Hafnium oxide thin films deposited from a filtered cathodic vacuum arc

The electrical and structural characteristics of hafnium oxide thin films reactively deposited from a filtered cathodic vacuum arc have been investigated. X-ray photoelectron spectroscopy was used to determine the deposition conditions (Ar/O₂ ratio) which produced stoichiometric HfO₂ films. Cross-sectional transmission electron microscopy showed that the micro-structure of the films was highly disordered with electron-diffraction analysis providing evidence for the presence of sub-nano-metre crystallites of the monoclinic HfO₂ (P2₁/c) phase. Further evidence for the presence of this phase was provided by measuring the O k-edge using electron energy loss spectroscopy and comparing it with calculations performed using FEFF8.2, a multiple scattering code. Surface imaging revealed that local film damage occurred in films deposited with substrate bias voltages exceeding −200 V. The current-leakage characteristics of the HfO₂ films deposited with a bias of approximately −100 V suggest that device grade HfO₂ films can be produced from a filtered cathodic vacuum arc.     

Comparative study of pulsed laser deposited HfO2 and Hf–aluminate films for high-k gate dielectric applications

The thermal stability and the electrical properties of HfO₂ and Hf–aluminate films prepared by the pulsed laser deposition technique have been investigated by X-ray diffraction, differential thermal analysis, capacitance–voltage correlation, leakage-current measurements and high-resolution transmission electron microscopy observation, respectively. A crystallization transformation from HfO₂ amorphous phase to polycrystalline monoclinic structure occurs at about 500 °C. In contrast, the amorphous structure of Hf–aluminate films remains stable at higher temperatures up to 900 °C. Rapid thermal annealing at 1000 °C for 3 min leads to a phase separation in Hf–aluminate films. Tetragonal HfO₂(111) is predominant, and Al₂O₃ separates from Hf–aluminate and is still in the amorphous state. The dielectric constant of amorphous HfO₂ and Hf–aluminate films was determined to be about 26 and 16.6, respectively, by measuring a Pt/dielectric film/Pt capacitor structure. A very small equivalent oxide thickness (EOT) value of 0.74 nm for a 3-nm physical thickness Hf–aluminate film on a n-Si substrate with a leakage current of 0.17 A/cm² at 1-V gate voltage was obtained. The interface at Hf–aluminate/Si is atomically sharp, while a thick interface layer exists between the HfO₂ film and the Si substrate, which makes it difficult to obtain an EOT of less than 1 nm. PACS 77.55.+f; 81.15.Fg; 73.40.Qv     

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     

Short-Range Order in Amorphous and Crystalline Ferroelectric Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript>

The microstructures of amorphous and polycrystalline ferroelectric Hf_0.5Zr_0.5O₂ films are studied by X-ray spectroscopy and ellipsometry. EXAFS spectra demonstrate that the amorphous film consists of an “incompletely mixed” solid solution of metallic oxides HfO₂ and ZrO₂. After rapid thermal annealing, the mixed Hf_0.5Zr_0.5O₂ oxide films have a more ordered polycrystalline structure, and individual Hf and Zr monoxide islands are formed in the films. These islands are several nanometers in size and have a structure that is similar to the monoclinic structure of HfO₂ and ZrO₂. The presence of the HfO₂ and ZrO₂ phases in the Hf_0.5Zr_0.5O₂ films is also detected by ellipsometry.     

Atomic layer deposition of HfO2 on graphene from HfCl4 and H2O

Atomic layer deposition of HfO₂ on unmodified graphene from HfCl₄ and H₂O was investigated. Surface RMS roughness down to 0.5 nm was obtained for amorphous, 30 nm thick hafnia film grown at 180°C. HfO₂ was also deposited in a two-step temperature process where the initial growth of about 1 nm at 170°C was continued up to 10–30 nm at 300°C. This process yielded uniform, monoclinic HfO₂ films with RMS roughness of 1.7 nm for 10–12 nm thick films and 2.5 nm for 30 nm thick films. Raman spectroscopy studies revealed that the deposition process caused compressive biaxial strain in graphene, whereas no extra defects were generated. An 11 nm thick HfO₂ film deposited onto bilayer graphene reduced the electron mobility by less than 10% at the Dirac point and by 30–40% far away from it.     

Effect of thermal annealing sequence on the crystal phase of HfO2 and charge trap property of Al2O3/HfO2/SiO2 stacks

In this study, we investigated the effect of a post annealing sequence on the HfO₂ crystal phase and the memory window of charge trap devices with TiN-Al₂O₃-HfO₂-SiO₂-Si stacks. The charge trap dielectrics of HfO₂ were deposited by atomic layer deposition and were annealed in an oxygen environment with or without Al₂O₃ blocking oxides. X-ray diffraction analysis showed that, after thermal annealing, the predominant crystal phase of HfO₂ is divided into tetragonal and monoclinic phase depending on the presence or absence of Al₂O₃ blocking oxide. In addition, deconvolution of X-ray diffraction spectra showed that, with increasing annealing temperature, the fraction of the tetragonal phase in the HfO₂ film was enhanced with the Al₂O₃ blocking oxide, while it was reduced without the Al₂O₃ blocking oxide. Finally, measurements of program/erase and increase-step-pulse programming showed that the charge trap efficiency and the memory window of the charge trap devices increased with decreasing fraction of tetragonal HfO₂.     

Zr-induced structural changes in Hf1−x Zr x O2 high-k thin films

The local symmetries around the Hf sites in thin films of Hf_1?x Zr _x O₂/Si(100) were probed using grazing incidence extended X-ray absorption fine-structure spectroscopy (EXAFS). The effects of the Zr incorporation on the local crystal symmetries were investigated using Hf L₃ EXAFS at the Beamline X23A2 of the Brookhaven National Laboratory. The Zr ratios in the various films were set to between 0.0 and 1.0. Significant changes in the local environment were observed for x = 0.25 or greater values. For x = 0.0, the film local structure around Hf sites remain in the equilibrium monoclinic phase as referenced from our previous studies on HfO₂ thin films on Si(100). When Zr is introduced, tetragonal symmetry around the Hf atom appears and becomes dominant at x = 0.63. Using the EXAFS theoretical simulations and non-linear least-square fit results, the fractions of the monoclinic versus tetragonal phases were identified in each film.     

Study of interfacial reactions and phase stabilization of mixed Sc, Dy, Hf high-k oxides by attenuated total reflectance infrared spectroscopy

Grazing angle attenuated total reflectance Fourier transform infrared spectroscopy is applied to study ultrathin film Hf⁴⁺, Sc³⁺ and Dy³⁺oxides, due to its high surface sensitivity. The (multi)metal oxides studied, are of interest as high-k dielectrics. Important properties affecting the permittivity, such as the amorphous or crystalline phase and interfacial reactions, are characterized.Dy₂O₃ is prone to silicate formation on SiO₂/Si substrates, which is expressed in DyScO₃ as well, but suppressed in HfDyO_x. Sc₂O₃, HfScO_x and HfO₂ were found to be stable in contact with SiO₂/Si. Deposition of HfO₂ in between Dy₂O₃ or DyScO₃ and SiO₂, prevents silicate formation, showing a buffer-like behavior for the HfO₂.Doping of HfO₂ with Dy or Sc prevents monoclinic phase crystallization. Instead, a cubic phase is obtained, which allows a higher permittivity of the films. The phase remains stable after anneal at high temperature.     

Hall effect of tetragonal and orthorhombic SrRuO3 films

High quality orthorhombic and tetragonal SrRuO₃ thin films were grown by pulsed laser deposition on SrTiO₃(001) and Ba_0.75Sr_0.25TiO₃ buffered LaAlO₃(001) substrates. Resistivity vs. temperature curves showed a slope change at a Curie temperature of 147.5 ± 2 K for 40 nm thick films irrespective of crystalline symmetry. The Hall resistivity of both films contained an anomalous Hall contribution. The anomalous Hall coefficient was positive throughout the whole temperature range for the tetragonal film, whereas it showed a sign change at 143 K for the orthorhombic film. This is a strong indication that the Berry‐phase mechanism is the dominant anomalous Hall effect mechanism in SrRuO₃. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Transmission electron microscopy studies of HfO2 thin films grown by chloride-based atomic layer deposition

Detailed transmission electron microscopy characterization of HfO₂ films deposited on Si(1 0 0) using atomic layer deposition has been carried out. The influence of deposition temperature has been investigated. At 226 °C, a predominantly quasi-amorphous film containing large grains of cubic HfO₂ (a₀ = 5.08 Å) was formed. Grain morphology enabled the nucleation sites to be determined. Hot stage microscopy showed that both the cubic phase and the quasi-amorphous phase were very resistant to thermal modification up to 500 °C. These observations suggest that nucleation sites for the growth of the crystalline cubic phase form at the growing surface of the film, rather homogeneously within the film. The films grown at higher temperatures (300-750 °C) are crystalline and monoclinic. The principal effects of deposition temperature were on: grain size, which coarsens at the highest temperature; roughness with increases at the higher temperatures due to the prismatic faceting, and texture, with texturing being strongest at intermediate temperatures. Detailed interfacial characterization shows that interfacial layers of SiO₂ form at low and high temperatures. However, at intermediate temperatures, interfaces devoid of SiO₂ were formed.     

Formation of ZrO<Subscript>2</Subscript> cubic phase microcrystals during crystallization of amorphous films deposited by laser ablation of Zr in an oxygen atmosphere

The structure and phase transformations during annealing of zirconium dioxide films grown by pulsed laser sputtering of a Zr target in an oxygen atmosphere have been studied by transmission electron microscopy and electron diffraction methods. The conditions of the formation of both amorphous and cubic ZrO₂ phases have been determined. The electron beam impact on the amorphous film in vacuum is accompanied by the formation of zirconium dioxide microcrystals with fcc lattice. The average grain size in the crystallized film is ～0.5 μm. The phase transformation is accompanied by film material densification. The relative change in the density during ZrO₂ crystallization is 10.27 ± 2.14%.     

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.     

Crystallization behaviors of ultrathin Al-doped HfO_2 amorphous films grown by atomic layer deposition

In this work, ultrathin pure HfO_2 and Al-doped HfO_2films(about 4-nm thick) are prepared by atomic layer deposition and the crystallinities of these films before and after annealing at temperatures ranging from 550℃ to 750℃ are analyzed by grazing incidence x-ray diffraction. The as-deposited pure HfO_2 and Al-doped HfO_2 films are both amorphous. After550-℃ annealing, a multiphase consisting of a few orthorhombic, monoclinic and tetragonal phases can be observed in the pure HfO_2 film while the Al-doped HfO_2 film remains amorphous. After annealing at 650℃ and above, a great number of HfO_2 tetragonal phases, a high-temperature phase with higher dielectric constant, can be stabilized in the Al-doped HfO_2 film. As a result, the dielectric constant is enhanced up to about 35. The physical mechanism of the phase transition behavior is discussed from the viewpoint of thermodynamics and kinetics.     

Investigation of thermal annealing effects on microstructural and optical properties of HfO2 thin films

In the present paper, we investigate the effect of thermal annealing on optical and microstructural properties of HfO₂ thin films (from 20 to 190 nm) obtained by plasma ion assisted deposition (PIAD). After deposition, the HfO₂ films were annealed in N₂ ambient for 3 h at 300, 350, 450, 500 and 750 °C. Several characterisation techniques including X-ray reflectometry (XRR), X-ray diffraction (XRD), spectroscopic ellipsometry (SE), UV Raman and FTIR were used for the physical characterisation of the as-deposited and annealed HfO₂ thin films. The results indicate that as-deposited PIAD HfO₂ films are mainly amorphous and a transition to a crystalline phase occurs at a temperature higher than 450 °C depending on the layer thickness. The crystalline grains consist of cubic and monoclinic phases already classified in literature but this work provides the first evidence of amorphous-cubic phase transition at a temperature as low as 500 °C. According to SE, XRR and FTIR results, an increase in the interfacial layer thickness can be observed only for high temperature annealing. The SE results show that the amorphous phase of HfO₂ (in 20 nm thick samples) has an optical bandgap of 5.51 eV. Following its transition to a crystalline phase upon annealing at 750 °C, the optical bandgap increases to 5.85 eV.     

铌酸钾钠基无铅压电陶瓷的X射线衍射与相变分析

分析了斜方相、四方相铌酸钾钠基无铅压电陶瓷材料的结构和X射线衍射图谱的特点. 对于铌酸钾钠基压电材料斜方相结构, 从构成晶胞的一个单斜原胞进行分析, 计算出X射线衍射谱上每个衍射角附近的衍射峰数目和相对强度. 提出了2θ在20°—60°范围内根据(1 0 2)衍射峰(52°附近)和(1 2 1)衍射峰(57°附近)劈裂的数目区分斜方和四方相的新方法. 对于多晶陶瓷粉末, 可以更简便的由22°(或45°)附近前后峰的相对高低来判断斜方、四方相. 关键词： 铌酸钾钠 无铅压电陶瓷 X射线衍射 相变     

Performance improvement of phase-change memory cell with Ge2Sb2Te5-HfO2 composite films

The phase-change characteristics of Ge₂Sb₂Te₅ (GST) films for phase-change random access memory (PCM) devices were improved by incorporating HfO₂ into GST film using cosputtering at room temperature. Phase separation (GST-rich nanocrystals were surrounded by HfO₂-rich amorphous phase) has been observed in annealed GST-HfO₂ composite films and the segregated domains exhibited a relatively uniform size. The reduced reset voltage of GST-HfO₂ based cell was due to the reduced programming volume by incorporating HfO₂ into GST. This work clearly reveals the highly promising potential of GST-HfO₂ composite films for application in PCM.     

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.     

Thermal stability of HfO2 nanotube arrays

Thermal stability of highly ordered hafnium oxide (HfO₂) nanotube arrays prepared through an electrochemical anodization method in the presence of ammonium fluoride is investigated in a temperature range of room temperature to 900 °C in flowing argon atmosphere. The formation of the HfO₂ nanotube arrays was monitored by current density transient characteristics during anodization of hafnium metal foil. Morphologies of the as-grown and post-annealed HfO₂ nanotube arrays were analyzed by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Although monoclinic HfO₂ is thermally stable up to 2000 K in bulk, the morphology of HfO₂ nanotube arrays degraded at 900 °C. A detailed X-ray photoelectron spectroscopy (XPS) study revealed that the thermal treatment significantly impacted the composition and the chemical environment of the core elements (Hf and O), as well as F content coming from the electrolyte. Possible reasons for the degradation of the nanotube at high temperature were discussed based on XPS study and possible future improvements have also been suggested. Moreover, dielectric measurements were carried out on both the as-grown amorphous film and 500 °C post-annealed crystalline film. This study will help us to understand the temperature impact on the morphology of nanotube arrays, which is important to its further applications at elevated temperatures.     

Monoclinic-tetragonal phase transition in zirconium and hafnium dioxides: A high-temperature raman scattering investigation

Zirconium dioxide ZrO₂ and hafnium dioxide HfO₂ are investigated using high-temperature Raman spectroscopy in the temperature range 300–2080 K, including the regions of the monoclinic-tetragonal phase transitions revealed in these materials. An analysis is made of the specific features observed in the evolution of the high-temperature Raman spectra of both the monoclinic (m) and tetragonal (t) modifications of ZrO₂ and HfO₂ with variations in the temperature. The polarized Raman spectra of the metastable tetragonal phases in solid solutions based on zirconia and hafnia are used to identify the symmetry of vibrations in the spectra of the tetragonal modifications of pure zirconium and hafnium dioxides, which exist at high temperatures.     

Effect of O2 gas partial pressure on structures and dielectric characteristics of rf sputtered ZrO2 thin films

Amorphous and polycrystalline zirconium oxide thin films have been deposited by reactive rf magnetron sputtering in a mixed argon/oxygen or pure oxygen atmosphere with no intentional heating of the substrate. The films were characterized by high-resolution transmission electron microscopy (HR-TEM), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and capacitance versus voltage (C-V) measurements to investigate the variation of structure, surface morphology, thickness of SiO₂-like interfacial layer as well as dielectric characteristics with different oxygen partial pressures. The films deposited at low oxygen partial pressures (less than 15%) are amorphous and dense with a smooth surface. In contrast, the films prepared at an oxygen partial pressure higher than 73% are crystallized with the microstructure changing from the mixture of monoclinic and tetragonal phases to a single monoclinic structure. The film structural transition is believed to be consequences of decrease in the oxygen vacancy concentration in the film and of increase of the energetically neutral particles in the plasma due to an increased oxygen partial pressure. SE measurements showed that significant interfacial SiO₂ growth has taken place above approximately 51%. The best C-V results in terms of relative dielectric constant values are obtained for thin films prepared at an oxygen partial pressure of 15%.