Microstructure and interfacial properties of HfO2-Al2O3 nanolaminate films

High-k HfO₂-Al₂O₃ composite gate dielectric thin films on Si(1 0 0) have been deposited by means of magnetron sputtering. The microstructure and interfacial characteristics of the HfO₂-Al₂O₃ films have been investigated by using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and spectroscopic ellipsometry (SE). Analysis by XRD has confirmed that an amorphous structure of the HfO₂-Al₂O₃ composite films is maintained up to an annealing temperature of 800 °C, which is much higher than that of pure HfO₂ thin films. FTIR characterization indicates that the growth of the interfacial SiO₂ layer is effectively suppressed when the annealing temperature is as low as 800 °C, which is also confirmed by spectroscopy ellipsometry measurement. These results clearly show that the crystallization temperature of the nanolaminate HfO₂-Al₂O₃ composite films has been increased compared to pure HfO₂ films. Al₂O₃ as a passivation barrier for HfO₂ high-k dielectrics prevents oxygen diffusion and the interfacial layer growth effectively.     

Defects in Si-Rich SiO2 Films Prepared by Radio-Frequency Magnetron Co-sputtering Using Variable Energy Positron Annihilation Spectroscopy

Si-rich SiO2 films prepared by rf magnetron co-sputtering method are studied by slow positron beams. The nega- tively charge point defects （probably Pb centres or peroxy radicals） at the silicon nanocluster （nc-Si）/SiO2 interface are observed by Doppler broadening spectra. Coincidence Doppler-broadening spectra show that positrons have a higher annihilation probability with core electrons nearby oxygen atoms than silicon atoms. The formation of N-related bonds may be the reason for the prevention of the migration reaction of Si and 0 atoms, hence nc-Si formation is inhibited by annealing in nitrogen compared to in vacuum.     

Electrical Characterization of Deep Trap Properties in High-k Thin-Film HfO2 Dielectric

Deep-trap properties of high-dielectric-constant （k） HfO2 thin films are investigated by deep-level transient spectroscopy and capacitance-voltage methods. The hole traps of the HfO2 dielectric deposited on a p-type Si substrate by sputtering are investigated in a metal-oxide-semiconductor structure over a temperature range of 300-500K. The potential depth, cross section and concentration of hole traps are estimated to be about 2.5eV, 1.8 ×10^-16 cm^2 and 1.0 × 10^16 cm^-3, respectively.     

Phase transformations in films deposited by laser ablation of Hf in an oxygen Atmosphere

The structure of the hafnium dioxide films grown during pulsed laser sputtering of an Hf target in an oxygen atmosphere is examined, and the phase transformations that occur in them at annealing are studied by transmission electron microscopy and electron diffraction. Amorphous, tetragonal, orthorhombic, and monoclinic HfO₂ phases are detected in the films. The tetragonal modification of HfO₂ exhibits an epitaxy effect on a KCl(001) substrate. When the amorphous film is annealed in vacuum or air, it crystallizes to form the monoclinic modification of HfO₂. The action of an electron beam on the amorphous film in vacuum leads to the formation of the orthorhombic and monoclinic modifications of HfO₂. The transformation from the orthorhombic to the monoclinic modification of HfO₂ is accompanied by a phase size effect. At the final stage of crystallization, the monoclinic modification represented by HfO₂ dendrite crystals is the predominant structural constituent.     

Morphology, composition and thermal stability of thin SiO2/HfO2 layers grown on silicon by electron-beam evaporation in vacuum

The results of integrated studies of thin-film structures based on silicon and hafnium dioxides on silicon grown by electron-beam evaporation in vacuum are presented. The surface morphology, structural and phase composition of these films depending on the annealing temperature within 500–1100°C are studied. Special consideration is given to the change in the state of the interfaces after annealing. It is determined that annealing in a flow of nitrogen with the addition of oxygen (～10 vol %) at 700°C does not lead to structural and phase changes in the films, but the intensity of the electron paramagnetic resonance (EPR) spectra of uncompensated bonds on the HfO₂-Si interface decreased. Annealing at higher temperatures stimulates crystallization of the HfO₂ films and hafnium silicate is formed on the SiO₂-HfO₂ interface and suboxide SiO _x appears on the HfO₂-Si interface.     

Characterization of HfOxNy gate dielectrics using a hafnium oxide as target

Hafnium oxynitride (HfO_xN_y) gate dielectric has been deposited on Si (1 0 0) by means of radio frequency (rf) reactive sputtering using directly a HfO₂ target in N₂/Ar ambient. The thermal stability and microstructural characteristics for the HfO_xN_y films have been investigated. XPS results confirmed that nitrogen was successfully incorporated into the HfO₂ films. XRD analyses showed that the HfO_xN_y films remain amorphous after 800 °C annealing in N₂ ambient. Meanwhile the HfO_xN_y films can also effectively suppress oxygen diffusion during high temperature annealing and prevent interface layer from forming between HfO_xN_y films and Si substrates. AFM measurements demonstrated that surface roughness of the HfO_xN_y films increase slightly as compared to those pure HfO₂ films after post deposition annealing. By virtue of building reasonable model structure, the optical properties of the HfO_xN_y films have been discussed in detail.     

Interface Evolution of TiN/Poly Si as Gate Material on Si/HfO2 Stack

TiN as gate electrode in Si/HfO₂/TiN/poly-Si stack is evaluated after the postmetal annealing treatments. Interface reactions are investigated usingelectron-energy-loss spectroscopy and x-ray photoelectron spectroscopy. The work function of the TiN/poly-Si stack shows strong dependence on the postmetal deposition annealing conditions. The interfacial product in TiN/poly-Si interface is inferred as TiSiN, which is beneficial for the whole high-k stack since TiSiN possesses higher work function compared to TiN and poly-Si.     

Investigation of the chemical state of ultrathin Hf-Al-O films during high temperature annealing

Al₂O₃ incorporated HfO₂ films grown by atomic layer deposition (ALD) were investigated by high-resolution X-ray photoelectron spectroscopy (HRXPS). The core level energy state of a 15 Å thick film showed a shift to higher binding energy, as the result of a silicate formation and Al₂O₃ incorporation. The incorporation of Al₂O₃ into the HfO₂ film had no effect on silicate formation at the interface between the film and Si, while the ionic bonding characteristics and hybridization effects were enhanced compared to a pure HfO₂ film. The dissociation of the film in an ultrahigh vacuum (UHV) is effectively suppressed compared to a pure HfO₂ film, indicating an enhanced thermal stability of Hf-Al-O. Any dissociated Al₂O₃ on the film surface was completely removed into the vacuum by vacuum annealing treatment over 850 °C, while HfO₂ contributed to Hf silicide formation on the film surface.     

Vacuum Annealing Induced Room-Temperature Ferromagnetism in Co0.1Ti0.9O2-δ Films Prepared by Sol-Gel Method

The Co-doped TiO2 films （Co0.1Ti0.9O2-δ） are prepared on silicon substrates by sol-gel method and post annealing. TheCo0.1Ti0.9O2-δ film annealed in air is non-ferromagnetic at room temperature. After further annealed in a vacuum, the room-temperature ferromagnetism （RTFM） is observed. Experimental evidences show that the RTFM in the Co0.1Ti0.9O2-δ film may come from the Co-doped TiO2 matrix and is related to the oxygen vacancies created by vacuum annealing.     

Structural and Magnetic Properties of Fe-Doped Anatase TiO2 Films Annealed in Vacuum

Structural and magnetic properties of Fe-doped anatase TiO2 films fabricated by sol-gel spin coating are investigated. X-ray diffraction measurements reveal that Fe^3＋ ions are incorporated into the TiO2 lattice. No ferromagnetism-related secondary phases and magnetic nanopaxticles are observed in the films. The presence of electron paramagnetic resonance signals at 9- 2.0 supports oxygen vacancies and/or defects generated in the films after annealing in vacuum. Magnetic measurements indicate that Fe-doped anatase TiO2 films are ferromagnetic at room temperature. These observations suggest that oxygen vacancies and/or defects axe energetically favorable for the long range Fe^3＋-Fe^3＋ ferromagnetic coupling in Fe-doped anatase TiO2 films.     

Evidence of GeO volatilization and its effect on the characteristics of HfO2 grown on Ge substrate

HfO₂ films are deposited by atomic layer deposition (ALD) using tetrakis ethylmethylamino hafnium (TEMAH) as the hafnium precursor, while O₃ or H₂O is used as the oxygen precursor. After annealing at 500℃ in nitrogen, the thickness of Ge oxide's interfacial layer decreases, and the presence of GeO is observed at the H₂O-based HfO₂ interface due to GeO volatilization, while it is not observed for the O₃-based HfO₂. The difference is attributed to the residue hydroxyl groups or H₂O molecules in H₂O-based HfO₂ hydrolyzing GeO₂ and forming GeO, whereas GeO is only formed by the typical reaction mechanism between GeO₂ and the Ge substrate for O₃-based HfO₂ after annealing. The volatilization of GeO deteriorates the characteristics of the high-κ films after annealing, which has effects on the variation of valence band offset and the C–V characteristics of HfO₂/Ge after annealing. The results are confirmed by X-ray photoelectron spectroscopy (XPS) and electrical measurements.     

Influences of Annealing on Residual Stress and Structure of HfO2 Films

HfO2 films are deposited on BK7 glass substrates by electron beam evaporation. The influences of annealing between 100℃ and 400℃ on residual stresses and structures of HfO2 films are studied. It is found that little differences of spectra, residual stresses and structures are obtained after annealing at lower temperatures. After annealing at higher temperatures, the spectra shift to short wavelength, the residual stress increases with the increasing annealing temperature. At the same time, the crystallite size increases and interplanar distance decreases. The variations of optical spectra and residual stress correspond to the evolutions of structures induced by annealing.     

Characterization of the interface between the Hf-based high-k thin film and the Si using spatially resolved electron energy-loss spectroscopy

The interfacial structures of HfO₂ and HfAlO thin films on Si have been investigated using spatially resolved electron energy-loss spectroscopy. We have found that interfaces are not atomically sharp, and variation in the symmetry of the local atomic coordination lasts for a couple of monolayers for both the as-deposited HfO₂ and the HfAlO samples. Annealing of the HfO₂ film in the oxygen environment leads to the formation of a thick SiO₂/SiO_x stack layer in-between the original HfO₂ and the Si substrate. As a comparison, the interfacial stability is significantly improved by Al incorporation into the HfO₂ film (forming HfAlO), which effectively reduced/eliminated the interfacial silicon oxide formation during the oxygen annealing process. The mechanism of the high-k film/substrate stabilization by Al incorporation is discussed based on the experimental results.     

Band bending and band alignment at HfO2/HfSixOy/Si interfaces

Band bending and band alignment at HfO₂/SiO₂/Si and HfO₂/Hf/SiO₂/Si interfaces were investigated using X-ray photoelectron spectroscopy. After Hf-metal pre-deposition, a 0.55 eV band bending in Si and a 1.80 eV binding energy decrease for Hf 4f and O 1s of HfO₂ were observed. This was attributed to the introduction of negative space charges at interface by Hf pre-deposition. Band bending decrease and synchronous binding energy increases of O 1s and Hf 4f for HfO₂ were observed during initial Ar⁺ sputtering of the Hf pre-deposited sample. This was interpreted through the neutralization of negative space charges by sputtering-induced oxygen vacancies.     

Influence of Different Substrates on Laser Induced Damage Thresholds at 1064nm of Ta2O5 Films

Ta2O5 films are prepared on Si, BK7, fused silica, antireflection （AR） and high reflector （HR） substrates by electron beam evaporation method, respectively. Both the optical property and laser induced damage thresholds （LIDTs） at 1064 nm of Ta2O5 films on different substrates are investigated before and after annealing at 673 K for 12 h. It is shown that annealing increases the refractive index and decreases the extinction index, and improves the O/Ta ratio of the Ta2O5 films from 2.42 to 2.50. Moreover, the results show that the LIDTs of the Ta2O5 films are mainly correlated with three parameters： substrate property, substoichiometry defect in the films and impurity defect at the interface between the substrate and the films. Details of the laser induced damage models in different cases are discussed.     

Study of reactions between HfO2 and Si in thin films with precise identification of chemical states by XPS

Reactions between HfO₂ and Si in HfSiO films during deposition and post-annealing have been studied. Intermixing of HfO₂ and Si is achieved by radio frequency sputtering with HfO₂/Si compound targets, and post-annealing is used to promote the reaction at different temperatures. The structural characteristics of the mixture, HfSiO films, are analyzed by X-ray photoelectron spectroscopy and X-ray diffraction, and a careful assessment of chemical states is performed for precise identification. XPS results show that with ratios of Si:Hf ranging from 0 to 0.3 in HfSiO films, Si fully reacts with HfO₂ to form silicate during deposition. However, SiO₂ appears when the ratio of Si:Hf rises to 1.2. When the annealing temperature reaches 600 °C, decomposition of hafnium silicate is observed and hafnium silicide forms in the bulk of the films. XRD results reveal that HfSiO films remain amorphous with the annealing temperature below 600 °C but crystallize at 800 °C.     

Behavior of oxygen in zinc oxide films through thermal annealing and its effect on sheet resistance

Behavior of oxygen in sputtering deposited ZnO films through thermal annealing and its effect on sheet resistance of the films were investigated. The crystallinities of the ZnO film were improved by post-deposition annealing in vacuum. However, the sheet resistance of ZnO film was dramatically decreased after post-deposition annealing in vacuum at more than 300 °C, while O₂ desorbed from the film. The oxygen vacancies which acted as donors were formed by the thermal annealing in vacuum. The sheet resistance of the films was recovered by annealing in oxygen ambient. In this paper, ¹⁸O₂ gas as an oxygen isotope was used as the annealing ambient in order to distinguish from ¹⁶O, which was constituent atom of the ZnO films. SIMS analysis revealed that ¹⁸O diffused into the ZnO film from the top surface by ¹⁸O₂ annealing. Therefore oxygen vacancies formed by the post-deposition annealing in vacuum could be compensated by the annealing in oxygen ambient.     

Layer structure variations of ultra-thin HfO2 films induced by post-deposition annealing

To meet challenges for a smaller transistor feature size, ultra-thin HfO₂ high-k dielectric has been used to replace SiO₂ for the gate dielectric. In order to accurately analyze the ultra-thin HfO₂ films by grazing incidence X-ray reflectivity (GIXRR), an appropriate material model with a proper layer structure is required. However, the accurate model is difficult to obtain, since the interfaces between layers of the ultra-thin HfO₂ films are not easily identified, especially when post-deposition annealing process is applied. In this paper, 3.0 nm HfO₂ films were prepared by atomic layer deposition on p-type silicon wafer, and annealed in Ar environment with temperatures up to 1000 °C. The layer structures and the role of the interfacial layer of the films in the post-deposition annealing processes were evaluated by X-ray diffraction and X-ray photoelectron spectroscopy (XPS). The experimental results and analysis showed that layer thicknesses, crystal phases and chemical structures of the ultra-thin HfO₂ films were significantly dependent on annealing temperatures. The binding energy shifts of Hf 4f, O 1s, and Si 2p elements revealed the formation of Hf silicate (Hf-O-Si bonding) with increasing annealing temperatures. Due to the silicate formation and increasing silicon oxide formation, the interface broadening is highly expected. The structure analysis of the GIXRR spectra using the modified material structure model from the XPS analysis confirmed the interfacial broadening induced by the post-deposition annealing.     

Low-temperature deposition of stoichiometric HfO2 on silicon: Analysis and quantification of the HfO2/Si interface from electrical and XPS measurements

An understanding of the exact structural makeup of dielectric interface is crucial for development of novel gate materials. In this paper a study of the HfO₂/Si interface created by the low-temperature deposition ultrathin stoichiometric HfO₂ on Si substrates by reactive sputtering is presented. Analysis, quantification and calculation of layer thickness of an HfO₂/Hf-Si-O_x/SiO₂ gate stack dielectrics have been performed, using X-ray photoelectron spectroscopy (XPS) depth profile method, angle resolved XPS and interface modeling by XPS data processing software. The results obtained were found to be in good agreement with the high frequency capacitance-voltage (C-V) measurements. The results suggest a development of a complex three layer dielectric stack, including hafnium dioxide layer, a narrow interface of hafnium silicate and broad region of oxygen diffusion into silicon wafer. The diffusion of oxygen was found particularly detrimental to the electrical properties of the stack, as this oxygen concentration gradient leads to the formation of suboxides of silicon with a lower permittivity, κ.     

Effect of Annealing Temperature on Structural and Optical Properties of N-Doped ZnO Films

Nitrogen-doped ZnO （ZnO：N） films are prepared by thermal oxidation of sputtered Zn3N2 layers on A1203 substrates. The correlation between the structural and optical properties of ZnO：N films and annealing temperatures is investigated. X-ray diffraction result demonstrates that the as-sputtered Zn3N2 films are transformed into ZnO：N films after annealing above 600℃. X-ray photoelectron spectroscopy reveals that nitrogen has two chemical states in the ZnO：N films： the No acceptor and the double donor （N2）o. Due to the No acceptor, the hole concentration in the film annealed at 700℃ is predicted to be highest, which is also confirmed by Hall effect measurement. In addition, the temperature dependent photoluminescence spectra allow to calculate the nitrogen acceptor binding energy.