Combined spectroscopic ellipsometry and attenuated total reflection analyses of Al2O3/HfO2 nanolaminates

The microstructure of thin HfO₂-Al₂O₃ nanolaminate high κ dielectric stacks grown by atomic vapor deposition has been studied by attenuated total reflection spectroscopy (ATR) and 8 eV spectroscopic ellipsometry (SE). The presence of Al₂O₃ below HfO₂ prevents the crystallisation of HfO₂ if an appropriate thickness is used, which depends on the HfO₂ thickness. A thicker Al₂O₃ is required for thicker HfO₂ layers. If crystallisation does occur, we show that the HfO₂ signature in both ATR and 8 eV SE spectra allows the detection of monoclinic crystallites embedded in an amorphous phase.     

Effects of physical growth conditions on the structural and optical properties of sputtered grown thin HfO2 films

HfO₂ thin films were prepared by reactive DC magnetron sputtering technique on (100) p-Si substrate. The effects of O₂/Ar ratio, substrate temperature, sputtering power on the structural properties of HfO₂ grown films were studied by Spectroscopic Ellipsometer (SE), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectrum, and X-ray photoelectron spectroscopy (XPS) depth profiling techniques. The results show that the formation of a SiO_x suboxide layer at the HfO₂/Si interface is unavoidable. The HfO₂ thickness and suboxide formation are highly affected by the growth parameters such as sputtering power, O₂/Ar gas ratio during sputtering, and substrate temperature. XRD spectra show that the deposited films have (111) monoclinic phase of HfO₂, which is also supported by FTIR spectra. XPS depth profiling spectra shows that highly reactive sputtered Hf atoms consume some of the oxygen atoms from the underlying SiO₂ to form HfO₂, leaving Si-Si bonds behind.     

Structural and electrical properties of HfO2/Dy2O3 gate stacks on Ge substrates

In the present work we report on the structural and electrical properties of metal-oxide-semiconductor (MOS) devices with HfO₂/Dy₂O₃ gate stack dielectrics, deposited by molecular beam deposition on p-type germanium (Ge) substrates. Structural characterization by means of high-resolution Transmission Electron Microscopy (TEM) and X-ray diffraction measurements demonstrate the nanocrystalline nature of the films. Moreover, the interpretation of the X-ray reflectivity measurements reveals the spontaneous growth of an ultrathin germanium oxide interfacial layer which was also confirmed by TEM. Subsequent electrical characterization measurements on Pt/HfO₂/Dy₂O₃/p-Ge MOS diodes show that a combination of a thin Dy₂O₃ buffer layer with a thicker HfO₂ on top can give very good results, such as equivalent oxide thickness values as low as 1.9 nm, low density of interfacial defects (2-5 × 10¹² eV^− 1 cm^− 2) and leakage currents with typical current density values around 15 nA/cm² at V_g = V_FB − 1V.     

The effects of O2/Ar ratio on the structure and properties of hafnium dioxide (HfO2) films

HfO₂ films at various O₂/Ar flow ratios were prepared by reactive dc magnetron sputtering. The effects of O₂/Ar ratio on the structure and properties of HfO₂ films were studied using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and UV-Visible spectroscopy. The results showed that the HfO₂ films were amorphous at different O₂/Ar ratios, and the atomic ratio of O/Hf in the HfO₂ films at high O₂/Ar ratio was nearly to 2:1. The peaks of Hf4f and O1s shifted to higher binding energy with increasing the oxygen flow proportion. The HfO₂ films at high O₂/Ar ratio had high transmissivity at the range of 400-1100 nm.     

Thickness dependence of high-k materials on the characteristics of MAHONOS structured charge trap flash memory

The electrical characteristics of tunnel barrier engineered charge trap flash (TBE-CTF) memory of MAHONOS (Metal/Al₂O₃/HfO₂/SiO₂/Si₃N₄/SiO₂/Si) structure were investigated. The stack of SiO₂/Si₃N₄/SiO₂ films were used as engineered tunnel barrier, HfO₂ and Al₂O₃ films were used as charge trap layer and blocking oxide layer, respectively. For comparison, the electrical characteristics of MONOS (Metal/SiO₂/Si₃N₄/SiO₂/Si), MONONOS (Metal/SiO₂/Si₃N₄/SiO₂/Si₃N₄/SiO₂/Si), and MAHOS (Metal/Al₂O₃/HfO₂/SiO₂/Si) were also evaluated. The energy band diagram was designed by using the quantum-mechanical tunnel model (QM) and then the CTF memory devices were fabricated. As a result, the optimized thickness combination of MAHONOS structure was confirmed. The tunnel barrier engineered MAHONOS CTF memory showed a considerable enhancement of program/erase (P/E) speeds, retention time and endurance characteristics.     

Growth characteristics and electrical properties of La2O3 gate oxides grown by thermal and plasma-enhanced atomic layer deposition

We comparatively investigated thermal and plasma-enhanced atomic layer deposition (T-ALD and PE-ALD, respectively) of lanthanium oxide (La₂O₃) films using tris(isopropyl-cyclopentadienyl)lanthanum [La(iPrCp)₃] as a La precursor. H₂O and O₂ plasma were used as reactants for T-ALD and PE-ALD La₂O₃, respectively. Both of the processes exhibited ALD mode growth with good self-saturation behavior and produced pure La₂O₃ films. However, PE-ALD La₂O₃ showed higher growth rate and dielectric constant value than those of T-ALD La₂O₃. In addition, lower leakage current density and interface state density were observed for PE-ALD La₂O₃, compared to those of the T-ALD La₂O₃. These experimental results indicate that the PE-ALD La₂O₃ process using La(iPrCp)₃ precursor can be one of the viable options applicable into future microelectronic industry.     

Transmittance enhancement of micro-grating structure sapphire with high-refractive index Y2O3 layer

The theoretical analysis of micro-grating structure sapphire (sapphire MGS) with Y₂O₃ layer using the finite-difference time-domain method is presented. The results show that the total transmittance and reflectance of Y₂O₃/sapphire MGS have a close relationship with the thickness of Y₂O₃ layer, where about 300 nm is the ideal thickness. According to the simulant results, 300 and 600 nm of thicknesses of Y₂O₃ layer deposited onto sapphire MGS substrate by reactive magnetron sputtering method are studied experimentally. The experimental results agree well with the calculated data and further have better optical properties because of the rough surface of Y₂O₃ layer. It illustrates that the 300-nm Y₂O₃/sapphire MGS exhibits the best increase in the total transmittance and diffuse transmittance due to the greater graded refractive index profile than sapphire MGS. The results of this paper have potential applications in solar cells and diffraction grating.     

Chemical structure and electrical properties of sputtered HfO2 films on Si substrates annealed by rapid thermal annealing

The chemical structure and electrical properties of HfO₂ thin film grown by rf reactive magnetron sputtering after rapid thermal annealing (RTA) were investigated. The chemical composition of HfO₂ films and interfacial chemical structure of HfO₂/Si in relation to the RTA process were examined by X-ray photoelectron spectroscopy. Hf 4f and O 1s core level spectra suggest that the as-deposited HfO₂ film is nonstoichiometric and the peaks shift towards lower binding energy after RTA. The Hf-Si bonds at the HfO₂/Si interface can be broken after RTA to form Hf-Si-O bonds. The electrical characteristics of HfO₂ films were determined by capacitance-voltage (C-V) and current density-voltage (J-V) measurements. The results showed that the density of fixed charge and leakage current density of HfO₂ film were decreased after the RTA process in N₂ atmosphere.     

Preparation and characterization of Nb2O5-Al2O3 composite oxide formed by cathodic electroplating and anodizing

Al foil was coated with niobium oxide by cathodic electroplating and anodized in a neutral boric acid solution to achieve high capacitance in a thin film capacitor. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) revealed the niobium oxide layer on Al to be a hydroxide-rich amorphous phase. The film was crystalline and had stoichiometric stability after annealing at temperatures up to 600 °C followed by anodizing at 500 V, and the specific capacitance of the Nb₂O₅-Al₂O₃ composite oxide was approximately 27% higher than that of Al₂O₃ without a Nb₂O₅ layer. The capacitance was quite stable to the resonance frequency. Overall, the Nb₂O₅-Al₂O₃ composite oxide film is a suitable material for thin film capacitors.     

Compositional, structural and electronic characteristics of HfO2 and HfSiO dielectrics prepared by radio frequency magnetron sputtering

HfO₂ and HfSiO films were prepared on Si substrates by using radio frequency magnetron sputtering (RFMS). Compositional, structural and electronic properties of the two films were investigated completely. X-ray photoelectron spectroscopy (XPS) spectra showed that the atom ratio of Hf to O was about 1:2 in the HfO₂ film and the chemical composition of the HfSiO film was Hf₃₇Si₇O₅₆. Grazing incidence X-ray diffraction (GI-XRD) patterns indicated crystallization in the HfO₂ film after 400 °C annealing, but there is no detectable crystallization in the HfSiO film after 800 °C annealing. C-V measurements indicated that the dielectric constants for the HfO₂ and HfSiO film were 20.3 and 17.3, respectively. The fixed charge densities were found to be 6.0 × 10¹² cm⁻² for the HfO₂ film and 3.7 × 10¹² cm⁻² for the HfSiO film. I-V characteristics showed that the average leakage current densities were 2.4 μA/cm² for the HfO₂ film and 0.2 μA/cm² for the HfSiO film at the gate bias of 1 V.     

A study of the erosion-corrosion behavior of nano-Cr2O3 particles reinforced Ni-based composite alloying layer in aqueous slurry environment

To investigate the role of nano-Cr₂O₃ particles on the erosion-corrosion behavior of composite alloying layer, a nano-Cr₂O₃ particles reinforced Ni-based composite alloying layer was fabricated onto AISI 316L stainless steel (SS) via a duplex surface treatment, consisting of Ni/nano-Cr₂O₃ predeposited by electric brush plating, and subsequent Ni-Cr-Mo-Cu multi-element surface alloying by a double glow process. The microstructure and composition of composite alloying layer were characterized by means of X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDS). The results indicated that the added nano-Cr₂O₃ particles were homogeneously distributed in the alloying layer and didn’t decompose or react with surrounding metal matrix under alloying temperature (1000 °C) condition. A series of electrochemical techniques, including potentiodynamic polarization, open circuit potential (OCP), current response and electrochemical impedance spectroscopy (EIS), was employed to evaluate the corrosion properties of nano-Cr₂O₃ particles reinforced composite alloying layer under various hydrodynamic conditions. Erosion-corrosion tests were conducted in 3.5% NaCl solution plus sand particles with varying concentration (50-150 g/L) at different rotation speeds (600-1100 rpm). To estimate the influence of the nature of different nano-particles on the erosion-corrosion property of composite alloying layer, nano-SiO₂ particles reinforced Ni-based composite alloying layer, single alloying layer and 316L SS was selected as the reference materials for all the corrosion and erosion-corrosion tests.     

Evolution of SiO2/Ge/HfO2(Ge) multilayer structure during high temperature annealing

Use of germanium as a storage medium combined with a high-k dielectric tunneling oxide is of interest for non-volatile memory applications. The device structure consists of a thin HfO₂ tunneling oxide with a Ge layer either in the form of continuous layer or discrete nanocrystals and relatively thicker SiO₂ layer functioning as a control oxide. In this work, we studied interface properties and formation kinetics in SiO₂/Ge/HfO₂(Ge) multilayer structure during deposition and annealing. This material structure was fabricated by magnetron sputtering and studied by depth profiling with XPS and by Raman spectroscopy. It was observed that Ge atoms penetrate into HfO₂ layer during the deposition and segregate out with annealing. This is related to the low solubility of Ge in HfO₂ which is observed in other oxides as well. Therefore, Ge out diffusion might be an advantage in forming well controlled floating gate on top of HfO₂. In addition we observed the Ge oxidation at the interfaces, where HfSiO_x formation is also detected.     

Blue PL and EL emissions from Bi-activated binary oxide thin-film phosphors

The photoluminescent (PL) and electroluminescent (EL) characteristics in the thin films of various Bi-activated binary oxide phosphors have been investigated. La₂O₃:Bi, Gd₂O₃:Bi and Y₂O₃:Bi phosphor thin films were prepared on thick BaTiO₃ ceramic sheet substrates by r.f. magnetron sputtering depositions followed by postannealing. Intense blue PL emissions were observed from all Bi-activated binary oxide phosphor thin films postannealed at a high temperature. Blue, whitish blue-green or blue-green emissions were observed from thin-film electroluminescent (TFEL) devices fabricated with a La₂O₃:Bi, a Gd₂O₃:Bi or a Y₂O₃:Bi thin-film emitting layer, respectively. In addition, high luminance with good color purity in blue EL was obtained in a TFEL device using a La₂O₃:Bi thin film prepared under optimized conditions.     

Improved dielectric properties of CaCu3Ti4O12 thin films on oxide bottom electrode of La0.5Sr0.5CoO3

We report on the effect of La_0.5Sr_0.5CoO₃ (LSCO) bottom electrode to the dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) thin films grown on Ir/Ti/SiO₂/Si substrates. Compared with the films grown directly on Ir/Ti/SiO₂/Si substrates, the dielectric constant has been increased greatly about 100%, and the dielectric loss decreased to lower than 0.2 in the frequency range of 1-100 kHz. The origin has been discussed in details based on the analysis of the X-ray diffraction and impedance spectra measurements. Results of the impedance spectra suggest that the absence of undesired interfacial layer between Ir/CCTO thin films might be one of the major reasons of the improvement of the dielectric properties when the LSCO was introduced as the bottom electrode.     

Interfacial microstructure and strength of diffusion brazed joint between Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiC and 9Cr1MoV steel

Joining of composite, Al₂O₃-TiC, with heat-resistant 9Cr1MoV steel, was carried out by diffusion brazing technology, using a combination of Ti, Cu and Ti as multi-interlayer. The interfacial strength was measured by shear testing and the result was explained by the fracture morphology. Microstructural characterization of the Al₂O₃-TiC/9Cr1MoV joint was investigated by X-ray diffraction (XRD) and scanning electron microscope (SEM) with energy-dispersion spectroscopy (EDS). The results indicate that a Al₂O₃-TiC/9Cr1MoV joint with a shear strength of 122 MPa can be obtained by controlling heating temperature at 1130°C for 60 min with a pressure of 12 MPa. Multi-interlayer Ti/Cu/Ti was fused fully and diffusion occurred to produce interfacial layer between Al₂O₃-TiC and 9Cr1MoV steel. The total thickness of the interfacial layer is about 100 μm and Ti₃AlC₂, TiC, Cu and Fe₂Ti are found to occur in the interface layer.     

Effect of leakage current and dielectric constant on single and double layer oxides in MOS structure

MOS structure of Al/Al₂O₃/n-Si, Al/TiO₂/n-Si and Al/Al₂O₃/TiO₂/n-Si was obtained by deposition of Al₂O₃ and TiO₂ on silicon substrate by RF Magnetron Sputtering system. The total thickness of the oxide layer ~ 40 ± 5 nm in the MOS structure was kept constant. Samples were characterized by X-Ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS), Impedance analyzer and Current-voltage (J-V) characteristics. The variations in the dielectric constant and tan δ of the MOS capacitor in the frequency range of 1000Hz-1MHz were measured by impedance analyzer. The variation in dielectric constant of the Al/Al₂O₃/TiO₂/n-Si multilayer compared to single layer of Al/Al₂O₃/n-Si and Al/TiO₂/n-Si is due to high probability of defects, lattice mismatch and interface interactions. The steep rise of Tan δ values in the Al/Al₂O₃/TiO₂/n-Si structure is due to the resonance effect of both Al₂O₃ and TiO₂ layers. The leakage current mechanisms of MOS structures were extracted from Schottky coefficient and Poole-Frenkel coefficient. Theoretical values of Schottky coefficients (β_SC) and Poole-Frenkel coefficients (β_PF) for each sample were estimated using the real part of the dielectric constant. The experimental values were calculated from J-V characteristics and compared with theoretical values. The appropriate model has been proposed. It was found that Schottky and Poole-Frenkel mechanisms are applicable at low and high field respectively for all MOS structures. The combination of Al/Al₂O₃/TiO₂/n-Si is found to be a promising structure with high dielectric constant and low leakage current suitable for MOS devices.     

Synthesis and characterization of Co3O4/RuO2 composite nanofibers fabricated by an electrospinning method

Co₃O₄-RuO₂ composite nanofibers (NFs) were synthesized by an electrospinning method and were calcinated at 400°C for 1 hr in air. Scanning electron microscopy and high-resolution transmission electron microscopy (HRTEM) examinations show that all the synthesized NFs have uniform surface morphology and their diameters are in the range of ~ 30-~70 nm. X-ray diffraction (XRD) results show that crystalline Co₃O₄ phase and RuO₂ phase coexist in the composite NF matrix which is confirmed by X-ray photoemission spectroscopy. In addition, the HRTEM energy-dispersive X-ray spectroscopy mapping results show that the Co₃O₄ and RuO₂ phases are uniformly distributed across the NF matrix.     

Characterization of ferroelectric/metal interface under the repeated polarization switching

Polarization fatigue mechanism in organic ferroelectrics, structures at interface between ferroelectric vinylidene fluoride oligomer and Al electrode under the repeated polarization switching process were investigated by high-resolution X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Al₂O₃ layer at interface was formed with increasing the number of polarization reversal. The formation of oxide layer will be strongly related to polarization reversal, thus the repeated charge and discharge process by polarization reversal may promote the oxidation of Al electrode. Furthermore, the structural and orientation changes in ferroelectric molecular films by applying the electric field were observed. The formation of Al₂O₃ layer, as well as the structural changes in thin films, is affected to polarization fatigue process of ferroelectric organic devices.     

Effect of atomic layer deposited ultra thin HfO2 and Al2O3 interfacial layers on the performance of dye sensitized solar cells

The objective of this work was to investigate the improvement in performance of dye sensitized solar cells (DSSCs) by depositing ultra thin metal oxides (hafnium oxide (HfO₂) and aluminum oxide (Al₂O₃)) on mesoporous TiO₂ photoelectrode using atomic layer deposition (ALD) method. Different thicknesses of HfO₂ and Al₂O₃ layers (5, 10 and 20 ALD cycles) were deposited on the mesoporous TiO₂ surface prior to dye loading process used for fabrication of DSSCs. It was observed that the ALD deposition of ultrathin oxides significantly improved the performance of DSSCs and that the improvement in the DSSC performance depends on the thickness of the deposited HfO₂ and Al₂O₃ films. Compared to a reference DSSC the incorporation of a HfO₂ layer resulted in 69% improvement (from 4.2 to 7.1%) in the efficiency of the cell and incorporation of Al₂O₃ (20 cycles) resulted in 19% improvement (from 4.2 to 5.0%) in the efficiency of the cell. These results suggest that ultrathin metal oxide layers affect the density and the distribution of interface states at the TiO₂/organic dye and TiO₂/liquid electrolyte interfaces and hence can be utilized to treat these interfaces in DSSCs.     

Effect of precursor structure on Cu(InGa)Se2 formation by reactive annealing

Precursor structures of Mo/CuGa/In, Mo/In/CuGa, Mo/In/CuGa/In and Mo/CuGaIn were prepared on thin sodium-free glass by the sputtering of CuGa and In targets. In-situ phase evolution of precursors with temperature was investigated by a high-temperature X-ray diffraction system, which verified the existence and transformation of several intermetallics: Cu₂In, Cu₁₁In₉, Cu₃Ga, Cu₇In₃, Cu₉Ga₄ and Cu₁₆In₉ as well as elemental In. MoSe₂ layers produced during selenization were detected by scanning electron microscope and X-ray diffraction, with their thicknesses varying by precursor structure. Adhesion strength of Cu(InGa)Se₂ to each Mo layer was assessed by applying CdS chemical bath deposition process to each sample.