Search

International audience; The growth of ZnTe nanowires and ZnTe-CdTe nanowire heterostructures is studied by \emph{in situ} transmission electron microscopy. We describe the shape, and the change of shape, of the solid gold nanoparticle during vapor-solid-solid growth. We show the balance between one-monolayer and two-monolayer steps which characterizes the vapor-liquid-solid and vapor-solid-solid growth modes of ZnTe. We discuss the likely role of the mismatch strain and lattice coincidence between gold and ZnTe on the predominance of two-monolayer steps during vapor-solid-solid growth, and on the subsequent self-regulation of the step dynamics. Finally, the formation of an interface between CdTe and ZnTe is described.

Thermal decomposition of GaAs nanowires is investigated. Radially it is faster for zinc-blende, due to nano-faceted sidewalls. In contrast, wurtzite forms stable single-faceted sidewalls with decomposition only via step-flow from the tip.

International audience; In this paper, we followed the formation sequences of the different manganese silicides by performing simple annealing at different temperatures of the deposited manganese (Mn) on silicon (Si) substrate. Phase change and transition temperatures have been reported. In situ x-ray diffraction (XRD) is used in two different chambers and the results obtained are presented in 3D figures. The surface roughness is first obtained by atomic force microscopy (AFM) and then by scanning electron microscopy (SEM) characterization. The latter is also used for the detection of the different superimposed layers after the formation of the different silicides obtained in the solid phase reaction (SPR). Focus ion beam (FIB) cuts were used to analyze the different layers obtained during silicide formation at these temperatures. In this study, we have obtained Mn15Si26 for high temperatures (above 850°C). Finally, an epitaxy of HMS (Mn15Si26) is obtained at high temperatures with a simple annealing process.

This work reports experiments on the oriented growth by electric field of free-standing carbon nanotubes(CNTs) by chemical vapor deposition (CVD) for field emission (FE) applications. The growths were observed in a scanning electron microscope (SEM) and in an environmental transmission electron microscope (ETEM) with the ETEM growths observed in real time. The effects of various applied voltage during growth will be presented. For high voltages, videos show that the maximum length of CNTs are limited either by the mechanical breakdown or FE induced thermal evaporation. Finally, the I(V) curves and current densities obtained will be presented with a focus on the different destruction mechanisms.

International audience; The growth of catalytic liquid metal nanodroplets on flat substrates is essential for many technological applications. However, the detailed nucleation and growth dynamics of these nanodroplets remains unclear. Here, using in situ Transmission Electron Microscopy (TEM) imaging, we track in real-time the growth of individual Ga nanodroplets from a beam of Ga vapor. We show that the nucleation and growth are driven by thermally-activated surface diffusion of Ga adatoms, with the diffusion activation energy of E_D=95±10 meV on a SiNx surface. More importantly, our analysis shows that Ga-dimers serve as the critical nucleation clusters and that the nanodroplet growth follows a power-law of form R(t)∝〖e^(〖-E〗_D⁄(k_B T)) (t-t_0 )〗^(1⁄2). These insights into the growth dynamics of metallic nanodroplets are essential for tailoring their size and density for their application in self-catalyzed growth of nanomaterials.

International audience; The first stages of the growth of the NiSi phase at the expense of θ-Ni2Si have been studied mainly by in-situ XRD measurements and atom probe tomography (APT) analysis. In-situ XRD isothermal annealing at different temperatures were performed on several samples in order to monitor the phase formation sequence, the time at which NiSi phase begin to form and its growth kinetics. These results show that while the phase formation sequence is the same, the time for the beginning of formation of NiSi varies from one sample to the other under the same isothermal temperature and experimental conditions. Comparing these findings with nucleation and growth models, the growth of the NiSi phase at the expense of θ-Ni2Si is controlled by nucleation compared to diffusion in the case of δ-Ni2Si as the first phase. The kinetics for the nucleation and lateral growth of the NiSi phase were deduced and the implications for the formation of this phase and for contacts are discussed.

Correlating the structure and composition of nanowires grown by the vapour-liquid-solid (VLS) mechanism with their electrical properties is essential for designing nanowire devices. In situ transmission electron microscopy (TEM) that can image while simultaneously measuring the current–voltage (I–V) characteristics of individual isolated nanowires is a unique tool for linking changes in structure with electronic transport. Here we grow and electrically connect silicon nanowires inside a TEM to perform in situ electrical measurements on individual nanowires both at high temperature and upon surface oxidation, as well as under ambient conditions. As-grown, the oxide-free nanowires have nonlinear I–V characteristics. We analyse the I–V measurements in terms of both bulk and injection limited transport models, finding Joule heating effects, bulk-limiting effects for thin nanowires and an injection-limiting effect for thick wires when high voltages are applied. When the nanowire surface is modified by in situ oxidation, drastic changes occur in the electronic properties. We investigate the relation between the observed geometry, changes in the surface structure and changes in electronic transport, obtaining information for individual nanowires that is inaccessible to other measuring techniques.

Crystal phase switching between the zincblende and wurtzite structures in III-V nanowires is crucial from the fundamental viewpoint as well as for electronic and photonic applications of crystal phase heterostructures. Here, the results of in situ monitoring of self-catalyzed vapor-liquid-solid growth of GaAs nanowires by molecular beam epitaxy inside a transmission electron microscope are presented. It is demonstrated that the occurrence of the zincblende or wurtzite phase in self-catalyzed nanowires is determined by the sole parameter, the droplet contact angle, which can be finely tuned by changing the group III and V fluxes. The zincblende phase forms at small (100°) and large (125°) contact angles, whereas pure wurtzite phase is observed for intermediate contact angles. Wurtzite nanowires are restricted by vertical sidewalls, whereas zincblende nanowires taper or develop the truncated edge at their top. These findings are explained within a dedicated model for the surface energetics. These results give a clear route for the crystal phase control in Au-free III-V nanowires. On a more general note, in situ growth monitoring with atomic resolution and at the technological-relevant growth rates is shown to be a powerful tool for the fine-tuning of material properties at the nanoscale.

International audience; Silicon germanium (SixGe1–x or SiGe) is an important semiconductor material for the fabrication of nanowire-based gate-all-around transistors in the next-generation logic and memory devices. During the fabrication process, SiGe can be used either as a sacrificial layer to form suspended horizontal Si nanowires or, because of its higher carrier mobility, as a possible channel material that replaces Si in both horizontal and vertical nanowires. In both cases, there is a pressing need to understand and develop nanoscale etching processes that enable controlled and selective removal of SiGe with respect to Si. Here, we developed and tested solution-based selective etching processes for SiGe in composite (SiNx/Si0.75Ge0.25/Si) vertical nanowires. The etching solutions were formed by mixing acetic acid (CH3COOH), hydrogen peroxide (H2O2), and hydrofluoric acid (HF). Here, CH3COOH and H2O2 react to form highly oxidizing peracetic acid (PAA or CH3 CO3H). The hydrofluoric acid serves both as a catalyst for PAA formation and as an etchant for oxidized SiGe. Our study shows that an increase in any of the two oxidizer (H2O2 and PAA) concentrations increases the etch rate, and the fastest etch rate of SiGe is associated with the highest PAA concentration. Moreover, using in situ liquid-phase TEM imaging, we tested the stability of nanowires during wet etching and identified the SiGe/Si interface to be the weakest plane; we found that once the diameter of the 160-nm-tall Si0.75Ge0.25 nanowire reaches ∼15 nm during the etching, the nanowire breaks at or very close to this interface. Our study provides important insight into the details of the nanoscale wet etching of SiGe and some of the associated failure modes that are becoming extremely relevant for the fabrication processes as the size of the transistors shrink with every new device generation.

International audience; In situ transmission electron microscopy reveals that an atomically thin crystalline phase at the surface of liquid Au–Si is stable over an unexpectedly wide range of conditions. By measuring the surface structure as a function of liquid temperature and composition, a simple thermodynamic model is developed to explain the stability of the ordered phase. The presence of surface ordering plays a key role in the pathway by which the Au–Si eutectic solidifies and also dramatically affects the catalytic properties of the liquid, explaining the anomalously slow growth kinetics of Si nanowires at low temperature. A strategy to control the presence of the surface phase is discussed, using it as a tool in designing strategies for nanostructure growth.

International audience; The droplet contact angle and morphology of the growth interface (vertical, tapered or truncated facets) are known to affect the zincblende (ZB) or wurtzite (WZ) crystal phase of III–V nanowires (NWs) grown by the vapor-liquid-solid method. Here, we present a model which describes the dynamics of the morphological evolution in self-catalyzed III–V NWs in terms of the time-dependent (or length-dependent) contact angle or top nanowire radius under varying material fluxes. The model fits quite well the contact angle dynamics obtained by in situ growth monitoring of self-catalyzed GaAs NWs in a transmission electron microscope. These results can be used for modeling the interface dynamics and the related crystal phase switching and for obtaining ZB-WZ heterostructures in III–V.

Crystal growth often proceeds by atomic step flow. When the surface area available for growth is limited, the nucleation and progression of the steps can be affected. This issue is particularly relevant to the formation of nanocrystals. We examine the case of Au-catalyzed GaAs nanowires, which we grow in a transmission electron microscope. Our in situ observations show that atomic layers nucleate at the periphery of the interface between the nanowire and the catalyst droplet. From this starting location, the atomic step flows within a restricted area of hexagonal shape. At specific partial coverages, the monolayer configuration changes abruptly. A simple model based on the geometry of the system and its edge energies explains these observations. In particular, we observe an inversion of the step curvature which reveals that the effective energy per unit length of monolayer edge is much lower at the interface periphery than inside the catalyst droplet.

cited By 0; International audience; The nucleation and lateral growth are more and more important steps for the thin film growth of a phase (silicide, intermetallic…) when the thin film thickness is in the range or below 10 nm. It might become crucial for contact in microelectronics that are in this range of thickness for actual devices and affect the properties of contacts in different parts of the devices. For reaction between 10 nm Ni(10%Pt) and (100)Si, it was shown that NiSi grows by nucleation and lateral growth at the epitaxial θ-Ni2Si/Si interface and forms precipitates having a large aspect ratio (large diameter and small thickness) were observed. In this work, the precipitate shape as well as the shape of the different interfaces close to the triple line are reproduced by using the model of Pasichnyy and Gusak for θ-Ni2Si/Si interfaces that are either curved or straight. The deduced interfacial energies and kinetics parameters enabling to obtain the characteristics of the precipitates are discussed and compared to the ones obtained by the model of El Kousseifi et al. The conditions for mechanical equilibrium and the implication for the contact formation are discussed. © 2018 Elsevier B.V.

International audience

Ni silicides used as contacts in source/drain and gate of advanced CMOS devices were analyzed by atom probe tomography (APT) at atomic scale. These measurements were performed on 45 nm nMOS after standard self-aligned silicide (salicide) process using Ni(5 at.% Pt) alloy. After the first annealing (RTA1), δ-Ni 2 Si was the only phase formed on gate and source/drain while, after the second annealing (RTA2), two different Ni silicides have been formed: NiSi on the gate and δ-Ni 2 Si on the source and drain. This difference between source/drain and gate regions in nMOS devices has been related to the Si substrate nature (poly or mono-crystalline) and to the size of the contact. In fact, NiSi seems to have difficulties to nucleate in the narrow source/drain contact on mono-crystalline Si. The results have been compared to analysis performed on 28 nm nMOS where the Pt concentration is higher (10 at.% Pt). In this case, θ-Ni 2 Si is the first phase to form after RTA1 and NiSi is then formed at the same time on source (or drain) and gate after RTA2. The absence of the formation of NiSi from δ-Ni 2 Si/Si(1 0 0) interface compared to θ-Ni 2 Si/Si(1 0 0) interface could be related to the difference of the interface energies. The redistributions of As and Pt in different silicides and interfaces were measured and discussed. In particular, it has been evidenced that Pt redistributions obtained on both 45 and 28 nm MOS transistors correspond to respective Pt distributions measured on blanket wafers.

In microelectronics, the increase in complexity and the reduction of devices dimensions make essential the development of new characterization tools and methodologies. Indeed advanced characterization methods with very high spatial resolution are needed to analyze the redistribution at the nanoscale in devices and interconnections. The atom probe tomography has become an essential analysis to study materials at the nanometer scale. This instrument is the only analytical microscope capable to produce 3D maps of the distribution of the chemical species with an atomic resolution inside a material. This technique has benefit from several instrumental improvements during last years. In particular, the use of laser for the analysis of semiconductors and insulating materials offers new perspectives for characterization. The capability of APT to map out elements at the atomic scale with high sensitivity in devices meets the characterization requirements of semiconductor devices such as the determination of elemental distributions for each device region. In this paper, several examples will show how APT can be used to characterize and understand materials and process for advanced metallization. The possibilities and performances of APT (chemical analysis of all the elements, atomic resolution, planes determination, crystallographic information…) will be described as well as some of its limitations (sample preparation, complex evaporation, detection limit, …). The examples illustrate different aspect of metallization: dopant profiling and clustering, metallic impurities segregation on dislocation, silicide formation and alloying, high K/metal gate optimization, SiGe quantum dots, as well as analysis of transistors and nanowires.

The reaction between an 11 nm Ni(10 at.% Pt) film on a Si substrate has been examined by in situ X-ray diffraction (XRD), atom probe tomography (APT) and transmission electron microscopy (TEM). In situ XRD experiments show the unusual formation of a phase without an XRD peak through consumption of the metal. According to APT, this phase has an Si concentration gradient in accordance with the θ-Ni2Si metastable phase. TEM analysis confirms the direct formation of θ-Ni2Si in epitaxy on Si(1 0 0) with two variants of the epitaxial relationship.

Metallic silicides have been used as contact materials on source/drain and gate in metal-oxide semiconductor (MOS) structure for 40 years. Since the 65 nm technology node, NiSi is the preferred material for contact in microelectronic due to low resistivity, low thermal budget, and low Si consumption. Ni(Pt)Si with 10 at.% Pt is currently employed in recent technologies since Pt allows to stabilize NiSi at high temperature. The presence of Pt and the very low thickness (

International audience

Atom probe tomography was used to study the redistribution of platinum during Ni(10at.%Pt) silicidation of n-doped polycrystalline Si. These measurements were performed after the two annealing steps of standard salicide process both on a field-effect transistor and on unpatterned region submitted to the same process. Very similar results are obtained in unpatterned region and in transistor gate contact. The first phase to form is not the expected @d-Ni"2Si but the non stoichiometric @q-Ni"2Si. Pt redistribution is strongly influenced by this phase and the final distribution is different from what is reported in literature.

Different FIB-based sample preparation methods for atom probe analysis of transistors have been proposed and discussed. A special procedure, involving device deprocessing, has been used to analyze by APT a sub-30nm transistor extracted from a SRAM device. The analysis provides three dimensional compositions of Ni-silicide contact, metal gate and high-k oxide of the transistor gate.

We visualize atomic level dynamics during Si nanowire growth using aberration corrected environmental transmission electron microscopy, and compare with lower pressure results from ultra-high vacuum microscopy. We discuss the importance of higher pressure observations for understanding growth mechanisms and describe protocols to minimize effects of the higher pressure background gas.

Controlled formation of non-equilibrium crystal structures is one of the most important challenges in crystal growth. Catalytically grown nanowires are ideal systems for studying the fundamental physics of phase selection, and could lead to new electronic applications based on the engineering of crystal phases. Here we image gallium arsenide (GaAs) nanowires during growth as they switch between phases as a result of varying growth conditions. We find clear differences between the growth dynamics of the phases, including differences in interface morphology, step flow and catalyst geometry. We explain these differences, and the phase selection, using a model that relates the catalyst volume, the contact angle at the trijunction (the point at which solid, liquid and vapour meet) and the nucleation site of each new layer of GaAs. This model allows us to predict the conditions under which each phase should be observed, and use these predictions to design GaAs heterostructures. These results could apply to phase selection in other nanowire systems.

The formation of self-assembled contacts between vapor-liquid-solid grown silicon nanowires and flat silicon surfaces was imaged in situ using electron microscopy. By measuring the structural evolution of the contact formation process, we demonstrate how different contact geometries are created by adjusting the balance between silicon deposition and Au migration. We show that electromigration provides an efficient way of controlling the contact. The results point to novel device geometries achieved by direct nanowire growth on devices.

Nanowire growth by the vapour-liquid-solid (VLS) process enables a high level of control over nanowire composition, diameter, growth direction, branching and kinking, periodic twinning, and crystal structure. The tremendous impact of VLS-grown nanowires is due to this structural versatility, generating applications ranging from solid-state lighting and single-photon sources to thermoelectric devices. Here, we show that the morphology of these nanostructures can be further tailored by using the liquid droplets that catalyse nanowire growth as a 'mixing bowl', in which growth materials are sequentially supplied to nucleate new phases. Growing within the liquid, these phases adopt the shape of faceted nanocrystals that are then incorporated into the nanowires by further growth. We demonstrate this concept by epitaxially incorporating metal-silicide nanocrystals into Si nanowires with defect-free interfaces, and discuss how this process can be generalized to create complex nanowire-based heterostructures.

The Ni silicide formed at low temperature on Si nanowire has been analyzed by atom probe tomography (APT) thanks to a special technique for sample preparation. A method of preparation has been developed using the focused ion beam (FIB) for the APT analysis of nanowires (NWs). This method allow for the measurement of the radial distribution when a NW is cut, buried in a protective metal matrix, and finally mounted on the APT support post. This method was used for phosphorous doped Si NWs with or without a silicide shell, and allows obtaining the concentration and distribution of chemical elements in three-dimensions (3D) in the radial direction of the NWs. The distribution of atoms in the NWs has been measured including dopants and Au contamination. These measurements show that δ-Ni2Si phase is formed on Si NW, Au is found as cluster at the Ni/δ-Ni2Si interface and P is segregated at the δ-Ni2Si/ Si NW interface. The results obtained on NWs after silicidation were compared with the silicide on the Si substrate, showing that the same silicide phase δ-Ni2Si formed in both cases (NWs and substrate).

In this study, TiN/La2O3/HfSiON/SiO2/Si gate stacks with thick high-k (HK) and thick pedestal oxide were used. Samples were annealed at different temperatures and times in order to characterize in detail the interaction mechanisms between La and the gate stack layers. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurements performed on these samples show a time diffusion saturation of La in the high-k insulator, indicating an La front immobilization due to LaSiO formation at the high-k/interfacial layer. Based on the SIMS data, a technology computer aided design (TCAD) diffusion model including La time diffusion saturation effect was developed.

The redistribution of fluorine during solid phase epitaxial regrowth (SPER) of preamorphized Si has been experimentally investigated, explained, and simulated, for different F concentrations and temperatures. We demonstrate, by a detailed analysis and modeling of F secondary ion mass spectrometry chemical-concentration profiles, that F segregates in amorphous Si during SPER by splitting in three possible states: (i) a diffusive one that migrates in amorphous Si; (ii) an interface segregated state evidenced by the presence of a F accumulation peak at the amorphous-crystal interface; (iii) a clustered F state. The interplay among these states and their roles in the F incorporation into crystalline Si are fully described. It is shown that diffusive F migrates by a trap limited diffusion mechanism and also interacts with the advancing interface by a sticking-release dynamics that regulates the amount of F segregated at the interface. We demonstrate that this last quantity determines the regrowth rate through an exponential law. On the other hand we show that neither the diffusive F nor the one segregated at the interface can directly incorporate into the crystal but F has to cluster in the amorphous phase before being incorporated in the crystal, in agreement with recent experimental observations. The trends of the model parameters as a function of the temperature are shown and discussed obtaining a clear energetic scheme of the F redistribution and incorporation in preamorphized Si. The above physical understanding and the model could have a strong impact on the use of F as a tool for optimizing the doping profiles in the fabrication of ultrashallow junctions.

The fluorine redistribution during partial solid-phase-epitaxial-regrowth at 650 degrees C of a preamorphized Si substrate implanted by F was investigated by atom probe tomography (APT), transmission electron microscopy, and secondary ions mass spectrometry. Three-dimensional spatial distribution of F obtained by APT provides a direct observation of F-rich clusters with a diameter of less than 1.5 nm. Density variation compatible with cavities and F-rich molecular ions in correspondence of clusters are in accordance with cavities filled by SiF4 molecules. Their presence only in crystalline Si while they are not revealed by statistical analysis in amorphous suggests that they form at the amorphous/crystal interface.

The three-dimensional spatial distribution of Al in the high-k metal gates of metal-oxide-semiconductor field-effect-transistors is measured by atom probe tomography. Chemical distribution is correlated with the transistor voltage threshold (VTH) shift generated by the introduction of a metallic Al layer in the metal gate. After a 1050 °C annealing, it is shown that a 2-A thick Al layer completely diffuses into oxide layers, while a positive VTH shift is measured. On the contrary, for thicker Al layers, Al precipitation in the metal gate stack is observed and the VTH shift becomes negative.

Atom probe tomography was used to study the redistribution of platinum and arsenic atoms after Ni(Pt) silicidation of As-doped polycrystalline Si. These measurements were performed on a field-effect transistor and compared with those obtained in unpatterned region submitted to the same process. These results suggest that Pt and As redistribution during silicide formation is only marginally influenced by the confinement in microelectronic devices. On the contrary, there is a clear difference with the redistribution reported in the literature for the blanket wafers. Selective etching used to remove the non-reacted Ni(Pt) film after the first rapid heat treatment may induce this difference.

International audience; We investigated the thermal evolution of end-of-range EOR defects in germanium and their impact on junction thermal stability. After solid-phase epitaxial regrowth of a preamorphized germanium layer, EOR defects exhibiting dislocation loop-like contrast behavior are present. These defects disappear during thermal annealing at 400 ° C, while boron electrical deactivation occurs. After the whole defect population vanishes, boron reactivation is observed. These results indicate that germanium self-interstitials, released by EOR defects, are the cause of B deactivation. Unlike in Si, the whole deactivation/reactivation cycle in Ge is found to take place while the maximum active B concentration exceeds its solubility limit.

International audience; We present a growth process relying on pulsed laser deposition for the elaboration of complex van der Waals heterostructures on large scales, at a 400°C CMOS-compatible temperature. Illustratively, we define a multilayer quantum well geometry through successive in situ growths, leading to WSe2 being encapsulated into WS2 layers. The structural constitution of the quantum well geometry is confirmed by Raman spectroscopy combined with transmission electron microscopy. The large-scale high homogeneity of the resulting 2D van der Waals heterostructure is also validated by macro-and microscale Raman mappings. We illustrate the benefit of this integrative in situ approach by showing the structural preservation of even the most fragile 2D layers once encapsulated in a van der Waals heterostructure. Finally, we fabricate a vertical tunneling device based on these large-scale layers and discuss the clear signature of electronic transport controlled by the quantum well configuration with ab initio calculations in support. The flexibility of this direct growth approach, with multilayer stacks being built in a single run, allows for the definition of complex 2D heterostructures barely accessible with usual exfoliation or transfer techniques of 2D materials. Reminiscent of the III−V semiconductors' successful exploitation, our approach unlocks virtually infinite combinations of large 2D material families in any complex van der Waals heterostructure design.