Interfaces analysis of the HfO2/SiO2/Si structure

The physical and chemical properties of the HfO₂/SiO₂/Si stack have been analyzed using cross-section HR TEM, XPS, IR-spectroscopy and ellipsometry. HfO₂ films were deposited by the MO CVD method using as precursors the tetrakis 2,2,6,6 tetramethyl-3,5 heptanedionate hafnium—Hf(dpm)₄ and dicyclopentadienil-hafnium-bis-diethylamide—Сp₂Hf(N(C₂H₅)₂)₂.The amorphous interface layer (IL) between HfO₂ and silicon native oxide has been observed by the HRTEM method. The interface layer comprises hafnium silicate with a smooth varying of chemical composition through the IL thickness. The interface layer formation occurs both during HfO₂ synthesis, and at the annealing of the HfO₂/SiO₂/Si stack. It was concluded from the XPS, and the IR-spectroscopy that the hafnium silicate formation occurs via a solid-state reaction at the HfO₂/SiO₂ interface, and its chemical structure depends on the thickness of the SiO₂ underlayer.     

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.     

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.     

Transmission electron microscopy characterization of HfO<Subscript>2</Subscript>/GaAs(001) heterostructures grown by molecular beam epitaxy

Transmission electron microscopy structural characterization of HfO₂/GaAs(001) heterostructures grown by molecular beam epitaxy with a film thickness of ∼ 5 nm was conducted. The study indicates that the room-temperature as-grown films are amorphous and the films crystallize into the monoclinic phase upon in situ post annealing at 540 °C in the growth chamber. Both types of films show an atomically sharp interface with GaAs(001) substrates. The crystalline monoclinic HfO₂ films exhibit c-oriented epitaxy on the substrate and consist of 90° domains. The formation of 90° domains in the heterostructures, the details of the domain-wall configurations, and the possible impact of the walls and the frequently observed anti-phase boundaries in the films on electrical properties of the heterostructures are discussed. PACS 68.37.Lp; 68.37.Og; 68.35.bg     

Formation of W/HfO2/Si gate structures using in situ magnetron sputtering and rapid thermal annealing

The W(150 nm)/HfO₂(5 nm)/Si(100) structures prepared in a single vacuum cycle by rf magnetron sputtering were subjected to rapid thermal annealing in argon. It is found that at an annealing temperature of 950°C, the tungsten oxide WO _x phase and the hafnium silicate HfSi _x O _y phase grow at the W/HfO₂ and HfO₂/Si(100) interfaces, respectively. Herewith, the total thickness of the oxide layeris 30% larger than that of the initial HfO₂ film. In addition, a decrease in the specific capacitance in accumulation C _max and in the dielectric constant k (from 27 to 23) is observed. At an annealing temperature of 980°C, intensive interaction between tungsten and HfO₂ takes place, causing the formation of a compositionally inhomogeneous Hf _x Si _y W _z O oxide layer and further decrease in C _max. It is shown that a considerable reduction in the leakage currents occurs in the W/HfO₂/X/Si(100) structures, where X is a nitride barrier layer.     

The microstructure of SiO thin films: from nanoclusters to nanocrystals

The microstructure and electronic structure of silicon-rich oxide (SRO) films were investigated using transmission electron microscopy and electron energy loss spectroscopy as the main analytical techniques. The as-deposited SRO film was found to be a single phase SiO_1.0, as suggested by its electronic structure characteristics determined by the valence electron energy loss spectrum. This single phase undergoes a continuous but incomplete phase decomposition to Si and SiO₂ for films annealed between 300 and 1100°C. The resulting Si phase first appears as ～2?nm-diameter amorphous clusters which grow to larger sizes at higher annealing temperatures, but only crystallize at a critical temperature between 800 and 900°C. This cluster/matrix configuration of the SRO films is consistent with the appearance of the interface plasmon and its oscillator strength as a function of the nanoparticle size. Three separate stages were identified in the sequence of annealed films that were characterized by the presence of single-phase SiO, amorphous silicon nanoclusters, and silicon nanocrystals, respectively. The presence of amorphous silicon nanoclusters in the intermediate stage, the mean size of which can be controlled via annealing, may offer an alternative to silicon nanocrystal composites for optical applications.     

Structural study of TiO2 thin films by micro-Raman spectroscopy

The Raman spectroscopy method was used for structural characterization of TiO₂ thin films prepared by atomic layer deposition (ALD) and pulsed laser deposition (PLD) on fused silica and single-crystal silicon and sapphire substrates. Using ALD, anatase thin films were grown on silica and silicon substrates at temperatures 125–425 °C. At higher deposition temperatures, mixed anatase and rutile phases grew on these substrates. Post-growth annealing resulted in anatase-to-rutile phase transitions at 750 °C in the case of pure anatase films. The films that contained chlorine residues and were amorphous in their as-grown stage transformed into anatase phase at 400 °C and retained this phase even after annealing at 900 °C. On single crystal sapphire substrates, phase-pure rutile films were obtained by ALD at 425 °C and higher temperatures without additional annealing. Thin films that predominantly contained brookite phase were grown by PLD on silica substrates using rutile as a starting material.     

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.     

Growth, microstructure and electrical properties of sputter-deposited hafnium oxide (HfO2) thin films grown using a HfO2 ceramic target

Hafnium oxide (HfO₂) thin films have been made by radio-frequency (rf) magnetron-sputtering onto Si(1 0 0) substrates under varying growth temperature (T_s). HfO₂ ceramic target has been employed for sputtering while varying the T_s from room temperature to 500 °C during deposition. The effect of T_s on the growth and microstructure of deposited HfO₂ films has been studied using grazing incidence X-ray diffraction (GIXRD), and high-resolution scanning electron microscopy (HR-SEM) coupled with energy dispersive X-ray spectrometry (EDS). The results indicate that the effect of T_s is significant on the growth, surface and interface structure, morphology and chemical composition of the HfO₂ films. Structural characterization indicates that the HfO₂ films grown at T_s < 200 °C are amorphous while films grown at T_s > 200 °C are nanocrystalline. An amorphous-to-crystalline transition occurs at T_s = 200 °C. Nanocrystalline HfO₂ films crystallized in a monoclinic structure with a (−1 1 1) orientation. An interface layer (IL) formation occurs due to reaction at the HfO₂-Si interface for HfO₂ films deposited at T_s > 200 °C. The thickness of IL increases with increasing T_s. EDS at the HfO₂-Si cross-section indicate that the IL is a (Hf, Si)-O compound. The electrical characterization using capacitance-voltage measurements indicate that the dielectric constant decreases from 25 to 16 with increasing T_s. The current-voltage characteristics indicate that the leakage current increases significantly with increasing T_s due to increased ILs.     

Investigation of silicon doped by zinc ions with a large dose

The formation of nanoparticles in СZn-Si(100) implanted with ⁶⁴Zn⁺ ions using a dose of 5 × 10¹⁶ cm^–2 and an energy of 50 keV at room temperature with subsequent thermal processing in oxygen at temperatures ranging from 400 to 900°C is studied. The surface topology is investigated with scanning electron (in the secondary emission mode) and atomic force microscopes. The structure and composition of the near-surface silicon layer are examined using a high-resolution transmission electronic microscope fitted with a device for energy dispersive microanalysis. An amorphized near-surface Si layer up to 130 nm thick forms when zinc is implanted. Amorphous zinc nanoparticles with an average size of 4 nm are observed in this layer. A damaged silicon layer 50 nm thick also forms due to radiation defects. The metallic zinc phase is found in the sample after low-temperature annealing in the range of 400–600°C. When the annealing temperature is raised to 700°C, zinc oxide ZnO phase can form in the near-surface layer. The complex ZnO · Zn₂SiO₄ phase presumably emerges at temperatures of 800°C or higher, and zinc-containing nanoparticles with lateral sizes of 20–50 nm form on the sample’s surface.     

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.     

Crystallisation kinetics and density profiles in ultra-thin hafnia films

Crystallisation onset temperatures as a function of chlorine contamination have been determined by grazing incidence diffraction on as-deposited ultra-thin HfO₂ films grown by Atomic Layer Deposition. The onset temperatures are positively correlated with chlorine content, suggesting defect-hindered crystallisation kinetics. Density profiles have been deduced by reflectometry measurements and a model independent analysis scheme. It is shown that the HfO₂/SiO₂-Si interface is electronically denser than the bulk of the HfO₂ film.     

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.     

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.     

Defect reduction and surface passivation of SiO2/Si by heat treatment with high-pressure H2O vapor

Heat treatment with high-pressure H₂O vapor was applied to improve interface properties of SiO₂/Si and passivate the silicon surface. Heat treatment at 180–420 °C with high-pressure H₂O vapor changed SiO_x films, 150 nm thick formed at room temperature by thermal evaporation in vacuum, into SiO₂ films with a Si-O-Si bonding network similar to that of thermally grown SiO₂ films. Heat treatment at 130 °C with 2.8×10⁵ Pa H₂O for 3 h reduced the recombination velocity for the electron minority carriers from 405 cm/s (as-fabricated 150-nm-thick SiO_x/Si) to 5 cm/s. Field-effect passivation was demonstrated by an additional deposition of defective SiO_x films on the SiO₂ films formed by heat treatment at 340 °C with high-pressure H₂O vapor. The SiO_x deposition reduced the recombination velocity from 100 cm/s to 48 cm/s. Received: 1 March 1999 / Accepted: 28 March 1999 / Published online: 24 June 1999     

Optical properties of multilayer structures

The possibility of using the ellipsometry method for investigation of the optical properties of multilayer films and structures is shown. The optical properties of structures HfO₂/SiO₂/Si, HfO₂/Si, ZrO₂/Si, Ta₂O₅/Si, and Al₂O₃/Si are studied. It is found that a layer of hafnium silicate is formed at the interface between the HfO₂ film and Si. Annealing of the structures in oxygen shows that oxides studied are oxygen-permeable and that the thickness of SiO₂ at the film-substrate interface increases. The growth rate of SiO₂ layers depends on the chemical nature of an oxide. Al₂O₃ films are impermeable for oxygen diffusion. The production of layers of alloys (Al₂O₃) _x (HfO₂)_{1 ? x} is optimized, which allows one to obtain layers with a homogeneous distribution of elements over the thickness.     

Atomic force microscopy study of the degradation mechanism of ultrathin HfO2 layers on silicon during vacuum annealing

A complex approach to study the initial stage of degradation of hafnium oxide dielectric films during vacuum thermal annealing up to T = 900°C is proposed. Spreading resistance, Kelvin probe, and force modulation methods are used in addition to surface topography measurements. It is found that degradation processes of ultrathin hafnium oxide layers in contact with silicon during vacuum annealing are characterized by strong spatial inhomogeneity, and it is demonstrated that some areas can be localized at different stages of this process.     

Formation of interfacial iron silicides on the oxidized silicon surface during solid-phase epitaxy

The early stages of iron silicide formation in the Fe/SiO _x /Si(100) ternary system during solid-phase epitaxy are studied by high-resolution (～100 meV) photoelectron spectroscopy using synchrotron radiation. The spectra of core and valence electrons taken after a number of isochronous heat treatments of the samples at 750°C are analyzed. It is found that the solid-phase reaction between Fe and Si atoms proceeds in the vicinity of the SiO _x /Si interface, which metal atoms reach when deposited on the sample surface at room temperature. Iron silicide starts forming at 60°C. Solid-phase synthesis is shown to proceed in two stages: the formation of the metastable FeSi interfacial phase with a CsCl-like structure and the formation of the stable β-FeSi₂ phase. During annealing, structural modification of the silicon oxide occurs, which shows up in the growth of the Si⁺⁴ peaks and attenuation of the Si⁺² peaks.     

Gd-doping of HfO2

An increase in the density of states between the oxygen 2p bands and the Fermi level is seen with increasing Gd concentrations. In addition, for the Gd-doped HfO₂ films, the Gd 4f photoexcitation peak at 5.5 eV below the valence band maximum was identified using resonant photoemission. Electrical measurements show pronounced rectification properties for lightly-doped Gd:HfO₂ films on p-Si and for heavily-doped Gd:HfO₂ films on n-Si, suggesting a crossover from n-type to p-type behavior with increasing doping level. In addition, there is an increase in the reverse bias current with neutron irradiation.