The effect of oxidation temperature on the nano crystalline structure of ZrO2 films deposited on silicon and glass substrates

Zirconium oxide (ZrO₂) films have been prepared by using ex situ thermal oxidation of sputtered Zr films on glass and silicon substrates. XRD patterns show that a highly monoclinic (111) preferential orientation of ZrO₂ phase can be formed with increasing the oxidation temperature. According to XRD patterns in all thermal oxidized samples silicon oxide phase is present as interfacial layer at the Zr (ZrO₂) / Si (glass) interface. In the case of silicon substrates, crystallite sizes obtained from ZrO₂ peak with higher intensity reveal an increase with substrate temperature. AFM measurement shows on the whole a decrease of average surface roughness with oxidation temperature. The electrical property of the prepared films is investigated by means of four point probe measurement. An abrupt increase of sheet resistivity occurs when the crystallinity of ZrO₂ phase enhances at higher temperature. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of zirconium oxide thin films on silicon substrate

The growth and characterization of zirconium oxide (ZrO₂) thin films prepared by thermal oxidation of a deposited Zr metal layer on SiO₂/Si were investigated. Uniform ZrO₂ thin film with smooth surface morphology was obtained. The thermal ZrO₂ films showed a polycrystalline structure. The dielectric constant of the ZrO₂ film has been shown to be 23, and the equivalent oxide thickness (EOT) of the ZrO₂ stacked oxide is in the range of 3.38–5.43 nm. MOS capacitors with ZrO₂ dielectric stack show extremely low leakage current density, less than 10^?6 A/cm² at ?4 V. Consequently, using this method, high-quality ZrO₂ films could be fabricated at oxidation temperature as low as 600 °C.     

Active planar waveguides based on sol–gel Er3+-doped SiO2–ZrO2 for photonic applications: Morphological,structural and optical properties

Er³⁺-doped glass-ceramic SiO₂–ZrO₂ optical planar waveguides were prepared by the sol–gel route using different SiO₂:ZrO₂ molar ratios (90:10, 85:15, 80:20 and 75:25). Multilayered films were deposited onto Si(1 0 0) substrates by the dip-coating technique. Structural characterization was performed using vibrational spectroscopy and X-ray diffraction. Some optical properties, densification and surface morphology of these films were investigated as a function of the SiO₂:ZrO₂ ratio, annealing temperature and time. Optical properties such as refractive index, number of propagating modes and attenuation coefficient were measured at 632.8, 543.5 and 1550 nm, by the prism coupling technique. Uniform surface morphology with roughness less than 0.5 nm. Low losses, less than 0.9 dB/cm at 612.8 nm in the TE₀ mode, were measured for the planar waveguides containing up to 25 mol% zirconium oxide. Luminescence of Er³⁺ in the near infrared was observed for the active nanocomposite.     

Effect of annealing temperatures on properties of sol‐gel grown ZnO‐ZrO2 films

Mixed ZnO‐ZrO₂ films have been obtained by sol‐gel technology. By using spin coating method, the films were deposited on Si and glass substrates. The influence of thermal annealings (the temperatures vary from 400 °C to 750 °C) on their structural properties has been studied. The structural behavior has been investigated by the means of XRD and FTIR techniques. The results revealed no presence of mixed oxide phases, the detected crystal phases were related to the hexagonal ZnO and to crystalline ZrO₂. The sol‐gel ZnO‐ZrO₂ films showed polycrystalline structure with a certain degree of an amorphous fraction. The optical transmittance reached 91% and it diminished with increasing the annealing temperatures. The optical properties of the sol‐gel ZnO‐ZrO₂ films, deposited on glass substrates are excellent with high transparency and better then those of pure ZrO₂ films, obtained at similar technological conditions. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Band alignment at the interfaces of Al2O3 and ZrO2-based insulators with metals and Si

Internal photoemission of electrons was used to determine the band alignment in metal (Mg, Al, Ni, Cu, Au)-oxide-silicon structures with Al₂O₃- and ZrO₂-based insulators. For Al₂O₃- and ZrO₂ layers grown on Si by atomic layer deposition the barrier height between the Si valence band and the oxide conduction band was found to be 3.25 and 3.1 eV, respectively. Thermal oxidation of the Si/oxide stacks results in a barrier height increase to ≈4 eV for both cases due to formation of a silicate interlayer. However, there is a significant sub-threshold electron emission both from silicon and metals, indicating a high density of states in the band gap of the insulators. These states largely determine the electron transport across metal oxides and may also account for a significant dipole component of the potential barrier at the metal/ZrO₂ and metal/Al₂O₃ interfaces.     

Atomic layer deposition of Al2O3, ZrO2, Ta2O5, and Nb2O5 based nanolayered dielectrics

Ta₂O₅, Ta-Nb-O, Zr-Al-Nb-O, and Zr-Al-O mixture films or solid solutions were grown on Si(1 0 0) substrates at 300 °C by atomic layer deposition. The equivalent oxide thickness of Ta₂O₅ based capacitors was between 1 and 3 nm. In Zr-Al-O films, the high permittivity of ZrO₂ was combined with high resistivity of Al₂O₃ layers. The permittivity, surface roughness and interface charge density increased with the Zr content and the equivalent oxide thickness was between 2.0 and 2.5 nm. In the Zr-Al-Nb-O films the equivalent oxide thickness remained at 1.8-2.0 nm.     

Crystallization of bismuth titanate and bismuth silicate grown as thin films by atomic layer deposition

Bismuth silicate and bismuth titanate thin films were deposited by atomic layer deposition (ALD). A novel approach with pulsing of two Bi-precursors was studied to control the Si/Bi atomic ratio in bismuth silicate thin films. The crystallization of compounds formed in the Bi₂O₃–SiO₂ and Bi₂O₃–TiO₂ systems was investigated. Control of the stoichiometry of Bi–Si–O thin films was studied when deposited on Si(1 0 0) and crystallization was studied for films on sapphire and MgO-, ZrO₂- and YSZ-buffered Si(1 0 0). The Bi–Ti–O thin films were deposited on Si(1 0 0) substrate. Both Bi–Si–O and Bi–Ti–O thin films were amorphous after deposition. Highly a-axis oriented Bi₂SiO₅ thin films were obtained when the Bi–Si–O thin films deposited on MgO-buffered Si(1 0 0) were annealed at 800 °C in nitrogen. The full-width half-maximum values for 200 peak were also studied. An excess of bismuth was found to improve the crystallization of Bi–Ti–O thin films and the best crystallinity was observed with Ti/Bi atomic ratio of 0.28 for films annealed at nitrogen at 1000 °C. Roughness of the thin films as well as the concentration depth distribution were also examined.     

Structural investigation and electronic band transitions of nanostructured TiO2 thin films

Titanium dioxide (TiO₂) thin film was deposited on n‐Si (100) substrate by reactive DC magnetron sputtering system at 250 °C temperature. The deposited film was thermally treated for 3 h in the range of 400‐1000 °C by conventional thermal annealing (CTA) in air atmosphere. The effects of the annealing temperature on the structural and morphological properties of the films were investigated by X‐ray diffraction (XRD) and atomic force microscopy (AFM), respectively. XRD measurements show that the rutile phase is the dominant crystalline phase for the film annealed at 800 °C. According to AFM results, the increased grain sizes indicate that the annealing improves the crystalline quality of the TiO₂ film. In addition, the formation of the interfacial SiO₂ layer between TiO₂ film and Si substrate was evaluated by the transmittance spectra obtained with FTIR spectrometer. The electronic band transitions of as‐deposited and annealed films were also studied by using photoluminescence (PL) spectroscopy at room temperature. The results show that the dislocation density and microstrain in the film were decreased by increasing annealing temperature for both anatase and rutile phases. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects of the Substrate Crystals upon the Structure of Thermal Oxide Layers on Si

Comparisons of Bragg reflections from thermal oxide thin films on Si wafers were made for five sets of samples with various kinds of substrates. The intensities of the reflections for the samples with the substrate of better quality were stronger than those of poor one, indicating that the structures of the crystalline SiO₂ in the oxide layer were related with the quality of the Si substrates. It is also shown that no diffraction peaks were observed from the oxide layers grown on Si substrates by chemical vapor deposition.     

Fabrication of (1 1 1)-oriented Si layers on SiO2 substrates by an aluminum-induced crystallization method and subsequent growth of semiconducting BaSi2 layers for photovoltaic application

We have prepared (1 1 1)-oriented Si layers on SiO₂ (fused silica) substrates from amorphous-Si(a-Si)/Al or Al/a-Si stacked layers using an aluminum-induced crystallization (AIC) method. The X-ray diffraction (XRD) intensity from the (1 1 1) planes of Si was found to depend significantly on growth conditions such as the thicknesses of Si and Al, deposition order (a-Si/Al or Al/a-Si on SiO₂), deposition technique (sputtering or vacuum evaporation) and exposure time of the Al layer to air before the deposition of Si. The crystal orientation of the Si layers was confirmed by θ−2θ, 2θ XRD and electron backscatter diffraction (EBSD). The photoresponse properties of semiconducting BaSi₂ films formed on the (1 1 1)-oriented Si layers by the AIC method were measured at room temperature. Photocurrents were clearly observed for photon energies greater than 1.25 eV. The external quantum efficiencies of the BaSi₂ were also evaluated.     

Noncrystalline silicon dioxide films on silicon: A review

Firstly, the importance of noncrystalline SiO₂ film in the manufacture of semiconductor devices and integrated circuits is pointed out. After some general remarks on the SiSiO₂ interface, various methods of preparing SiO₂ films on silicon are discussed with emphasis on thermal oxidation of silicon. The transport processes are compared with those occurring in fused silica. Then, the properties of the SiSiO₂ interface structure are summarized; a properly prepared interface is very perfect. This is due to the structural flexibility of noncrystalline SiO₂. Finally, the structural aspects of noncrystalline SiO₂ are discussed on the basis of the chemistry of the SiO bond in which the π component plays a special role. The high degree of short-range order is responsible for many excellent properties of the oxide film. Disruption of the short-range order results in network defects and development of some degree of local order along a direction which it is assumed to give rise to channels. These defects are unique to topologically disordered solids. In this and many other respects, noncrystalline SiO₂ is more similar to siloxane polymers than typical ionic or covalent crystals.     

Interface and material characterization of thin Al2O3 layers deposited by ALD using TMA/H2O

Thin Al₂O₃ layers were grown by atomic layer deposition using trimethylaluminum (TMA) and water as precursors on 1.2 nm thermal SiO₂ and HF cleaned Si surfaces. The stoichiometry and the contamination (H, OH and C) of as-deposited and N₂ annealed thick Al₂O₃ layers were characterized by secondary ion mass spectrometry (SIMS), elastic recoil detection analysis (ERDA) and X-ray photoelectron spectroscopy (XPS). We show a perturbed region (≈5 nm thick) at the Al₂O₃/Si interface by XPS and Auger electron spectrometry (AES). Post-deposition annealings induced important interface oxidation, Si atoms injection and SiO₂/Al₂O₃ mixture whereas the initial interface was abrupt. Silicon oxidation before Al₂O₃ growth highly limits interfacial oxidation and improves interfacial quality. We proposed that OH groups may play a key role to explain silicon oxidation during post-deposition annealings in inert ambience with low oxygen contamination levels.     

Anomalous amorphous SiO2 films

Anomalous SiO₂ films have been prepared by sputtering Si in a mixture of Ar-10% O₂ at 77 K. The same sputtering conditions at room temperature yield normal SiO₂ which means that the anomaly is produced by the low temperature deposition. The anomaly reveals itself in several physical properties. The density of the anomalous SiO₂ is 1.72 as compared with 2.20 for bulk and the dielectric constant is about 50% larger than bulk and with a much stronger temperature dependence. The infrared (ir) spectrum of the anomalous SiO₂ is only slightly different from bulk SiO₂ but esr experiments reveal about 3 × 10¹⁸ spins cm which do not exist in bulk SiO₂. These anomalous films are extremely stable: upon heating only a small amount of oxygen (1 part in 10⁵) evolves at 440°C but the density and IR spectrum remain unchanged up to 1300°C. Annealing at 1500°C completely removes the ESR signal and returns the ir spectrum and the density to that of cristobalite. An electron diffraction and transmission electron microscopy study reveals that the anomalous SiO₂ films consist of essentially bulk like SiO₂ clusters about 250 Å in diameter separated by a low density network. The low density network undoubtedly contains unbound O atoms and the SiSi bonds which give rise to the esr signal. The structural model can account for all the anomalous properties.     

Effect of laser fluence on c‐axis orientation of LiNbO3 piezoelectric films on nanocrystalline diamond by pulsed laser deposition

Completely c‐axis oriented LiNbO₃ piezoelectric films have been deposited on nanocrystalline diamond (NCD)/Si substrates with SiO₂ buffer layer by pulsed laser deposition. The amorphous SiO₂ buffer layer was formed on NCD/Si substrates by sol‐gel method. The c‐axis orientation and crystallinity of LiNbO₃ films are strongly dependent on the laser fluence, and the laser fluence 3.6 J/cm² is found to be the optimal value for the growth of oriented LiNbO₃ film, which has a smooth surface with composed of a large mount of uniform grains. The average surface roughness of LiNbO₃ films is about 6.7 nm.     

Photoelectron spectroscopy study of the effect of substrate doping on an HfO2/SiO2/n-Si gate stack

Core level photoelectron spectroscopy has been used to investigate the effect of substrate doping on the binding energies of 1 nm HfO₂/0.6 nm SiO₂/Si films. A characteristic 0.26–0.30 nm Hf_0.35Si_0.65O₂ silicate interface is formed between the gate oxide and the SiO₂ layer with an equivalent oxide thickness of 0.5 nm. High substrate doping shifts the Fermi level upwards by 0.5 eV. An interface dipole forms giving rise to a shift in the local work function. Screening from substrate electrons is confined to the SiO₂/Si interface. The principal contributions modifying the core level binding energies in the oxide are the doping dependant Fermi level position and the interface dipole strength.     

Effects of oxide buffer layers on the microstructure and electrical properties of PLZST 2/87/10/3 antiferroelectric thin films

In the present work, the effects of oxide buffer layers, such as ZrO₂, CeO₂ and TiO₂, on the microstructure and electrical properties of (Pb_0.97La_0.02)(Zr_0.87Sn_0.10Ti_0.03)O₃ (PLZST 2/87/10/3) antiferroelectric (AFE) thin films were investigated systematically. X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) pictures illustrated that the crystalline orientation and surface microstructure of PLZST 2/87/10/3 AFE thin films had a close relation with these oxide buffer layers. As a result, the final electrical properties of AFE films were tuned by these buffer layers. Electrical measurements result showed that the dielectric properties, polarization characteristic and current–field curves of AFE thin films could be tailored by selecting a proper oxide buffer layer.     

Characterization of ALCVD-Al2O3 and ZrO2 layer using X-ray photoelectron spectroscopy

The atomic layer chemical vapor deposition (ALCVD) deposited Al₂O₃ and ZrO₂ films were investigated by ex situ X-ray photoelectron spectroscopy. The thickness dependence of band gap and valence band alignment was determined for these two dielectric layers. For layers thicker than 0.9 nm (Al₂O₃) or 0.6 nm (ZrO₂), the band gaps of the Al₂O₃ and ZrO₂ films deposited by ALCVD are 6.7±0.2 and 5.6±0.2 eV, respectively. The valence band offsets at the Al₂O₃/Si and ZrO₂/Si interface are determined to be 2.9±0.2 and 2.5±0.2 eV, respectively. Finally, the escape depths of Al 2p in Al₂O₃ and Zr 3p3 in ZrO₂ are 2.7 and 2.0 nm, respectively.     

Structural and optical properties of thin films prepared from surface modified ZrO2

This paper describes the preparation and characterization of ZrO₂ thin films deposited on silicon wafer by spin coating method. Nanocrystalline ZrO₂ was synthesized by hydrothermal method using zirconium (IV)-n-propoxide as a precursor material. Surface of the ZrO₂ particles was then modified with 2-acetoacetoxyethyl methacrylate used as a copolymer for coatings. The optical properties, nanostructure and surface morphology of the thin films prepared from surface modified ZrO₂ nanoparticles were examined by optical spectroscopy, X-ray diffraction and scanning electron microscopy, respectively. It was found that the films deposited on silicon wafer have crystalline structure of monoclinic (111) at temperature of 150 °C. It was observed that films depict very dense material that does not present any granular or columnar structure. It was found that optical transparency of thin ZrO₂ films distributed in the range of 30-40 percent in the spectral range 400-800 nm. Refractive index of ZrO₂ films were determined as functions of ZrO₂ content and it was found that the refractive index increases from 1.547 to 1.643 with increased ZrO₂ content.     

An electron diffraction study of amorphous silicon oxide films

Amorphous silicon oxide films have been examined by high energy electron diffraction using the sector-microphotometer method of data collection common to gas phase electron diffraction. This data was analyzed with a least-squares procedure that is designed to minimize extraneous detail in the radial distribution function obtained by the Fourier sine transform of the interference function. The results of this analysis for thin film SiO₂ show that the overall bonding topology of the thin film agress well with that of bulk (vitreous) SiO₂ examined by X-ray diffraction. The experimental short distance parameters for the films whose composition was determined to be ～SiO_1.3, SiO, and SiO_0.8 are found to be consistent with those expected for a mixture of tetrahedrally bonded amorphous Si and SiO₂ phases in which the scale of the Si-like and SiO₂-like regions is of the order of a few basic tetrahedral units. This result is in agreement with previous examinations of SiO powder by X-rays and a previous examination of thin silicon oxide films by electron diffraction.     

Ablation and compaction of amorphous SiO2 irradiated with ArF excimer laser

The structure of amorphous SiO₂ exposed to ArF excimer laser irradiation was examined. Threshold fluence for causing ablation with a single pulse depended on sample preparation: more specifically, 1 J/cm² for thermally grown SiO₂ films on silicon and 2.5 J/cm² for bulk SiO₂. It was found that the bond angle of Si-O-Si was reduced by irradiation near the interface of thermally grown SiO₂ films. In contrast, evolution of the bond angle by irradiation was absent in both the bulk SiO₂ and SiO₂ film-near the top surface, even though the concentration of puckered four-membered rings deduced from Raman spectra dramatically increased. It is assumed that planar three-membered rings were generated in the SiO₂ thin layer near the interface, and puckered four-membered rings were generated in the bulk SiO₂. The concentration of both the Si³⁺ and Si²⁺ structure was increased at a fluence of 800 mJ/cm² with an increasing number of pulses, although generation of both was absent at higher fluence for a single pulse. The author proposes that the structure of SiO₂ is created by flash heating and quenching by pulse laser irradiation. Structural similarities were found between the irradiated SiO₂ and SiO₂ at high temperatures.