MODELLO 1

PROGETTO DI RICERCA / PROJECT

COGNOME E NOME CANDIDATO CORSO DI DOTTORATO

1) Titolo del progetto / Project title

A simulation approach to study the mechanical properties of Titanium Nitride.

2) Sommario / Abstract
This report will describe the project proposal for the research program that will lead Yonas Tirffe to the PhD degree at
the University of Milan, including scope, project descriptions and work plan. The main work will be carried out in the
MLMS group at the department of theoretical physics. Although titanium nitride is among the most extensively
studied, a simulation approach to elucidate the detail knowledge of relevant mechanical properties is lacking. In this
PhD project, we intended to study mechanical properties relevant to its industrial application. Experimentally by high-
resolution scanning transmission electron microscopy different types dislocations in the core structure of titanium
nitride were identified. Density functional theory, modified embedded atom method (MEAM) potential and machine
learning interatomic potential simulations will be performed to complement the experimental observations by
recovering the atomic structure of the different dislocation types, estimating Peierls stresses and providing insights on
the chemical bonding nature at the core. A variety of dislocation types in titanium nitride will be considered to
complement experimentally observed nanoscale and macroscopic properties of titanium nitride.

3) Obiettivi e rilevanza dei risultati ottenibili nel contesto dello stato dell’arte / Project aims and their
relevance in the context of the state of the art
The overall objective of this project is to investigate the mechanical properties of titanium nitride that are relevant to
its industrial application. In particular, the dislocation of core structure in titanium nitride due the shear stress on
different plane direction will be studied to identify the preferred slip planes and to suggest an energetically-favored
dislocation types, these dislocations profoundly influence material’s mechanical, chemical, optical electronic
properties and locally modify the atomic and electronic structure which may act as sinks for impurities and vacancies,
thus understanding of the preferred dislocation structures and their cores can potentially be used for improving
ceramic properties and enhance the toughness of materials. The study will be approached theoretically to complement
the experimentally observed dislocation types available in the literature.
4) Descrizione del progetto / Project description
1. Introduction

Crystallographic dislocations are extensively studied, one dimensional defects that extremely influence material’s
mechanical, chemical, optical, and electronic properties [1-4]. Numerically produced elastic deformation and the
conjugated strain fields at the dislocation core locally modify the atomic and electronic structure which may act as
sinks for impurities and vacancies [3] and act as pathways for enhanced mass transport (pipe - diffusion) [5, 6] as a
result of that have influence on macroscopically observed properties. More importantly, the nucleation, motion and
interaction of dislocations govern plastic deformation and is determined by operative slip systems [1, 2]. Such favored
slip systems and other dislocation-related mechanisms are intimately associated to the core structure of its dislocations.
In many aspects, a thorough characterization of dislocation cores at the atomic and electronic structure level is of the
utmost importance for understanding various material’s properties.

Titanium nitride is a well-studied transition metal nitride and is used in hard coating [7, 8], microelectronic [9, 10] and
optical material applications [11]. It is thermally and electrically conductive, wear-resistant, and has a high thermal
stability owing to its rock-salt structure that consists of bonds with mixed ionic, metallic, and covalent character [12-
14]. Because of this, the dislocation structures and slip in titanium nitride are affected by the directional nature of the
bonds near the core [15-17]. Complementary electronic-structure analyses are therefore necessary to probe the effect of
core-induced lattice distortion on the local bonding character. Dislocations are well-studied defects in metals and
semiconductors [18] but only few reports have tried to elucidate the dislocation core structures in ceramics at the
atomic scale [3, 19]. Previous studies

Figure 1. Sole type dislocation core in a silp system[3] and the slab with periodic boundary condition[19]

on dislocations in titanium nitride were based on nanoindentation of single crystal films, or microscopy observations of
polycrystalline samples. Experimentally, it has been observed that the {111}<110> and {110}<110> slip systems are
activated during room-temperature nanoindentation of thin lamellas with respect to the <111> and <100> directions,
respectively [ 20, 21]. The observation of the {111}<110> slip, however, was through nucleation of Shockley partials
during indentation in the [111] direction [13]. Transmission electron microscopy observations of edge dislocations
were also reported for polycrystalline titanium nitride, including the relation between dislocation density and grain
sizes [22]. While perfect {110}<110> edge dislocations and Shockley partial dislocations have been observed
experimentally through controlled deformation, A simulation approach core structure dislocation are less well studied
or not even reported in titanium nitride or other rock-salt carbides and nitrides. Knowledge of the atomic-scale
structure and energetics of these defects is mostly lacking. This is unfortunate since accurate identification and
characterization of different dislocation core structures is important for understanding their effect on macroscopic
properties. For example, the density and mobility of pre-existing dislocations around crack tips and grain boundaries
largely govern plasticity and thus affect the toughness of ceramics [4]. Moreover, studies of preferred dislocation core
structures show that atomic-scale distortions at the core can help to explain a material’s thermal-electric breakdown
[3]. Further, understanding of the preferred dislocation structures and their cores can potentially be used for improving
ceramic properties and performance through dislocation engineering and toughening mechanisms [3, 4, 23]. Detailed
atomic-level characterization of dislocations in titanium nitride by transmission electron microscopy is typically
hindered by high densities of defects, such as interstitials, vacancies, dislocations, and internal interfaces present at
phase and grain boundaries and macro particles present in coatings commonly grown for industrial applications [24].
Figure 2 Cross-sectional HAADF-STEM images and X-ray -2 diffractogram of the sputter-deposited TiN (001) films [b]

In this project, all experimentally observed core structure dislocation types and other energetically-favored core
structure dislocation types in titanium nitride will be studied theoretically based on density functional theory (DFT),
modified embedded atom method (MEAM) potential and machine learning interatomic potential simulations to gain
insight the nature of bonding environment at the dislocation core structure.

2. Methods

Here I will introduce the primary computational tools and techniques which will be employed in this project studies.
These include various supportive molecular tools as well as packages used for computer aided simulations. The
methods are shortly described as well as their specific application in the research.

Calculations of dislocation core structures and their properties will be based on quantum mechanics description in the
framework of density functional theory (DFT) and on classical simulations using the modified embedded atom method
(MEAM) potential [25]. The core structures of different dislocation types, including the experimentally observed
initially generated using the Atomsk code [26]. Thereafter, the atomic positions will be relaxed using the MEAM
potential implemented in the LAMMPS software [27]. The reliability of MEAM model has been proven by
comparison with microscopy observations of titanium-based materials subject to load as well as DFT and ab initio
molecular dynamics simulations of mechanical and thermodynamic properties [28-30]. The dislocation core energies
will be assessed using different supercell configurations. For Peierls stress evaluations, supercells with a sufficiently
large number of atoms which contain an isolated core will be employed. The supercells are periodic only parallel to the
dislocation line. Shear deformation will be incremented up to dislocation glide. The Peierls stress will determined as
the shear stress required to activate dislocation motion. DFT calculations will be carried out using the VASP code
implemented with the projector augmented wave method [31, 32]. Effects of exchange and correlation on one-electron
potentials and total energies will be evaluated using the generalized gradient approximation with the parametrization
by Perdew, Burke, and Ernzerhof [33]. The reciprocal space will be represented by Γ-point sampling. The dislocation
cores obtained by MEAM structural optimization will be used as input into DFT calculations. The supercells
containing around 1200 atoms and will be periodic only along the dislocation line. Relaxation of atomic positions
around the dislocation core (see below) will be iterated up to an accuracy of 10-5 eV/supercell, with forces on atoms
smaller than 0.01 eV/Å. The electronic density of states (DOS) and electron-transfer maps will be calculated for the
relaxed configurations. The latter will be obtained by subtracting the overlapping electron density of non-interacting
atoms from the self-consistent charge density of the relaxed supercells. The effect induced by local lattice distortions
on Ticore - Ncore bond strengths has been assessed by partitioning the wavefunctions into two-center molecular
orbitals [34]. Hence, a DFT-based approach will be employed to extract the overlap population (OP) of Ti - N bonds in
bulk regions and at the dislocation core. The OP is a projection of the DOS into bonding (OP > 0) or antibonding (OP
< 0) interactions between different pairs of atomic orbitals.

3. Schedule/Time of Research

A preliminary time schedule of the project is listed including an outline of the work which will be emphasized.

3.1 Autumn and Winter 2023/24

§ Introduction machine learning interatomic potential simulations.

§ Simulation training, for example using Atomsk code.

§ Computer Script for input files for LAMMPs.

§ Department duties.

3.2 Spring and Summer 2024

§ Courses relevant to the project.

§ Prepare input files.

§ Discussions with coworkers.

§ Participate online conference.

§ Generate dislocation types.

§ LAMMPs and VASP simulations.

§ Computer scripts for properties of interest.

§ Department duties.

3.3 Autumn and Winter 2024/25

§ Continue prepare input files.

§ Continue discussion with coworkers.

§ Continue participate online conference.

§ Continue generate dislocation types.

§ Continue scripts and simulation.

§ One international conference.

§ Submit two manuscripts for publication.

3.4 Spring and Summer 2025

§ Continue prepare input files.

§ Continue discussion with coworkers.

§ Continue participate online conference.

§ Continue generate dislocation types.

§ Continue scripts and simulation.

§ One international conference.

§ Submit one manuscripts for publication.

§ Begin to sum up previous results

§ Department duties.

3.5 Autumn and Winter 2025/26

§ Continue generate dislocation types.

§ Continue scripts and simulation.

§ Department duties.

3.6 Spring and Summer 2026

§ Finish thesis and submission

§ Department duties

5) Bibliografia / References
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Il progetto dovrà avere almeno 2.000 e non più di 4.000 parole, bibliografia esclusa.
The project should have at least 2,000 and not more than 4,000 words, excluding references.