The influence of a poly-Si intermediate layer on the crystallization behaviour of Ni-Ti SMA magnetron sputtered thin films

Shape memory alloy Ni-Ti thin films as sputtered are amorphous if the substrate is not intentionally heated during deposition. Therefore, these films have to be heat treated to induce crystallization in order to exhibit the shape-memory effect. Several films have been prepared by dc magnetron sputtering and then studied concerning the influence of the type of substrate (single-crystal Si, polycrystalline Si) on the crystallization kinetics and the final structure. The structural development of the films during crystallization (at a constant temperature of 430 °C) has been studied by X-ray diffraction in grazing incidence geometry off-plane (GIXD) at a synchrotron-radiation beamline. These experiments allow us to establish a correlation between the deposition conditions and the kinetics of crystallization. For films deposited at an electrode distance of 70 mm on a Si(100) substrate, a longer crystallization time is needed compared with films obtained at 40 mm, for otherwise fixed deposition parameters. The analysis of the nucleation kinetics by using the Johnson–Mehl–Avrami equation leads to exponents between 2.6 and 3. The presence of an intermediate layer of poly-Si drastically enhances the crystallization process. Additionally, ex situ annealing of identical samples at 500 °C during 1 h and complementary characterization of the structure and morphology of the films by cross-sectional transmission electron microscopy and selected-area electron diffraction were performed. The temperature dependence of the electrical resistivity was measured, identifying the phase transformation temperature ranges. An increase of the overall resistivity with the precipitation of Ni₄Ti₃ has been detected. Results obtained by X-ray reflectometry and GIXD suggest that during crystallization excess nickel is driven into an amorphous region ahead of the crystal/amorphous interface, thus leading to a higher concentration of Ni at the surface and further precipitation of Ni₄Ti₃. PACS 81.15.Cd; 61.10.Nz; 68.55.Jk     

Surface chemical states of barium zirconate titanate thin films prepared by chemical solution deposition

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin films grown on Pt/Ti/SiO₂/Si(1 0 0) substrates were prepared by chemical solution deposition. The structural and surface morphology of BZT thin films has been studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the random oriented BZT thin film grown on Pt/Ti/SiO₂/Si(1 0 0) substrate with a perovskite phase. The SEM surface image showed that the BZT thin film was crack-free. And the average grain size and thickness of the BZT film are 35 and 400 nm, respectively. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Ti, and Zr exist mainly in the forms of BZT perovskite structure.     

Growth of sputter-deposited Ni-Ti thin films: Effect of a SiO2 buffer layer

In-situ X-ray diffraction (XRD) during the growth of Ni-Ti thin films was chosen in order to investigate their texture development using a deposition chamber installed at a synchrotron radiation beamline. Near-equiatomic films were co-sputtered from Ni-Ti and Ti targets. The texture evolution during deposition is clearly affected by the substrate type and the ion bombardment of the growing film. On naturally oxidized Si(100) substrates, the Ni-Ti B2 phase starts by stacking onto (h00) planes, and as the thickness increases evolves into a (110) fibre texture. For the deposition on thermally oxidized Si(100) substrates, this pronounced cross-over is only observed when a substrate bias voltage (-45 V) is applied. The oxide layer plays an important role on the development of the (100) orientation of the B2 phase during deposition on heated substrates (≈470 °C). If this layer is not thick enough (naturally oxidized Si substrate) or if a bias voltage is applied, a cross-over and further development of the (110) fibre texture is observed, which is considered as an orientation that minimizes surface energies. Electrical resistivity measurements showed different behaviour during phase transformation for the Ni-Ti film deposited on thermally oxidized Si without bias and those on thermally oxidized Si(100) with bias and on naturally oxidized Si(100) without bias. This is related to stresses resultant from the fact that the Ni-Ti films are attached to the substrates as well as with the existence of distinct textures. PACS 81.15.Cd; 61.10.Nz; 68.55.Jk     

Investigation of oxidation resistance of Ni-Ti film used as oxygen diffusion barrier layer

Ni-Ti films prepared at 10 W and 70 W by rf magnetron sputtering are investigated as the oxygen diffusion barrier layer, it is found that crystallinity of Ni-Ti film does not greatly depend on the deposition power. X-ray photoelectron spectroscopy indicates that Ni is still in the form of metallic state from the binding energies of both Ni 2p_3/2 and Ni 2p_1/2 spectra for the sample with 10 W prepared Ni-Ti, however, Ni is oxidized for 70 W prepared Ni-Ti film. Moreover, the (La_0.5Sr_0.5)CoO₃/Pb(Zr_0.40Ti_0.60)O₃/(La_0.5Sr_0.5)CoO₃ capacitor grown on high power prepared Ni-Ti film is leaky, however, the capacitor on low power prepared Ni-Ti film possesses very promising physical properties (i.e. remnant polarization of ∼27 μC/cm² at 5 V and maximum dielectric constant of 940). Leakage current density of the capacitor grown on low power prepared Ni-Ti film is further investigated, it meets ohmic behavior (<1.0 V) and agrees well with the space-charge-limited current theory (>1.0 V).     

Investigation the effects of the excess Pb content and annealing conditions on the microstructure and ferroelectric properties of PZT (52-48) films prepared by sol-gel method

The effects of the PbO volatilization, excess Pb content of PbZr_0.52Ti_0.48 (PZT) precursor, PbTiO₃ (PT) seeding layers and annealing condition on the microstructures, surface morphologies, preferred orientation and ferroelectric properties of PbZr_0.52Ti_0.48 films were systematically investigated. PZT films with a variety of excess Pb (0-20%) were spin-deposited on Si(1 0 0) and Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by sol-gel technique. The films composition, Pb/Zr/Ti/O atom rate and Pb loss were semiquantitative analyzed by X-ray photoelectron spectrometer (XPS). When the excess Pb of PZT precursor was 10%, the Pb/Zr/Ti/O atomic rate of the fabricated films was very close to the designed rate of 1:0.52:0.48:3. The XRD and AFM investigations confirmed that PT seeding layer promoted the PZT films perovskite phase transformation and grains growth with (1 1 0) plane preferred orientation, accordingly lowered perovskite phase crystallization temperature and reduced Pb loss. The PZT films annealed in O₂ flow demonstrated better microstructure and ferroelectric properties comparing with films annealed in air by double remnant polarization increase and 8% coercive field increase. The underlying mechanism was also investigated.     

Investigation of thin TiO2 films cosputtered with Si species

Titanium dioxide (TiO₂) films were fabricated by cosputtering titanium (Ti) target and SiO₂ or Si slice with ion-beam-sputtering deposition (IBSD) technique and were postannealed at 450 °C for 6 h. The variations of oxygen bonding, which included high-binding-energy oxygen (HBO), bridging oxygen (BO), low-binding-energy oxygen (LBO), and three chemical states of titanium (Ti⁴⁺, Ti³⁺ and Ti²⁺) were analyzed by X-ray photoelectron spectroscopy (XPS). The enhancement of HBO and reduction of BO in O 1s spectra as functions of SiO₂ or Si amount in cosputtered film imply the formation of Si-O-Ti linkage. Corresponding increase of Ti³⁺ in Ti 2p spectra further confirmed the property modification of the cosputtered film resulting from the variation of the chemical bonding. An observed correlation between the chemical structure and optical properties, refractive index and extinction coefficient, of the SiO₂ or Si cosputtered films demonstrated that the change of chemical bonding in the film results in the modification of optical properties. Furthermore, it was found that the optical properties of the cosputtered films were strongly depended on the cosputtering targets. In case of the Si cosputtered films both the refractive indices and extinction coefficients were reduced after postannealing, however, the opposite trend was observed in SiO₂ cosputtered films.     

Effect of buffer layers on the property of Pb(Zr,Ti)O3-Pb(Mn,W,Sb,Nb)O3 thin films grown by pulsed laser deposition

New ferroelectric Pb(Zr,Ti)O₃-Pb(Mn,W,Sb,Nb)O₃ (PZT-PMWSN) thin film has been deposited on a Pt/Ti/SiO₂/Si substrate by pulsed laser deposition. Buffer layer was adopted between film and substrate to improve the ferroelectric properties of PZT-PMWSN films. Effect of a Pb(Zr_0.52Ti_0.48)O₃ (PZT) and (Pb_0.72La_0.28)Ti_0.93O₃ (PLT) buffer layers on the stabilization of perovskite phase and the suppression of pyrochlore phase has been examined. Role of buffer layers was investigated depending on different types of buffer layer and thickness. The PZT-PMWSN thin films with buffer layer have higher remnant polarization and switching polarization values by suppressing pyrochlore phase formation. The remnant polarization, saturation polarization, coercive field and relative dielectric constant of 10-nm-thick PLT buffered PZT-PMWSN thin film with no pyrochlore phase were observed to be about 18.523 μC/cm², 47.538 μC/cm², 63.901 kV/cm and 854, respectively.     

Structural and ferroelectric properties of Bi4Ti3O12 thin films on IrO2 prepared by rf magnetron sputtering

Bismuth titanate, Bi₄Ti₃O₁₂, thin films were grown on IrO₂/SiO₂/Si substrates by radio-frequency magnetron sputtering. Crystallinity and microstructure of the films were characterized over a wide range of oxygen mixing ratio (OMR) during deposition. X-ray fluorescence spectra reveal that the cation content of the films is dependent upon the OMR, suggesting that control of Bi to Ti ratio is possible by the oxygen content in the sputtering atmosphere. Rutherford backscattering spectrometry measurements also show that oxygen content of the BTO film grown with an OMR = 0.5is close to a stoichiometric phase. In addition, Bi–O bonding chemistry is studied by X-ray photoelectron spectroscopy. Polarization vs. voltage loop shows that remnant polarization, P_r, is +12 μC/cm². Received: 26 November 1999 / Accepted: 26 November 1999 / Published online: 9 August 2000     

Ti-doping induced antiferroelectric to ferroelectric phase transition and electrical properties in Sm-PbZrO3 thin films

The antiferroelectric (Pb_0.985Sm_0.01) (Zr_1-xTi_x)O₃ (Ti-PSZO) thin films were synthesized on Pt(111)/Ti/SiO₂/Si substrates using a chemical solution deposition method. The films were crystallized in the perovskite phase with a preferential orientation along (111) direction. With Ti doping in PSZO, a gradual transformation from antiferroelectric to ferroelectric phase transition was noticed at room temperature owing to the Ti doping induced lattice distortion. The phase transition has been confirmed through the P - E hysteresis loops, X-ray diffraction (peak shifting), capacitance-voltage measurements, and Raman scattering analysis. The thin film with Ti = 0.15 doping displayed a ferroelectric behavior with high dielectric constant and large dielectric tunability of about 62%. Also, Ti doping altered the Curie temperature (T_c) and enhanced the order of dielectric diffuseness. It is believed that Ti-doping in PSZO is an effective way to induce an antiferroelectric - ferroelectric phase transition and to tailor the electrical characteristics of PSZO thin films.     

Room-temperature pulsed laser deposition and dielectric properties of amorphous Bi3.95Er0.05Ti3O12 thin films on conductive substrates

Bi_3.95Er_0.05Ti₃O₁₂ (BErT) thin films were prepared on Pt/Ti/SiO₂/Si and indium-tin-oxide (ITO)-coated glass substrates at room temperature by pulsed laser deposition. These thin films were amorphous with uniform thickness. Excellent dielectric characteristics have been confirmed. The amorphous BErT thin films deposited on the Pt/Ti/SiO₂/Si and ITO-coated glass substrates exhibited almost the same dielectric constant of 52 with a low dielectric loss of less than 0.02 at 1 kHz. Meanwhile, the dielectric properties of the thin films had an excellent bias voltage stability and thermal stability. The amorphous BErT thin films might have potential applications in microelectronic and optoelectronic devices.     

Influence of MgO and ZrO2 buffer layers on dielectric properties of Ba(Zr0.20Ti0.80)O3 thin films prepared by sol-gel processing

Ba(Zr_0.20Ti_0.80)O₃ (BZT) thin films are deposited on Pt(1 1 1)/Ti/SiO₂/Si, MgO and ZrO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si substrates by a sol-gel process. The BZT thin films directly grown on Pt(1 1 1)/Ti/SiO₂/Si substrates exhibit highly (1 1 1) preferred orientation, while the films deposited on Pt(1 1 1)/Ti/SiO₂/Si substrates with MgO and ZrO₂ buffer layers show highly (1 1 0) preferred orientation. At 100 kHz, dielectric constants are 417, 311 and 321 for the BZT thin films grown on Pt(1 1 1)/Ti/SiO₂/Si, MgO and ZrO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si substrates, respectively. The difference in dielectric properties of three BZT films can be attributed to the series capacitance effect, interface conditions and their orientations.     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Phase compositions and ferroelectric properties of Pb(Zr0.52,Ti0.48)O3 thin films with different highly orientations prepared by a sol-gel route

It is shown that different highly oriented Pb(Zr_0.52,Ti_0.48)O₃ films can be obtained on Pt/Ti/SiO₂/Si substrate using a sol-gel technique. The effects of pyrolysis temperature on the orientation, phase composition and ferroelectric properties of the films are investigated. It is found the ferroelectric hysteresis loops of (1 1 1)-oriented film, (1 1 1) and (1 0 0) mix-oriented film can both be saturated when the external electric field is large enough, whereas the hysteresis loop of (1 0 0)-oriented film is difficult to saturate. The analysis of X-ray diffraction indicated the possibility of different phase composition in different oriented films under large film residual stress. Higher remnant polarization (53 μC/cm²) for (1 0 0)-oriented film can be attributed to its more tetragonal phase composition, which results in that the in-plane domain switching can continuously occur with external electric field increasing.     

Effects of texture on the dielectric properties of Ba(Zr0.2Ti0.8)O3 thin films prepared by pulsed laser deposition

Ba(Zr_0.2Ti_0.8)O₃ (BZT) thin films were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by a pulsed laser deposition process. The BZT thin films directly grown on annealed and un-annealed Pt/Ti/SiO₂/Si substrates exhibited random and high (100) orientations, respectively. The dielectric constant of a 400-nm-thick BZT film with (100) orientation was 331, which was higher than that of a BZT film with random orientation (∼236). This result is attributed to the fact that the polar axis of the (100)-oriented films was more tilted away from the normal to the film surface than that of the randomly oriented films. Also, the tunabilities of BZT thin films with random and (100) orientations were ∼50% and ∼59% at an applied field of 400 kV/cm, respectively. Improved tunability has been attributed to the (100) texture of the film leading to an enhancement of the in-plane-oriented polar axis. PACS 77.22.-d; 77.55.+f; 77.80.-e; 77.84.-s     

Studies of structure and composition of a Pt-based basic electrode for deposition of PZT ferroelectric films on silicon substrates

In this study it has been found that a TiO₂/Ti double adhesion layer is used for SiO₂/Si substrate and a YSZ layer is used for SiO₂/Si and Si substrates to achieve high residual polarization of PZT layers on platinum. Epitaxial deposition of YSZ on Si(100) provides an atomically smooth platinum layer textured in the [100] direction. The produced PZT films are mostly textured in the [111] direction; their residual polarization is 5–15 μC/cm².     

Microstructure of annealed Ti48.5Ni(51.5– x )Cu x (x = 6.2–33.5) thin films

(Ni, Cu)-rich Ti–Ni–Cu amorphous films with a Cu content of 6.2–33.5 at. % formed by sputtering were annealed at 773, 873 and 973 K for 1 h and their microstructures investigated. Two types of precipitate were observed in the annealed films: a Ti(NiCu)₂ phase for the Ti_48.5Ni₄₀Cu_11.5, Ti_48.6Ni_35.9Cu_15.5, Ti_48.3Ni_28.4Cu_23.3 and Ti_48.3Ni_23.9Cu_27.8 films, plus a TiCu phase for the Ti_48.5Ni₁₈Cu_33.5 films. These precipitates were found to have coherency with the B2 matrix in the films annealed at 773 K and were densely distributed within the grains. However, in the films annealed at 873 K, their size increased 10-fold and their density decreased. Annealing at 973 K promoted grain-boundary precipitation and, accordingly, the density of the precipitates in the grain interiors decreased. On the other hand, the annealed Ti_48.9Ni_44.9Cu_6.2 films showed no precipitates in their grain interiors, but the number of grain-boundary precipitates increased with increasing annealing temperature. It was also found that grain size decreased with increasing Cu content and was significantly decreased for the Ti_48.5Ni₁₈Cu_33.5 films.     

Dielectric and piezoelectric properties of the Ba0.92Ca0.08Ti0.95Zr0.05O3 thin films grown on different substrate

Lead free Ba_0.92Ca_0.08Ti_0.95Zr_0.05O₃ (BCZT) thin films were deposited on Pt/Ti/SiO₂/Si and LaNiO₃(LNO)/Pt/Ti/SiO₂/Si substrates by a sol–gel processing technique, respectively. The effects of substrate on structure, dielectric and piezoelectric properties were investigated in detail. The BCZT thin films deposited on LNO/Pt/Ti/SiO₂/Si substrates exhibit (100) orientation, larger grain size and higher dielectric tunability (64%). The BCZT thin films deposited on Pt/Ti/SiO₂/Si exhibit (110) orientation, higher Curie temperature (75 °C), better piezoelectric property (d₃₃ of 50 pm/V) and lower dielectric loss (0.02). The differences in dielectric and piezoelectric properties in the two kinds of oriented BCZT films should be attributed to the difference of structure, in-plane stress and polarization rotation in orientation engineered BCZT films.     

Effect of measuring factors on ferroelectric properties of?Bi3.15Nd0.85Ti3O12 thin films prepared by sol–gel method for?non-volatile memory

Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by the sol–gel method. The phase composition was detected by XRD, the microstructure was characterized by AFM, and the effect of measuring factors (such as environmental temperature, working frequency, and voltage) on the ferroelectric properties was investigated. The films show the single Bi-layered Aurivillius phase with random orientation. At room temperature, the remanent polarization (2P _r) and the coercive field (2E _c) are 39.1 μC/cm² and 160.5 kV/cm, respectively, and a BNT capacitor shows fatigue-free behavior and memory retention. With the decrease of temperature, 2V _c increases, J decreases slightly, and the general trend of 2P _r is decreased. With the increase of frequency, 2P _r declines and 2V _c increases.     

Study of the plasmas produced during the deposition of TiC/SiC thin films in a hybrid magnetron-laser system

Time- and spatially-resolved optical emission spectroscopy was performed to characterize the plasma produced in a hybrid magnetron-sputtering-laser deposition system, which is used for TiC or SiC thin films preparation. A graphite target was ablated by a KrF excimer laser (λ=248 nm,τ=20 ns) and either Ti or Si targets were used for DC magnetron sputtering in argon ambient. Spectra were measured in the range 250–850 nm. The evolution of the spectra with varying magnetron powers (0–100 W) and argon pressures (0.3–10 Pa) was studied. Spectra of the plasmas produced by a) the magnetron alone, b) the ablation laser alone, and c) the magnetron and the ablation laser together, were recorded. Spectra (a) were dominated by Ar atoms and Ar⁺ ions. Emission lines of Ti and Si were detected, when Ti target and Si target was used, respectively. Spectra (b) revealed emission of C, C⁺, C₂, Ar, Ar⁺. Spectra (c) showed presence of all previously mentioned species and further of Ti⁺ ions emission was detected. The research was supported by Grant Agency of the Czech Republic No. 202/06/02161, GA ASCR project number A1010110/01 and Institutional Research Plan AV CR No. AV0Z 10100522.     

Effects of substrates on the structure and dielectric properties of Ba(Sn0.15Ti0.85)O3 thin films

Ba(Sn_0.15Ti_0.85)O₃ (BTS) thin films were grown on Pt(1 1 1)/Ti/SiO₂/Si and LaNiO₃(LNO)/Pt(1 1 1)/Ti/SiO₂/Si substrates by a sol-gel processing technique, respectively. The BTS thin films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si and annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates exhibited strong (1 1 1) and perfect (1 0 0) orientations, respectively. The BTS thin films grown on un-annealed Pt(1 1 1)/Ti/SiO₂/Si substrates showed random orientation with intense (1 1 0) peak, while the films deposited on un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate exhibited random orientation with intense (1 0 0) peak, respectively. The dielectric constant of the BTS films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si, annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si, un-annealed Pt(1 1 1)/Ti/SiO₂/Si and un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates was 512, 565, 386 and 437, respectively, measured at a frequency of 100 kHz. A high tunability of 49.7% was obtained for the films deposited on annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate, measured at the frequency of 100 kHz with an applied electric field of 200 kV/cm. The high tunability has been attributed to the (1 0 0) texture of the films and larger grain sizes.