The thermal stability and structural characteristics for gate stack structure of HfO2 dielectrics deposited by atomic-layer deposition (ALD) were investigated. The structural characteristics and chemical state of the HfO2 films in relation to the film thickness and postannealing temperature were examined by x-ray diffraction and x-ray photoelectron spectroscopy. An interfacial layer of hafnium silicate with an amorphous structure was grown on the oxidized Si substrate at an initial growth stage. The structural characteristics of the HfO2 films are closely affected by the interfacial layer and are depended on the thickness of the films. The 45 Å thick HfO2 film with an amorphous structure was changed into a polycrystalline structure after rapid temperature annealing of 750 °C for 5 min, while thicker films were grown into a polycrystalline structure of monoclinic or tetragonal crystal structure. The silicate layer grown at the interfacial region is not stable even at 700 °C under ultrahigh vacuum condition and changes into the silicide layers.
The structural characteristics and the chemical state of a HfO2–Al2O3 nanolaminate structure, depending on the postannealing temperature, were examined by x-ray diffraction and x-ray photoelectron spectroscopy. The structural stability is significantly enhanced up to 870 °C and so is able to sustain its amorphous and laminate structure. However, the laminate structure is drastically broken at the annealing temperature of 920 °C and the crystallization is locally generated. In particular, the formation of the interfacial layer during the postannealing treatment is effectively suppressed in the nanolaminated structure. The dielectric constant of the nanolaminate structure calculated from the accumulation capacitance increases from ∼10 to ∼17 as the annealing temperature increases. This change is closely related to the degree of the mixture composed by Al2O3 and HfO2.
Thermal stability of HfO2 high-k gate dielectric on GaAs is investigated. Compared to HfO2 gate dielectric, significant improvements in interfacial properties as well as electrical characteristics were found by constructing a Al2O3/HfO2/Al2O3 dielectric stack. At elevated temperatures, the amorphous Al2O3 layers were effective in inhibiting crystallization of HfO2. Since the passivating Al2O3 layers prevent interfacial oxide and trap charge formation, it aids in reducing the increasing rate of equivalent oxide thickness as well as capacitance-voltage hysteresis. Transmission electron microscopy and x-ray photoelectron spectroscopy data supported the improved electrical characteristic of GaAs metal-oxide-semiconductor capacitors with Al2O3/HfO2/Al2O3 gate dielectric stack.
Oxygen-incorporated Ge2Sb2Te5 (GST) films were deposited using ion beam sputtering deposition. Sheet resistance in films with 16.7% oxygen content decreased at a higher annealing temperature than that of undoped GST films, while resistance in films with an oxygen content of over 21.7% decreased dramatically at lower temperatures. X-ray diffraction patterns showed crystallization to face-centered cubic phase was suppressed. However, phase separation to a hexagonal structure was observed in films with an oxygen content of over 21.7%. Extended x-ray absorption fine structure data of Ge K edge showed Ge was bonded to O as well as Te. Moreover, a stoichiometric GeO2 phase was not observed, while phase separation into Sb2O3 and Sb2Te3 occurred. The results indicate Ge–Te bonds with oxygen are related to structural stability.
Phosphorus has low solubility in silicon, but nonequilibrium incorporation of phosphorus exhibits unusual high strain and low contact resistance for advanced Si-based metal-oxide-semiconductor field-effect transistors. Despite recent technological breakthroughs, the origin of tensile strain and electrical deactivation in P-doped Si films is not yet fully understood. Here, by using a combination of experiments and first-principles calculations, we investigate the effect of nonequilibrium phosphorus incorporation into Si lattices and subsequent annealing on structural, electrical, and bonding properties of P-doped Si films. Quantitative structural analyses reveal that the high tensile strain is generated by the incorporation of P into Si substitutional sites irrespective of the distribution of P atoms. More importantly, we found that advanced postgrowth annealing lead to significantly enhanced electrical properties while keeping the same physical states without loss of induced strain. To explore the reason for improved performances, we conducted the comprehensive theoretical calculations that present the contributions of dopant incorporation and vacancy formation to structural, chemical, and electrical properties, thereby providing atomic insights into the underlying physical mechanism of the electrical deactivation. Our findings indicate that the tensile strain can be controlled by manipulating the number of substitutionally incorporated P atoms, and electrical properties may be enhanced by reducing the vacancy concentration using advanced postannealing processes or low temperature growth conditions.
Al 2 O 3 incorporated HfO2 films grown by atomic layer deposition were investigated using various measurement tools. The accumulation capacitance of the Al2O3 incorporated into HfO2 film increases as the postannealing temperature increases because of changes in interfacial and upper layer thickness and in interfacial stoichiometry. The core-level energy state of a 15 Å thick film shows a shift to higher binding energy, as the result of silicate formation and Al2O3 incorporation. The incorporation of Al2O3 into the HfO2 film has no effect on silicate formation at the interface between the film and Si, while the ionic bonding characteristics and hybridization effects are enhanced compared to a pure HfO2 film. Any dissociated Al2O3 on the film surface is completely removed by a vacuum annealing treatment over 850 °C, while HfO2 contributes to Hf silicide formation on the surface of the film.
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