Influence of alloying elements on the phase formation of ultrathin Ni (<10nm) on Si(001) substrates

The influence of Ni thickness on the formation of Nickel silicides was systematically investigated between 0 and 15nm. Annealing thickness gradients distinguishes films that agglomerate (>5nm) and films that are morphologically stable (<5nm). Alloying the initial Ni layer influences this critical thickness to higher (Al, Co) and lower (Ge, Pd, Pt) values. Pole figures and in situ XRD provides information to understand this observed shift in critical thickness

Impurity-enhanced solid-state amorphization : the Ni-Si thin film reaction altered by nitrogen

Solid-state amorphization, the growth of an amorphous phase during annealing, has been studied in a wide variety of thin film structures. Whereas research on the remarkable growth of such a metastable phase has mostly focused on strictly binary systems, far less is known about the influence of impurities on such reactions. In this paper, the influence of nitrogen, introduced via ion implantation, is studied on the solid-state amorphization reaction of thin (35 nm) Ni films with Si, using in situ x-ray diffraction (XRD), ex situ Rutherford backscattering spectrometry, XTEM, and synchrotron XRD. It is shown that due to small amounts of nitrogen (<2 at.%), an amorphous Ni-Si phase grows almost an order of magnitude thicker during annealing than for unimplanted samples. Nitrogen hinders the nucleation of the first crystalline phases, leading to a new reaction path: the formation of the metal-rich crystalline silicides is suppressed in favour of an amorphous Ni-Si alloy; during a brief temperature window between 330 and 350 degrees C, the entire film is converted to an amorphous phase. The first crystalline structure to grow is the orthorhombic NiSi phase. We demonstrate that this impurity-enchanced solid-state amorphization reaction occurs only under specific implantation conditions. In particular, the initial distribution of nitrogen upon implantation is crucial: sufficient nitrogen impurities must be present at the interface throughout the reaction. Introducing implantation damage without nitrogen impurities (e.g. by implanting a noble gas) does not cause the enhanced solid-state amorphization reaction. Moreover, we show that the stabilizing effect of nitrogen on amorphous Ni-Si films (with a composition ranging from 40% to 50% Si) is not restricted to thin film reactions, but is a general feature of the Ni-Si system

Low energy ion-solid interactions: a quantitative experimental verification of binary collision approximation simulations

Ultra-low energy ion implantation has become an attractive method for doping of two-dimensional materials and ultra-thin films. The new dynamic Monte Carlo program IMINTDYN based on the binary collision approximation allows a reliable prediction of low energy implantation profiles and target compositional changes, as well as efficient simulation of high energy light ion scattering. To demonstrate the quality of these predictions and simulations, we present a model case experiment where we implanted W ions into tetrahedral amorphous carbon with low (10 keV) and ultra-low (20 eV) ion energies and analyzed the W implantation profiles with high resolution Rutherford backscattering spectrometry (HR-RBS). This experiment is compared with a complete simulation of all aspects of ion-solid-interactions of the experiment using the new IMINTDYN program. A unique novel simulation option, also relevant for implantation into 2D materials, is the inclusion of the vacancy as target species with dynamic vacancy generation and annihilation. Whereas simulations neglecting vacancy formation cannot reproduce the measured implantation profiles, we find excellent agreement between simulated and measured HR-RBS spectra. We also demonstrate the important role of simultaneous weak collisions in the binary collision approximation at low projectile energies

The influence of Al alloying on silicide formation, morphology and texture between a thin (<20 nm) Ni film and Si(001)

The influence of Al on the phase formation between Ni and Si(001) was investigated by altering the Al concentration and the Ni thickness. In a first series of samples, 20 nm Ni on a Si (001) substrate was alloyed between 0 and 50 at. % Al. The phase formation was examined during heating by sheet resistance and XRD. Small additions of Al (0- 28%) in the Ni layer result in a mono-silicide layer. Polefigure measurements indicate that the axiotaxial texture of NiSi is less prominent and that the grain size is smaller when compared with silicides originating from pure Ni. When heated to higher temperatures, these samples form an epitaxial layer, identified as NiSi2. Without the addition of Al, NiSi2 is known to grow in two epitaxial orientations. When Al is added, the orientation defined by NiSi2(12̄2)//Si(001) and NiSi2(11̄0)//Si(101) is hindered, possibly causing a smoother interface with the Si substrate. Adding more than 30 at.% of Al results in a highly different phase formation where no NiSi formation could be observed. A second series of samples investigated the addition of Al for Ni films thinner than 10 nm. Ultrathin Ni layers are known to react directly into an epitaxial NiSi2 phase without first forming NiSi. When alloyed with Al, the critical thickness for this phenomenon to occur is elevated from 4-5 nm to 8 nm, indicating that the addition of Al is beneficial for the growth of epitaxial NiSi2

Phase formation in intermixed Ni-Ge thin films: Influence of Ge content and low-temperature nucleation of hexagonal nickel germanides

In this study, we focus on phase formation in intermixed Ni-Ge thin films as they represent a simplified model of the small intermixed interface layer that is believed to form upon deposition of Ni on Ge and where initial phase formation happens. A combinatorial sputter deposition technique was used to co-deposit a range of intermixed Ni-Ge thin films with Ge concentrations varying between 0 and 50 at.%Ge in a single deposition on both Ge (100) and inert SiO2 substrates. In situ X-ray diffraction and transmission electron microscopy where used to study phase formation. In almost the entire composition range under investigation, crystalline phases where found to be present in the as-deposited films. Between 36 and 48 at.%Ge, high-temperature hexagonal nickel germanides were found to occur metastabily below 300 °C, both on SiO 2 and Ge (100) substrates. For Ge concentrations in the range between 36 and 42 at.%, this hexagonal germanide phase was even found to be present at room temperature in the as-deposited films. The results obtained in this work could provide more insight in the phase sequence of a pure Ni film on Ge. © 2013 Elsevier B.V. All rights reserved.publisher: Elsevier articletitle: Phase formation in intermixed Ni–Ge thin films: Influence of Ge content and low-temperature nucleation of hexagonal nickel germanides journaltitle: Microelectronic Engineering articlelink: http://dx.doi.org/10.1016/j.mee.2013.09.004 content_type: article copyright: Copyright © 2013 Elsevier B.V. All rights reserved.status: publishe

A case study of ALD encapsulation of quantum dots: embedding supported CdSe/CdS/ZnS quantum dots in a ZnO matrix

We study the encapsulation of monolayers of CdSe/CdS/ZnS core/shell/shell quantum dots (QDs) in a ZnO matrix by atomic layer deposition (ALD) in order to gain insight in the interaction between quantum dots and ALD precursors and the resulting metal oxide coating. Using in situ XRF and GISAXS, we show the inhibition of ZnO growth on as-deposited QDs. Growth can, however, be triggered by exposing the QDs to a single pulse of trimethylaluminum (TMA) vapor. Such a TMA pretreatment results in the substitution of 35-40% of the surface Zn by Al. Whereas this drops by half the photoluminescence quantum yield of the QDs, we argue that this replacement primes the QD monolayer for ZnO growth by ALD. Finally, the evolution of the GISAXS pattern during subsequent ALD growth attests the preservation of the ordering of the QDs in the monolayer. These results illustrate the important interplay between highly reactive ALD precursors and the QD surface

Controlling the formation and stability of ultra-thin nickel silicides - An alloying strategy for preventing agglomeration

© 2018 Author(s). The electrical contact of the source and drain regions in state-of-the-art CMOS transistors is nowadays facilitated through NiSi, which is often alloyed with Pt in order to avoid morphological agglomeration of the silicide film. However, the solid-state reaction between as-deposited Ni and the Si substrate exhibits a peculiar change for as-deposited Ni films thinner than a critical thickness of tc = 5 nm. Whereas thicker films form polycrystalline NiSi upon annealing above 450 ° C, thinner films form epitaxial NiSi2 films that exhibit a high resistance toward agglomeration. For industrial applications, it is therefore of utmost importance to assess the critical thickness with high certainty and find novel methodologies to either increase or decrease its value, depending on the aimed silicide formation. This paper investigates Ni films between 0 and 15 nm initial thickness by use of "thickness gradients," which provide semi-continuous information on silicide formation and stability as a function of as-deposited layer thickness. The alloying of these Ni layers with 10% Al, Co, Ge, Pd, or Pt renders a significant change in the phase sequence as a function of thickness and dependent on the alloying element. The addition of these ternary impurities therefore changes the critical thickness tc. The results are discussed in the framework of classical nucleation theory.status: publishe

Interplay between relaxation and Sn segregation during thermal annealing of GeSn strained layers

© 2016 Author(s). The effect of thermal annealing on epitaxial GeSn (6.5% Sn) strained layers grown on Ge-buffered Si(100) wafers has been investigated using Rutherford backscattering spectrometry and X-ray diffraction to unambiguously determine the Sn substitutional content as well as the elastic strain in the layers. Vacuum annealing at temperatures below 400 °C for 20 min has no noticeable effect on the strain in the epitaxial layers. Once the temperature was raised above 400 °C, however, relaxation of the layer sets in and the GeSn layer has essentially completely relaxed following a 20 min anneal at 650 °C. Using Rutherford backscattering and channelling spectrometry to provide compositional information as a function of depth enables one to monitor the effect of the thermal anneal on the Sn distribution throughout the layer, and also to directly extract their substitutional fraction (i.e., their solubility in the lattice). The results obtained show that when the relaxation initially sets in both the Ge and the Sn remain firmly bound in substitutional lattice sites and it is only around 600 °C, and after substantial relaxation has taken place, that Sn is finally expelled from lattice sites and diffuses to the surface of the sample.status: publishe

A Case Study of ALD Encapsulation of Quantum Dots: Embedding Supported CdSe/CdS/ZnS Quantum Dots in a ZnO Matrix

© 2016 American Chemical Society. We study the encapsulation of monolayers of CdSe/CdS/ZnS core/shell/shell quantum dots (QDs) in a ZnO matrix by atomic layer deposition (ALD) in order to gain insight in the interaction between quantum dots and ALD precursors and the resulting metal oxide coating. Using in situ XRF and GISAXS, we show the inhibition of ZnO growth on as-deposited QDs. Growth can, however, be triggered by exposing the QDs to a single pulse of trimethylaluminum (TMA) vapor. Such a TMA pretreatment results in the substitution of 35-40% of the surface Zn by Al. Whereas this drops by half the photoluminescence quantum yield of the QDs, we argue that this replacement primes the QD monolayer for ZnO growth by ALD. Finally, the evolution of the GISAXS pattern during subsequent ALD growth attests the preservation of the ordering of the QDs in the monolayer. These results illustrate the important interplay between highly reactive ALD precursors and the QD surface.status: publishe