Laser irradiation of SrTiO3 single crystals

Excimer laser irradiation (248 nm, 34 ns) of SrTiO₃(100)single crystals was studied in order to resolve the feasibility of obtaining well-defined patterned structures. Spots irradiated with a single pulse in the 0.4-1 J/cm² fluence range presented a pattern of cracks along crystallographic directions, which do not propagate beyond the borders, and no ejected material was observed on the non- irradiated areas. Arrays were patterned by translating the single crystal, and different morphologies were found depending on the width of the tracks. Tracks 10 7m wide or more developed a pattern of cracks, whereas 3 7m wide tracks did not. Artificial arrays in magnetoresistive La_2/3Sr_1/3MnO₃ thin films were prepared by using SrTiO₃(100) single-crystal substrates in which arrays had been previously patterned. The interfaces originated a substantial low-field tunnel magnetoresistance.     

Structural and electrical properties of La0.5Sr0.5CoO3 films on SrTiO3 and porous a-Al2O3 substrates

Films of La_0.5Sr_0.5CoO₃ (LSCO) have been deposited on specially treated TiO₂-terminated (001) SrTiO₃ substrate surfaces and on macroporous polycrystalline !-Al₂O₃ substrates, having a mean pore diameter of 80 nm, by pulsed laser deposition. The films deposited on SrTiO₃ are good conducting, (001) textured, and exceptionally smooth (1-2 Å for 100 nm thick films). LSCO films deposited on porous !-Al₂O₃ are polycrystalline and exhibit good crystallographic and electrical properties despite the large substrate roughness and the differences in lattice parameters and crystal structure between the film and the substrate. Different growth modes have been observed on the porous !-Al₂O₃ substrates depending on the oxygen pressure during film deposition. Films grown at an oxygen pressure of 10^-1 mbar are macroporous, whereas films grown at 10^-2 mbar completely cover the substrate pores. In the latter case, strain effects lead to film cracking.     

Preferential orientation of modified SrBi2Nb2O9 ferroelectric thin films prepared by pulsed laser deposition

We report on the deposition of SrBi₂Nb₂O₉ and Sr_1-xNa_xBi_2-xTe_xNb₂O₉ ferroelectric thin films on Pt/TiO₂/SiO₂/(100)Si substrates using the pulsed laser deposition technique. Deposition on substrates heated to 600-700 °C produces {11l} film texture and dense films with grain sizes up to about 500 nm. The recrystallization at 700 °C of amorphous films deposited at lower temperatures enhances the contribution of the {100} and {010} orientations. These films show smaller grain size, namely 50-100 nm. {11l}-oriented Sr_1-xNa_xBi_2-xTe_xNb₂O₉ films have remnant polarization P_rۆ 7C/cm², a coercive field E_c䏐 kV/cm and dielectric constant, )𪓴. The low value of P_r is probably related to the low fraction of grains with the ferroelectric axis in the direction of the applied field, E. The recrystallized films have more grains with the ferroelectric axis parallel to E; however, they have a low resistivity which so far has prevented electrical characterization.     

Atomic Diffusion in Cu/Si （111） and Cu/SiO2/Si （111） Systems by Neutral Cluster Beam Deposition

The Cu films are deposited on two kinds of p-type Si （111） substrates by ionized duster beam （ICB） technique. The interface reaction and atomic diffusion of Cu/Si （111） and Cu/SiO2/Si （111） systems are studied at different annealing temperatures by x-ray diffraction （XRD） and Rutherford backscattering spectrometry （RBS）. Some significant results are obtained： For the Cu/Si （111） samples prepared by neutral dusters, the interdiffusion of Cu and Si atoms occurs when annealed at 230℃. The diffusion coefficients of the samples annealed at 230℃ and 500℃ are 8.5 ×10^-15 cm^2.s^-1 and 3.0 ×10^-14 cm^2.s^-1, respectively. The formation of the copper-silicide phase is observed by XRD, and its intensity becomes stronger with the increase of annealing temperature. For the Cu/SiO2//Si （111） samples prepared by neutral dusters, the interdiffusion of Cu and Si atoms occurs and copper silicides are formed when annealed at 450℃. The diffusion coefficients of Cu in Si are calculated to be 6.0 ×10^-16 cm^2.s^-1 at 450℃, due to the fact that the existence of the SiO2 layer suppresses the interdiffusion of Cu and Si.     

Ablation of transparent solids during self-limited deposition of diamond-like films from liquid hydrocarbons

A novel effect is studied of self-limitation of the diamond-like film thickness during laser irradiation of the interface of transparent substrates with liquid aromatic hydrocarbons. The interface is exposed through the transparent substrate to radiation of a copper vapor laser (wavelength of 510.6 nm, pulse duration of 20 ns). The thickness of diamond-like film increases linearly to 80-100 nm with the number of laser pulses and then saturates, while the substrate is ablated with nearly constant rate. This ablation rate depends on the thermal expansion coefficient of the substrate (glass, fused silica, sapphire, or CaF₂). The absorption of extinction coefficient of deposited films measured by ellipsometry is of order of 10⁴ cm^-1 and is sufficient to cause the significant heating of the interface. The ablation of the transparent substrates is due to their unequal thermal expansion compared to the diamond-like film having different thermal expansion coefficient. The measured ablation rates scale from 0.2 Å/pulse for glass to 4.5 Å/pulse for CaF₂. A 7m spatial resolution of the ablation process has been demonstrated for fused silica.     

Pulsed KrF laser deposited GaN/TiN/Si(111) heterostructures by sequential TiN and liquid Ga laser ablation

GaN/TiN heterostructures were deposited on 4° miscut Si(111) substrates by pulsed KrF laser ablation of TiN through vacuum, followed by reactive pulsed KrF laser ablation of liquid Ga through 70-75 mTorr of microwave-activated NH₃. Deposition temperatures of 950 °C and 1050 °C were employed for the TiN layer while 900 °C was employed for the GaN layer. The targets were positioned 5 cm from the substrate and ablated by using a reimaging beamline at a nominal energy density of 3-4 J/cm². X-ray diffraction (XRD) revealed a highly textured heterostructure with GaN(0001)//TiN(111)//Si(111) and with a rocking curve width for both GaN(0001) and TiN(111) equal to ~1.1°. The mosaic spread through the TiN(001) reflection was ~1.3°, whereas that of the GaN(101_1) was undetectable because of low S/N. Scanning electron microscopy revealed large oriented 10 7m-sized hexagonal crystallites decorating large depressions in the TiN film with many smaller pits also present. The effect of substrate processing and TiN film processing on pit formation was explored.     

Electrical and optical properties of indium tin oxide thin films grown by pulsed laser deposition

Indium tin oxide (ITO) thin films (200-400 nm in thickness) have been grown by pulsed laser deposition (PLD) on glass substrates without a post-deposition anneal. The electrical and optical properties of these films have been investigated as a function of substrate temperature and oxygen partial pressure during deposition. Films were deposited at substrate temperatures ranging from room temperature to 300 °C in O₂ partial pressures ranging from 0.1 to 100 mTorr. For 300 nm thick ITO films grown at room temperature in oxygen pressure of 10 mTorr, the electrical conductivity was 2.6᎒^-3 Q^-1cm^-1 and the average optical transmittance was 83% in the visible range (400-700 nm). For 300 nm thick ITO films deposited at 300 °C in 10 mTorr of oxygen, the conductivity was 5.2᎒^-3 Q^-1cm^-1 and the average transmittance in the visible range was 87%. Atomic force microscopy (AFM) measurements showed that the RMS surface roughness for the ITO films grown at room temperature was ~7 Å, which is the lowest reported value for the ITO films grown by any film growth technique at room temperature.     

Deposition of highly oriented Bi12SiO20 thin films on Y-stabilized zirconia and SiO2 by pulsed-laser deposition

We describe the deposition and characterization of Bi₁₂SiO₂₀ (bismuth silicon oxide; BSO) thin films on Y-stabilized zirconia (YSZ) and SiO₂ glass substrates by pulsed-laser deposition (PLD) for the application of an electric field sensor. It was found that all films deposited on YSZ substrates heated at 400 °C and more were crystallized and the (310) plane was perpendicular to the substrate normal. The highly (310) oriented crystallized films were even deposited on SiO₂ glass substrates, and this will make it possible to grow the crystallized films on the end surface of a SiO₂ glass fiber.     

Synthesis and characterization of laser ablated TiNi films

TiNi thin films with BaTiO₃ and PbZr_0.52Ti_0.48O₃ (PZT) as buffer layers were deposited on Si(100) substrates by the pulsed laser deposition (PLD) method. Buffer layers (BaTiO₃ and PZT) were deposited at 600 °C in oxygen (O₂) environment and TiNi films were deposited on the top of the buffer layer in presence of 15 mTorr nitrogen (N₂) at various deposition temperatures (50, 300, and 500 °C). Synthesis and characterization of TiNi films were investigated from the crystallographic point of view by using X-ray diffractometer (XRD) and atomic force microscope (AFM) techniques. It is found that buffer layer of BaTiO₃ and PZT have improved the crystallinity of TiNi films deposited at higher temperatures. The TiNi/PZT film was uniform compared to TiNi/BaTiO3 film with the exception of agglomerates that appeared throughout the layer.     

Role of bismuth precursor in crystallization of SrBi2Ta2O9 thin films

Crystallization of SrBi₂Ta₂O₉ (SBT) thin films was studied as a function of viscosity of bismuth precursor and baking temperature, in order to fabricate capacitors with improved ferroelectric properties. SBT thin films were deposited on to Pt substrates using a chemical solution deposition (CSD) technique. Post-deposition anneal at 750 °C for 1 h in oxygen atmosphere revealed a significant influence of baking temperature and the viscosity of bismuth precursor on the microstructure and the ferroelectric properties of SBT thin films. A high baking temperature (350 °C) and a low viscosity of bismuth precursor (8 cp) yielded larger amounts of Bi₂O₃ secondary phase, smaller SBT grains (104 nm), and lower remanent polarization (P_r=2.0 7c/cm²). Additionally, these films exhibited a very high rate of ageing (>45% reduction in P_r after 7 days). A modified CSD process is suggested, which could suppress the formation of Bi₂O₃ secondary phase. Films fabricated using modified CSD technique exhibited a much larger grain size of 165 nm, higher P_r of 7.2 7c/cm², and significantly improved ageing characteristics (<1% reduction in P_r after 7 days). A qualitative model to describe the ageing in SBT-based capacitors is also suggested.     

Large-area pulsed laser deposition of YBCO thin films: homogeneity and surface

YBCO thin films and buffer layers are deposited by a special PLD setup with an 8-cm line focus on cylindrical targets and substrate scanning perpendicular to it. Different kinds of substrates (SrTiO₃, MgO, LaAlO₃, Y-ZrO₂and sapphire) as large as 7᎜ cm² were coated with YBCO. Two important aspects of the presented PLD setup will be discussed in detail: the method of substrate heating and the variation of the angle between the incident laser beam and the target surface ("wobbling"). The surface of the target material has been investigated by SEM. The influence of target "wobbling" on the time stability of the plasma will be discussed. The homogeneity of the deposited YBCO films with respect to structural and electrical properties has been investigated by XRD, RBS/channeling, and spatially resolved inductive measurements of T_c and j_c. The values of j_c on 7᎜ cm²in situ buffered sapphire substrates are 2.0 MA/cm² at (77 K, 0 T) with a j_c variation of less than ᆨ%.     

Room-Temperature Ferromagnetism in Zn1-xMnxO Thin Films Deposited by Pulsed Laser Deposition

Zn1-xMnxO （x = O.Olq3.1） thin films with a Curie temperature above 300K are deposited on Al2O3 （0001） substrates by pulsed laser deposition. X-ray diffraction （XRD）, ultraviolet （UV）-visible transmission and Raman spectroscopy are employed to characterize the microstructural properties of these films. Room temperature ferromagnetism is observed by superconducting quantum interference device （SQUID）. The results indicate that Mn doping introduces the incorporation of Mn^2＋ ions into the ZnO host matrix and the insertion of Mn^2＋ ions increases the lattice defects, which is correlated with the ferromagnetism of the obtained films. The doping concentration is also proven to be a crucial factor for obtaining highly ferromagnetic Zn1-xMnxO films.     

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.     

Piezoelectric Pb0.7La0.2TiO3 prepared by pulsed laser deposition on (100)InP

La-modified PbTiO₃ (PLT) thin films have been deposited by pulsed laser deposition on (100)InP substrates. The nominal target composition was selected to optimize piezoelectric properties of the material. It is shown that PLT deposition on as-received InP produces amorphous PLT films because of the presence of a native oxide on the substrate. PLT films deposited on bare InP have poor adhesion as a result of the surface reoxidation of the substrate due to the high oxygen pressure required for the deposition of stoichiometric PLT. To prevent substrate oxidation, several buffer oxides (CeO₂, ZrO₂, SrO, Y-stabilized ZrO₂, MgO, and SrTiO₃) have been grown in vacuum on (100)InP. Highest-quality heteroepitaxy was found with Y-stabilized ZrO₂ (YSZ), being 𘜄¢{100} YSZ𘜄¢{100} InP oriented. The PLT deposited on this buffer layer is oriented with the [101] direction perpendicular to the substrate surface plane.     

Laser-induced positive ion and neutral atom/molecule emission from single-crystal CaHPO4·2 H2O: The role of electron-beam-induced defects

We examine laser-induced ion and neutral emissions from single-crystal CaHPO₄·2 H₂O (brushite), a wide-band-gap, hydrated inorganic single crystal, with 248-nm excimer laser radiation. Both laser-induced ion and neutral emissions are several orders of magnitude higher following exposure to 2 keV electrons at current densities of 200 7A/cm² and doses of 1 C/cm². In addition to intense Ca⁺ signals, electron-irradiated surfaces yield substantial CaO⁺, PO⁺, and P⁺ signals. As-grown and as-cleaved brushite show only weak neutral O₂ and Ca emissions, whereas electron-irradiated surfaces yield enhanced O₂, Ca, PO, PO₂, and P emissions. Electron irradiation (i) significantly heats the sample, leading to thermal dehydration (CaHPO₄ formation) and pyrolysis (Ca₂P₂O₇ formation) and (ii) chemically reduces the surface via electron stimulated desorption. The thermal effects are accompanied by morphological changes, including recrystallization. Although complex, these changes lead to high defect densities, which are responsible for the dramatic enhancements in the observed laser desorption.     

Highly (100) oriented Pb(Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>)O<Subscript>3</Subscript>/LaNiO<Subscript>3</Subscript> films grown on amorphous substrates by pulsed laser deposition

Pb(Zr_0.52Ti_0.48)O₃ (PZT)/LaNiO₃ (LNO) thin films with highly (100) out of plane orientation were produced on SiO₂/Si(100) and alkaline earth aluminosilicate glass substrates by pulsed laser deposition (PLD). Orientations of both PZT and LNO films were evaluated using X-ray diffraction. The pure (100)-oriented PZT/LNO films were obtained under optimized deposition conditions. Time of flight-secondary ion mass spectrometry analysis showed that LNO could effectively block interdiffusion between the PZT films and the substrates. Fairly smooth surfaces of the PZT films with roughness of about 4 nm were observed using an atomic force microscope. Cross sectional examination revealed that the films grew in columnar grains. The PZT films grown on both SiO₂/Si and glass substrates demonstrated very good ferroelectric characteristic at room temperature with remnant polarization of up to 26 μC/cm². PACS 79.20.DS; 77.84.DY; 78.70.Ck     

Large crystalline grain growth using current-induced Joule heating

Electrical-current-induced Joule heating was applied to crystallization of 60-nm-thick amorphous silicon films formed on glass substrates. 3-7s-pulsed voltages were applied to silicon films connected with a capacitance in parallel. Coincident irradiation with 28-ns-pulsed excimer laser melted films partially and reduced its resistance. Complete melting for 12 7s and a low cooling rate at 1.1᎒⁸ K/s were achieved by Joule heating from electrical energy accumulated in the capacitance at 0.22 7F. For 7.4᎒¹⁷ cm^-3 phosphorus-doped films, analysis of temperature change in the electrical conductivity gave that the density of defect states localized at grain boundaries was 1.5᎒¹² cm^-2. Formation of 3.5-7m-long crystalline grains was observed by transmission electron micrograph. Preferential crystalline orientation was (110).     

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.     

Transport Behaviour of La0.8Sr0.2AlO3 Thin Film on Oxygen Deficient SrTiO3 Substrate

La_0.8Sr_0.2AlO₃ (LSAO) thin films are grown on SrTiO₃ (STO) and MgO substrates by laser molecular beam epitaxy. The LSAO thin film on oxygen deficient STO substrate exhibits metallic behaviour over the temperature range of 80--340K. The optical transmittance spectrum indicates that theLSAO thin films on MgO substrate are insulating at room temperature. The transport properties of LSAO thin films on STO substrates deposited in different oxygen pressure are compared. Our results indicate that oxygen vacancies in STO substrates should be mainly responsible for the transport behaviour of LSAO thin films.     

Pulsed-laser deposition of Ta-doped PZT ferroelectric films for memory applications using conductive oxide La0.25Sr0.75CoO3 and SrRuO3 electrodes

New methods for fabricating highly 𘚡¢-oriented and complete 𘜏¢-textured Pb(Ta_0.05Zr_0.48Ti_0.47)O₃ (PTZT) films on Pt/TiO₂/SiO₂/Si(001) substrates by pulsed-laser deposition have been developed using conductive oxide La_0.25Sr_0.75CoO₃ and SrRuO₃ electrodes. The 𘚡¢-preferred orientated PTZT ferroelectric capacitor was not subjected to loss of its polarization after 1᎒¹⁰ switching cycles at an applied voltage of 5 V and a frequency of 1 MHz, and the 𘜏¢-textured PTZT film capacitor retains 94.7% of its polarization after 1.5᎒¹⁰ switching cycles at 5 V and 50 kHz. The PTZT capacitors using these conductive oxide electrodes have low leakage current dominated by Schottky field emission mechanism.