Effect of oxygen vacancies on adhesion at the Nb/Al2O3 and Ni/ZrO2 interfaces

The atomic and electronic structures of the Nb/Al₂O₃(0001) and Ni/ZrO₂(001) interfaces are calculated using density-functional theory. The formation energy of oxygen vacancies is estimated in bulk materials and in surface layers and interfaces for different uppermost atomic layers of oxide surfaces. The work of separation of metal films from oxide surfaces is determined. The effect of oxygen vacancies on the bonding of transition metals to atoms of a substrate determining adhesion at the metal-oxide interfaces is discussed. It is shown that the Nb(Ni)-O interaction at the interfaces weakens in the presence of surface oxygen vacancies.     

Ab-initio investigation of Ni(Fe)/ZrO2(0 0 1) and Ni-Fe/ZrO2(0 0 1) interfaces

The atomic and electronic structures of Me/ZrO₂(0 0 1) interfaces, where Me is Ni, Fe or a Ni-Fe alloy, are investigated by the plane wave pseudopotential method within density-functional theory. The work of separation of metal films from oxide substrate for the O- and Zr-terminated Me/ZrO₂(0 0 1) interfaces is calculated. High adhesion at both Me/(ZrO₂)_O and Me/(ZrO₂)_Zr interfaces is found. The effect of oxygen vacancies on the adhesion at the metal-ceramic interfaces is also investigated. It is shown that Ni(Fe)-O interaction at the O-terminated interface weakens in the presence of interfacial oxygen vacancies. At interfaces with Ni-Fe alloys the adhesion depends strongly on the composition of the interfacial layers and their magnetic properties.     

Adhesion of niobium films to differently oriented α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> surfaces

The atomic and electronic structures of the Nb/α-Al₂O₃ interface are studied by the electron density functional method. The structural and electronic properties of three corundum surfaces, as well as chemical bonds produced by metallic niobium films at variously oriented interfaces, are discussed. Relations between the electronic structure, geometry, and mechanical properties of the interfaces are analyzed. It is shown that the adhesion of niobium films to a great extent depends on the type of oxide surface.     

Theoretical study of adhesion at the metal-zirconium dioxide interfaces

The atomic and electronic structure of the interfaces between metals with body-centered cubic (bcc) and face-centered cubic (fcc) structures and zirconium dioxide is studied systematically using the ab initio methods of the electron density functional theory (DFT). It is shown that high adhesion properties can be attained at the nonstoichiometric polar Me(001)/ZrO₂(001) interface with bcc metals from the middle of the 4d–5d periods (Mo, Ta, W, and Nb). Charge transfer from the metal to the oxide substrate ensures the strong ionic chemical bond on the metal-ceramic interfaces. The structural and electronic factors responsible for lowering of adhesion at differently oriented interfaces are analyzed. It is shown that a decrease of adhesion at the (110) nonpolar stoichiometric interface is due to an increase in the interfacial spacing as well as a decrease in the number of metal-oxygen bonds. The effect of doping with oxides (CaO, MgO, and Y₂O₃) stabilizing zirconium dioxide at low temperatures on the adhesion energy at the Me(001)/ZrO₂(001) interface is analyzed.     

Adhesion at the interfaces between BCC metals and α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Ab initio calculations of the atomic and electronic structures of Me(111)/α-Al₂O₃(0001) interfaces (Me = V, Cr, Nb, Mo, Ta, W) in the framework of density functional theory are reported. The energies of separation of metal films from oxide surfaces have been calculated. The structural and electronic factors responsible for the strong adhesion of bcc metal films on the oxygen termination of the surface of aluminum oxide have been analyzed.     

Segregation of Aluminium at Nickel-Sapphire Interfaces

Sessile drop experiments of pure liquid Ni on the basal surface of pure sapphire were conducted under controlled atmosphere and temperature. This system has been traditionally considered as non-reactive, based on thermodynamic assessments. However, the results of this study demonstrate that a capillary driven interaction exists between the pure liquid Ni and the sapphire, which causes the dissolution of the sapphire substrate mainly at the triple junction. Oxygen and Al resulting from the dissolution process diffuse into Ni and segregate at its interfaces with the atmosphere and the sapphire (probably as Al _x O _y clusters), which reduces the interface energy. It is considered that this reduction is beneficial for the adhesion of both liquid and solid Ni on sapphire. The amount of Al introduced into the drop, and hence the segregation of Al that affects the interface energy (and adhesion), are related to the size of the sessile drop.     

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.     

Theoretical investigations of the (110) interface between the full Heusler alloys and GaAs

The ab initio calculations of the electronic structure and magnetic properties of the (110) interface between Co₂YZ (Y = Cr or Mn and Z = Al, Si, or Ge) and GaAs are carried out by means of the density functional theory depending on the contact configuration. It is revealed that two of four possible atomic interface configurations have high spin polarization. For Co₂MnSi/GaAs(110), one of the contacts has almost 100% spin polarization. Calculations of the adhesion energy on the interfaces allow the most stable contacts to be established.     

Molecular dynamics simulation comparison of atomic scale intermixing at the amorphous Al2O3/semiconductor interface for a-Al2O3/Ge, a-Al2O3/InGaAs, and a-Al2O3/InAlAs/InGaAs

The structural properties of a-Al₂O₃/Ge, a-Al₂O₃/In_0.5Ga_0.5As and a-Al₂O₃/In_0.5Al_0.5As/InGaAs interfaces were investigated by density-functional theory (DFT) molecular dynamics (MD) simulations. Realistic a-Al₂O₃ samples were generated using a hybrid classical-DFT MD “melt and quench” approach. The interfaces were formed by annealing at 700 K/800 K and 1100 K with subsequent cooling and relaxation. The a-Al₂O₃/Ge interface demonstrates pronounced interface intermixing and interface bonding exclusively through Al–O–Ge bonds generating high interface polarity. In contrast, the a-Al₂O₃/InGaAs interface has no intermixing, Al–As and O–In/Ga bonding, low interface polarity due to nearly compensating interface dipoles, and low substrate deformation. The a-Al₂O₃/InAlAs interface demonstrated mild intermixing with some substrate Al atoms being adsorbed into the oxide, mixed Al–As/O and O–Al/In bonding, medium interface polarity, and medium substrate deformation. The simulated results demonstrate strong correlation to experimental measurements and illustrate the role of weak bonding in generating an unpinned interface for metal oxide/semiconductor interfaces.     

Metal/TiO<Subscript>2</Subscript> interfaces for memristive switches

The interfaces between metal electrodes and the oxide in TiO₂-based memristive switches play a key role in the switching as well as in the I–V characteristics of the devices in different resistance states. We demonstrate here that the work function of the metal electrode has a surprisingly minor effect in determining the electronic barrier at the interface. In contrast, Ti oxides can be readily reduced by most electrode metals. The amount of oxygen vacancies created by these chemical reactions essentially determines the electronic barrier at the device interfaces.     

C60 growth on Si(100), GaSe(0001) and GeS(001)

C₆₀ films have been grown in ultra high vacuum on various crystalline substrates and the structure of the films has been investigated by low energy electron diffraction (LEED) and high resolution electron energy loss spectroscopy (HREELS). The C₆₀ films form randomly oriented nanocrystals on Si(100), mesoscopic polycrystals on GaSe(0001) and microscopic single crystals on GeS(001). The vibrational structure of the C₆₀/substrate interfaces is analyzed in detail by HREELS carried out in the dipole and impact scattering regimes. It is shown that the epitaxy of C₆₀ on GeS(001) is induced by the weak van der Waals bonding and the peculiar corrugation of the substrate surface.     

Nb-Al合金高温氧化机理

通过自编软件建立了铝氧化膜与基体铌界面的原子集团模型,用递归法计算了合金的原子埋置能、原子结合能等电子参数,从电子层面分析铌合金高温氧化机理.研究表明:铝通过晶界扩散偏聚在合金表面,并与氧结合生成致密的Al2O3氧化膜,阻挡氧向铌基体扩散.晶界和稀土元素能提高氧化膜与基体间的原子结合能,增加其界面的结合强度,加强氧化膜与基体铌间的黏附性.因此,通过在合金中添加稀土元素或细化合金晶粒均能提高铌合金的抗高温氧化性能.     

Advanced ion beam technology for versatile oxide thin film formation

Various oxide films, such as SnO₂, In₂O₃, Al₂O₃, SiO₂, ZnO, and Sn-doped In₂O₃ (ITO) have been deposited on glass and polymer substrates by advanced ion beam technologies including ion-assisted deposition (IAD), hybrid ion beam, ion beam sputter deposition (IBSD), and ion-assisted reaction (IAR). Physical and chemical properties of the oxide films and adhesion between films and substrates were improved significantly by these technologies. By using the IAD method, non-stoichiometry, crystallinity, and microstructure of the films were controlled by changing assisted oxygen ion energy and arrival ratio of assisted oxygen ion to evaporated atoms. IBSD method has been carried out for understanding the growth mode of the films on glass and polymer substrate. Relationships between microstructure and electrical properties in ITO films on polymer and glass substrates were intensively investigated by changing ion energy, reactive gas environment, substrate temperature, etc. Smooth-surface ITO films (R_rms ⩽ 1 nm and R_p−v ⩽ 10 nm) for organic light-emitting diodes were developed with a combination of deposition conditions with controlling microstructure of a seed layer on glass. IAR surface treatment enormously enhanced the adhesion of oxide films to polymer substrate. In the case of Al₂O₃ and SiO₂ films, the oxygen and moisture barrier properties were also improved by IAR surface treatment. The experimental results of the oxide films prepared by the ion beam technologies and its applications will be represented in detail.     

Fe-Cr-Al合金氧化膜形成机理电子理论研究

通过自编软件建立了Fe-Cr-Al合金表面、氧化膜/基体界面模型,采用递归法计算了合金元素在Fe-Cr-Al合金表面、氧化膜/基体界面的环境敏感镶嵌能、亲和能、结合能、态密度等电子结构参数.从电子层次系统研究了Fe-Cr-Al合金氧化膜的形成机理、稀土元素和杂质硫对氧化膜形成过程及黏附性的影响机理.研究表明Fe-Cr-Al合金中Al的偏聚驱动力远大于Y,Cr.氧化初期氧从合金表面向合金内部扩散,合金内部Al向合金表面扩散,使合金形成富铝、氧表面层;氧与Al间的亲和力较大（亲和能低）,氧原子容易与Al结合生成Al₂O₃保护膜;合金中加入Y后,Y在合金表面偏聚,抑制Al向合金表面扩散,氧化膜的横向生长得到有效控制,从而避免氧化膜皱褶形貌的发生,提高氧化膜的黏附性;合金内部的S通过扩散汇集在基体/氧化膜界面,S使界面区原子的总能增高,总态密度降低,减小了界面的稳定性,进而削弱氧化膜与合金基体的结合力. 关键词： 电子结构 高温氧化 Fe-Cr-Al合金     

Transient ionic space charges in thin oxide films

The initial step of anodic growth of thin oxide films (1 to 100 nm) on Al and Ta is the simultaneous emission of metal cations from the interface metal/oxide and oxygen ions from the interface oxide/electrolyte. These ions represent mobile space charges which migrate through the oxide film to the opposite interfaces. This process requires times from μs to 10⁴ s, depending on the field strength and the film thickness and was monitored in the time domain (current transients of potential steps, 10⁻⁶ s to 10⁴ s). The movement of the ionic space charges can be used to determine the concentration of mobile ions, the film thickness, the thickness distribution of nonhomogeneous films and the temperature of extreme thin films. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Ion scattering (Me+ → Me) by monatomic films

Discusses the results of computer simulation of the scattering of metal ions low energy (E ₀ = 2–530 eV) films those metals (Me⁺ → Me) with thickness of few atomic layers on a crystalline substrate, conducted in the framework of the model of multi-particle interactions. The effect of conservation for scattered ions with large values of energy, depending from the film crystal structure, has been realized as in the case of scattering on monocrystalls [1]. It has been determined, that the 3–5 atomic layers coating can save the substrate surface from its interaction with bombarding ions in the energy region E ₀ up to 500 eV.     

Study of intermixing and Zr-silicide formation using swift heavy ion irradiation

Swift heavy ion (SHI) beam induced irradiation is an established technique for investigating structural modifications in thin films depending on the S _e sensitivity of material. Intermixing due to 120 MeV Au ion irradiation at different fluences from 10¹² to 10¹⁴ ions/cm² has been reported as a function of ion fluence in a-Si/Zr/a-Si thin films on Si substrate. The samples are characterized before (pristine) and after irradiation using Grazing Incident X-ray Diffraction (GIXRD) and Rutherford Backscattering Spectroscopy (RBS), which confirm the formation of ZrSi at thin film interface. It is suggested that mixing is mainly due to electronic energy loss since the energy transferred from high energy ions seems to create a transient molten zone along the ion track. It is found that the interface mixing increases linearly with the increase in ion fluence. The mixing effect explained in the framework of Thermal spike model. The irradiation effect on the surface roughness of the system is measured using Atomic Force Microscopy (AFM) technique. The current conduction mechanism and Schottky barrier height are also calculated by taking I–V curves across the Metal/Si junction.     

Efficient approach to metal/metal oxide interfaces within variable charge model

A modified procedure of calculating the energy of metal/oxide interfaces and surfaces in the frame of the CTIP + EAM model (charge transfer ionic potential + embedded atom method) has been developed. According to the proposed approach, local charges and positions of atoms are determined only in a restricted zone surrounding the interface, while in the remaining region they are fixed. As a result, the number of variables undergoes a significant reduction, which enables carrying out efficient calculations for metal/oxide systems. The modified procedure has been applied to studying the relaxation of the α-Al₂O₃ surface. Using three different forms of the CTIP + EAM model present in literature, it has been shown that the correctness of the obtained results is conditioned by the appropriate relation between the CTIP and EAM components. Finally, the relaxation of the Ni/α-Al₂O₃ interface has been examined.     

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.     

Influence of treatment in the (O2,H2) plasma on the structure and physical properties of SnO x films

The influence of treatment in hydrogen and oxygen glow discharge plasmas on the structural and optical properties of 270- to 350-nm-thick SnO _x films prepared using magnetron sputtering and the sol-gel method on the glass substrate has been considered. It has been demonstrated that the plasmas exert segregating and destroying effects on the structure of crystal grains, the transparency of films, and on their porosity. It has been established that treatment in the hydrogen glow discharge plasma makes it possible in principle to prepare crystal-amorphous nanostructures in which tin oxide nanocrystals of high quality alternate with tin oxide clusters.