Influence of passivating interlayer on Ge/HfO2 and Ge/Al2O3 interface band diagrams

The energy band alignment between Ge, HfO₂ and Al₂O₃ was analyzed as influenced by passivating interlayers (ILs) of different composition (GeO₂, Ge₃N₄, Si/SiO_x). From internal photoemission and photoconductivity experiments we found no IL-sensitive dipoles at the Ge/HfO₂ interfaces, the latter being universally characterized by conduction and valence band offsets of 2.1 and 3.0 eV, respectively. However, in the case of HfO₂ growth using H₂O-based atomic layer deposition, the Ge oxide IL appears to have a narrower bandgap, 4.3 eV, than the 5.4–5.9 eV gap of bulk germania. Accordingly, formation of this IL yields significantly reduced barriers for hole and, particularly, electron injection from Ge into the insulator. Changing to a H-free process for HfO₂ and Al₂O₃ deposition suppresses the formation of the narrow-gap Ge oxide.     

In situ atomic layer deposition and synchrotron-radiation photoemission study of Al2O3 on pristine n-GaAs(0 0 1)-4 × 6 surface

This work presents the in situ reflection high-energy electron diffraction (RHEED), scanning tunneling microscopy (STM) and synchrotron-radiation photoemission studies for the morphological and interfacial chemical characterization of in situ atomic layer deposited (ALD) Al₂O₃ on pristine molecular beam epitaxy (MBE) grown Ga-rich n-GaAs (1 0 0)-4 × 6 surface. Both the RHEED pattern and STM image demonstrated that the first cycle of ALD-Al₂O₃ process reacted immediately with the GaAs surface. As revealed by in situ synchrotron-radiation photoemission studies, two types of surface As atoms that have excess in charge in the clean surface served as reaction sites with TMA. Two oxidized states were then induced in the As 3d core-level spectra with chemical shifts of +660 meV and +1.03 eV, respectively.     

Effective formation of interface controlled Y2O3 thin film on Si(1 0 0) in a metal-(ferroelectric)-insulator-semiconductor structure

Yttrium was deposited on the chemical oxide of Si and annealed under vacuum to control the interface for the formation of Y₂O₃ as an insulating barrier to construct a metal-ferroelectric-insulator-semiconductor structure. Two different pre-annealing temperatures of 600 and 700 °C were chosen to investigate the effect of the interface state formed after the pre-annealing step on the successive formation of Y₂O₃ insulator and Nd₂Ti₂O₇ (NTO) ferroelectric layer through annealing under an oxygen atmosphere at 800 °C. Pre-anneal treatments of Y-metal/chemical-SiO₂/Si at 600 and 700 °C induced a formation of Y₂O₃ and Y-silicate, respectively. The difference in the pre-anneal temperature induced almost no change in the electrical properties of the Y₂O₃/interface/Si system, but degraded properties were observed in the NTO/Y₂O₃/interface/Si system pre-annealed at 600 °C when compared with the sample pre-annealed at 700 °C. C-V characteristics of the NTO/Y₂O₃/Si structured system showed a clockwise direction of hysteresis, and this gap could be used as a memory window for a ferroelectric-gate. A smaller hysteric gap and electrical breakdown values were observed in the NTO/Y₂O₃/Si system pre-annealed at 600 °C, and this was due to an unintentional distribution of the applied field from the presence of an interfacial layer containing Y-silicate and SiO₂ phases.     

Influence of the oxidation temperature on the non-trigonal Ge dangling bonds at the (1 0 0)Ge/GeO2 interface

GeO₂ was proposed as valuable passivation layer at the surface with Ge to integrate oxide with high dielectric constant in Ge-based logic devices. Hence, the identification of the defects present at different Ge/GeO₂ interfaces becomes a mandatory issue to predict the electrical features of devices based on such materials. High sensitive electrically detected magnetic resonance measurements were performed to study the microstructure of defects occurring at such an interface. The influence of the oxidation temperature on the electrically active paramagnetic traps was investigated.     

Structural and electrical properties of Er-doped HfO2 and of its interface with Ge (0 0 1)

Er-doped HfO₂ thin films with Er content ranging from 0% to 15% are deposited by atomic layer deposition on native oxide free Ge(001). The crystallographic phase is investigated by X-ray diffraction and is found to depend on the Er%. The cubic fluorite structure develops on Ge for Er% as low as 4% and is stable after annealing at 400 °C in N₂. Microstrain increases with increasing the Er content within the fluorite structure. Time of flight secondary ion mass and electron energy loss spectroscopy evidence a Ge diffusion from the substrate that results in the formation of a Ge-rich interfacial region which does not present a structural discontinuity with the oxide. The diffusion of Ge is enhanced by the annealing and causes a reordering of the crystal lattice. In annealed films the interface defect density measured by low temperature conductance measurements is found to decrease with decreasing the Er content.     

Photoemission study of the Si(1 1 1)-native SiO2/copper phthalocyanine (CuPc) ultra-thin film interface

The Ultraviolet and X-ray Photoemission Spectroscopy (UPS, XPS) investigation was done to examine the interface formation between deposited copper phthalocyanine (CuPc) thin films and covered with native oxide n- and p-type silicon Si(1 1 1) substrates. The UPS results indicated the existence of small interface dipole effect for very first layer of CuPc deposited on both types of substrates. The dipoles were oriented differently depending on silicon conductivity type. In this paper we present that near the inorganic/organic interface the phthalocyanine’s molecular orbital levels shift downwards 0.20 ± 0.05 eV in the case of n-Si substrate and upwards 0.25 ± 0.05 eV for p-Si indicating the different displacement of the negative charge within the interface region. This tendency was also confirmed by conducted XPS study of the core levels. It is highly probable that band bending-like shift is provoked by the continuous change of CuPc molecule orientation induced by interface polarization layer.     

Admittance spectroscopy of traps at the interfaces of (1 0 0)Si with Al2O3, ZrO2, and HfO2

Admittance (ac) measurements were carried out to determine the interface trap density (D_it) as a function of energy E in the Si bandgap at interfaces of Si with different insulating oxides (Al₂O₃, ZrO₂, HfO₂). The results are compared to those of the conventional thermal SiO₂/Si interface. The results show that a significant portion of the interface trap density in the as-deposited and de-hydrogenated samples is related to the amphoteric Si dangling bond defects (P_b0 -centers). The D_it is much enhanced for the Al-containing insulators as compared to Si/SiO₂ but can be reduced by annealing in O₂. As to annealing in H₂, efficient passivation of P_b0 centers by hydrogen is achieved for Si/ZrO₂ and Si/HfO₂ interfaces, yet it fails for Si/Al-containing oxide entities. Among the insulators studied, the results suggest HfO₂ to be the best choice of an alternative insulator.     

Direct measurement of interfacial structure in epitaxial Gd2O3 on GaAs (0 0 1) using scanning tunneling microscopy

The epitaxial growth of Gd₂O₃ on GaAs (0 0 1) has given a low interfacial density of states, resulting in the demonstration of the first inversion-channel GaAs metal-oxide-semiconductor field-effect transistor. Motivated by the significance of this discovery, in this work, cross-sectional scanning tunneling microscopy is employed herein to obtain precise structural and electronic information on these epitaxial films and interfaces. At the interface, the interfacial stacking of Gd₂O₃ films is directly correlated with the stacking sequence of the substrate GaAs. Additionally, from the local electronic states across the gate oxides, the spatial extent of the GaAs wavefunctions into the oxide dielectric may suggest a minimum Gd₂O₃ thickness to be of bulk properties.     

Optimization of Al2O3/ZrO2 nanolaminate structure for thin-film encapsulation of OLEDs

We report thin-film moisture barriers based on Al₂O₃/ZrO₂ nanolaminates grown by ALD for an encapsulation of OLEDs. In order to optimize the moisture-barrier performance of the nanolaminates, the most important factors affecting the performance were sought by measuring WVTR of the nanolaminates via an electrical Ca test. We found out that both the number of interfaces in the nanolaminates and the thickness of ZrO₂ in a unit layer were responsible for the performance. By optimizing the nanolaminate structure, the moisture-barrier performance was enhanced up to 350% from a single layer of the same thickness. The WVTR of 30-nm-thick optimized nanolaminate barrier was 2 × 10⁻⁴ g/(m² day) or less at ambient condition. A storage-lifetime measurement of an OLED with a 100-nm-thick encapsulation layer showed that it could exceed 70,000 h if stored at ambient condition.     

Density functional theory study of first-layer adsorption of ZrO2 and HfO2 on Ge(1 0 0)

Density functional theory was used to performed a survey of transition metal oxide (MO₂ = ZrO₂, HfO₂) ordered molecular adsorbate bonding configurations on the Ge(1 0 0)-4 × 2 surface. Surface binding geometries of metal-down (O-M-Ge) and oxygen-down (M-O-Ge) were considered, including both adsorbate and displacement geometries of M-O-Ge. Calculated enthalpies of adsorption show that bonding geometries with metal-Ge bonds (O-M-Ge) are essentially degenerate with oxygen-Ge bonding (M-O-Ge). Calculated electronic structures indicate that adsorbate surface bonding geometries of the form O-M-Ge tend to create a metallic interfaces, while M-O-Ge geometries produce, in general, much more favorable electronic structures. Hydrogen passivation of both oxygen and metal dangling bonds was found to improve the electronic structure of both types of MO₂ adsorbate systems, and induced the opening of true semiconducting band gaps for the adsorbate-type M-O-Ge geometries. Shifts observed in the DOS minima for both O-M-Ge and M-O-Ge adsorbate geometries are consistent with surface band bending induced by the adsorbate films, where such band bending extends much further into the Ge substrate than can be modeled by the Ge slabs used in this work.     

Electrical and interfacial characteristics of nanolaminate (Al2O3/ZrO2/Al2O3) gate stack on fully depleted SiGe-on-insulator

The structural and electrical characteristics of a novel nanolaminate Al₂O₃/ZrO₂/Al₂O₃ high-k gate stack together with the interfacial layer (IL) formed on SiGe-on-insulator (SGOI) substrate have been investigated. A clear layered Al₂O₃ (2.5 nm)/ZrO₂ (4.5 nm)/Al₂O₃ (2.5 nm) structure and an IL (2.5 nm) are observed by high-resolution transmission electron microscopy. X-ray photoelectron spectroscopy measurements indicate that the IL contains Al-silicate without Ge atom incorporation. A well-behaved C–V behavior with no hysteresis shows the absence of Ge pileup or Ge segregation at the gate stack/SiGe interface.     

Au/CaF2/nSi(1 1 1) tunnel emitter phototransistor

Owing to the improved growth technology of the 1-2 nm calcium fluoride films on silicon, tunnel metal-insulator-semiconductor transistors have been fabricated. Measured output characteristics show both saturation and active mode of operation. Estimated value of current gain exceeds 1000 approaching the theoretically estimated value in this system. This result supports the candidacy of calcium fluoride for being a vital dielectric in silicon-based functional electronics.     

Comparative study of AlGaN/GaN metal-oxide-semiconductor heterostructure field-effect transistors with Al2O3 and HfO2 gate oxide

AlGaN/GaN metal-oxide-semiconductor heterostructure field-effect transistors (MOSHFETs) with Al₂O₃ gate oxide which was deposited by atomic layer deposition (ALD) were fabricated and their performance was then compared with that of AlGaN/GaN MOSHFETs with HfO₂ gate oxide. The capacitance (C)-voltage (V) curve of the Al₂O₃/GaN MOS diodes showed a lower hysteresis and lower interface state density than the C-V curve of the HfO₂/GaN diodes, indicating better quality of the Al₂O₃/GaN interface. The saturation of drain current in the I_D-V_GS relation of the Al₂O₃ AlGaN/GaN MOSHFETs was not as pronounced as that of the HfO₂ AlGaN/GaN MOSHFETs. The gate leakage current of the Al₂O₃ MOSHFET was five to eight orders of magnitude smaller than that of the HfO₂ MOSHFETs.     

Stack engineering of low-temperature-processing Al2O3 dielectrics prepared by nitric acid oxidation for MOS structure

The electrical characteristics of low-temperature-processing Al₂O₃ films were studied. With an anodization SiO₂ film as a buffer layer, Al₂O₃ dielectric was grown on it by oxidizing an ultra-thin aluminum film in nitric acid, followed by a surface DAC-ANO compensation. The significant development is, when the Al₂O₃ film fabrication of this experiment was repeated, which means one more same Al₂O₃ layer deposition, the sample demonstrated satisfactory electrical properties.     

Origin of electron mobility enhancement in (1 1 1)-oriented InGaAs channel metal-insulator-semiconductor field-effect-transistors

Electrical and physical characteristics of the Al₂O₃/InGaAs interfaces with (1 1 1)A and (1 0 0) orientations were investigated in an attempt to understand the origin of electron mobility enhancement in the (1 1 1)A-channel metal-insulator-semiconductor field-effect-transistor. The (1 1 1)A interface has less As atoms of high oxidation states as probed by X-ray photoelectron spectroscopy. The electrical measurements showed that energy distribution of the interface traps for the (1 1 1)A interface is shifted toward the conduction band as compared to that for the (1 0 0) interface. Laterally-compressed cross-section transmission electron microscopy images showed that the characteristic lengths of the interface roughness are different between the (1 1 1)A and (1 0 0) interfaces. The contributions of the Coulomb and roughness scattering mechanisms are discussed based on the experimental results.     

Highly (1 0 0)-oriented Pb(Zr0.20Ti0.80)O3/(Pb1−xLax)Ti1−x/4O3 multilayered thin films prepared by RF magnetron sputtering

The Pb(Zr_0.20Ti_0.80)O₃/(Pb_1−xLa_x)Ti_1−x/4O₃ (x = 0, 0.10, 0.15, 0.20) (PZT/PLT_x) multilayered thin films were in situ deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering technique with a PbO_x buffer layer. With this method, all PZT/PLT_x multilayered thin films possess highly (1 0 0) orientation. The PbO_x buffer layer leads to the (1 0 0) orientation of the multilayered thin films. The effect of the La content in PLT_x layers on the dielectric and ferroelectric properties of the PZT multilayered thin films was systematically investigated. The enhanced dielectric and ferroelectric properties are observed in the PZT/PLT_x (x = 0.15) multilayered thin films. The dielectric constant reaches maximum value of 365 at 1 KHz for x = 0.15 with a low loss tangent of 0.0301. Along with enhanced dielectric properties, the multilayered thin films also exhibit large remnant polarization value of 2P_r = 76.5 μC/cm², and low coercive field of 2E_c = 238 KV/cm.     

Electronic structure at interfaces of cubic Gd2O3 with embedded Si nanocrystals

The electronic structure of silicon nanocrystals (∼2-6 nm in size) embedded in cubic Gd₂O₃ epi-layers grown on (1 1 1) Si was analyzed using spectroscopic ellipsometry and photocharging methods. With decreasing nanocrystal size down to the 2 nm range, the optical absorption exhibits a spectacular shift in spectral threshold to 2.9 ± 0.1 eV, as compared to the 1.12 eV absorption edge of the bulk Si crystal. This shift suggests a significant influence of quantum confinement on the Si nanocrystal/oxide interface band diagram, which effect is shown to be predominantly caused by an upshift of the nanocrystal conduction band.     

Growth and structural properties of crystalline LaAlO3 on Si (0 0 1)

Crystalline LaAlO₃ was grown by oxide molecular beam epitaxy (MBE) on Si (0 0 1) surfaces utilizing a 2 ML SrTiO₃ buffer layer. This SrTiO₃ buffer layer, also grown by oxide MBE, formed an abrupt interface with the silicon. No SiO₂ layer was detectable at the oxide-silicon interface when studied by cross-sectional transmission electron microscopy. The crystalline quality of the LaAlO₃ was assessed during and after growth by reflection high energy electron diffraction, indicating epitaxial growth with the LaAlO₃ unit cell rotated 45° relative to the silicon unit cell. X-ray diffraction indicates a (0 0 1) oriented single-crystalline LaAlO₃ film with a rocking curve of 0.15° and no secondary phases. The use of SrTiO₃ buffer layers on silicon allows perovskite oxides which otherwise would be incompatible with silicon to be integrated onto a silicon platform.     

Effects of Bi segregation on the tensile properties of Cu/Cu3Sn(1 0 0) interface

The relaxed-type tensile processes of the clean and Bi segregated Cu/Cu₃Sn(1 0 0) interfaces were investigated by the ab initio calculations based on the density functional theory. Fracture occurs at the Cu/Cu₃Sn interface which has the lowest adhesion energy and tensile strength compared to the Cu/Cu and Cu₃Sn/Cu₃Sn interlayers. The theoretical tensile strength of the clean interface is 8.04 GPa, while that of 10% Bi segregated interface drops to 4.72 GPa. According to the atomic and electronic analyzes during tensile test, failure originates from the break of interfacial bonding and the extension of charge depletion region through the interface, when the supercell stretching exceeds the critical tensile strain of 12% for clean interface and 9.5% for Bi segregated interface. Large Bi atom not only introduces interfacial distortion but also reduces the hybridization of surrounding Cu and Sn atoms, which cause the weakening of interfacial mechanical strength of SnBi solder joints.