Deposition and dielectric properties of CaCu3Ti4O12 thin films on Pt/Ti/SiO2/Si substrates using pulsed-laser deposition

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully deposited on Pt/Ti/SiO₂/Si(1 0 0) substrates using pulsed-laser deposition technique. The crystalline structure and the surface morphology of the CCTO thin films were greatly affected by the substrate temperature and oxygen pressure. Thin films with a (2 2 0) preferential orientation were obtained at the substrate temperature above 700 °C and oxygen pressure above 13.3 Pa. The 480-nm thin films deposited under 720 °C and 26.6 Pa have a fairly high dielectric constant of near 2000 at 10 kHz and room temperature. The values of the dielectric constant and loss and their temperature-dependence under different frequency are comparable with those obtained in the epitaxial CCTO films grown on oxide substrates.     

Preparation of highly c-axis-oriented Bi4Ti3O12 thin films and their crystallographic, dielectric and optical properties

Bismuth titanate (Bi₄Ti₃O₁₂) thin films with a high c-axis orientation up to 99% were prepared on (100)-oriented silicon wafers by r.f. planar magnetron sputtering using a Bi₂TiO₅ ceramic target at a substrate temperature of 600 °C. From the Auger electron spectroscopy depth profile of the film, there is no evidence of interdiffusion of a specific element between the film and the substrate. Relative dielectric constant of these films depends on film thickness. The behavior was explained assuming a low-dielectric-constant interface layer. Using this assumption, the relative dielectric constant of Bi₄Ti₃O₁₂ film was estimated to be approximately 140. This value is close to that along the c axis in a bulk form. The remanent polarization and the coercive field were 0.8 μC cm⁻² and 20 kV cm⁻¹, respectively.     

Comparative analysis for the crystalline and ferroelectric properties of Pb(Zr,Ti)O3 thin films deposited on metallic LaNiO3 and Pt electrodes

The crystalline quality and ferroelectricity of the Pb(Zr,Ti)O₃ (PZT) films deposited on the metallic LaNiO₃ (LNO) and Pt electrodes were comparatively analyzed to investigate the possibility for their application to non-volatile memory devices. LNO thin films were successfully deposited on various substrates by using r.f. magnetron sputtering even at a low temperature ranging from 250 to 500 °C, and the ferroelectric PZT thin films were spin-coated onto the LNO and Pt bottom electrodes. Metallic LNO thin films exhibited [100] orientation irrespective of the substrate species and PZT films coated onto LNO films had highly a- and c-axis orientations, while those with Pt bottom electrode were polycrystalline. PZT films with LNO bottom electrode had smaller grain size and larger dielectric constant compared to those grown on the Pt electrode. The ferroelectric thin films fabricated on LNO bottom electrode displayed an asymmetric D–E hysteresis loop, which was explained by the defect effects formed at the interface. Especially, the LNO/PZT/LNO capacitor was found to significantly improve the polarization fatigue and the effects of the LNO electrodes to the fatigue were discussed.     

Enhanced ferroelectric properties of multilayer SrBi2Ta2O9/SrBi2Nb2O9 thin films for NVRAM applications

Ferroelectric SrBi₂Ta₂O₉/SrBi₂Nb₂O₉ (SBT/SBN) multilayer thin films with various stacking periodicity were deposited on Pt/TiO₂/SiO₂/Si substrate by pulsed laser deposition technique. The X-ray diffraction patterns indicated that the perovskite phase was fully formed with polycrystalline structure in all the films. The Raman spectra showed the frequency of the O–Ta–O stretching mode for multilayer and single layer SrBi₂(Ta_0.5Nb_0.5)₂O₉ (SBNT) samples was 827–829 cm⁻¹, which was in between the stretching mode frequency in SBT (813 cm⁻¹) and SBN (834 cm⁻¹) thin films. The dielectric constant was increased from 300 (SBT) to 373 at 100 kHz in the double layer SBT/SBN sample with thickness of each layer being 200 nm. The remanent polarization (2P_r) for this film was obtained 41.7 μC/cm², which is much higher, compared to pure SBT film (19.2 μC/cm²). The coercive field of this double layer film (67 kV/cm) was found to be lower than SBN film (98 kV/cm).     

Electric characterization of HfO2 thin films prepared by chemical solution deposition

Hafnium dioxide (HfO₂) thin films were prepared on Si substrates using the chemical solution deposition (CSD) method. The Au/HfO₂/n-Si/Ag structures were characterized by X-ray diffraction (XRD), C–V curves and leakage current measurements. A relative dielectric constant of about 13.5 was obtained for the 65 nm HfO₂ film. Atomic force microscopy (AFM) measurements show uniform surfaces of the films. C–V hysteresis was found for the metal-oxide-semiconductor (MOS) structures with HfO₂ films of 52 and 65 nm thick. It is found that the width of C–V windows is related with the thickness of the HfO₂ films. Furthermore, the C–V hysteresis reveals the possibility of stress-effect, suggesting that it is possible to use HfO₂ to build an MOS structure with controllable C–V windows for memory devices. The leakage current decreases as the film thickness increases and a relatively low leakage current density has been achieved with the HfO₂ film of 65 nm.     

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.     

Microwave dielectric properties of W-doped Ba0.6Sr0.4TiO3 thin films grown on (001) MgO by pulsed laser deposition with a variable oxygen deposition pressure

The microwave dielectric properties of Ba_0.6Sr_0.4TiO₃ 1 mol% W-doped thin films deposited using pulsed laser deposition, are improved by a novel oxygen deposition profile. The thin films were deposited onto (001) MgO substrates at a temperature of 720 °C. A comparison is made between three different oxygen ambient growth conditions. These include growth at a single oxygen pressure (6.7 Pa) and growth at two oxygen pressures, one low (6.7 Pa) and one high (46.7 Pa). Films were deposited in a sequence that includes both a low to high and a high to low transition in the oxygen deposition pressure. Following deposition, all films were post-annealed in 1 atm of oxygen at 1000 °C for 6 h. The dielectric Q (defined as 1 / tanδ) and the dielectric constant, ε_r, were measured at room temperature, at 2 GHz, using gap capacitors fabricated on top of the dielectric films. The percent dielectric tuning (defined as (ε_r(0 V) − ε_r(40 V)) / ε_r(0 V) × 100) and figure of merit (FOM) (defined as percent dielectric tuning × Q(0 V)) were calculated. The film deposited using the two-stage growth conditions, 6.7 / 46.7 Pa oxygen, showed a maximum Q(0 V) value with high percent dielectric tuning and gave rise to a microwave FOM twice as large as the single stage growth condition. The improved dielectric properties are due to initial formation of a film with reduced interfacial strain, due to the formation of defects at the film/ substrate interface resulting in a high Q(0 V) value, followed by the reduction of oxygen vacancies which increases the dielectric constant and tuning.     

GaGeTe films as phase-change optical recording media

Ga₂₀Ge₃₀Te₅₀ thin films deposited by vacuum evaporation on various substrates have been studied for their structural and optical properties. The as-deposited amorphous films were crystallized by thermally annealing them. The optical constants of the amorphous films indicate semiconducting behaviour (n> k). The optical bandgap (E_g) determined from Tauc's plot is 0.7 eV. The change in reflectance on crystallization has been utilized to obtain maximum optical contrast by optimising the thickness of the film.     

Thickness and erbium doping effects on the electrical properties of lead zirconate titanate thin films

Thin films of erbium doped lead zirconate titanate (PZT) of different thickness were deposited by sol–gel technique on Pt/TiO₂/SiO₂/Si substrates. Capacitance–voltage measurements show that the dielectric constant continuously increases with the thickness. This is interpreted in terms of effects due to a low permittivity interfacial layer in series with the ferroelectric bulk. The linear fit of the reciprocal of capacitance vs. thickness leads to a true dielectric constant of the ferroelectric of 774 and interfacial capacitance of 14.6 nF. The leakage current properties also depend on thickness and temperature. The calculated interfacial potential barrier height amounts to 0.81 and 0.74 eV, respectively for erbium doped and pure PZT thin films.     

Effects of p(O2) and p(CO2) on epitaxial growth of BaTiO3 thin films on MgO(100) substrates by using metal organic acid salts

BaTiO₃ thin films were prepared by using metal organic acid salts on MgO(100) substrates, which have large lattice-misfit with BaTiO₃. Amorphous films prefired at 470°C were crystallized to BaTiO₃ phase by heat treatment at higher temperature. Crystallinity and in-plane alignment of the prepared films were found to depend on the heat-treatment conditions. BaTiO₃ films with high crystallinity but poor (100)-orientation were obtained in air at higher than 1200°C. Whereas, (100)-oriented epitaxial BaTiO₃ film was fabricated by annealing at 900°C under low oxygen partial pressure (p(O₂)). Low carbon dioxide partial pressure (p(CO₂)) is also found to be essential for preparation of epitaxial BaTiO₃ films on MgO substrates by using metal organic acid salts.     

Chemical bath deposition of indium sulphide thin films: preparation and characterization

Indium sulphide (In₂S₃) thin films have been successfully deposited on different substrates under varying deposition conditions using chemical bath deposition technique. The deposition mechanism of In₂S₃ thin films from thioacetamide deposition bath has been proposed. Films have been characterized with respect to their crystalline structure, composition, optical and electrical properties by means of X-ray diffraction, TEM, EDAX, optical absorption, TRMC (time resolved microwave conductivity) and RBS. Films on glass substrates were amorphous and on FTO (flourine doped tin oxide coated) glass substrates were polycrystalline ( phase). The optical band gap of In₂S₃ thin film was estimated to be 2.75 eV. The as-deposited films were photoactive as evidenced by TRMC studies. The presence of oxygen in the film was detected by RBS analysis.     

Growth of calcium carbonate by the atomic layer chemical vapour deposition technique

Thin films of CaCO₃ (calcite) have been grown with the atomic layer chemical vapour deposition (ALCVD) technique, using Ca(thd)₂ (Hthd=2,2,6,6-tetramethylheptan-3,5-dione), CO₂, and ozone as precursors. Pulse parameters for the ALCVD-type growth are found and self-limiting reaction conditions are established between 200 and 400 °C. Calcium carbonate films have been deposited on soda-lime glass, Si(100), -Al₂O₃(001), -Al₂O₃(012), -SiO₂(001), and MgO(100) substrates. The observed textures were: in-plane oriented films with [100](001)CaCO₃ [100](001)Al₂O₃ and [100](001)CaCO₃[110](001)Al₂O₃ on -Al₂O₃(001), amorphous films on -Al₂O₃(012) when grown at 250 °C, and columnar oriented films on soda-lime glass, Si(001), -SiO₂(001), and MgO(100) substrates with (00l) and (104) parallel to the substrate plane at 250 and 350 °C, respectively. The film topography was studied by atomic force microscopy and AC impedance characteristics were measured on as-deposited films at room temperature. The films were found to be insulating with a dielectric constant (_r) typically approximately 8. Thin films of CaO were obtained by heat treatment of the carbonate films at 670 °C in a CO₂-free atmosphere, but the thermal decomposition led to a significant increase in surface roughness.     

Improved fatigue properties of lead zirconate titanate films made on oxygen-implanted platinum electrodes

Pb(Zr_0.3Ti_0.7)O₃ (PZT) thin film capacitors fabricated on an oxygen-implanted Pt bottom electrode were studied. Oxygen was implanted at a low acceleration voltage (40 kV) and dose (1×10¹⁵ cm⁻²). Structural examination by grazing-incident X-ray diffraction (GIXD) and chemical analysis by X-ray photoelectron spectroscopy (XPS) revealed that the implantation generated a very thin amorphous top surface layer (approx. 20 nm), which contained approximately 7% of oxygen that stayed in the film in the form of PtO bonding. The amorphous layer, however, resumed the crystalline structure accompanied by the dissociation of PtO under the rapid thermal annealing at 600 °C for 5 min. The remnant polarization of sol–gel derived Pb(Zr_0.3Ti_0.7)O₃ (PZT) films fabricated on the oxygen-implanted Pt was slightly reduced from 11.92 μC/cm² for the PZT capacitors fabricated on a Pt electrode without implanted oxygen to 9.07 μC/cm². Nevertheless, the fatigue endurance was significantly increased. The switching polarization of PtO_x/PZT/Pt (O-implanted) capacitors remained within 95% of the starting value after 4×10¹⁰ switching cycles, which is comparable to that of PZT capacitors made with other conducting oxides.     

应力对蓝宝石衬底上生长二氧化钒薄膜结构和光电性能的调控

利用脉冲激光沉积技术在蓝宝石衬底上生长不同厚度的VO₂薄膜, 对薄膜的结构、表面形貌和光电性能进行研究。结果表明: 所沉积的VO₂薄膜为具有单晶性能、表面平整的单斜晶相的VO₂薄膜, 相变前后, 方块电阻的变化可达到3~4个数量级, 在波长为2500 nm的透过率变化最高可达56%, 优化的可视透过率(T_lum)和太阳能调节率( ∆T_sol )为43.2%和8.7%。薄膜受到的应力对VO₂薄膜有重要影响, 可以通过调节薄膜的厚度对VO₂薄膜光电性能实现调控。当VO₂薄膜厚度较小时, 薄膜受到拉应力, 拉应力能使相变温度显著降低, 金属-绝缘体转变性能(MIT)不但与载流子浓度的变化相关, 而且还受载流子迁移率变化的影响;当VO₂薄膜厚度较大时, 薄膜受到压应力, VO₂薄膜的相变温度接近块体VO₂的相变温度, MIT转变主要来自于载流子浓度在相变前后的变化, 其载流子迁移率几乎不变。     

Fabrication and Optical Properties of Pb(Mg/sub 1/3/Nb/sub 2/3/)O/sub 3/-PbTiO/sub 3/Thin Films on Si Substrates Using the PLD Method

Epitaxial 0.67Pb(Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ (PMN-PT) thin films with electro-optic effects were fabricated on (La_0.5Sr_0.5)CoO₃(LSCO)/CeO₂/YSZ-buffered Si(001) substrates using double-pulse excitation pulsed laser deposition (PLD) method with a mask placed between the target and the substrate. Epitaxial growth of PMN-PT thin films was undertaken using the two-step growth method of PMN-PT film. The PMN-PT seed layer was deposited at 500degC on the LSCO/CeO₂/YSZ/Si, which temperature was the same as that used for LSCO deposition. The PMN-PT thin films were deposited on the PMN-PT seed layer at 600degC, which enables growth of high-crystallinity PMN-PT films with smooth surfaces. We obtained optimum fabrication conditions of PMN-PT film with micrometer-order thickness. Resultant films showed high crystallinity with full width at half maximum (FWHM)=0.73 deg and 1.6 mum thickness. Electro-optic properties and the refractive index value were measured at 633 nm wavelength using the prism coupling method. The obtained refractive index was 2.59. The electro-optic coefficients r₁₃ and r₃₃ were determined by applying the electrical field between a semitransparent, thin top electrode of Pt and a bottom LSCO electrode. The electro-optic coefficient was r₁₃=17 pm/V at transverse electric field (TE) mode and r₃₃=55 pm/V at transverse magnetic field (TM) mode.     

Preparation and characterization of YBa2Cu3O7−x high Tc superconducting thin films deposited by S-gun sputtering

We have prepared YBa₂Cu₃O_7−x high T_c superconducting (HTS) thin films on (100) yttria-stabilized zirconia (YSZ) and LaAlO₃ (LAO) substrates, using a 2 kW S-gun in an off-axis mode. By varying the temperature of the substrates, films with a axis and c axis orientations were readily obtained. The X-ray diffraction pattern and Laue pattern confirmed that films with a axis orientation exhibited a single-crystal texture. All films had a good mirror-like surface. For films grown on YSZ substrates, scanning electron microscopy (SEM) revealed a clear distinction between the surfaces of the films grown at various temperatures (520–780°C). Films grown on LAO substrates exhibited even smoother and flatter surfaces. The SEM changes will be discussed in correlation with J_c. The best HTS thin films were obtained on LAO substrates at a temperature of 820°C, with T_c=89 K and J_c=1×10⁶ A cm^-2 (77 K).     

Deposition of BaTiO3 thin films by plasma MOCVD

Barium titanium trioxide (BaTiO₃) thin films were deposited on fused silica or silicon wafer substrate from barium dipivaloylmethanate (II) (Ba(dpm)₂) and titanium tetraisopropoxide (IV) (TTIP) used as precursors in an oxygen microwave plasma. The substrates were dielectrically heated and the substrate temperatures were around 900 K during the film deposition. The deposition was performed for 15 min and the deposits were identified as BaTiO₃ by means of X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectroscopy, and ellipsometry. Oxygen and barium atoms and TiO and CO molecules were identified in the plasma. These species would produce higher deposition rates at lower substrate temperatures than those did in the usual thermal metalorganic chemical vapor deposition (MOCVD). The dielectric constant of the BaTiO₃ thin film that was directly deposited on the silicon wafer substrate was as low as 10¹ order of magnitude. Because the deposit reacted with the substrate and an interdiffusional layer was formed, the platinum layer was coated on the silicon wafer substrate in order to prevent the formation of an interdiffusional layer. The dielectric constant then increased to 10³ order of magnitude.     

Dielectric properties of (Ba,Ca)(Zr,Ti)O3/CaRuO3 heterostructure thin films prepared by pulsed laser deposition

(Ba_0.90Ca_0.10)(Zr_0.25Ti_0.75)O₃ (BCZT) thin films were grown on Pt/Ti/SiO₂/Si substrates without and with a CaRuO₃ (CRO) buffer layer using pulsed laser deposition (PLD). The structure and surface morphology of the films have been characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). At room temperature and 1 MHz, the dependence of dielectric constant and tunability of the films with electric field were investigated; the dielectric constant and tunability are 725 and 47.0%, 877 and 50.4%, respectively, for the BCZT film on Pt/Ti/SiO₂/Si substrates without and with the CRO buffer layer at 400 kV/cm. The tunability of the BCZT/CRO heterostructure thin films on Pt/Ti/SiO₂/Si substrates was higher than that of the BCZT thin films on Pt/Ti/SiO₂/Si substrates. The high constant likely results from the oxide electrode (CRO).     

Thickness dependence of structural and ferroelectric properties of sol-gel Pb(Zr0.56Ti0.44)0.90(Mg1/3Nb2/3)0.10O3 films

Sol-gel Pb(Zr_0.56Ti_0.44)_0.90(Mg_1/3Nb_2/3)_0.10O₃ (PZT-PMN) films were prepared onto the Ti/Pt/Ti bottom electrode by multilayer spin coating. The film thickness ranged from 0.22 to 0.88 μm. The Pt top electrodes were deposited on the PZT-PMN films by DC sputtering. The structural and ferroelectric properties of PZT-PMN films were investigated as a function of film thickness by X-ray diffraction (XRD), scanning electron microscopy (SEM), cross-sectional transmission electron microscopy (XTEM), and by measuring the relative permittivity. The film retains the tetragonal perovskite structure with the [111] and [100] preferred orientations perpendicular to the film surface independent of film thickness. The [100] texture increases with increasing film thickness although the [111] texture is always predominant. The film consists of columnar grains. The average grain size is nearly independent of film thickness. The surface layer containing fine grains about 30 nm in diameter is induced on the top of the film. As the film thickness exceeds 0.44 μm, the number of the fine grains decreases remarkably. The crystalline interface layer about 10 nm thick is formed between the film and the bottom electrode. This interface layer is composed of Pt, Pb, Zr, Ti and O, while it is rich in Ti and deficient in Pb and O as compared with the inside of the film. The measured relative permittivity of the film increases with increasing film thickness, following the low permittivity interface model. On the basis of this model, the relative permittivity is estimated to be 3200 for the intrinsic PZT-PMN film, 750 for the surface layer and 50 for the interface layer.     

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.