Structural, electrical, and optical studies on rapid thermally processed ferroelectric BaTiO3 thin films prepared by metallo-organic solution deposition technique

Polycrystalline BaTiO₃ thin films having the perovskite structure were successfully produced on platinum coated silicon, bare silicon, and fused quartz substrate by the combination of the metallo-organic solution deposition technique and post-deposition rapid thermal annealing treatment. The films exhibited good structural, electrical, and optical properties. The electrical measurements were conducted on metal-ferroelectric-metal (MFM) and metal-ferroelectric-semiconductor (MFS) capacitors. The typical measured small signal dielectric constant and dissipation factor at a frequency of 100 kHz were 255 and 0.025, respectively, and the remanent polarization and coercive field were 2.2 μC cm⁻² and 25 kV cm⁻¹, respectively. The resistivity was found to be in the range 10¹⁰–10¹² Ω·cm, up to an applied electric field of 100 kV cm⁻¹, for films annealed in the temperature range 550–700 °C. The films deposited on bare silicon substrates exhibited good film/substrate interface characteristics. The films deposited on fused quartz were highly transparent. An optical band gap of 3.5 eV and a refractive index of 2.05 (measured at 550 nm) was obtained for polycrystalline BaTiO₃ thin film on fused quartz substrate. The optical dispersion behavior of BaTiO₃ thin films was found to fit the Sellmeir dispersion formula well.     

Fabrication of robust Bi3.25La0.75Ti3O12 thin film resistant to hydrogen damage

Ferroelectric bismuth lanthanum titanate (Bi_3.25La_0.75Ti₃O₁₂; BLT) thin films were deposited on Pt/TiO₂/SiO₂/Si substrate by chemical solution deposition method. The films were crystallized in the temperature range of 600–700 °C. The spontaneous polarization (P_s) and the switching polarization (2P_r) of BLT film annealed at 700 °C for 30 min were 22.6 μC/cm² and 29.1 μC/cm², respectively. Moreover, the BLT capacitor did not show any significant reduction of hysteresis for 90 min at 300 °C in the forming gas atmosphere.     

Deposition of HfO2 thin films on ZnS substrates

HfO₂ thin films with columnar microstructure were deposited directly on ZnS substrates by electron beam evaporation process. SiO₂ thin films, deposited by reactive magnetron sputtering, were used as buffer layers, HfO₂ thin films of granular microstructure were obtained on SiO₂ interlayer by this process. X-ray diffraction patterns demonstrate that the as-deposited HfO₂ films are in an amorphous-like state with small amount of crystalline phase while the HfO₂ films annealed at 450 °C in O₂ for 30 min and in Ar for 150 min underwent a phase transformation from amorphous-like to monoclinic phase. Antireflection effect in certain infrared wave band, such as 3–6 μm, 4–12 μm, 4–8 μm and 3–10 μm, can be observed, which was dependent on the thickness of thin films. The cross-sectional images of HfO₂ films, obtained by field emission scanning electron microscopy, revealed that there was no distinct morphological change upon annealing.     

The effect of rapid thermal annealing on structural and electrical properties of TiB2 thin films

This work reports on the effect of post-deposition rapid thermal annealing on the structural and electrical properties of deposited TiB₂ thin films. The TiB₂ thin films, thicknesses from 9 to 450 nm, were deposited by e-beam evaporation on high resistivity and thermally oxidized silicon wafers. The resistivity of as-deposited films varied from 1820 μΩ cm for the thinnest film to 267 μΩ cm for thicknesses greater than 100 nm. In the thickness range from 100 to 450 nm, the resistivity of TiB₂ films has a constant value of 267 μΩ cm.

A rapid thermal annealing (RTA) technique has been used to reduce the resistivity of deposited films. During vacuum annealing at 7 × 10⁻³ Pa, the film resistivity decreases from 267 μΩ cm at 200 °C to 16 μΩ cm at 1200 °C. Heating cycles during RTA were a sequence of 10 s. According to scanning tunneling microscopy analysis, the decrease in resistivity may be attributed to a grain growth through polycrystalline recrystallization, as well as to an increase in film density.

The grain size and mean surface roughness of annealed films increase with annealing temperature. At the same time, the conductivity of the annealed samples increases linearly with grain size. The obtained results show that RTA technique has a great potential for low resistivity TiB₂ formation.     

Structural, optical and electrical characterization of spray-deposited TiO2 thin films

Titanium oxide (TiO₂) thin films were deposited onto glass substrates by means of spray pyrolysis method using methanolic titanyl acetyl acetonate as precursor solution. The thin films were deposited at three different temperatures namely 350, 400 and 450 °C. As-deposited thin films were amorphous having 100–300 nm thickness. The thin films were subsequently annealed at 500 °C in air for 2 h. Structural, optical and electrical properties of TiO₂ thin films have been studied. Polycrystalline thin films with rutile crystal structure, as evidenced from X-ray diffraction pattern, were obtained with major reflexion along (1 1 0). Surface morphology and growth stages based on atomic force microscopy measurements are discussed. Electrical properties have been studied by means of electrical resistivity and thermoelectric power measurements. Optical study shows that TiO₂ possesses direct optical transition with band gap of 3.4 eV.     

Annealing effects on the thermoelectric power of thin copper and silver films

The effect of annealing on the thermoelectric power of thin copper and silver films has been investigated. Using Matthiessen's rule, the thermoelectric power is separated into three components: S₀ due to bulk lattice scattering, S_s due to surface scattering and S_i due to scattering by imperfections. The values of S₀ and S_s are independent of the film thickness, whereas S_i varies with film thickness. However, S_i approaches a constant value for both copper and silver when the film thickness is larger than 1000 Å. The values of S_s obtained for copper and silver films are 1.33 μV/°K and 3.23 μV/°K respectively. For thicker films (t>1000 Å), the values of S_i for copper and silver films are 3.89 μV/°K and 9.63 μV/°K respectively.     

Fabrication and characterization of (1−x)SrBi2Ta2O9–xBi3TaTiO9 layered structure solid solution thin films for ferroelectric random access memory (FRAM) applications

We report on the properties of (1−x)SrBi₂Ta₂O₉–xBi₃TaTiO₉ solid solution thin films for ferroelectric non-volatile memory applications. The solid solution thin films fabricated by modified metalorganic solution deposition technique showed much improved properties compared to SrBi₂Ta₂O₉. A pyrochlore free crystalline phase was obtained at a low annealing temperature of 600°C and grain size was found to be considerably increased for the solid solution compositions. The film properties were found to be strongly dependent on the composition and annealing temperatures. The measured dielectric constant of the solid solution thin films was in the range 180–225 for films with 10–50% of Bi₃TaTiO₉ content in the solid solution. Ferroelectric properties of (1−x)SrBi₂Ta₂O₉–xBi₃TaTiO₉ thin films were significantly improved compared to SrBi₂Ta₂O₉. For example, the observed remanent polarization (2P_r) and coercive field (E_c) values for films with 0.7SrBi₂Ta₂O₉–0.3Bi₃TaTiO₉ composition, annealed at 650°C, were 12.4 μC/cm² and 80 kV/cm, respectively. The solid solution thin films showed less than 5% decay of the polarization charge after 10¹⁰ switching cycles and good memory retention characteristics after about 10⁶ s of memory retention. The improved microstructural and ferroelectric properties of (1−x)SrBi₂Ta₂O₉–xBi₃TaTiO₉ thin films compared to SrBi₂Ta₂O₉, especially at lower annealing temperatures, suggest their suitability for high density FRAM applications.     

Ferroelectric properties of BiFeO3 films grown by sol–gel process

Several methods have been used to prepare ferroelectromagnetic BiFeO₃ films. In this paper, we adopted a sol–gel process to fabricate BiFeO₃ films on indium tin oxide (ITO)/glass substrates. X-ray diffraction pattern indicated that the samples are randomly oriented. Cross section scanning microscopy showed that the thicknesses of both films were about 1.2 μm and no apparent diffusion between the BiFeO₃ films and ITO/glass substrates. Remnant polarization of 2.0 and 1.75 μC/cm² were identified by the measuring of electric hysteresis loops for the films annealed at 500 and 600 °C respectively at an applied field of 108 kV/cm. Dielectric property and loss factor were investigated as a function of frequency. In addition, magnetism was detected at 77 K.     

Drying temperature effects on microstructure, electrical properties and electro-optic coefficients of sol-gel derived PZT thin films

Transparent lead zirconium titanate (PZT) thin film is suitable for a variety of electro-optic application, and the increasing of the electro-optic coefficient of PZT film is one of the important factors for this application. In this study, the main processing variable for improving an electro-optic coefficient was the drying temperature: 300, 350, 450 and 500°C in sol-gel derived PZT thin films. The highest linear electro-optic coefficient (1.65×10⁻¹⁰ (m/V)) was observed in PZT film dried at 450°C. The PZT film showed the highest perovskite content, polarization (P_max=49.58 μC/cm², P_r=24.8 μC/cm²) and dielectric constant (532). A new two-beam polarization (TBP) interferometer with a reflection configuration was used for electro-optic testing of PZT thin films which allows measurement of the linear electro-optic coefficient of thin film with strong Fabry–Perot (FP) effect usually present in PZT thin film.     

CdSe band-splitting on thermal annealed films

Semiconducting polycrystalline CdSe thin films were prepared on glass substrates by chemical bath at 65 °C. As-deposited films grew in the metastable cubic sphalerite (S) crystalline structure with good stoichiometry. Upon thermal annealing (TA) in Ar+Se₂ atmosphere at different temperatures in the range 200–500 °C, the gradual phase transformation from cubic modification to hexagonal wurtzite (W) stable phase could be observed. From optical absorption measurements the fundamental energy band gap (E_g) and the second electronic transition (E_g+ΔE_g) were calculated for as-deposited and thermal annealed films. For TA350 °C, S-phase dominates the crystalline structure and only the spin orbit (ΔE_so) contribution to ΔE_g is present. Above 350 °C, the W-phase dominates and the energy splitting (ΔE_cf), owed to crystal field contribution and originated by the loss of lattice symmetry, should be added to ΔE_so in order to complete ΔE_g in the W-phase. The values ΔE_so=0.389±0.011 eV and ΔE_cf=0.048±0.018 eV were found from our analysis, and T_c=350 °C was here defined as the critical point of the phase transformation.     

Electrochromic properties of nanocrystalline MoO3 thin films

Electrochromic MoO₃ thin films were prepared by a sol–gel spin-coating technique. The spin-coated films were initially amorphous; they were calcined, producing nanocrystalline MoO₃ thin films. The effects of annealing temperatures ranging from 100 °C to 500 °C were investigated. The electrochemical and electrochromic properties of the films were measured by cyclic voltammetry and by in-situ optical transmittance techniques in 1 M LiClO₄/propylene carbonate electrolyte. Experimental results showed that the transmittance of MoO₃ thin films heat-treated at 350 °C varied from 80% to 35% at λ = 550 nm (ΔT =  45%) and from 86% to 21% at λ ≥ 700 nm (ΔT =  65%) after coloration. Films heat-treated at 350 °C exhibited the best electrochromic properties in the present study.     

Effects of Annealing on the Conductivity of C60 Thin Films

Films of C₆₀, at different stages of annealing of T_t=200°and 300°C have been electrically characterized over the temperature domain from -130°C to T_t. X-ray diffraction revealed a random polycrystalline fee structure with stacking defects of an intrinsic nature, due to deposition conditions. The value of room-temperature conductivity was found to be in the range (6.3-1.0) *10^-10 (0cm)^-1. In the stable annealed state the conductivity showed an activated temperature dependence above 423 K and a non-activated dependence below 330-280 K. The activation energies E_a = 0.8 eV (film thickness 0.70 μm) and E_a = 1.0 eV (film thickness 2.40 μm) were in good agreement with the energy gap values (1.63 eV and 2.08 eV) which were deduced from the absorption spectral dependence. Annealing decreased the non-activated contribution to conduction, extending the intrinsic conduction temperature range.     

Physics of very thin ITO conducting films with high transparency prepared by DC magnetron sputtering

The preparation of very thin indium tin oxide (ITO) films with extremely high transparency and suitable resistivity, as well as resistivity stability for long term use, is described. In order to obtain these properties, amorphous suboxide films were first prepared and then annealed. Suboxide films with a thickness of 20 to 30 nm were prepared on PET film and glass substrates at a temperature of 60 °C using In₂O₃---SnO₂ targets with a SnO₂ content of 0 to 10 wt% by DC magnetron sputtering in a pure argon gas atmosphere. The films were annealed at a temperature of 150 °C for 1 to 100 h in air. The resistivity of films on PET films was, depending on the SnO₂ content, on the order of 10⁻³ ω cm. An average transmittance above 97% in the visible wavelength range and a resistivity of about 4 × 10⁻³ ω cm, as well as resistivity stability, were attained in ITO films with a SnO₂ content of about 1 wt% prepared on PET films by the low-temperature process. It is thought that these properties result from crystallization which occurred during the annealing, duration up to about 25 h.     

Epitaxial growth of RuO2 thin films by metal-organic chemical vapor deposition

Conductive RuO₂ thin films were epitaxially grown on LaAlO₃(100) and MgO(100) substrates by metal-organic chemical vapor deposition (MOCVD). The deposited RuO₂ films were crack-free, and well adhered to the substrates. The RuO₂ film is (200) oriented on LaAlO₃ (100) substrates at deposition temperature of 600°C and (110) oriented on MgO(100) substrates at deposition temperature of 350°C and above. The epitaxial growth of RuO₂ on MgO and LaAlO₃ is demonstrated by strong in-plane orientation of thin films with respect to the major axes of the substrates. The RuO₂ films on MgO(100) contain two variants and form an orientation relationship with MgO given by RuO₂(110)//MgO(100) and RuO₂[001]//MgO[011]. The RuO₂ films on LaAlO₃(100), on the other hand, contain four variants and form an orientation relationship with LaAlO₃ given by RuO₂(200)//LaAlO₃(100) and RuO₂[011]//LaAlO₃[011]. Electrical measurements on the RuO₂ thin films deposited at 600°C show room-temperature resistivities of 40 and 50 μΩ cm for the films deposited on the MgO and LaAlO₃ substrates, respectively.     

Pyroelectric properties of BST/PLT composite thick films with addition of xPbO–(1 − x)B2O3 glass

The Ba_xSr_1−xTiO₃ (BST)/Pb_1−xLa_xTiO₃ (PLT) composite thick films (20 μm) with 12 mol% amount of xPbO–(1 − x)B₂O₃ glass additives (x = 0.2, 0.35, 0.5, 0.65 and 0.8) have been prepared by screen-printing the paste onto the alumina substrates with silver bottom electrode. X-ray diffraction (XRD), scanning electron microscope (SEM) and an impedance analyzer and an electrometer were used to analyze the phase structures, morphologies and dielectric and pyroelectric properties of the composite thick films, respectively. The wetting and infiltration of the liquid phase on the particles results in the densification of the composite thick films sintered at 750 °C. Nice porous structure formed in the composite thick films with xPbO–(1 − x)B₂O₃ glass as the PbO content (x) is 0.5 ≥ x ≥ 0.35, while dense structure formed in these thick films as the PbO content (x) is 0.8 ≥ x ≥ 0.65. The volatilization of the PbO in PLT and the interdiffusion between the PLT and the glass lead to the reduction of the c-axis of the PLT phase. The operating temperature range of our composite thick films is 0–200 °C. At room temperature (20 °C), the BST/PLT composite thick films with 0.35PbO–0.65B₂O₃ glass additives provided low heat capacity and good pyroelectric figure-of-merit because of their porous structure. The pyroelectric coefficient and figure-of-merit F_D are 364 μC/(m² K) and 14.3 μPa^−1/2, respectively. These good pyroelectric properties as well as being able to produce low-cost devices make this kind of thick films a promising candidate for high-performance pyroelectric applications.     

Effect of the microwave oven on structural, morphological and electrical properties of SrBi4Ti4O15 thin films grown on Pt/Ti/SiO2/Si substrates by a soft chemical method

Thin films of SrBi₄Ti₄O₁₅ (SBTi), a prototype of the Bi-layered-ferroelectric oxide family, were obtained by a soft chemical method and crystallized in a domestic microwave oven. For comparison, films were also crystallized in a conventional method at 700 °C for 2 h. Structural and morphological characterization of the SBTi thin films were investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. Using platinum coated silicon substrates, the ferroelectric properties of the films were determined. Remanent polarization P_r and a coercive field E_c values of 5.1 μC/cm² and 135 kV/cm for the film thermally treated in the microwave oven and 5.4 μC/cm² and 85 kV/cm for the film thermally treated in conventional furnace were found. The films thermally treated in the conventional furnace exhibited excellent fatigue-free characteristics up to 10¹⁰ switching cycles indicating that SBTi thin films are a promising material for use in non-volatile memories.     

Photoluminescence properties of the Yb:Er co-doped Al2O3 thin film fabricated by microwave ECR plasma source enhanced RF magnetron sputtering

The Yb:Er co-doped Al₂O₃ thin film was deposited on oxidized silicon wafers by microwave ECR plasma source enhanced RF magnetron sputtering, and annealed from 800 °C to 1000 °C. The photoluminescence at 1.53 μm of thin film was obtained under room temperature. The mixture phase structure of γ and θ is observed by XRD, and the compositions of the thin film are investigated by EPMA. The maximum PL intensity was achieved with O₂:Ar at 1:1, annealing temperature at 900 °C, and experimental ratio of Yb:Er at 1:3.6. The energy transfer mechanism between Er and Yb ions is supported by theoretical analysis and experiment results.     

Characterization of ultrasonic spray pyrolysed ruthenium oxide thin films

The ultrasonic spray pyrolysis (USP) technique was employed to deposit ruthenium oxide thin films. The films were prepared at 190°C substrate temperature and further annealed at 350°C for 30 min in air. The films were 0.22 μ thick and black grey in color. The structural, compositional and optical properties of ruthenium oxide thin films are reported. Contactless transient photoconductivity measurement was carried out to calculate the decay time of excess charge carriers in ruthenium oxide thin films.     

Reactions in Au/Nb bilayer thin films

The interdiffusion and intermetallic compound formation of Au/Nb bilayer thin films annealed at 200–400 °C have been investigated. The bilayer thin films were prepared by electron beam deposition. The Nb film was 50 nm thick and the Au film was 50–200 nm thick. The interdiffusion of annealed specimens was examined by measuring the electrical resistance and depth-composition profile and by transmission electron microscopy. Interdiffusion between the thin films was detected at temperatures above 325 °C in a vacuum of 10^-4 Pa. The intermetallic compound Au₂Nb₃ and other unknown phases form during annealing at over 400 °C. The apparent diffusion constants, determined from the penetration depth for annealing at 350 °C, are 3.5 × 10⁻¹⁵ m² s⁻¹ for Nb in Au and 8.6 × 110^7minus;15 m² s⁻¹ for Au in Nb. The Au surface of the bilayer films becomes uneven after annealing at over 400 °C due to the reaction.