Epitaxial growth and electrical measurement of single crystalline Pb(Zr0.52Ti0.48)O3 thin film on Si(001) for micro-electromechanical systems

We report in this work the epitaxial growth and the electrical characteristics of single crystalline Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin film on SrTiO₃(STO)-buffered Si(001) substrate. The STO buffer layer deposited by molecular beam epitaxy allows a coherent oxide/Si interface leading enhanced PZT crystalline quality. 70 nm-thick PZT (52:48) layer was then grown on STO/Si(001) by sol-gel method. X-ray diffraction demonstrates the single crystalline PZT film on Si substrate in the following epitaxial relationship: [110] PZT (001)//[110] STO (001)//[100] Si (001). The macroscopic electrical measurements show a hysteresis loop with memory window of 2.5 V at ± 7 V sweeping range and current density less than 1 μA/cm² at 750 kV/cm. The artificial domains created by piezoresponse force microscopy with high contrast and non-volatile properties provide further evidence for the excellent piezoelectric properties of the single crystalline PZT thin film.     

Pulsed laser deposition of epitaxial ferroelectric Pb(Zr,Ti)O3 films on silicon substrates

We report on the epitaxial growth and electrical properties of Pb_0.52Zr_0.48TiO₃ (PZT) thin films deposited by Pulsed Laser Deposition (PLD) on SrTiO₃ (STO)-buffered Si(001). Previously to PZT growth, 40 nm-thick (La,Sr)MnO₃ (LSMO) layer was deposited to serve as electrical bottom electrode. The 200 nm-thick PZT film epitaxy was optimized by PLD on STO-buffered Si(001).The high contrast of stable artificially poled ferroelectric surfaces evidences the good ferroelectric properties of the PZT thin film. The structural as well as the physical properties of the PZT/LSMO/STO/Si(001) structure prove that very good quality layers have been obtained for films grown on silicon substrate.     

Residual stresses and Raman shift relation in anatase TiO2 thin film

Anatase TiO₂ film (100-1000 nm thick) grown on glass, sapphire (0001), and Si (100) substrates by pulsed dc-magnetron reactive sputtering were evaluated for stress and strain analysis using Raman spectroscopy and curvature measurement techniques. The X-ray analysis revealed that films prepared for this study were purely anatase, and the measurements indicate that the film exhibit that (101) is the preferred growth orientation of the crystallites, especially for the film thicker than 100 nm. Curvature measurements and Raman spectroscopy, with 514.5 nm excitation wavelength, phonon line shift were used for stress analysis. A comparison between Raman lineshapes and peak shifts yields information on the strain distribution as a function of film thickness. The measurements of residual stresses for crystalline anatase TiO₂ thin film showed that all thin film were under compressive stress. A correlation between Raman shifts and the measured stress from the curvature measurements was established. The behavior of the anatase film on three different substrates shows that the strain in film on glass has a higher value compared to the strain on sapphire and on silicon substrates. The dominant 144 cm^− 1E_g mode in anatase TiO₂ clearly shifts to a higher value by 0.45-5.7 cm^− 1 depending on the type of substrate and film thickness. The measurement of the full width at half maximum values of 0.59-0.80 (2θ°) for the anatase (101) peaks revealed that these values are greater than anatase powder 0.119 (2θ°) and this exhibits strong crystal anisotropy with thermal expansion.     

Fe3Si nanodots epitaxially grown on Si(111) substrates using ultrathin SiO2 film technique

Ultrahigh density (> 10¹² cm⁻²) Fe₃Si nanodots (NDs) are epitaxially grown on Si(111) substrates by codeposition of Fe and Si on the ultrathin SiO₂ films with ultrahigh density nanovoids. We used two kinds of methods for epitaxial growth: molecular beam epitaxy (MBE) and solid phase epitaxy. For MBE, low temperature (< 300 °C) growth of the Fe₃Si NDs is needed to suppress the interdiffusion between Fe atoms deposited on the surfaces and Si atoms in the substrate. These epitaxial NDs exhibited the ferromagnetism at low temperatures, which were expected in terms of the application to the magnetic memory device materials.     

Precursor chemistry for the solution deposition of epitaxial La0.66Sr0.33MnO3 (LSMO) thin films

A new chemical solution deposition method for the epitaxial growth of La_0.66Sr_0.33MnO₃ (LSMO) thin films from metal acetates, acetylacetonates and propionic acid is presented. Using this method, epitaxial LSMO thin films were grown on (001) SrTiO3 (STO) single crystalline substrates in the temperature range from 800 °C to 1100 °C, both in air and in oxygen atmosphere. The LSMO thin films exhibit good structural and electrical properties. The FWHM of the ω-scan for the (002) peak has a mean value of 0.06°. The Curie temperature of the LSMO thin films is about 320 K and 350 K for the annealed in oxygen and air, respectively.     

Photocatalytic activities of TiO2 thin films prepared on Galvanized Iron substrate by plasma-enhanced atomic layer deposition

Titanium dioxide (TiO₂) thin films were prepared on Galvanized Iron (GI) substrate by plasma-enhanced atomic layer deposition (PE-ALD) using tetrakis-dimethylamido titanium and O₂ plasma to investigate the photocatalytic activities. The PE-ALD TiO₂ thin films exhibited relatively high growth rate and the crystal structures of TiO₂ thin films depended on the growth temperatures. TiO₂ thin films deposited at 200 °C have amorphous phase, whereas those with anatase phase and bandgap energy about 3.2 eV were deposited at growth temperature of 250 °C and 300 °C. From contact angles measurement of water droplet, TiO₂ thin films with anatase phase and Activ™ glass exhibited superhydrophilic surfaces after UV light exposure. And from photo-induced degradation test of organic solution, anatase TiO₂ thin films and Activ™ glass decomposed organic solution under UV illumination. The anatase TiO₂ thin film on GI substrate showed higher photocatalytic efficiency than Activ™ glass after 5 h UV light exposure. Thus, we suggest that the anatase phase in TiO₂ thin film contributes to both superhydrophilicity and photocatalytic decomposition of 4-chlorophenol solution and anatase TiO₂ thin films are suitable for self-cleaning applications.     

Epitaxial growth and exchange coupling of spinel ferrimagnet Ni0.3Zn0.7Fe2O4 on multiferroic BiFeO3

Thin films of the zinc nickel ferrite, Zn_0.7Ni_0.3Fe₂O₄ (ZNFO), were deposited by the RF magnetron sputtering on a number of substrates, including (001) oriented single crystals of LaAlO₃ (LAO) and SrTiO₃ (STO), polycrystalline Pt/Si, and epitaxial films of BiFeO₃ (BFO) and LaNiO₃ (LNO). Except for the films on Pt/Si, the ZNFO films grown on other substrates were epitaxial and their magnetic properties were affected by the heteroepitaxy induced strains. Typically, the coercivity (H_c) was increased with the strain, i.e. H_c varied from 31 Oe for the 150 nm thick polycrystalline films grown on Pt/Si, to 55 Oe and 155 Oe for the 20 nm thick epitaxial films grown on BFO and LAO, respectively. The saturation magnetization of the epitaxial films was reduced accordingly to about 470 emu/cm³ from 986 emu/cm³ in the polycrystalline films. The all-oxide architecture allowed field-annealing to perform at the temperature above the Neel temperature of BFO (~ 370 °C), after which clear exchange bias was observed.     

Epitaxial orientation and morphology of β-FeSi2 produced on a flat and a patterned Si(001) substrates

The epitaxial growth of β-FeSi₂ films produced on flat and patterned Si(001) substrates under various substrate temperatures (T_s) with deposition rates of Fe (V_Fe) was investigated by transmission electron microscopy (TEM). In the film deposited on the flat Si(001) substrate, precipitates of flat-bottom shaped β-FeSi₂ and those of round-bottom shaped α-FeSi₂ were formed at T_s = 500 °C and V_Fe = 0.02 nm/s. The β-FeSi₂ adopted the epitaxy to (001)_Si plane, while α-FeSi₂ selected the epitaxy to {111}_Si planes inside the Si matrix. At T_s = 350 °C and V_Fe = 0.01 nm/s, a continuous β-FeSi₂ layer were formed epitaxially on the Si(001) substrate without forming α-FeSi₂. It was found that the lower temperature and the higher Fe-concentration suppress the formation of α-FeSi₂ and promote the formation of β-FeSi₂. In addition, the morphology of β-FeSi₂ changed from fine isolated precipitates (islands) to a continuous layer with increasing the deposition rate and the substrate temperature. In the film deposited on the patterned Si(001) substrate at T_s = 500 °C and V_Fe = 0.02 nm/s, on the other hand, both β- and α-FeSi₂ precipitates were formed on the top-hills and the valleys of the patterned substrate, while only α-FeSi₂ precipitates were formed on the sidewalls. These results demonstrate that not only the growth conditions but also geometric situations affect strongly the epitaxial growth of FeSi₂ precipitates.     

Third-order optical nonlinearities in anatase and rutile TiO2 thin films

Titanium dioxide (TiO₂) films have been fabricated on fused quartz and Si(001) substrates by pulsed laser deposition technique and the single-phase anatase and rutile films were obtained under the optimal conditions. The surface images and optical transmission spectra were investigated by scanning electron microscopy and double beam spectrophotometer, respectively. The values of optical band-gap and linear refractive index of the anatase and rutile films were determined. The optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. Through the open-aperture and closed-aperture Z-scan measurements, the real and imaginary parts of the third-order nonlinear optical susceptibility were calculated and the results show that the anatase phase TiO₂ films exhibit larger nonlinear refractive effects compared with rutile phase. The figure of merit, T, defined by T = βλ/n₂, was calculated to be 0.8 for anatase films, meeting the requirement of T < 1 and showing potential applications in all-optical switching devices.     

Enhanced ferroelectric properties of Mg doped (Ba,Sr)TiO3 thick films grown on (001) SrTiO3 substrates

Highly (001)-oriented 1 mol% Mg doped (Ba_0.67,Sr_0.33)TiO₃ (BST) films with a thickness of 1.25 μm were grown on (110) SrRuO₃/(001) SrTiO₃ substrates by pulsed laser deposition. X-ray diffraction measurements reveal that the BST thick films have very high crystalline quality, and have a distorted lattice with a large tetragonality a/c = 1.012. The BST thick films have a remanent polarization (P_r) value as large as 10.1 μC/cm² and a coercive electric field (E_c) value of 65.0 kV/cm. The films possess dielectric constant and loss values of ε_r = 385.36 and tgδ = 0.038 at 1 kHz and room temperature. The leakage currents of the films are on the order of 10^− 5 A/cm² at ± 150 kV/cm. The mechanism for enhancing electric properties of the Mg doped BST films was also discussed.     

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.     

Effect of working pressure on the properties of BaTiO3-CoFe2O4 composite films deposited on STO (100) by PLD

The BaTiO₃-CoFe₂O₄ (BTO-CFO) composite films were grown on SrTiO₃ (STO) (100) substrates at 750 °C under various working pressures by pulsed laser deposition. The composite film grew into a supersaturated single phase at the working pressure of 10 mTorr, BTO and CFO (00 l) oriented hetero-epitaxial films on STO (100) at 100 mTorr, and a polycrystalline composite film at 500 mTorr. The slow growth rate at high working pressure led to the phase separation in the composite film. The CFO was compressively strained along out-of-plane due to the lattice mismatch with the BTO matrix phase. The BTO-CFO composite film grown at 100 mTorr showed reversible switching of ferroelectric polarization and magnetic hysteresis with strong magnetic anisotropy.     

TiO2 nanorod films grown on Si wafers by a nanodot-assisted hydrothermal growth

We report the controlled hydrothermal growth of rutile TiO₂ nanorods on Si wafers by using an anatase TiO₂ nanodot film as an assisted growth layer. The anatase nanodot film was prepared on the wafer by phase-separation-induced self-assembly and subsequent heat-treatment at 500 °C. The nanodots on the wafer were then subjected to hydrothermal treatment to induce the growth of rutile TiO₂ nanorod films. The size and dispersion density of the resulting TiO₂ nanorods could be varied by adjusting the Ti ion concentration in the growth solution. The TiO₂ nanorods were of the rutile phase and grew in the [001] direction. The growth mechanism reveals that the growth of the rutile nanorods was wholly dependent on the existence of rutile TiO₂ seeds, which could be formed by the dissolution-reprecipitation of the anatase nanodots during hydrothermal treatment or under the high-temperature conditions of the subsequent heat-treatment of the as-prepared nanodots. In controlling the rutile nanorod growth, the anatase nanodots show more efficiency than a dense anatase film. Preliminary evaluations of the rutile nanorod films have demonstrated that the wettability changed from highly hydrophobic to superhydrophilic and that the photocatalytic activity was enhanced with increasing nanorod dispersion density.     

Structure, morphology and optical properties of nanocrystalline yttrium oxide (Y2O3) thin films

Yttrium oxide (Y₂O₃) thin films were grown onto Si(1 0 0) substrates using reactive magnetron sputter-deposition at temperatures ranging from room temperature (RT) to 500 °C. The effect of growth temperature (T_s) on the growth behavior, microstructure and optical properties of Y₂O₃ films was investigated. The structural studies employing reflection high-energy electron diffraction RHEED indicate that the films grown at room temperature (RT) are amorphous while the films grown at T_s = 300-500 °C are nanocrystalline and crystallize in cubic structure. Grain-size (L) increases from ∼15 to 40 nm with increasing T_s. Spectroscopic ellipsometry measurements indicate that the size-effects and ultra-microstructure were significant on the optical constants and their dispersion profiles of Y₂O₃ films. A significant enhancement in the index of refraction (n) (from 2.03 to 2.25) is observed in well-defined Y₂O₃ nanocrystalline films compared to that of amorphous Y₂O₃. The observed changes in the optical constants were explained on the basis of increased packing density and crystallinity of the films with increasing T_s. The spectrophotometry analysis indicates the direct nature of the band gap (E_g) in Y₂O₃ films. E_g values vary in the range of 5.91-6.15 eV for Y₂O₃ films grown in the range of RT-500 °C, where the lower E_g values for films grown at lower temperature is attributed to incomplete oxidation and formation of chemical defects. A direct, linear relationship between microstructure and optical parameters found for Y₂O₃ films suggest that tuning optical properties for desired applications can be achieved by controlling the size and structure at the nanoscale dimensions.     

Two-step growth of SrTiO<Subscript>3</Subscript> films on Sr-modulated Si(001) substrates

Perovskite-type SrTiO₃ (STO) films have been grown on the Sr-modulated Si(001) substrates using two-step growth method with a molecular beam epitaxy technique. About 6 Å Sr was deposited on the surface of chemically formed SiO₂/Si at 800 C, which resulted in the formation of Si(001)-Sr(2 × 1) surface. About 250-Å-thick STO films have been deposited on the Si(001)-Sr(2 × 1) surface at 350 C in the O₂ partial pressure of approximately 3 × 10^–7 Torr (first step), followed by an annealing at 600 C in a pressure of 3 × 10^–9 Torr (second step). Reflection high-energy electron diffraction patterns of grown films become elongated streaky features after the annealing, suggesting the solid-phase epitaxial growth of STO. The presence of strong STO(001) and STO(002) diffraction peaks in X-ray diffraction measurements suggests that the high-quality crystalline STO films grow on the Sr-modulated Si(001) substrates by the two-step growth method. Atomic force microscopy image shows the smooth surface with root mean square roughness of about 18 Å.     

Ni silicide formation on epitaxial Si1 − yCy/(001) layers

The formation of Ni silicides on Si_1 − yC_y (y = 0.01 and 0.018) epilayers grown on Si(001) has been investigated. The presence of C atoms was found to significantly retard the growth kinetics of NiSi and enhances the thermal stability of thin NiSi films. For Ni(11 nm)/Si_0.982C_0.018 samples, the process window of NiSi was shifted and extended to 450-700 °C. Moreover, there was an additional strain introduced into the Si_1 − yC_y epilayers during Ni silicidation. This work shows the potential of Ni silicidation on Si_1yC_y for device applications.     

Structural and magnetic properties of CoFe2O4 thin films deposited by laser ablation on Si (001) substrates

Cobalt ferrite (CoFe₂O₄) thin films have been deposited on Si (001) substrates, with different substrate temperatures (T_dep = 25 °C − 600 °C). The films were prepared by pulsed laser ablation with a KrF excimer laser (wavelength λ = 248 nm). The oxygen pressure during deposition was 2 × 10⁻² mbar. The films structure was studied by X-ray diffraction (XRD) and their surface was examined by scanning electron microscopy (SEM). The magnetic properties were measured with a vibrating sample magnetometer (VSM). For low deposition temperatures, the films presented a mixture of a CoFe₂O₄ phase, with the cubic spinel structure, and cobalt and iron antiferromagnet oxides with CoO and FeO stoichiometries. As the deposition temperature increased, the CoO and FeO relative content strongly decreased, so that for T_dep = 600 °C the films were composed mainly by polycrystalline CoFe₂O₄. The magnetic hysteresis cycles measured in the films were horizontally shifted due to an exchange coupling field (H_exch) originated by the presence of the antiferromagnetic phases. The exchange field decreased with increasing deposition temperature, and was accompanied by a corresponding increase of the coercivity and remanence ratio of the cycles. This behavior was due to the strong reduction of the CoO and FeO content, and to the corresponding dominance of the CoFe₂O₄ phase on the magnetic properties of the thin films.     

Effects of periodicity and oxygen partial pressure on the crystallinity and dielectric property of artificial SrTiO3/BaTiO3 superlattices integrated on Si substrates by pulsed laser deposition method

Epitaxial SrTiO₃(STO)/BaTiO₃(BTO) artificial superlattices have been grown on TiN buffered Si (001) substrates by pulsed laser deposition method and the effects of stacking periodicity and processing oxygen partial pressure on their crystallinity and dielectric properties were studied. The crystal orientation, epitaxy nature, and microstructure of STO/BTO superlattices were investigated using X-ray diffraction and transmission electron microscopy. The TiN buffer layer and superlattice thin films were grown with cube-on-cube epitaxial orientation relationship of [110](001)_films∣∣[110](001)_TiN∣∣[110](001)_Si. The c-axis lattice parameter of the STO/BTO superlattice decreased from 0.412 nm to 0.406 nm with increasing oxygen partial pressure and the dielectric constants, measured at the frequency of 100 kHz at room temperature, of the superlattices with 2 nm/2 nm periodicity increased from 312 at 1 × 10^− 5 Torr to 596 at 1 × 10^− 3 Torr. The dielectric constants of superlattices grown at oxygen partial pressure of 1 × 10^− 3 Torr increased from 264 to 678 with decreasing periodicity of the superlattices from 10 nm/10 nm to 1 nm/1 nm.     

Growth of stoichiometric TiO2 thin films on Au(100) substrates by molecular beam epitaxy

The present study reports on the growth of thin TiO₂ films onto Au(100) single crystals by Ti evaporation in a reactive O₂ atmosphere at two different substrate temperatures: room temperature (RT) and 300 °C. The growth of the oxide films was monitored by means of X-ray photoemission spectroscopy, while the valence and conduction band electronic structure was investigated by UV and inverse photoemission spectroscopy, respectively.The TiO₂ film grows epitaxially on the Au(100) substrate at 300 °C exhibiting the rutile (100) surface. The evolution of the Ti 2p lineshape with the oxide coverage shows the presence of reduced oxide species (characterized by Ti^3 + ions) at the Au(100) interface. A crystalline and stoichiometric TiO₂ oxide is produced at high substrate temperature, while growth at RT gives a measurable concentration of defects. Post growth annealing in ultra-high vacuum of the RT grown film increases this concentration, while subsequent annealing in O₂ atmosphere restores the sample to the as-grown conditions.     

Epitaxy of In0.01Ga0.99As on Ge/offcut Si (001) virtual substrate

In_0.01Ga_0.99As thin films free of anti-phase domains were grown on 7° offcut Si (001) substrates using Ge as buffer layers. The Ge layers were grown by ultrahigh vacuum chemical vapor deposition using ‘low/high temperature’ two-step strategy, while the In_0.01Ga_0.99As layers were grown by metal-organic chemical vapor deposition. The etch-pit counting, cross-section and plane-view transmission electron microscopy, room temperature photoluminescence measurements are performed to study the dependence of In_0.01Ga_0.99As quality on the thickness of Ge buffer. The threading dislocation density of Ge layer was found to be inversely proportional to the square root of its thickness. The threading dislocation density of In_0.01Ga_0.99As on 300 nm thick Ge/offcut Si was about 4 × 10⁸ cm^− 2. Higher quality In_0.01Ga_0.99As can be obtained on thicker Ge/offcut Si virtual substrate. We found that the threading dislocations acted as non-radiative recombination centers and deteriorated the luminescence of In_0.01Ga_0.99As remarkably. Secondary ion mass spectrometry measurement indicated as low as 10¹⁶ cm^− 3 Ge unintended doping in In_0.01Ga_0.99As.