Thermal stability of amorphous molybdenum trioxide films prepared at different oxygen partial pressures by reactive DC magnetron sputtering

Thin films of MoO₃ were prepared on quartz and Si (1 0 0) substrates by reactive dc magnetron sputtering of a Mo target in an oxygen and argon atmosphere. The structural and optical changes induced in the films due to post-growth annealing have been systematically studied by Rutherford backscattering (RBS), X-ray diffraction (XRD), X-ray reflectivity (XRR) and by optical methods. RBS studies reveal no change in composition of the films upon annealing at high temperatures. Grazing angle XRD studies show that the as-deposited films are amorphous and crystallize to β-MoO₃ phase with small contribution of α-MoO₃ upon annealing at 300 °C. The film prepared at 0.40 Pa transforms to α-MoO₃ upon annealing at 650 °C, while the film deposited at 0.19 Pa still has some β-MoO₃ phase contribution. XRR measurements reveal that the film thickness decreases upon annealing with simultaneous increase of film density. The surface roughness of the films strongly increases after crystallization. The contraction of the film deposited at 0.40 Pa is much greater than the contraction of the film prepared at 0.19 Pa. The mass variation of the film deposited at 0.19 Pa and that deposited at 0.40 Pa are completely different. The optical properties of MoO₃ films deposited at 0.19 and 0.40 Pa are changed strongly by annealing.     

Large area Ba1 − xSrxTiO3 thin films for microwave applications deposited by pulsed laser ablation

Large area Ba_1 − xSr_xTiO₃ (BST) thin films with x = 0.4 or x = 0.5 were deposited on 75 mm diameter Si wafers in a pulsed laser deposition (PLD) chamber enabling full-wafer device fabrication using standard lithography. The deposition conditions were re-optimized for large PLD chambers to obtain uniform film thickness, grain size, crystal structure, orientation, and dielectric properties of BST films. X-ray diffraction and microstructural analyses on the BST films grown on Pt/Au/Ti electrodes deposited on SiO₂/Si wafers revealed films with (110) preferred orientation with a grain size < 100 nm. An area map of the thickness and crystal orientation of a BST film deposited on SiO₂/Si wafer also showed (110) preferred orientation with a film thickness variation < 6%. Large area BST films were found to have a high dielectric tunability of 76% at an electric field of 400 kV/cm and dielectric loss tangent below 0.03 at microwave frequencies up to 20 GHz and a commutation quality factor of ~ 4200.     

High dielectric tunability of Ba0.6Sr0.4TiO3 thin film deposited by radio-frequency magnetron sputtering

In microwave tunable devices, one of the major challenges encountered is the simultaneous minimization of the material's dielectric loss and maximization of dielectric tunability. In this work, Ba_0.6Sr_0.4TiO₃ thin film with the thickness of 300 nm was deposited on Pt/SiO₂/Si substrates using radio-frequency magnetron sputtering technique, and its dielectric properties were investigated. Due to the high temperature annealing process at substrate temperature of 600 °C, well-crystallized Ba_0.6Sr_0.4TiO₃ film was deposited. The dielectric constant and dielectric loss of the film at 100 kHz are 300 and 0.033, respectively. Due to the good crystallinity of the Ba_0.6Sr_0.4TiO₃ films deposited by radio-frequency magnetron sputtering, high dielectric tunability up to 38.3% is achieved at a low voltage of 4.5 V.     

Enhanced ferroelectric properties of Pb(Zr0.80Ti0.20)O3/PbO thin films prepared by radio frequency magnetron sputtering

The Pb(Zr_0.80Ti_0.20)O₃ (PZT) thin films with and without a PbO buffer layer were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by radio frequency (rf) magnetron sputtering method. The PbO buffer layer improves the microstructure and electrical properties of the PZT thin films. High phase purity and good microstructure of the PZT thin films with a PbO buffer layer were obtained. The effect of the PbO buffer layer on the ferroelectric properties of the PZT thin films was also investigated. The PZT thin films with a PbO buffer layer possess better ferroelectric properties with higher remnant polarization (P_r = 25.6 μC/cm²), and lower coercive field (E_c = 60.5 kV/cm) than that of the films without a PbO buffer layer (P_r = 9.4 μC/cm², E_c = 101.3 kV/cm). Enhanced ferroelectric properties of the PZT thin films with a PbO buffer layer is attributed to high phase purity and good microstructure.     

Tl2Ba2CaCu2O8 thin films on 2 in. LaAlO3(0 0 1) substrates

High quality Tl₂Ba₂CaCu₂O₈ (Tl-2212) superconducting thin films are prepared on both sides of 2 in. LaAlO₃(0 0 1) substrates by off-axis magnetron sputtering and post-annealing process. XRD measurements show that these films possess pure Tl-2212 phase with C-axis perpendicular to the substrate surface. The thickness unhomogeneity of the whole film on the 2 in. wafer is less than 5%. The superconducting transition temperatures T_cs of the films are around 105 K. At zero applied magnetic field, the critical current densities J_cs of the films on both sides of the wafer were measured to be above 2 × 10⁶ A/cm² at 77 K. The microwave surface resistance R_s of film was as low as 350 μΩ at 10 GHz and 77 K. In order to test the suitability of Tl-2212 thin films for passive microwave devices, 3-pole bandpass filters have been fabricated from double-sided Tl-2212 films on LaAlO₃ substrates.     

Directed evolution of α-grains in thin metastable-Al2O3 films deposited on Si(100) after post-deposition annealing

A 250-nm-thick Al₂O₃ film was deposited on a Si(100) by a radio-frequency magnetron sputtering and annealed at 1100 °C for various periods of time in air. In the matrix composed of fine metastable-Al₂O₃ grains of 50-100 nm in diameter, large α-Al₂O₃ grains of about 2-10 μm in diameter appeared, interestingly aligning themselves along various directions. The compressive stress developed in the alumina films because the thermal expansion coefficient of the film was higher than that of the silicon substrate. The stress distribution in the film is expected to be inhomogeneous due to some discontinuities or defects, such as arrays of dislocation pits and steps on the surface of the Si substrate, which could be generated by intersections of the substrate surface and the slip and twin planes in the Si substrate. The enhanced phase transformation into α-Al₂O₃ along various directions is suggested to arise from such discontinuities or defects.     

Ferroelectricity of ultrathin ferroelectric Langmuir-Blodgett polymer films on conductive LaNiO3 electrodes

LaNiO₃ (LNO) films with a surface roughness rms of 0.384 nm and a sheet resistance of about 200 Ω were prepared on SrTiO₃ and Si/SiO₂ substrates respectively by rf magnetron sputtering technique. The surface of LNO on Si/SiO₂ substrate is smoother than that on SrTiO₃ substrate. A nominal 2-monolayer (ML) poly(vinylidenefluoride-trifluoroethylene) film with a thickness of about 3 nm was deposited on LNO coated Si/SiO₂ substrate by Langmuir-Blodgett (LB) technology. Piezoresponse force microscopy (PFM) measurements show that the LB films demonstrate an obvious feature of polarization switching and good voltage durability. The results suggest that the ultrathin polymer films may be utilized to explore ferroelectric tunnel junctions.     

Growth and properties of highly orientated Sr0.75Ba0.25Nb2O6 thin films on silicon substrates with MgO or TiN buffer layers

Sr_0.75Ba_0.25Nb₂O₆ (SBN75) thin films were deposited on silicon substrate with MgO (100) or TiN (100) buffer layer by radio-frequency magnetron sputtering technique. X-ray diffraction confirmed that a 900 °C annealed SBN self-buffer layer introduced before SBN deposition can lead to the highly c-axis orientation of SBN75 thin film on MgO buffer layer. Energy-dispersive spectrometry analysis showed that the SBN75 films had target-film composition transfer and the TiN buffer layer was partially oxidized during SBN growth. The refractive index of SBN films on both MgO/Si and TiN/Si substrates was determined by fitting the measured reflectance curves with Sellmeier dispersion model in the visible region and the micro-structures were studied by scanning electron microscopy. In this paper, the conditions for SBN/MgO/Si treated as waveguide structure were also discussed.     

Oxidation of magnetron sputtered La-Si thin films for solide oxide fuel cell electronlytes

La-Si thin films were deposited on stainless steel substrates by magnetron sputtering from pure La and Si targets. The Si/(Si + La) atomic ratio in the films was varied from 43.2 to 59.3% by adjusting the discharge current on the La target. The films had a homogeneous chemical composition down to the substrate and sharp interfaces. Annealing the films in air at 1173 K promotes the formation of apatite-structure La_9.33Si₆O₂₆ and the diffusion of different species from the film to the substrate and vice-versa, resulting in broadening the interfaces. X-Ray diffraction showed that all the as-deposited films had an amorphous structure. The formation of the LaSi₂ phase at intermediate temperatures was observed for the films deposited with higher Si contents while the films deposited with lower Si contents remained amorphous up to the start of the apatite structure crystallization process. The lanthanum silicate apatite-like phase (La_9.33Si₆O₂₆) was obtained only after annealing at 1173 K, excepted for the film with the lower Si content which is already partially crystallized after annealing at 1073 K. Quite pure La_9.33Si₆O₂₆ was obtained only after annealing the film with the highest Si content (Si/(Si + La) = 59.3%) although the theoretical Si/(Si + La) atomic ratio for apatite structure lanthanum silicate is 39%. For the other films, La₂O₃ was always detected when the lanthanum silicate phase was formed. Both phenomena clearly resulted from the strong diffusion of silicon excess towards the stainless steel substrate.     

Large electrocaloric effect of highly (100)-oriented 0.68PbMg1/3Nb2/3O3-0.32PbTiO3 thin films with a Pb(Zr0.3Ti0.7)O3/PbOx buffer layer

0.68PbMg_1/3Nb_2/3O₃-0.32PbTiO₃ (PMN-PT) thin films with a lead zirconate titanate Pb(Zr_0.3Ti_0.7)O₃ (PZT)/PbO_x buffer layer were deposited on Pt/TiO₂/SiO₂/Si substrates by radio frequency magnetron sputtering technique, and pure perovskite crystalline phase with highly (100)-preferred orientation was formed in the ferroelectric films. We found that the highly (100)-oriented thin films possess not only excellent dielectric and ferroelectric properties but also a large electrocaloric effect (13.4 K at 15 V, i.e., 0.89 K/V) which is attributed to the large electric field-induced polarization and entropy change during the ferroelectric-paraelectric phase transition. The experimental results indicate that the use of PZT/PbO_x buffer layer can induce the crystal orientation and phase purity of the PMN-PT thin films, and consequently enhance their electrical properties.     

Scaling behavior and structure transition of ZrO2 films deposited by RF magnetron sputtering

ZrO₂ thin films were deposited onto Si wafers and glass slides by reactive rf magnetron sputtering with varying conditions of substrate temperature (T_s). Structural analysis was carried out using high-resolution transmission electron microscopy (HRTEM) and atomic force microscopy (AFM). The scaling behavior of the AFM topographical profiles was analyzed using one-dimensional power spectral density method (1DPSD). Morphological and structural evolution of ZrO₂ films have been studied in relation to T_s. With substrate temperatures ranging from RT to 550 °C, the structural transition of the films is a-ZrO₂ (below 250 °C) → m-ZrO₂ with a little a-ZrO₂ (450 °C) → m-ZrO₂ with a little t-ZrO₂ (550 °C). The roughness exponent α is 1.53 ± 0.02, 1.04 ± 0.01, 1.06 ± 0.05, 1.20 ± 0.03 for ZrO₂ thin films deposited at RT, 250 °C, 450 °C, and 550 °C, respectively. Quantitative surface characterization by spatially resolved 1DPSD analyses identified three different growth mechanisms of surface morphology for ZrO₂ thin films deposited at RT, 250∼450 °C and 550 °C. The evolution and interactions of surface roughness and microstructure are discussed in terms of surface diffusion, grain growth, and flux shadowing mechanisms.     

Structure and magnetic properties of high coercive [PrFeBx/Cu]n films with out-of-plane orientation

Pr-Fe-B single layer and [PrFeB_x/Cu]_n films were prepared by magnetron sputtering on Si substrate heated at 650 °C. The influence of the composition and thickness of Cu spacer layer on the structure and magnetic properties of films with out-of-plane orientation are investigated. The [PrFeB_x/Cu]_n films present an enhanced coercivity and a lower remanence, in comparison with the results of Pr-Fe-B single layer. The coercivity H_c⊥ of about 19.7 kOe and the remanence ratio M_r/M_s of about 0.90 are achieved in the Mo(50 nm) / [PrFeB(300 nm) / Cu(2 nm)]₂ / Mo(50 nm) film.     

Fabrication of high frequency ZnO thin film SAW devices on silicon substrate with a diamond-like carbon buffer layer using RF magnetron sputtering

Diamond-like carbon (DLC) film is a promising candidate for surface acoustic wave (SAW) device applications because of its higher acoustic velocity. A zinc oxide (ZnO) thin film has been deposited on DLC film/Si substrate by RF magnetron sputtering; the optimized parameters for the ZnO sputtering are RF power density of 0.55 W/cm², substrate temperature of 380 °C, gas flow ratio (Ar/O₂) of 5/1 and total sputter pressure of 1.33 Pa. The results showed that when the thickness of the ZnO thin films was decreased, the phase velocity of the SAW devices increased significantly.     

Growth and characterization of (Pb,La)(Zr,Ti)O3 thin film epilayers on SrTiO3-buffered Si(001)

Ferroelectric Pb_0.92La_0.08Zr_0.4Ti_0.6O₃ (PLZT) thin films were deposited on SrTiO₃-buffered Si(001) substrate by on-axis radio frequency magnetron sputtering. X-ray diffraction analysis revealed epitaxial growth of monocrystalline PLZT films, with an (001) rocking curve full width at half maximum of ∼ 0.3°. φ-scans showed 45° in-plane orientation of the perovskite unit cell relative to that of silicon. The elemental composition of the thin film heterostructure was examined by Auger sputter depth profiling measurements. The recorded profiles suggest that the SrTiO₃ buffer layer serves not only as a template for epitaxial growth, but also as a barrier suppressing Pb-Si interdiffusion between the PLZT layer and the Si substrate. The surface roughness of the PLZT layer was measured at ∼ 4 nm for films with ∼ 500 nm thickness. Wavelength dispersions for the refractive index (n) and the extinction coefficient (k) were obtained from spectroscopic ellipsometry measurements, with n ∼ 2.48 at the main communication wavelength λ = 1550 nm and k < 0.001 for λ > 650 nm. Recorded polarization vs. electric field loops for the PLZT epilayer, with a SrRuO₃ electrode layer interposed between PLZT and SrTiO₃, showed a remnant polarization P_r ≈ 40 µC/cm² and coercive field E_c ≈ 100 kV/cm. These findings suggest that the sputter-deposited PLZT thin films retain the functional properties critical to ferroelectric and electro-optic device applications, also when integrated on a semiconductor substrate.     

Influence of high temperature processing of sol-gel derived barium titanate thin films deposited on platinum and strontium ruthenate coated silicon wafers

Thin films of barium titanate (BTO) of 200 nm thickness, derived from an alkoxide-carboxylate sol-gel process, were deposited on Pt/Ti and SrRuO₃/ZrO₂-8%Y₂O₃ coated Si wafers. Films with a dense columnar microstructure were obtained by repeated deposition of thin amorphous layers from low-concentrated sols, and crystallization at 800 °C. This method added 10 nm thickness to the crystalline BTO film in each deposition step. The harsh processing conditions had a negative impact on the platinized silicon wafers, where Pt-Si silicides were formed. This led to diffusion of Si into BTO and interfacial silicate formation. The interfacial silicate layer was the cause of deteriorated dielectric and ferroelectric properties of the BTO layer. Use of SrRuO₃/ZrO₂-8%Y₂O₃/Si substrates solved the problem. No diffusion of Si was observed, and BTO films with good dielectric and ferroelectric properties were obtained.     

Realization of phosphorus-doped p-type ZnO thin films via diffusion and thermal activation

ZnO thin films were initially deposited on a heavily phosphorus-doped Si (n⁺-Si) substrate by radio frequency magnetron sputtering. The transition from n-type ZnO to p-type one was realized by phosphorus diffusing from Si substrate to ZnO film and being thermally activated during post annealing. Crystal structures of the ZnO films were confirmed to be highly c-axis oriented wurtzite structure by X-ray diffraction experiment. Photoluminescence spectra of the ZnO films showed strong ultraviolet emissions originated from the recombination of the band-edge excitons. The composition of the films was measured by X-ray photoelectron spectroscopy, and a typical concentration of phosphorus was about 0.48% corresponding to the order of atomic density of 10¹⁹/cm³. The hole concentration of the film was + 1.28 × 10¹⁹/cm³ measured by Hall effect apparatus. Formation of the p-type ZnO films can be further confirmed by the rectifying I-V curves of p-ZnO/n⁺-Si heterojunctions.     

Growth of La0.7Sr0.3MnO3 films on Si(0 0 1) using SrMnO3 template layer

Using RF magnetron sputtering, we have successfully grown (1 1 0) orientated La_0.7Sr_0.3MnO₃ (LSMO) films on Si(0 0 1) wafers using SrMnO₃ (SMO) as a template layer. The X-ray diffraction (XRD) patterns of the SMO/Si heterostructures indicate that SMO grows along the (1 1 0) orientation, the orientation relationship between the SMO thin film and the Si (0 0 1) substrate being given by (0 1 1)_SMO∣∣(0 0 1)_Si and [01]_SMO∣∣[0 1 0]_Si. From the XRD patterns of the LSMO/SMO/Si heterostructures, we find that with an increase of substrate temperature, the required thickness of SMO, which plays an effective role of tuning the preferential orientation of LSMO, will decrease at first and then increase. It is thought that this originates from the fact that the crystallization of SMO is not perfect at low temperatures whereas too high a temperature results in reaction and diffusion at the interface of the two layers.     

Growth of 3C-SiC on 150-mm Si(100) substrates by alternating supply epitaxy at 1000 °C

To lower deposition temperature and reduce thermal mismatch induced stress, heteroepitaxial growth of single-crystalline 3C-SiC on 150 mm Si wafers was investigated at 1000 °C using alternating supply epitaxy. The growth was performed in a hot-wall low-pressure chemical vapor deposition reactor, with silane and acetylene being employed as precursors. To avoid contamination of Si substrate, the reactor was filled in with oxygen to grow silicon dioxide, and then this thin oxide layer was etched away by silane, followed by a carbonization step performed at 750 °C before the temperature was ramped up to 1000 °C to start the growth of SiC. Microstructure analyses demonstrated that single-crystalline 3C-SiC is epitaxially grown on Si substrate and the film quality is improved as thickness increases. The growth rate varied from 0.44 to 0.76 ± 0.02 nm/cycle by adjusting the supply volume of SiH₄ and C₂H₂. The thickness nonuniformity across wafer was controlled with ± 1%. For a prime grade 150 mm virgin Si(100) wafer, the bow increased from 2.1 to 3.1 μm after 960 nm SiC film was deposited. The SiC films are naturally n type conductivity as characterized by the hot-probe technique.     

Microstructure and nano-scratch behaviors of La0.7Sr0.3MnO3 films

The La_0.7Sr_0.3MnO₃ (LSMO) films were prepared at various substrate temperatures on si(100) by DC magnetron sputtering method. The microstructure and nano-scratch behaviors of the films were investigated. The results indicate that the films are single phase with perovskite distorted cubic structure and the texture orientation changes obviously with the increase of substrate temperature. A smooth and dense nanocrystalline LSMO film is obtained at high substrate temperature. The (110) preferred orientation growth is beneficial to the improvement of nano-scratch resistance of the films. The friction coefficient between the films and the diamond tip depends on the critical load (L_c). Elastic deformation is the dominant deformation mechanism and the friction coefficient is about 0.08-0.14 for all the films when the loading normal load is less than L_c. When the loading load is larger than L_c, the delamination or detachment of the films occur and the friction coefficient increases abruptly near the L_c. The films deposited at 480 °C and 680 °C possess higher L_c which is about 77 mN due to lower hardness. The suitable decrease in hardness can enhance cohesion strength and scratch resistance of the films.     

Structure and mechanical properties of ZrO2 films deposited by gas flow sputtering

ZrO₂ films were deposited by reactive gas flow sputtering (GFS) where voltage is applied to a cyindrical hollow-cathode target from a DC source, the discharge being produced at relatively high sputtering pressure. In this system, secondary electrons form a major component of the total current flow and lead to heating of the substrate which in turn has an effect on the properties of deposited films. The present experiments were carried out under the following conditions: Ar gas flow rate of 200 sccm, O₂ flow rate FO₂ in the range between 0.003 and 1 sccm, and sputtering power (P_S) in the range of 50-800 W. The reults showed that the crystal structure of the films deposited for P_S below 200 W was monoclinic but for P_S above 400 W, the films included tetragonal cystals of stable structure formed at high temperature by the electron bombardment. The films were formed with grains of 20-100 nm in diameter in a porous structure. The mechanical properties of the films were determined by a nanoindentation technique. Martens hardness (H_M) of the porous films was found to be in the range between 220 and 330 MPa which is substantially less than that of films typically deposited by rf magnetron sputtering.