Off-axis pulsed laser deposition system for epitaxial oxide growth on substrates up to 2 inches in diameter

A novel off-axis pulsed-laser deposition (PLD) system for ferroelectric oxide thin films has been developed. The substrates are mounted "upside-down" and are rotating. The maximum substrate size is 2 inches in diameter. The optical and structural properties of the grown BaTiO₃ films are compared to the films produced by an on-axis PLD system. The stoichiometry and thickness were checked with Rutherford backscattering spectrometry (RBS). The crystalline quality and orientation were investigated with X-ray diffraction (XRD) and Rutherford backscattering spectrometry in channeling configuration (RBS/C). Using atomic force microscopy, the rms surface roughness was measured. The BaTiO₃ films grown on MgO form a planar optical waveguide. The optical losses and the refractive indices of these waveguides were determined with a prism coupling setup. Films grown on 10᎒ mm² MgO (100) substrates in on-axis geometry show optical waveguide losses less than 3 dB/cm.     

Low-temperature growth of Y2O3 thin films by ultraviolet-assisted pulsed laser deposition

Thin Y₂O₃ films have been grown on (100) Si using an in-situ ultraviolet-assisted pulsed laser deposition (UVPLD) technique. When compared to conventional pulsed laser deposited (PLD) films under similar conditions, the UVPLD-grown films exhibited better structural and optical properties, especially those grown at lower substrate temperatures, from 200 °C to 400 °C. X-ray diffraction investigations showed that the films grown were highly crystalline and textured. According to X-ray photoelectron spectroscopy and Rutherford backscattering spectrometry investigations, UVPLD-grown Y₂O₃ films have a better overall stoichiometry and contain less physisorbed oxygen than the conventional PLD-grown films. The refractive index values, measured in the range 300-750 nm by using variable-angle spectroscopic ellipsometry, were similar to those of a reference Y₂O₃ film.     

Low-temperature growth of epitaxial ZnO films on (001) sapphire by ultraviolet- assisted pulsed laser deposition

ZnO thin films have been grown on thin Si₃N₄ membranes and (001) sapphire substrates by an ultraviolet-assisted pulsed laser deposition (UVPLD) technique. The microstructure of the films grown on Si₃N₄ membranes, investigated by transmission electron microscopy, showed that crystalline and textured films can be grown by UVPLD at a substrate temperature of only 100 °C. For deposition temperatures higher than 400 °C, ZnO films grown on sapphire substrates were found to be epitaxial by Rutherford backscattering (RBS) and X-ray diffraction measurements. The minimum yield of channeling RBS spectra recorded from films deposited at 550 °C was around 2% and the FWHM of the rocking curve for the (002) diffraction peak was 0.17°; these values are similar to those recorded from ZnO layers grown by conventional PLD at 750 °C.     

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.     

Adjusting chemical bonding of hard amorphous CSixNy thin films by N*-plasma-assisted pulsed laser deposition

Hard amorphous carbon silicon nitride thin films have been grown by pulsed laser deposition (PLD) of various carbon silicon nitride targets by using an additional nitrogen RF plasma source on [100] oriented silicon substrates at room temperature. The influence of the number of laser shots per target site on the growth rate and film surface morphology was studied. Up to about 30 at. % nitrogen and up to 20 at. % silicon were found in the films by Rutherford backscattering spectroscopy (RBS) and X-ray photoelectron spectroscopy (XPS). The XPS of the films showed a clear correlation of binding energy to the variation of PLD parameters. The films show a universal hardness value up to 23 GPa (reference value for silicon substrate 14 GPa) in dependence on target composition and PLD parameters. The results emphasise the possibility of variation of chemical bonding and corresponding properties, such as nanohardness, of amorphous CSi_xN_y thin films by the plasma-assisted PLD process.     

Pulsed laser deposition of carbon nitride films by a sub-ps laser

CN_x (0.01-2 to 0.6 mbar the nitrogen content of the films increases monotonously, as determined by X-ray photoelectron spectroscopy. Raman spectroscopy reveals that the films consist predominantly of highly amorphous carbon.     

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.     

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.     

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.     

Highly reproducible large-area and double-sided pulsed laser deposition of HTSC YBCO:Ag thin films for microwave applications

Large-area pulsed laser deposition (PLD) producing high-quality YBa₂Cu₃O_7-x (YBCO) thin films on both sides of R-plane sapphire substrates with CeO₂ buffer layer is used routinely to optimize planar microwave stripline filters for satellite and mobile communication systems. A relatively simple PLD arrangement with fixed laser plume and rotating substrate, with an offset between the laser plume and the center of the substrate is employed to deposit laterally homogeneous 3-inch-diameter Ag-doped YBCO thin films. The YBCO:Ag films are about 250 nm thick and have laterally homogeneous critical current densities of more than 3.5 MA/cm² at 77 K and homogeneous maps of microwave surface resistance R_s of about 40 m Q at 145 GHz and 77 K. The R_s at 8.5 GHz and 77 K, determined in the center position of the YBCO:Ag films, remains constant at about 370 7 Q up to a microwave surface magnetic field of about 10 mT. After experience with more than 700 double-sided 3-inch-diameter films, a high degree of homogeneity and reproducibility of j_c and R_s is reached. The PLD-YBCO:Ag films are suitable for microwave applications envisaged for future communication systems.     

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%.     

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.     

Vacuum versus gas environment for the synthesis of nanocomposite films by pulsed-laser deposition

Nanocomposite films formed by Cu nanocrystals (NCs) with sizes <10 nm embedded in an amorphous Al₂O₃ host have been grown by alternate pulsed-laser deposition both in vacuum and in a buffer gas (Ar) up to pressures of 0.1 Torr. The dimensions, dimension distributions, and shape of the NC produced in vacuum and in Ar up to pressures of 5᎒^-3 Torr follow a similar trend as a function of the Cu areal density. This allows us to conclude that the nucleation and growth of the NC are dominated by processes occurring at the substrate surface rather than in the gas phase. For Ar pressures ̓᎒^-2 Torr, the anisotropy of the NC is enhanced, the deposition rate decreases abruptly and a significant amount of the buffer gas is incorporated into the host, thus leading to the formation of a porous material.     

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.     

A Charge-Trap Memory Device with a Composition-Modulated Zr-Silicate High-k Dielectric Multilayer Structure

We report a novel charge-trap memory device with a composition-modulated Zr-silicate high-k dielectric mul- tilayer structure prepared by using the pulsed laser deposition technique. The device employs amorphous （ZrO2）0.5（SiO2）0.5 as the tunneling and blocking oxide layers, and ZrO2 nanocrystals as the trapping storage layer. Zr02 nanocrystals are precipitated from the phase separation of （ZrO2）0.5（SiO2）0.2 films annealed at 800℃, and isolated from each other within the amorphous （ZrO2）0.5（SiO2）0.5 matrix. Our charge trapping device shows a memory window of 2.6 V and a stored electron density of 1×10^13/cm2.     

Low-temperature preparation of SrxBi2+yTa2O9 ferroelectric thin film by pulsed laser deposition and its application to a metal–ferroelectric–nitride–oxide–semiconductor structure

Preferentially (105)-oriented Sr_xBi_2+yTa₂O₉ (SBT) thin films on SiN/SiO₂/p-Si(100) prepared by the pulsed laser deposition (PLD) method at a temperature as low as 400 °C, which is the lowest process temperature for growing SBT ferroelectric thin films on a silicon nitride film. Excess Bi promotes crystallization of the SBT film. A metal-ferroelectric-nitride-oxide-semiconductor (MFNOS) structure, which is very important in ferroelectric gate memory FET, has been fabricated by depositing the SBT film on silicon nitride-oxide-silicon. The MFNOS structures show capacitance-voltage (C-V) hysteresis corresponding to ferroelectric hysteresis. A memory window of the C-V hysteresis is improved, to be as high as 3.5 V in the SBT(400 nm)/SiN_x(7 nm)/SiO₂(18 nm)/Si compared with the window of 2.7 V in the SBT(400 nm)/SiO₂(27 nm)/Si (MFOS), where the thicknesses of their insulator layers are nearly the same. Little degradation is induced in the C-V characteristics of the SiN_x/SiO₂/p-Si structure when depositing the SBT film by PLD at low temperature. It is also found that the SiN_x layer acts as a diffusion barrier against component atoms in the SBT film during its deposition. Finally, the MFNOS structure prepared at the low temperature is very promising for a next-generation ferroelectric gate memory FET.     

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.     

Measurement and Analysis of Composition and Depth Profile of H in Amorphous Si1-xCx:H Films

Composition in amorphous Si1-xCx：H heteroepitaxial thin films on Si （100） by plasma enhanced chemical vapour deposition （PECVD） is analysed. The unknown x （0.45-3.57） and the depth profile of hydrogen in the thin films are characterized by Rutherford backscattering spectrum （RBS）, resonance-nuclear reaction analysis （R-NRA） and elastic recoil detection （ERD）, respectively. In addition, the depth profile of hydrogen in the unannealed thin films is compared to that of the annealed thin films with rapid thermal annealing （RTA） or laser spike annealing （LSA） in nitrogen atmosphere. The results indicate that the stoichiometric amorphous SiC can be produced by PECVD when the ratio of CH4/SiH4 is approximately equal to 25. The content of hydrogen decreases suddenly from 35% to 1% after 1150℃ annealing. RTA can reduce hydrogen in SiC films effectively than LSA.     

LaNiO3 under-electrode layers for the growth of textured (Pb0.4Zr0.6)TiO3 thin films using pulsed laser deposition

We investigated the structural properties of LaNiO₃ thin films of three different thicknesses deposited by pulsed laser deposition on Si(001) mainly by using a synchrotron X-ray scattering measurement. The LaNiO₃ thin films were grown with the (00l) preferred growth direction, showing completely random distribution in the in-plane direction. In the early stage of the growth, the film was almost unstrained. However, as the film grew further, tensile strain was markedly involved. Also its surface became rougher but its crystalline quality improved significantly with increasing film thickness. A completely (00l)-oriented (Pb_0.4Zr_0.6)TiO₃ thin film was successfully grown on such a LaNiO₃/Si(001) substrate at a substrate temperature of 350 °C by using the same pulsed laser deposition. Our results show that the LaNiO₃ film can serve effectively as a bottom electrode layer for the preparation of a well-oriented (Pb_0.4Zr_0.6)TiO₃ thin film on Si substrates.     

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.