Pd-Si薄膜固相反应的透射电子显微镜研究

本工作利用透射电子显微术研究了Pd-Si薄膜固相反应的初始生成相及生成相Pd₂Si与(111)取向Si衬底的取向关系随Pd膜厚度、退火温度等因素的变化规律。实验结果表明:在衬底保持室温的条件下,Pd沉积到Si(111)上时也能够生成一层外延的Pd₂Si,其厚度足以在常规的选区电子衍射中产生明显的信号。在170℃退火时,Pd-Si反应即可持续到生成200nm厚的外延的Pd₂Si。在Pd膜厚度为400nm的条件下,Pd₂Si与Si(111)衬底的取向关系为[0001]_(Pd2Si)轴织构。 关键词：     

Identification of nickel silicide phases on a silicon surface from Raman spectra

We have demonstrated the effectiveness of Raman spectroscopy for monitoring nickel silicide formation processes on the surface of silicon wafers, with deposition of a composite metal layer (nickel, platinum, and vanadium) under industrial process conditions in microelectronics. The observed shift of all the NiSi lines toward lower energies is associated with formation of the metastable silicide phase Ni_1?x Pt _x Si, which leads to the presence of stresses in the lattice as a result of the increase in the distances between atoms.     

The interface reaction of high-k La2Hf2O7/Si thin film grown by pulsed laser deposition

The La₂Hf₂O₇ films have been deposited on Si (1 0 0) substrate by using pulsed laser deposition (PLD) method. X-ray diffraction (XRD) demonstrates that the as-grown film is amorphous and crystallizes after 1000 °C annealing. The interface structure is systematically studied by Synchrotron X-ray reflectivity (XRR), Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). Silicide, silicate and SiO_x formations from interfacial reaction are observed on the surface of the Si substrate in the as-grown film. The impact of silicide formation on the electrical properties is revealed by capacitance-voltage (C-V) measurements. By post-deposition annealing (PDA), silicide can be effectively eliminated and C-V property is obviously improved.     

Formation and magnetic properties of the silicon-cobalt interface

Formation of the Si/Co interface and its magnetic properties have been studied by high-resolution photoelectron spectroscopy with synchrotron radiation. The experiments have been performed in situ in superhigh vacuum (5 × 10^?10 Torr) with coating thicknesses up to 2 nm. It has been found that, in the initial stage of silicon deposition on the surface of polycrystalline cobalt maintained at room temperature, ultrathin layers of the Co₃Si, Co₂Si, CoSi, and CoSi₂ silicides are formed. The three last phases are nonmagnetic, and their formation gives rise to fast decay of magnetic linear dichroism in photoemission of Co 3p electrons. At deposition doses in excess of ～0.4 nm Si, a film of amorphous silicon grows on the sample surface. It has been established that the Si/Co interphase boundary is stable at temperatures up to ～250°C and that further heating of the sample brings about escape of amorphous silicon from the sample surface and initiates processes involving silicide formation.     

Analysis of the structure and magnetic properties of an interface in multilayered (Fe/Si) N nanostructures with the surface-sensitive XMCD method

The structural and magnetic properties of (Fe/Si) _N nanostructures obtained by successive deposition on the SiO₂/Si(100) surface at a temperature of the substrate of 300 K have been studied. The thicknesses of all Fe and Si layers have been determined by transmission electron microscopy measurements. The magnetic properties have been studied by the X-ray magnetic circular dichroism (XMCD) method near the Fe L _{3, 2} absorption edges. The orbital (m _l ) and spin (m _S ) contributions to the total magnetic moment of iron have been separated. The thicknesses of magnetic and nonmagnetic iron silicide on the Si/Fe and Fe/Si interfaces have been determined with the surface sensitivity of the XMCD method and the model of the interface between the nonmagnetic and weakened magnetic phases.     

Synchrotron investigations of Si/Mo/Si…c-Si (100) multilayer nanoperiodic structures

This paper presents the results of the investigation of c-Si/[Si/Mo] _n /Si multilayer nanoperiodic structures by X-ray absorption near-edge structure (XANES) spectroscopy using synchrotron radiation. Changes in the fine structure of XANES MoL _2,3 spectra confirm the formation of the silicide phase on heterophase interfaces Si/Mo/Si due to the solid-phase interactions between silicon and molybdenum layers.     

Surfactant effect of Sb on the growth of MnSi1.7 layers on Si(0 0 1)

Deposition of one monolayer of Sb prior to the deposition of Mn at 600 °C is observed to increase the MnSi_1.7 island density by about two orders of magnitude as well as to change the crystalline orientation of the silicide grains. The preferential epitaxial orientation of MnSi_1.7 grains grown by this process is determined to be MnSi_1.7(1 0 0)[0 1 0]||Si(0 0 1)[1 0 0]. This growth procedure results in the silicide growth into the Si matrix. For comparison, the same deposition process carried out without Sb leads to silicide formation on top of the substrate surface. The observed morphological changes of the MnSi_1.7 layers can be explained by a reduced surface diffusion of the Mn atoms on Si(0 0 1) in presence of the Sb monolayer. Additionally, lateral Si diffusion is considered to be nearly suppressed, which is responsible for the observed silicide growth into the substrate.     

Initial stages of iron silicide formation on the Si(1 0 0)2 × 1 surface

The initial stages of iron silicide growth on the Si(1 0 0)2 × 1 surface during solid-phase synthesis were investigated by photoelectron spectroscopy using synchrotron radiation. The experiments were made on iron films of 1-50 monolayer (ML) thickness in the temperature range from room temperature to 750 °С. Our results support the existence of three stages in the Fe deposition on Si(1 0 0) at room temperature, which include formation of the Fe-Si solid solution, Fe₃Si silicide and an iron film. The critical Fe dose necessary for the solid solution to be transformed to the silicide is found to be 5 ML. The solid-phase reaction was found to depend on the deposited metal dose. At 5 ML, the reaction begins at 60 °С, and the solid-phase synthesis leads to the formation of only metastable silicides (FeSi with the CsCl-type structure, γ-FeSi₂ and α-FeSi₂). A specific feature of this process is Si segregation on the silicide films. At a thickness of 15 ML and more, we observed only stable phases, namely, Fe₃Si, ε-FeSi and β-FeSi₂.     

Thickness dependent formation and properties of GdSi2/Si(100) interfaces

Epitaxial and polycrystalline orthorhombic GdSi₂ films were grown on Si(100) substrates by solid phase reaction between Si and Gd films at different thicknesses of the Gd film . The most important property of these GdSi₂/Si interfaces was defect formation. This was investigated by studying the properties of the Schottky barriers by means of current voltage and capacitance–voltage characteristics, deep level transient spectroscopy by double crystal X-ray diffractometry, and transmission electron microscopy. Epitaxial growth of the silicide layer ensured a relatively low interface defect density (about 10¹⁰ cm^-2), while the non-epitaxial growth induced defects of a much higher density (about 10¹² cm^-2). The defects generated during the silicide formation are located within a depth of about 10 nm from the GdSi₂/Si interface. PACS 68.55.-a; 73.40.-c; 81.15-zThis revised version was published in March 2005. References 10-17 were added in the online version (pdf file).     

Reactive epitaxy of cobalt disilicide on Si(111)

A study of the mechanism governing the initial stages in silicide formation under deposition of 1–10 monolayers of cobalt on a heated Si(111) 7×7 crystal is reported. The structural data were obtained by an original method of diffraction of inelastically scattered medium-energy electrons, which maps the atomic structure of surface layers in real space. The elemental composition of the near-surface region to be analyzed was investigated by Auger electron spectroscopy. Reactive epitaxy is shown to stimulate epitaxial growth of a B-oriented CoSi₂(111) film on Si(111). In the initial stages of cobalt deposition (1–3 monolayers), the growth proceeds through island formation. The near-surface layer of a CoSi₂(111) film about 30 Å thick does not differ in elemental composition from the bulk cobalt disilicide, and the film terminates in a Si-Co-Si monolayer triad.     

Processes of silicide formation in the Fe/Si(111)7 × 7 system

The initial stages of the formation of iron silicides in the Fe/Si(111)7 × 7 system in the course of solid-phase epitaxy are investigated using high-resolution photoelectron spectroscopy (～100 meV) with synchrotron radiation. The spectra of the Si 2p core and valence-band electrons obtained after deposition of iron coverages of up to 28 monolayers on the surface of the sample and subsequent isochronous annealings at 650°C are measured and analyzed. It is shown that the first to form under Fe deposition is an ultrathin film of the metastable silicide FeSi with a CsCl-type structure, on which a layer of the Fe-Si solid solution with segregated silicon grows. At coverages in excess of 10 monolayers, an iron film grows on the surface of the sample. Annealing of a silicon crystal coated with a Fe layer leads to the sequential formation of two stable silicide phases, namely, the ?-FeSi and β-FeSi₂ phases, in the near-surface region of the sample. It is found that the process of solid-phase synthesis of the ?-FeSi phase passes through the stage of transformation of the iron film into the Fe-Si solid solution.     

Silicidation in Ni/Si thin film system investigated by X-ray diffraction and Auger electron spectroscopy

Silicide formation induced by thermal annealing in Ni/Si thin film system has been investigated using glancing incidence X-ray diffraction (GIXRD) and Auger electron spectroscopy (AES). Silicide formation takes place at 870 K with Ni₂Si, NiSi and NiSi₂ phases co-existing with Ni. Complete conversion of intermediate silicide phases to the final NiSi₂ phase takes place at 1170 K. Atomic force microscopy measurements have revealed the coalescence of pillar-like structures to ridge-like structures upon silicidation. A comparison of the experimental results in terms of the evolution of various silicide phases is presented.     

AES and factor analysis study of silicide growth at the Pd/c-Si interface

We have measured the evolution of a palladium/silicon interface under consecutive annealing periods, performed at 200°C in UHV conditions. The interface was analyzed by means of Auger electron spectroscopy combined with factor analysis applied in a sequential way. We found that silicide appears only after annealing and evolves until all the palladium is consumed. A silicon compound different from silicide, identified as Pd_xSi with x<2 is found at the interface Pd/Si and Pd₂Si/Si, before and after annealing respectively.     

Magnetic-dichroism study of iron silicides formed at the Fe/Si(100) interface

The interplay between the phase composition, electronic structure, and magnetic properties of the Fe/Si(100)2×1 interface has been studied at the initial stages of its formation (at Fe doses up to 8 Å). The experiments were carried out in ultra high vacuum by using high-resolution photoelectron spectroscopy with synchrotron radiation. The interface magnetic properties were examined in terms of magnetic linear dichroism in angle-resolved Fe 3p core-level photoemission. It was found that at room temperature a disordered Fe–Si solid solution is formed at the first stage of Fe deposition (≤3.4 Å). In the coverage range of 3.4–4.3 Å the solid solution transforms into Fe₃Si. However, the in-plane ferromagnetic ordering of the silicide occurs only at 6.8 Å Fe that demonstrates the thickness dependence of the magnetic properties of Fe₃Si. The subsequent sample annealing to 150°C transforms Fe₃Si to ε-FeSi, leading to the disappearance of ferromagnetic behavior.     

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.     

Study of ultrathin iron silicide films grown by solid phase epitaxy on the Si(001) surface

Ultrathin films of iron silicide have been grown by high-temperature annealing of 0.14-to O.5O-nm-thick Fe films deposited on the Si(001) surface at room temperature. It has been found that annealing leads to the formation of nanoislands of iron silicide on the surface, so that their type depends on the thickness of the Fe film. High-energy electron diffraction and atomic force microscopy measurements have revealed that the deposition of Fe films less than 0.32 nm thick on the Si(001) surface stimulates epitaxial growth of both three-dimensional β-FeSi₂ and two-dimensional γ-FeSi₂ islands. It has been found that, for Fe coverages of more than 0.32 nm thick, a complete transition to solide phase epitaxy is observed only for two-dimensional β-FeSi₂ islands. The effect of prolonged annealing at 850°C on the morphology of the surface of the iron silicide film has been investigated.     

The role of phase separation for self-organized surface pattern formation by ion beam erosion and metal atom co-deposition

We investigate the ripple pattern formation on Si surfaces at room temperature during normal incidence ion beam erosion under simultaneous deposition of different metallic co-deposited surfactant atoms. The co-deposition of small amounts of metallic atoms, in particular Fe and Mo, is known to have a tremendous impact on the evolution of nanoscale surface patterns on Si. In previous work on ion erosion of Si during co-deposition of Fe atoms, we proposed that chemical interactions between Fe and Si atoms of the steady-state mixed Fe _x Si surface layer formed during ion beam erosion is a dominant driving force for self-organized pattern formation. In particular, we provided experimental evidence for the formation of amorphous iron disilicide. To confirm and generalize such chemical effects on the pattern formation, in particular the tendency for phase separation, we have now irradiated Si surfaces with normal incidence 5 keV Xe ions under simultaneous gracing incidence co-deposition of Fe, Ni, Cu, Mo, W, Pt, and Au surfactant atoms. The selected metals in the two groups (Fe, Ni, Cu) and (W, Pt, Au) are very similar regarding their collision cascade behavior, but strongly differ regarding their tendency to silicide formation. We find pronounced ripple pattern formation only for those co deposited metals (Fe, Mo, Ni, W, and Pt), which are prone to the formation of mono and disilicides. In contrast, for Cu and Au co-deposition the surface remains very flat, even after irradiation at high ion fluence. Because of the very different behavior of Cu compared to Fe, Ni and Au compared to W, Pt, phase separation toward amorphous metal silicide phases is seen as the relevant process for the pattern formation on Si in the case of Fe, Mo, Ni, W, and Pt co-deposition.     

Surfactant-mediated growth of CoSi2 on Si(100)

Thin co-deposited CoSi₂ films grown at 500–600°C on Si(100) are studied by scanning tunneling microscopy (STM). With a Si rich deposition we observe initially the formation of elongated three-dimensional CoSi₂ islands. The use of one preadsorbed atomic layer of As as a surfactant results in a drastic increase of the island density. This effect appears to be a consequence of a decreased rate of surface diffusion of Co and Si. At higher coverages the roughness of the CoSi₂ film is reduced considerably by the surfactant. The results are discussed with regard to the method of allotaxy which allows the fabrication of buried silicide layers. Here, the requirements for small precipitates and high growth temperature can possibly be met more efficiently using As as a surfactant.     

Role of buried ultra thin interlayer silicide on the growth of Ni film on Si(100) substrate

The presence of a buried, ultra-thin amorphous interlayer in the interface of room temperature deposited Ni film with a crystalline Si(100) substrate has been observed using cross sectional transmission electron microscopy (XTEM). The electron density of the interlayer silicide is found to be 2.02 e/?³ by specular X-ray reflectivity (XRR) measurements. X-ray diffraction (XRD) is used to investigate the growth of deposited Ni film on the buried ultra-thin silicide layer. The Ni film is found to be highly textured in an Ni(111) plane. The enthalpy of formation of the Ni/Si system is calculated using Miedema’s model to explain the role of amorphous interlayer silicide on the growth of textured Ni film. The local temperature of the interlayer silicide is calculated using enthalpy of formation and the average heat capacity of Ni and Si. The local temperature is around 1042 K if the interlayer compound is Ni₃Si and the local temperature is 1389 K if the interlayer compound is Ni₂Si. The surface mobility of the further deposited Ni atoms is enhanced due to the local temperature rise of the amorphous interlayer and produced highly textured Ni film. Received: 2 March 2000 / Accepted: 28 March 2000 / Published online: 11 May 2000     

Formation of the Co/Si(110) interface: Phase composition and magnetic properties

The formation of the Co/Si(110)16 × 2 interface and its magnetic properties are studied by high-energy-resolution photoelectron spectroscopy using synchrotron radiation and magnetic linear dichroism in the photoemission of core electrons. It is shown that a cobalt coating less than 7 Å thick deposited on the silicon surface at room temperature results in the formation of an ultrathin (1.7 Å) interfacial cobalt silicide layer and a layer of silicon-cobalt solid solution. The ferromagnetic ordering of the interface is observed at an evaporation dose corresponding to 6–7 Å in which case a cobalt metal film begins to grow on the solid solution layer. During 300°C-annealing of the sample covered by a nanometer-thick cobalt layer, the metal film gradually disappears and four silicide phases arise: metastable ferromagnetic silicide Co₃Si and three stable nonmagnetic silicides (Co₂Si, CoSi, and CoSi₂).