Synthesis and characterization of Pb(Zr0.54Ti0.46)O3 thin films on (100)Si using textured YBa2Cu3O7−δ and yttria-stabilized zirconia buffer layers by laser physical vapor deposition technique

We have fabricated high-quality <001> textured Pb(Zr_0.54Ti_0.46)O₃ (PZT) thin films on (00l)Si with interposing <001> textured YBa₂Cu₃O_7−δ (YBCO) and yttria-stabilized zirconia (YSZ) buffer layers using pulsed laser deposition (KrF excimer laser, λ, = 248 nm, τ = 20 nanosecs). The YBCO layer provides a seed for PZT growth and can also act as an electrode for the PZT films, whereas YSZ provides a diffusion barrier as well as a seed for the growth of YBCO films on (001)Si. These heterostructures were characterized using x-ray diffraction, high-resolution transmission electron microscopy, and Rutherford backscattering techniques. The YSZ films were deposited in oxygen ambient (∼9 × 10⁻⁴ Torr) at 775°C on (001)Si substrate having <001>YSZ // <001>Si texture. The YBCO thin films were deposited in-situ in oxygen ambient (200 mTorr) at 650°C. The temperature and oxygen ambient for the PZT deposition were optimized to be 530°C and 0.4-0.6 Torr, respectively. The laser fluence to deposit this multilayer structure was 2.5-5.0 J/cm². The <001> textured perovskite PZT films showed a dielectric constant of 800-1000, a saturation polarization of 37.81 μC/cm², remnant polarization of 24.38 μC/cm² and a coercive field of 125 kV/cm. The effects of processing parameters on microstructure and ferroelectric properties of PZT films and device implications of these structures are discussed.     

Influence of the annealing temperature on the ferroelectric properties of niobium-doped strontium–bismuth tantalate

Characteristics of ferroelectric thin films of niobium-doped strontium–bismuth tantalate (SBTN), which were deposited by magnetron sputtering on Pt/TiO₂/SiO₂/Si substrates, are investigated. To form the ferroelectric structure, deposited films were subjected to subsequent annealing at 700–800°C in an O₂ atmosphere. The results of X-ray diffraction showed that the films immediately after the deposition have an amorphous structure. Annealing at 700–800°C results in the formation of the Aurivillius structure. The dependences of permittivity, residual polarization, and the coercitivity of SBTN films on the modes of subsequent annealing are established. Films with residual polarization 2P_r = 9.2 µC/cm², coercitivity 2E_c = 157 kV/cm, and leakage current 10^–6 A/cm² are obtained at the annealing temperature of 800°C. The dielectric constant and loss tangent at frequency of 1.0 MHz were ε = 152 and tan δ = 0.06. The ferroelectric characteristics allow us to use the SBTN films in the capacitor cell of high density ferroelectric random-access non-volatile memory (FeRAM).     

Low Fatigue in Epitaxial Pb(Zr<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>)O<Subscript>3</Subscript> on Si Substrates with LaNiO<Subscript>3</Subscript> Electrodes by RF Sputtering

Epitaxial PZT (001) thin films with a LaNiO₃ bottom electrode were deposited by radio-frequency (RF) sputtering onto Si(001) single-crystal substrates with SrTiO₃/TiN buffer layers. Pb(Zr_0.2Ti_0.8)O₃ (PZT) samples were shown to consist of a single perovskite phase and to have an (001) orientation. The orientation relationship was determined to be PZT(001)[110]∥LaNiO₃(001)[110]∥SrTiO₃ (001)[110]∥TiN(001)[110]∥Si(001)[110]. Atomic force microscope (AFM) measurements showed the PZT films to have smooth surfaces with a roughness of 1.15 nm. The microstructure of the multilayer was studied using transmission electron microscopy (TEM). Electrical measurements were conducted using both Pt and LaNiO₃ as top electrodes. The measured remanent polarization P _r and coercive field E _c of the PZT thin film with Pt top electrodes were 23 μC/cm² and 75 kV/cm, and were 25 μC/cm² and 60 kV/cm for the PZT film with LaNiO₃ top electrodes. No obvious fatigue after 10¹⁰ switching cycles indicated good electrical endurance of the PZT films using LaNiO₃ electrodes, compared with the PZT film with Pt top electrodes showing a significant polarization loss after 10⁸ cycles. These PZT films with LaNiO₃ electrodes could be potential recording media for probe-based high-density data storage.     

Effect of the film thickness on the crystal structure and ferroelectric properties of (Hf0.5Zr0.5)O2 thin films deposited on various substrates

In this work, the effect of the film thickness on the crystal structure and ferroelectric properties of (Hf_0.5Zr_0.5)O₂ thin films was investigated. The thin films were deposited on (111) Pt-coated SiO₂, Si, and CaF₂ substrates with thermal expansion coefficients of 0.47, 4.5, and 22×10⁻⁶/°C, respectively. From the X-ray diffraction measurements, it was found that the (Hf_0.5Zr_0.5)O₂ thin films deposited on the SiO₂ and CaF₂ substrates experienced in-plane tensile and compressive strains, respectively, in comparison with the films deposited on the Si substrates. For films deposited on all three substrates, the volume fraction of the monoclinic phase increased with increasing film thickness, with the SiO₂ substrate having the lowest monoclinic phase volume fraction at all film thicknesses tested. The grain size of the films, which is an important factor for the formation of the ferroelectric phase, remained almost constant at about 10 nm in diameter regardless of the film thickness and type of substrate utilized. Ferroelectricity was observed for the 17 nm-thick films deposited on SiO₂ and Si substrates, and the maximum remanent polarization (P_r) value of 9.3 µC/cm² was obtained for films deposited on the SiO₂ substrate. In contrast, ferroelectricity with P_r=4.4 µC/cm² was observed only for film on SiO₂ substrate in case of 55 nm-thick films. These results suggest that the films under in-plane tensile strain results in the larger ferroelectricity for 17 nm-thick films and have a ferroelectricity up to 55 nm-thick films.     

Hierarchically Ordered Nano‐Heterostructured PZT Thin Films with Enhanced Ferroelectric Properties

Realization of ferroelectric (FE) devices based on the polarization effects of Pb(Zr_0.52Ti_0.48)O₃ (PZT) has reinforced the investigation of this material in multiple dimensions and length scales. Multi‐level hierarchical nanostructure engineering in PZT thin films offer dual advantages of variable length‐scale and dimensionality. Here, the growth of hierarchically ordered PZT nano‐hetero­structures (Nhs) from PZT seed‐layer deposited on SrTiO₃:Nb (100) substrates, using a physical/chemical combined methodology involving pulsed laser deposition (PLD) and hydrothermal processes, is reported. Systematic SEM, TEM, and Raman spectroscopy studies reveal mixed hetero‐ and homo‐epitaxial growth mechanism. In the final stage, 3D Nh units cross‐link and form a dense network‐like Nh PZT thin‐film. FE polarizations are measured without using any polymer fill‐layer which otherwise introduces huge dielectric losses and lowers the polarization values for a FE device. In benefit, well saturated and symmetric FE hysteresis loops are observed with high degree of squareness and a high remnant polarization (54 μC cm^‐2 at a coercive field of 237 kV cm^‐1). This work provides a pathway towards preparing hierarchical PZT Nhs offering coherent design of high‐performance FE capacitors for data storage technologies in future.     

Epitaxial ferroelectric PbZrxTi1–xO3 thin films for non-volatile memory applications

Epitaxial ferroelectric PbZr_xTi_1–xO₃ (PZT) thin film capacitors with SrRuO₃ (SRO) bottom electrodes have been fabricated by pulsed laser deposition on LaAlO₃ (0 0 1) substrates. X-ray diffraction measurements revealed that epitaxial heterostructures with a high crystalline quality were obtained. Ferroelectric capacitors were defined by thermal evaporation of aluminium contact pads onto the PZT films. Remnant polarizations of about 13 μC/cm² and coercive fields of about 150 kV/cm are obtained at a frequency of 10 Hz. The capacitors show very little fatigue of the remnant polarization with cumulative switching. A tendency to imprint, arising from the use of asymmetric electrodes, is observed.     

Pyroelectric characteristics of thin PbTiO3 and la-modified PbTiO3 films on platinum films for infrared sensors

In this work, we grew lead titanate (PbTiO₃) and La-modified PbTiO₃ thin films on platinized silicon (Si(100)) substrates under controlled substrate temperature and ambient by a modified jet-vapor deposition (JVD) process described in this paper. The x-ray diffraction patterns obtained from these films showed a single-phase perovskite structure. We examined locally homogeneity and thickness of these films through the comparative use of laser Raman spectroscopy. We also collected Raman and x-ray data on pure PbTiO₃, as well as prepared lead zirconate titanate (PZT) (54/46), and PZT (50/50) films using the JVD process. This paper discusses the temperature variations of the pyroelectric and dielectric properties of three compositions of La-modified PbTiO₃ films containing 5.2% to 15% of La, respectively, with a view toward studying the effect of La in place of Pb on these electrical properties. We detected significant pyroelectric currents on all three La-modified PbTiO₃ films before performing poling treatments, and observed pyroelectric coefficeints as high as 84 nC/cm²·°C in the poled La-doped PbTiO₃ films containing 5.2% La. The pyroelectric coefficient and dielectric constant varied significantly with La content. We compared the calculated figures of merit, which were based on the measured physical properties, with pure PbTiO₃ as well as PZT and lead lanthanide zirconate titanate (PLZT) films. These properties just described illustrate that these films would be suitable for IR detectors.     

Heteroepitaxy of HgCdTe(112) infrared detector structures on Si(112) substrates by molecular-beam epitaxy

High-quality, single-crystal epitaxial films of CdTe(112)B and HgCdTe(112)B have been grown directly on Si(112) substrates without the need for GaAs interfacial layers. The CdTe and HgCdTe films have been characterized with optical microscopy, x-ray diffraction, wet chemical defect etching, and secondary ion mass spectrometry. HgCdTe/Si infrared detectors have also been fabricated and tested. The CdTe(112)B films are highly specular, twin-free, and have x-ray rocking curves as narrow as 72 arc-sec and near-surface etch pit density (EPD) of 2 × 10⁶ cm⁻² for 8 μm thick films. HgCdTe(112)B films deposited on Si substrates have x-ray rocking curve FWHM as low as 76 arc-sec and EPD of 3-22 × 10⁶ cm⁻². These MBE-grown epitaxial structures have been used to fabricate the first high-performance HgCdTe IR detectors grown directly on Si without use of an intermediate GaAs buffer layer. HgCdTe/Si infrared detectors have been fabricated with 40% quantum efficiency and R₀A = 1.64 × 10⁴ Ωm₂ (0 FOV) for devices with 7.8 μm cutoff wavelength at 78Kto demonstrate the capability of MBE for growth of large-area HgCdTe arrays on Si.     

Structural,Optical and Electrical Properties of Polycrystalline CuO Thin Films Prepared by Magnetron Sputtering

Cupric oxide thin films were deposited on silicon and sapphire substrates by reactive radio frequency magnetron sputtering at different substrate temperatures. The results showed that the CuO films were composed of different sizes of CuO nano-grains and the CuO films deposited on Si substrates showed a more dense and uniform surface than that deposited on Al₂O₃ substrates. It was noted that both the CuO films deposited on Si and Al₂O₃ substrates revealed only CuO related diffractions and the preferred orientation of the CuO films changed from (002) to (111) as the substrate temperature increased. Moreover, the carrier concentration was 1.141?×?10¹⁸ cm^?3 and the mobility was 0.401 cm²/v s at 450°C substrate temperature. The controllable electrical properties of the films can be achieved by the variation of crystal quality arising from the substrate temperature.     

Deposition,post-deposition annealing,and characterization of epitaxial Ge films grown on Si(100) by pyrolysis of GeH4

As a first step towards developing heterostructures such as GaAs/Ge/Si entirely by chemical vapor deposition, Ge films have been deposited on (100) Si by the pyrolysis of GeH₄. The best films are grown at 700° C and are planar and specular, with RBS minimum channeling yields of ≈4.0% (near the theoretical value) and defect densities of 1.3 x 10⁸ cm⁻². Variations of in-situ cleaning conditions, which affect the nature of the Si substrate surface, greatly affect the ability to get good epitaxial growth at 700° C. The majority of the defects found in the Ge films are extrinsic stacking faults, formed by dissociation of misfit and thermal expansion accommodation dislocations. The stacking fault density is not significantly reduced by post-deposition annealing, as is the case for the dislocations observed in MBE Ge films. It is suggested that lowering the CVD growth temperature through the use of high vacuum deposition equipment would result in dislocation defects like those of MBE films which could then be annealed more effectively than stacking faults. Films with defect densities equivalent to MBE Ge films (~2 x 10⁷ cm⁻²) could then probably be produced.     

Surface-induced highly oriented perylo[1,12-b,c,d]selenophene thin films for high performance organic field-effect transistors

Epitaxial crystallization of perylo[1,12-b,c,d]selenophene (PESE) on highly oriented polyethylene (PE) substrate through vapor phase deposition has been achieved. Oriented PESE crystals with different crystalline morphologies can be fabricated by changing the temperature of PE substrate during vacuum evaporation. When the PE substrate temperature is lower than 70 °C, sparsely dispersed PESE lathlike crystals are produced with their long axis preferentially aligned perpendicular to the chain direction of PE crystals. While the close films of PESE with lathlike crystals aligned with long axis parallel to the chain direction of PE film were obtained above 90 °C. Transistors based on expitaxially crystallized PESE films have been fabricated and the transistor properties were also studied. It is found that transistors show different electrical characteristics depending on the preparation conditions of expitaxially crystallized PESE films. The transistors based on the PESE/PE-SiO₂/Si with PESE deposited on oriented PE film at low temperature, i.e., <70 °C, display a similar poor properties with the PESE/OTS-SiO₂/Si type transistors. However, when the deposition temperature was elevated to 90 °C, the transistors exhibit a maximum field-effect mobility of 4.4 × 10⁻² cm² V⁻¹ s⁻¹ and maximum on/off ratio of 2.0 × 10⁵, which are about 2 orders of magnitudes higher than the PESE/OTS-SiO₂/Si based transistors.     

Preparation of (Pb0.88La0.12)TiO3 thin films for dynamic random access memory by low pressure-metalorganic chemical vapor deposition

La-modified lead titanate (PLT) thin films were prepared by hot-wall type low pressure-metalorganic chemical vapor deposition method. Pb(dpm)₂, La(dpm)₃, and titanium tetraisopropoxide were used as source materials. The films were deposited at 500°C under the low pressure of 1000 mTorr and then annealed at 650°C for 10 min in oxygen ambient. Sputter-deposited platinum electrodes and 180 nm thick PLT thin films were employed to form MIM capacitors with the best combination of high charge storage density (26.7 μC/cm² at 3V) and low leakage current density (1.5 × 10^-7 A/cm² at 3V). The measured dielectric constant and dielectric loss were 1000∼1200 and 0.06∼0.07 at zero bias and 100 kHz, respectively.     

Epitaxial TiN based contacts for silicon devices

We have grown high quality epitaxial TiN/Si(100) and Cu/TiN/Si(100) heterostructures by pulsed laser deposition. The epitaxial TiN films have the same low (15 μΩ-cm) resistivity as TiSi₂ (C-54) phase with excellent diffusion barrier properties. In addition, Schottky barrier height of TiN was close to that of TiSi₂ (0.6-0.7 eV). Auger and Raman spectroscopy revealed that the films were stoichiometric TiN and free from oxygen impurities. The x-ray diffraction and transmission electron microscope (TEM) results showed that the TiN films deposited at 600°C were single crystal in nature with epitaxial relationship TiN|| Si. The Rutherford baskscattering channeling yield for TiN films was found to be in the range of 10–13%. The epitaxy of Cu on TiN was found to be cube-on-cube, i.e., Cull<100>TiN||Si. The Cu/TiN and TiN/Si interfaces were found to be quite sharp without any indication of interfacial reaction. The growth mechanism of copper on TiN was found to be three-dimensional. We discuss domain matching epitaxy as a mechanism of growth in these large lattice mismatch systems, where three lattice constants of Si(5.43?) match with four of TiN(4.24?) and seven units of Cu(3.62?) match with six of the TiN. Thus, for next generation of device complementary metal oxide semiconductor structures, Cu/TiN/Si(100) contacts hold considerable promise, particularly since Cu is a low resistivity metal (1.6 μΩ-cm) and is considerably more resistant to electromigration than Al. The implications of these results in the fabrication of advanced microelectronic devices are discussed.     

Selective silicon epitaxy by photo-chemical vapor deposition at a very low temperature of 160°C

We have grown epitaxial Si films by the photo-chemical vapor deposition (photo-CVD) technique with SiH₄ and H₂ at a very low-temperature of 160°C. Epitaxial films were grown on silicon substrates, while amorphous-like films were deposited on glass substrates. Furthermore, it was found from the atomic hydrogen etching which was produced by photo-dissociation of hydrogen that the etching rate of amorphous silicon was much higher than that of crystal silicon. By using these selectively, we have demonstrated selective epitaxial growth of silicon by the photo-CVD technique followed by the atomic hydrogen photo-etching. Furthermore, heavily phosphorus-doped silicon films (>1 × 10²¹ cm¹⁻³) were also selectively grown by this novel technique.     

Enhanced Thermoelectric Properties of Antimony Telluride Thin Films with Preferred Orientation Prepared by Sputtering a Fan-Shaped Binary Composite Target

p-Type antimony telluride (Sb₂Te₃) thermoelectric thin films were deposited on BK7 glass substrates by ion beam sputter deposition using a fan-shaped binary composite target. The deposition temperature was varied from 100°C to 300°C in increments of 50°C. The influence of the deposition temperature on the microstructure, surface morphology, and thermoelectric properties of the thin films was systematically investigated. x-Ray diffraction results show that various alloy composition phases of the Sb₂Te₃ materials are grown when the deposition temperature is lower than 200°C. Preferred c-axis orientation of the Sb₂Te₃ thin film became obvious when the deposition temperature was above 200°C, and thin film with single-phase Sb₂Te₃ was obtained when the deposition temperature was 250°C. Scanning electron microscopy reveals that the average grain size of the films increases with increasing deposition temperature and that the thin film deposited at 250°C shows rhombohedral shape corresponding to the original Sb₂Te₃ structure. The room-temperature Seebeck coefficient and electrical conductivity range from 101 μV K^?1 to 161 μV K^?1 and 0.81 × 10³ S cm^?1 to 3.91 × 10³ S cm^?1, respectively, as the deposition temperature is increased from 100°C to 300°C. An optimal power factor of 6.12 × 10^?3 W m^?1 K^?2 is obtained for deposition temperature of 250°C. The thermoelectric properties of Sb₂Te₃ thin films have been found to be strongly enhanced when prepared using the fan-shaped binary composite target method with an appropriate substrate temperature.     

Effect of titanium dioxide (TiO2) seed layer on the phase composition of 0.7Pb (Mg1/3Nb2/3)O3-0.3PbTiO3 film prepared by pulsed laser deposition

Lead-magnesium niobate-lead titanate (PMN-PT) thin films with and without the TiO₂ seed layer were deposited on Pt/Ti/SiO₂/Si substrates through pulsed laser deposition. The study aimed to characterize the effect of the TiO₂ seed layer on the phase composition and properties of PMN-PT film. Without the TiO₂ seed layer, the pure perovskite phase could be obtained in the thinner PMN-PT film while with the TiO₂ seed layer, the pure perovskite phase was formed in the thicker PMN-PT film. The ferroelectric properties of PMN-PT films with the TiO₂ seed layer were exhibited. As a result, the maximum amount of remnant polarization reached the amount of 32 μC/cm² for the PMN-PT thin film with the TiO₂ seed layer.     

A Coherently Strained Monoclinic [111]PbTiO3 Film Exhibiting Zero Poisson's Ratio State

[111]‐Oriented perovskite oxide films exhibit unique interfacial and symmetry breaking effects, which are promising for novel quantum materials as topological insulators and polar metals. However, due to strong polar mismatch and complex structural reconstructions on (111) surfaces/interfaces, it is still challenging to grow high quality [111] perovskite heterostructures, let alone explore the as‐resultant physical properties. Here, the fabrication of ultrathin PbTiO₃ films grown on a SrTiO₃(111) substrate with atomically defined surfaces, by pulsed laser deposition, is reported. High‐resolution scanning transmission electron microscopy and X‐ray diffraction reveal that the as‐grown [111]PbTiO₃ films are coherent with the substrate and compressively strained along all in‐plane directions. In contrast, the out‐of‐plane lattices are almost unchanged compared with that of bulk PbTiO₃, resulting in a 4% contraction in unit cell volume and a nearly zero Poisson's ratio. Ferroelectric displacement mapping reveals a monoclinic distortion within the compressed [111]PbTiO₃, with a polarization larger than 50 µC cm^?2. The present findings, as further corroborated by phase field simulations and first principle calculations, differ significantly from the common [001]‐oriented films. Fabricating oxide films through [111] epitaxy may facilitate the formation of new phase components and exploration of novel physical properties for future electronic nanodevices.     

Influence of substrate temperature on the properties of fluorinated silicon-nitride thin films deposited by IC-RPECVD

Fluorinated silicon-nitride films have been prepared from an Ar/SiF₄/NH₃ gas mixture by inductively coupled remote plasma-enhanced chemical vapor deposition (IC-RPECVD) at different substrate temperatures, ranging from 150 to 300°C. All of the resulting deposited silicon-nitride films were free of Si-H bonds, showed high dielectric breakdown fields (≥8 MV cm^?1), and had root mean square (rms) surface roughness values below 3 Å. The films’ refractive indices and the contents of O and F remain constant, but Si/N ratios drop from 5 to 2 and N-H bond concentrations decrease in the range (1.3–0.9) × 10²² cm^?3 as the substrate temperature increases. The density of interface states (D_it) with c-Si was reduced from 2.4 × 10¹² to 8 × 10¹¹ eV^?1 cm^?2 at substrate temperatures ≥250°C.     

High performance sol–gel spin-coated titanium dioxide dielectric based MOS structures

High-κ TiO₂ thin films have been fabricated using cost effective sol–gel and spin-coating technique on p-Si (100) wafer. Plasma activation process was used for better adhesion between TiO₂ films and Si. The influence of annealing temperature on the structure-electrical properties of titania films were investigated in detail. Both XRD and Raman studies indicate that the anatase phase crystallizes at 400 °C, retaining its structural integrity up to 1000 °C. The thickness of the deposited films did not vary significantly with the annealing temperature, although the refractive index and the RMS roughness enhanced considerably, accompanied by a decrease in porosity. For electrical measurements, the films were integrated in metal-oxide-semiconductor (MOS) structure. The electrical measurements evoke a temperature dependent dielectric constant with low leakage current density. The Capacitance–voltage (C–V) characteristics of the films annealed at 400 °C exhibited a high value of dielectric constant (~34). Further, frequency dependent C–V measurements showed a huge dispersion in accumulation capacitance due to the presence of TiO₂/Si interface states and dielectric polarization, was found to follow power law dependence on frequency (with exponent ‘s’=0.85). A low leakage current density of 3.6×10⁻⁷ A/cm² at 1 V was observed for the films annealed at 600 °C. The results of structure-electrical properties suggest that the deposition of titania by wet chemical method is more attractive and cost-effective for production of high-κ materials compared to other advanced deposition techniques such as sputtering, MBE, MOCVD and ALD. The results also suggest that the high value of dielectric constant ‘κ‘ obtained at low processing temperature expands its scope as a potential dielectric layer in MOS device technology.     

Photoluminescent properties of ZnO thin films grown on SiO2/Si(100) by metal-organic chemical vapor deposition

We report on the photoluminescent (PL) properties of ZnO thin films grown on SiO₂/Si(100) substrates using low pressure metal-organic chemical vapor deposition. The growth temperature of the films was as low as 400°C. From the PL spectra of the films at 10–300 K, strong PL peaks due to free and bound excitons were observed. The origin of the near bandedge emission peaks was investigated measuring temperature-dependent PL spectra. In addition, the Zn O films demonstrated a stimulated emission peak at room temperature. Upon illumination with an excitation density of 1 MW/cm², a strong, sharp peak was observed at 3.181 eV.