron transition of the Co BaTiO3 nano-composite films. The PL emission band ranging from 1.9 to 2.2eV is reported. The AS and PL spectra suggest that the band gap is in the range of 3.28-3.7eV.