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.     

Structure and thermal stability of (Zr0.6Al0.4)O1.8 thin film on strained SiGe layer

Zr_0.6Al_0.4O_1.8 dielectric films were deposited directly on strained SiGe substrates at room temperature by ultra-high vacuum electron-beam evaporation (UHV-EBE) and then annealed in N₂ under various temperatures. X-ray diffraction (XRD) reveals that the onset crystallization temperature of the Zr_0.6Al_0.4O_1.8 film is about 900 °C, 400 °C higher than that of pure ZrO₂. The amorphous Zr_0.6Al_0.4O_1.8 film with a physical thickness of ∼12 nm and an amorphous interfacial layer (IL) with a physical thickness of ∼3 nm have been observed by high-resolution transmission electron microscopy (HRTEM). In addition, it is demonstrated there is no undesirable amorphous phase separation during annealing at temperatures below and equal to 800 °C in the Zr_0.6Al_0.4O_1.8 film. The chemical composition of the Zr_0.6Al_0.4O_1.8 film has been studied using secondary ion mass spectroscopy (SIMS).     

Thermostability of amorphous zirconium aluminate high-k layers

One challenge in the development of high-k dielectric films is to preserve their amorphous nature during the processing of CMOS. In this work, the feasibility of using ZrO₂-Al₂O₃ binary alloys to obtain a stable homogeneous amorphous structure in a high-k layer is investigated. In situ high temperature X-ray diffraction tests show that the onset crystallisation temperature of the binary alloy with 42 and 61 mol% Al₂O₃ is 900, 400 °C higher than that of the pure ZrO₂. After rapid thermal process anneals up to 900 °C, the ZrAl_xO_y film remains amorphous. At 1000 °C, tetragonal ZrO₂ forms in the ZrAl_xO_y film. In addition, it is demonstrated that there is no undesirable amorphous phase separation during annealing at temperatures below and equal to 900 °C in the ZrO₂-Al₂O₃ system.     

Microstructure and dielectric properties of La2O3 films prepared by ion beam assistant electron-beam evaporation

Ultrathin La₂O₃ gate dielectric films were prepared on Si substrate by ion assistant electron-beam evaporation. The growth processing, interfacial structure and electrical properties were investigated by various techniques. From XRD results, we found that the La₂O₃ films maintained the amorphous state up to a high annealing temperature of 900 °C for 5 min. From XPS results, we also discovered that the La atoms of the La₂O₃ films did not react with silicon substrate to form any La-compound at the interfacial layer. However, a SiO₂ interfacial layer was formed by the diffusion of O atoms of the La₂O₃ films to the silicon substrate. From the atomic force microscopy image, we disclosed that the surface of the amorphous La₂O₃ film was very flat. Moreover, the La₂O₃ film showed a dielectric constant of 15.5 at 1 MHz, and the leakage current density of the La₂O₃ film was 7.56 × 10⁻⁶ A/cm² at a gate bias voltage of 1 V.     

Electrical properties of Al2O3 film deposited at low temperatures

Amorphous Al₂O₃ films were deposited on p-Si by rf magnetron sputtering to investigate their potential as a gate dielectric in organic thin film transistors (OTFTs). The deposition was performed at room temperature, 200 and 300 °C using Al₂O₃ and Al targets. Achieved Al₂O₃ films have higher capacitance values than thermally grown SiO₂ as characterized by capacitance-voltage measurements. It is also found from current-voltage and roughness measurements that the leakage current and the surface roughness can be least when the films are deposited at room temperature. The capacitance of the film obtained from the Al₂O₃ target appears higher than that of the Al₂O₃ film from the Al target while the results of electrical breakdown are opposite. These room temperature processes are promising for applications to the gate dielectrics of organic TFTs.     

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.     

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.     

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.     

Influence of CoO addition on phase separation and crystallization of glasses of the ZnO–Al2O3–SiO2–TiO2 system

The evolution of structure, phase composition and spectroscopic properties of CoO-doped (up to 5 mol%) titania-containing zinc aluminosilicate glasses with their heat-treatment has been studied using Raman scattering, small angle X-ray scattering, X-ray diffraction analysis and optical absorption spectra. Addition of cobalt oxide was observed to facilitate amorphous phase separation of the parent glass and gahnite, ZnAl₂O₄, crystallization. Cobalt oxide entered phases formed during low-temperature heat-treatments (720 °C), i.e., amorphous phase, enriched in ZnO, Al₂O₃ and TiO₂ and crystalline phase of gahnite. The absorption of these glass-ceramics was defined mainly by tetrahedral Co²⁺ ions located in gahnite nanocrystals. As the temperature was increased further, traces of anosovite solid solution appeared and then decomposed. Even after high-temperature heat-treatments, a certain portion of Co²⁺ ions remained in amorphous zinc aluminotitanate phase and in octahedral sites of inversed gahnite spinel. In glass-ceramics, the residual high silica amorphous phase contained a small quantity of [TiO₄] centers, which content was smaller in Co:ZAS samples as compared with non-doped glass-ceramics.     

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.     

Dielectric properties of Zr-Sn-Ti-O thin films prepared by pulsed laser deposition

Zr_0.26Sn_0.23Ti_0.51O₂ (ZSTO) films with a dielectric constant of about 40 have been prepared directly on silicon substrates by pulsed laser deposition at 600 °C. TEM observation showed that the as-deposited films are amorphous. Differential thermal analysis showed that the ZSTO films crystallize at about 620 °C. Capacitance-voltage (C-V) characteristics of metal-oxide-semiconductor (MOS) composed of Pt/ZSTO/Si prepared at different deposition temperature have been measured. The EOT of the MOS structures with the same ZSTO physical thickness increased slightly when the deposition temperature increased. The EOT is about 4.2 nm for the 40 nm ZSTO deposited at 600 °C. The leakage current characteristics of ZSTO films for the as deposited, post-annealed in oxygen ambient and post-annealed in nitrogen ambient by rapid thermal annealing have been studied comparatively. The films post-annealed in nitrogen ambient have the lowest leakage current and the as-deposited films have the largest leakage current characteristics. It is proposed that amorphous Zr-Sn-Ti oxide stabilized at 600 °C is a potential dielectric material for dynamic random access memory and high k dielectric gate applications.     

Dielectric relaxation study of hydrogen exposure as a source of two-level systems in Al2O3

An important question in the manufacture of superconducting electronics is how to control the two-level systems found in amorphous insulators. The present article shows that hydrogen has a marked impact on the two-level systems in thin films of reactively sputtered Al₂O₃, a standard tunnel oxide for Josephson junctions. The magnitude of dielectric relaxation current in Al₂O₃ films, believed to be caused by two-level systems, is shown to increase monotonically with the flow rate of H₂ into the chamber during deposition. This points toward a potential need for controlling hydrogen during the manufacture of superconducting electronics utilizing Al₂O₃.     

Preparation and characterization of ZnO-TiO2 films obtained by sol-gel method

The sol-gel route has been applied to obtain ZnO-TiO₂ thin films. For comparison, pure TiO₂ and ZnO films are also prepared from the corresponding solutions. The films are deposited by a spin-coated method on silicon and glass substrates. Their structural and vibrational properties have been studied as a function of the annealing temperatures (400-750 °C). Pure ZnO films crystallize in a wurtzite modification at a relatively low temperature of 400 °C, whereas the mixed oxide films show predominantly amorphous structure at this temperature. XRD analysis shows that by increasing the annealing temperatures, the sol-gel Zn/Ti oxide films reveal a certain degree of crystallization and their structures are found to be mixtures of wurtzite ZnO, Zn₂TiO₄, anatase TiO₂ and amorphous fraction. The XRD analysis presumes that Zn₂TiO₄ becomes a favored phase at the highest annealing temperature of 750 °C. The obtained thin films are uniform with no visual defects. The optical properties of ZnO-TiO₂ films have been compared with those of single component films (ZnO and TiO₂). The mixed oxide films present a high transparency with a slight decrease by increasing the annealing temperature.     

Study of the nucleation and growth of TiO2 and ZnO thin films by means of molecular dynamics simulations

The nucleation and growth of titanium dioxide (TiO₂) and zinc oxide (ZnO) thin films on Fe₂O₃ (hematite), Al₂O₃ (α-alumina) and SiO₂ (α-quartz) are studied by molecular dynamics simulations. The results show the formation of a strong interface region between the substrate and the film in the six systems studied here. A combination of polycrystalline and amorphous phases are observed in the TiO₂ films grown on the three substrates. ZnO deposition on the Fe₂O₃ and Al₂O₃ crystals yields a monocrystalline film growth. The ZnO film deposited on the SiO₂ crystal exhibits less crystallinity. The simulation results are compared with experimental results available in the literature.     

Influence of annealing condition on the properties of sputtered hafnium oxide

Hafnium oxide thin films were deposited on p-type (1 0 0) silicon wafers by reactive dc magnetron sputtering. Prior to the deposition of HfO₂ films, a thin Hf film was deposited. Sputtered HfO₂ thin films deposited at room temperature remain amorphous at T<650°C and orthorhombic phases were observed above 650 °C. The monoclinic phase which is a stable HfO₂ polymorphic form appeared after annealing above 800 °C. Capacitance equivalent thickness values decreased and leakage characteristics are improved by the Hf interlayer and O₂ settlement process. The decrease of accumulation capacitance values upon annealing is due to the growth of an interfacial layer upon post-annealing. The flat band voltage (V_FB) shifts negatively due to positive charge generated during post-annealing.     

The Effect of Annealing Temperature on Electrical Properties of SrBi2Ta2O9/Insulators/Si(MFIS) Structure for NDRO-type FRAM Devices

We have fabricated Pt/SBT/insulator/Si structure for the transistor gate in MFIS-FET and investigated the electrical properties of MFIS structure with various insulator materials. SrBi₂Ta₂O₉ films as a ferroelectric layer were deposited by metal organic decomposition (MOD) technique, on various insulator structures including SiON, and Al₂O₃ as well as on Pt/Ti/SiO₂/Si structures. The effect of annealing temperature on the electrical properties of MFIS structures was investigated in order to analyze the applicability to conventional CMOS process. Although the remnant polarization of SBT films for MFM structure was increased with increasing annealing temperature, the memory window which has a relationship with remnant polarization of ferroelectrics was differently displayed with insulator structure in MFIS structure.     

Quenched glasses in the systems of Li2O with Al2O3, Ga2O3 and Bi2O3

By rapid quenching in a twin roller apparatus, glass was found to occur widely in the systems of Li₂O with Al₂O₃, Ga₂O₃, Bi₂O₃ and in mixed systems. Examination of the resulting flakes by X-ray powder diffraction, differential thermal analysis, and capacitance data revealed the occurrence of glass, glass transitions, crystallization exotherms and the nature of some of the crystallization paths.The log ionic conductivity of the glasses was found to follow a linear relationship with the Li concentration. Evidence was observed for three new metastable crystalline phases, one in the Li₂OAl₂O₃ system and two in the Li₂OBi₂O₃ system. The latter system also showed evidence for the occurrence of two glasses at almost all compositions.     

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)     

Study on crystallization kinetics of Al65Cu20Ti15 amorphous alloy

The crystallization behavior and thermal stability of amorphous phases of Al₆₅Cu₂₀Ti₁₅ alloy obtained by mechanical alloying were investigated by using in-situ X-ray diffraction and differential scanning calorimetry (DSC) under non isothermal and isothermal conditions. The result of a Kissinger analysis shows that the activation energy for crystallization is 1131 kJ/mol. The higher stability against crystallization of Al₆₅Cu₂₀Ti₁₅ amorphous alloy is attributed to the stronger interaction of atoms in the Al-Cu-Ti system and formed of complicated compound like Al₅CuTi₂ and Al₄Cu₉ as primary phases. The isothermal crystallization was modeled by using the Johnson-Mehl-Avrami (JMA) equation. The Avarami exponents suggest that the isothermal crystallization is governed by a three-dimensional diffusion-controlled growth.     

Phase separation and crystallization in the system SiO2-Al2O3-P2O5-B2O3-Na2O glasses

The phase separation and crystallization behavior in the system (80 − X)SiO₂ · X(Al₂O₃ + P₂O₅) · 5B₂O₃ · 15Na₂O (mol%) glasses was investigated. Glasses with X = 20 and 30 phase separated into two phases, one of which is rich in Al₂O₃-P₂O₅-SiO₂ and forms a continuous phase. Glasses containing a larger amount of Al₂O₃-P₂O₅ (X = 40 and 50) readily crystallize and precipitates tridymite type AlPO₄ crystals. It is estimated that the phase separation occurs forming continuous Al₂O₃-P₂O₅-SiO₂ phase at first, and then tridymite type AlPO₄ crystals precipitate and grow in this phase. Highly transparent glass-ceramics comparable to glass can be successfully obtained by controlling heat treatment precisely. The crystal size and percent crystallinity of these transparent glass-ceramics are 20-30 nm and about 50%, respectively.