The properties of Ba0.5Sr0.5TiO3 thin film prepared by RF magnetron sputtering from powder target

The Ba_0.5Sr_0.5TiO₃ (BST) thin film with the thickness of 400 nm deposited from powder target is prepared by the radio-frequency magnetron sputtering technique. The deposition rate of BST film is estimated to be 45 nm/min, which is very fast for ferroelectric materials. The dielectric properties of the as-prepared BST thin film are demonstrated. High dielectric tunability up to 42.7% and low dielectric loss small to 0.01 are achieved at a low applied voltage of 5 V. The results demonstrate that the RF magnetron sputtering from powder target is a versatile, novel technique for the deposition of high-quality ferroelectric thin films.     

Synthesis of Na0.5Bi0.5TiO3 anisotropic particles with grain orientation by conversion of Na0.5Bi4.5Ti4O15 crystals

A novel method for synthesizing Na_0.5Bi_0.5TiO₃ (BNT) anisotropic particles with grain orientation is reported. Anisotropically shaped particles of BNT were prepared by conversion of Na_0.5Bi_4.5Ti₄O₁₅ (NBT15) single crystals. Platelet NBT15 was produced by molten-salt synthesis. They were converted to BNT by second molten-salt synthesis at 800–1200 °C. NBT15 single-crystal platelets were transformed into platelet particles of polycrystalline BNT. The reaction is topotaxial, those recrystallized BNT were oriented with (h 0 0) plane parallel to the platelet. The use of converted BNT particles as seed was confirmed by performing templated grain growth (TGG) of BNT with 5% grain-oriented, anisotropic particles of BNT.     

Impedance spectroscopy and relaxation phenomena of (Na,K) excess Na0.5K0.5NbO3 thin films grown by chemical solution deposition

Na_0.5K_0.5NbO₃ (NKN) and 10 mol% (Na,K) excess Na_0.5K_0.5NbO₃ (NKN10) thin films on Pt/Ti/SiO₂/Si substrate were prepared by chemical solution deposition. Crystallization of NKN10 thin films was confirmed by X-ray diffraction. The (Na,K) excess Na_0.5K_0.5NbO₃ thin film shows a ferroelectric P-E hysteresis loop. Dielectric properties and impedance spectroscopy of thin films were investigated in the frequency range from 0.1 Hz to 100 kHz and the temperature range of 25 ~ 500 °C. By analyzing the complex impedance relaxation with Cole-Cole plots, we found impedance relaxations for the thin film. The contribution of electrical conduction is discussed in relation to grain, grain boundary, and interface effects.     

Chemical vapor deposition of NiSi using Ni(PF3)4 and Si3H8

NiSi_x films were deposited using chemical vapor deposition (CVD) with a Ni(PF₃)₄ and Si₃H₈/H₂ gas system. The step coverage quality of deposited NiSi_x was investigated using a horizontal type of hot-wall low pressure CVD reactor, which maintained a constant temperature throughout the deposition area. The step coverage quality improved as a function of the position of the gas flow direction, where PF₃ gas from decomposition of Ni(PF₃)₄ increased. By injecting PF₃ gas into the Ni(PF₃)₄ and Si₃H₈/H₂ gas system, the step coverage quality markedly improved. This improvement in step coverage quality naturally occurred when PF₃ gas was present, indicating a strong relationship. The Si/Ni deposit ratio at 250 °C is larger than at 180 °C. It caused a decreasing relative deposition rate of Ni to Si. PF₃ molecules appear to be adsorbed on the surface of the deposited film and interfere with faster deposition of active Ni deposition species.     

Growth of nanocrystalline diamond films in CCl4/H2 ambient

We investigated the growth characteristics of the nanocrystalline diamond films using CCl₄/H₂ as gas sources in a hot-filament chemical vapor deposition (CVD) reactor. Successful growth of nanocrystalline diamond at typical growth condition of 1.5-2.5% CCl₄ and 550-730 °C substrate temperature has been demonstrated. Glancing angle X-ray diffraction (XRD) clearly indicated the formation of diamond in the films. Typical root-mean-square surface roughness of 10-15 nm and an optimal root-mean-square surface roughness of 6 nm have been achieved. Transmission electron microscopy (TEM) analyses indicated that nanocrystalline diamond film with an average grain size in the range of 10-20 nm was deposited from 2.5% CCl₄/H₂ at 610 °C. Effects of different source gas composition and substrate temperature on the grain nucleation and grain growth processes, whereby the grain size of the nanocrystalline film could be controlled, were discussed.     

Effect of post-annealing treatment in oxygen on dielectric properties of K0.5Na0.5NbO3 thin films prepared by chemical solution deposition

K_0.5Na_0.5NbO₃ thin films were prepared on Pt/Ti/SiO₂/Si substrates by chemical solution deposition method with different annealing temperatures of 550 °C, 600 °C, 700 °C. The post-annealing treatment was introduced at 550 °C for 3 min in oxygen ambient. It is found that the films were composed of pure provskite phase, and the post-annealing treatment promoted the crystallization and improved the quality of the films, which resulted in the enhancement of the dielectric property of the films. The effect of the post-annealing on the dielectric properties of the films was also discussed.     

Preparation and characterization of new visible-light-driven BaCo0.5Nb0.5O3 photocatalyst

A new type of visible-light-driven photocatalyst BaCo_0.5Nb_0.5O₃ was successfully synthesized via a sol-gel process in this study. After heating the precursors at 1000 °C, a pure perovskite phase was obtained. The particle size and crystallinity of BaCo_0.5Nb_0.5O₃ powders markedly increased with a rise in the calcination temperature. The band gap of BaCo_0.5Nb_0.5O₃ calculated from the UV-visible spectra was found to be less than that of titania. BaCo_0.5Nb_0.5O₃ was demonstrated to have photocatalytic activity under visible light irradiation and this activity significantly depended on the synthesis temperature. The sol-gel derived powders were found to have better photocatalytic activity than the solid-state derived powders because of the reduced particle size and increased surface area.     

Structural and optical studies of nanocrystalline V2O5 thin films

We report the structural and optical properties of nanocrystalline thin films of vanadium oxide prepared via evaporation technique on amorphous glass substrates. The crystallinity of the films was studied using X-ray diffraction and surface morphology of the films was studied using scanning electron microscopy and atomic force microscopy. Deposition temperature was found to have a great impact on the optical and structural properties of these films. The films deposited at room temperature show homogeneous, uniform and smooth texture but were amorphous in nature. These films remain amorphous even after postannealing at 300 °C. On the other hand the films deposited at substrate temperature T_S > 200 °C were well textured and c-axis oriented with good crystalline properties. Moreover colour of the films changes from pale yellow to light brown to black corresponding to deposition at room temperature, 300 °C and 500 °C respectively. The investigation revealed that nanocrystalline V₂O₅ films with preferred 001 orientation and with crystalline size of 17.67 nm can be grown with a layered structure onto amorphous glass substrates at temperature as low as 300 °C. The photograph of V₂O₅ films deposited at room temperature taken by scanning electron microscopy shows regular dot like features of nm size.     

Deposition and characterization of smooth ultra-nanocrystalline diamond film in CH4/H2/Ar by microwave plasma chemical vapor deposition

The smooth ultra-nanocrystalline diamond (UNCD) films were prepared by microwave plasma chemical vapor deposition (MWCVD) using argon-rich CH₄/H₂/Ar plasmas with varying argon concentration from 96% to 98% and negative bias voltage from 0 to −150 V. The influences of argon concentration and negative bias voltage on the microstructure, morphology and phase composition of the deposited UNCD films are investigated by using scanning electron microscopy (SEM), X-ray diffraction (XRD), atom force microscopy (AFM), and visible and UV Raman spectroscopy. It was found that the introduction of argon in the plasma caused the grain size and surface roughness decrease. The RMS surface roughness of 9.6 nm (10 micron square area) and grain size of about 5.7 nm of smooth UNCD films were achieved on Si(100) substrate. Detailed experimental results and mechanisms for UNCD film deposition in argon-based plasma are discussed. The deposited highly smooth UNCD film is also expected to be applicable in medical implants, surface acoustic wave (SAW) devices and micro-electromechanical systems (MEMS).     

Growth studies and characterization of silicon nitride thin films deposited by alternating exposures to Si2Cl6 and NH3

We deposited silicon nitride films by alternating exposures to Si₂Cl₆ and NH₃ in a cold-wall reactor, and the growth rate and characteristics were studied with varying process temperature and reactant exposures. The physical and electrical properties of the films were also investigated in comparison with other silicon nitride films. The deposition reaction was self-limiting at process temperature of 515 and 557 °C, and the growth rates were 0.24 and 0.28 nm/cycle with Si₂Cl₆ exposure over 2 × 10⁸ L. These growth rates with Si₂Cl₆ are higher than that with SiH₂Cl₂, and are obtained with reactant exposures lower than those of the SiH₂Cl₂ case. At process temperature of 573 °C where the wafer temperature during Si₂Cl₆ pulse is 513 °C, the growth rate increased with Si₂Cl₆ exposure owing to thermal deposition of Si₂Cl₆. The deposited films are nonstoichiometric SiN, and were easily oxidized by air exposure to contain 7-8 at.% of oxygen in the bulk film. The deposition by using Si₂Cl₆ exhibited a higher deposition rate with lower reactant exposures as compared with the deposition by using SiH₂Cl₂, and exhibited good physical and electrical properties that were equivalent or superior to those of the film deposited by using SiH₂Cl₂.     

Anatase TiO2 films crystallized on SnO2:F substrates in an aqueous solution

Anatase TiO₂ films were fabricated on SnO₂:F substrates in an aqueous solution. The films were constructed of assemblies of nano-TiO₂. Surface of the films showed large roughness due to nano/micro-asperity of the assemblies. The thickness was increased to 260 nm, 360 nm, 600 nm and 760 nm with the deposition time of 2 h, 5 h, 25 h and 48 h, respectively. The films showed strong intensity of 004 X-ray diffraction possibly because the needles, i.e., nano-TiO₂, elongated along the c-axis. Low-temperature synthesis of crystalline anatase TiO₂ films has a great deal of potential in the development of electronic devices, optical devices, dye-sensitized solar cells, photocatalytic devices and biomolecule sensors.     

The effect of sputtering gas pressure on structure and photocatalytic properties of nanostructured titanium oxide self-cleaning thin film

Titanium oxide thin films were deposited by DC reactive magnetron sputtering on ZnO (80 nm thickness)/soda-lime glass and SiO₂ substrates at different gas pressures. The post annealing on the deposited films was performed at 400 °C in air atmosphere. The results of X-ray diffraction (XRD) showed that the films had anatase phase after annealing at 400 °C. The structure and morphology of deposited layers were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface grain size and roughness of TiO₂ thin films after annealing were around 10-15 nm and 2-8 nm, respectively. The optical transmittance of the films was measured using ultraviolet-visible light (UV-vis) spectrophotometer and photocatalytic activities of the samples were evaluated by the degradation of Methylene Blue (MB) dye. Using ZnO thin film as buffer layer, the photocatalytic properties of TiO₂ films were improved.     

Properties of La-substituted Na0.5Bi4.5Ti4O15 ferroelectric thin films

Ferroelectric Na_0.5La_0.5Bi₄Ti₄O₁₅ (NaLaBTi) thin films were prepared by a chemical solution deposition method. The NaLaBTi thin films annealed at 750 °C under oxygen atmosphere were randomly oriented polycrystalline. Electrical properties of the NaLaBTi thin films were compared to Na_0.5Bi_4.5Ti₄O₁₅ thin films and better properties were observed in the NaLaBTi thin films. Remnant polarization (2P_r) and coercive electric field (2E_c) were 43 µC/cm² and 204 kV/cm at an applied electric field of 478 kV/cm, respectively. Leakage current density was 1.95 × 10^− 6 A/cm² at 100 kV/cm. Dielectric constant and dielectric loss were 805 and 0.05 at 1 kHz, respectively. Switchable polarization was suppressed by 15% after 1.44 × 10¹⁰ switching cycles.     

Structural and optical characterization of CuInSe2 films deposited by hot wall vacuum evaporation method

Copper indium diselenide (CuInSe₂) compound was prepared by direct reaction of high-purity elemental copper, indium and selenium. CuInSe₂ thin films were deposited onto well-cleaned glass substrates by a hot wall deposition technique using quartz tubes of different lengths (0.05, 0.07, 0.09, 0.11 and 0.13 m). X-ray diffraction studies revealed that all the deposited films are polycrystalline in nature and exhibit chalcopyrite structure. The crystallites were found to have a preferred orientation along the (1 1 2) direction. Micro-structural parameters of the films such as grain size, dislocation density, tetragonal distortion and strain have been determined. The grain sizes in the films were in the range of 65-250 nm. As the tube length increases up to 0.11 m the grain size in the deposited films increases, but the strain decreases. The film deposited using the 0.13 m long tube has smaller grain size and more strain. CuInSe₂ thin films coated using a tube length of 0.11 m were found to be highly crystalline when compared to the films coated using other tube lengths; it has also been found that films possess the same composition (Cu/In=1.015) as that of the bulk. Scanning electron microscope analysis indicates that the films are polycrystalline in nature. Structural parameters of CuInSe₂ thin films deposited under higher substrate temperatures were also studied and the results are discussed. The optical absorption coefficient of CuInSe₂ thin films has been estimated as 10⁴ cm⁻¹ (around 1050 nm). The direct band gap of CuInSe₂ thin films was also determined to be between 1.018 and 0.998 eV.     

Investigation and characterization of radio frequency sputtered Cr1.8Ti0.2O3−δ thin films derived by citrate, sol-gel and solid state routes

Cr_1.8Ti_0.2O_3−δ (CTO) powders were prepared by citrate, sol-gel and solid-state routes, respectively. The effect of preparation methods on the morphology of sputtered thin films was further investigated. X-ray diffraction patterns of the powders and films confirmed a single phase CTO. No impurity was observed even after sintering the powders at 1000 °C for 24 h. X-ray photoelectron spectroscopy analysis showed that Cr 2p (577.8 eV), and O 1 s (531.5 eV) core levels of the sputtered films have ∼1 eV variation in their binding energy positions compared to those of CTO powders. The atomic force microscopy analysis showed the grains of the films obtained by sputtering sol-gel powders had the smallest size in the range of 7-58 nm. The surface roughness of the thin films had the lowest value at 0.70 nm, whereas those obtained from solid state solution had the maximum value of 2.51 nm.     

Large third-order optical nonlinearity of SrBi2Nb2O9 thin films fabricated by pulsed laser deposition

SrBi₂Nb₂O₉ (SBN) thin films with a single phase of layered perovskite structure have been fabricated on fused quartz substrates at room temperature by pulsed laser deposition. The XRD and AFM analysis indicated that the films had better crystallinity, less rough surface morphology, and larger grain size with increasing oxygen pressure. The nonlinear optical properties of the samples were determined using a single beam Z-scan technique at a laser wavelength of 532 nm with laser duration of 25 ps. The real and imaginary parts of the third-order nonlinear optical susceptibility χ⁽³⁾ of the films were measured to be 3.18 × 10^− 8 esu and 5.94 × 10^− 9 esu, respectively.     

Synthesis and Magnetic Properties of L0.5Sr0.5Mn0.5M0.5O3 (L = Y, Pr; M = Cu, Ru)

A new Mn-containing material with nominal composition L_0.5Sr_0.5Mn_0.5M_0.5O₃ (L = Y or Pr; M = Cu or Ru), as well as Y_0.5Sr_0.5MnO₃ for comparison, were synthesized. The results of the XRD and EDX analyses show that the obtained samples are single-phased and isostructural, with L_1–xA_xMnO₃. The L_0.5Sr_0.5Mn_0.5Cu_0.5O₃ material displays a PM behavior down to 8 K where paramagnetic–antiferromagnetic transition begins. The Pr_0.5Sr_0.5Mn_0.5Cu_0.5O₃ sample has a broad transition at 210 K and a magnetoresistance of 34% at 128 K. The Pr_0.5Sr_0.5Mn_0.5Ru_0.5O₃ material has a paramagnetic–ferromagnetic transition beginning at 330 K and a ferromagnetic–antiferromagnetic one at about 160 K. The obtained value of T _c is the highest for the Pr-containing manganites. The roles of Pr/Sr ratio, anisotropy, and intergranular effects in the samples are discussed.     

Multi-stage evaporation of Cu2ZnSnS4 thin films

Multi-stage evaporation is a well-established method for the controlled growth of chalcopyrite thin films. To apply this technique to the deposition of Cu₂ZnSnS₄ thin films we investigated two different stage sequences: (A) using Cu₂SnS₃ as precursor to react with Zn-S and (B) using ZnS as precursor to react with Cu-Sn-S. Both Cu₂SnS₃ and ZnS are structurally related to Cu₂ZnSnS₄. In case (A) the formation of copper tin sulphide in the first stage was realized by depositing Mo/SnS_x/CuS (1 < x < 2) and subsequent annealing. In the second stage ZnS was evaporated in excess at different substrate temperatures. We assign a significant drop of ZnS incorporation at elevated temperatures to a decrease of ZnS surface adhesion, which indicates a self-limited process with solely reactive adsorption of ZnS at high temperatures. In case (B) firstly ZnS was deposited at a substrate temperature of 150 °C. In the second stage Cu, Sn and S were evaporated simultaneously at varying substrate temperatures. At temperatures above 400 °C we find a strong decrease of Sn-incorporation and also a Zn-loss in the layers. The re-evaporation of elemental Zn has to be assumed. XRD measurements after KCN-etch on the layers prepared at 380 °C show for both sample types clearly kesterite, though an additional share of ZnS and Cu₂SnS₃ can not be excluded. SEM micrographs reveal that films of sample type B are denser and have larger crystallites than for sample type A, where the porous morphology of the tin sulphide precursor is still observable. Solar cells of these absorbers reached conversion efficiencies of 1.1% and open circuit voltages of up to 500 mV.     

Preparation of La0.8Sr0.2Cr0.97V0.03O3 − δ films for solid oxide fuel cell application

La_0.8Sr_0.2Cr_0.97V_0.03O_3 − δ (LSC) is commonly studied as a ceramic interconnect material as well as a coating material for metallic interconnects for solid oxide fuel cell applications. However, it is difficult to sinter this type of material to high density. In order to overcome this problem and to study the material in form of a thin film we have used Pulsed Laser Deposition to obtain a dense, uniform film with the right stochiometry. Investigation of preparation-parameter dependence of the LSC films deposited on a stainless steel substrate during pulsed-laser deposition was carried out. The LSC films were deposited with KrF excimer laser (248 nm) on a stainless steel substrate at different oxygen pressure and substrate temperatures. The substrate temperature (873-1073 K) and the oxygen background pressure (5-20 Pa) were varied in order to obtain optimal growth conditions. The surface morphology and structural information of the films were obtained using scanning electron microscope (SEM) and X-ray diffraction, respectively. Under the optimal preparation-parameter conditions: substrate temperature of 1023 K and an oxygen pressure of 10 Pa the structure of the film agreed with the target structure and the SEM micrographs show that the surfaces are homogeneous, smooth, crack-free and dense.     

Synthesis of a novel langanite-type compound La3Al5.5Nb0.5O14 by the sol-gel process

Langanite (La₃Ga_5.5Nb_0.5O₁₄, LGN) and its isomorphs are a few piezoelectric materials which have the unique temperature compensation and piezoelectric properties. But the high Ga₂O₃ content makes them very expensive and limits their applications. We reported a new langanite-type compound La₃Al_5.5Nb_0.5O₁₄ (LAN) which has the advantage of no Ga₂O₃ content. Chemically homogeneous La₃Al_5.5Nb_0.5O₁₄ sol was synthesized using La (NO₃)₃·6H₂O, Al (NO₃)₃·9H₂O and niobium citrate as starting materials. Single-phased LAN powder was prepared by decomposition of a citrate polymer precursor and subsequent reactions at high temperatures. TG-DTA, XRD and FTIR were employed to investigate the transformation process of gel to LAN powder. The results showed that, after calcination at 900 °C, pure La₃Al_5.5Nb_0.5O₁₄ polycrystalline powder with a narrow particle size distribution was obtained, which has the same structure with La₃Ga_5.5Nb_0.5O₁₄.