arXiv subjects

L. Hultman

Publications and source records attributed to L. Hultman.

17 recordsLinked to original sources

arXiv2025

Three-fold Superstructured Superlattice HfN/HfAlN Thin Films for Enhanced Toughness

To simultaneously achieve high hardness and high toughness in protective coatings remains a fundamental challenge. Here, we harness the superlattice architecture to combine Koehler hardening while the coherent interfaces reduce the crack driving force and improve toughness, enabling coatings that are both hard and damage tolerant. We design and fabricate epitaxial HfN$_{1.33}$/Hf$_{0.76}$Al$_{0.24}$N$_{1.15}$ superlattices, deposited on MgO(001) substrates using low-energy, high-flux ion-assisted reactive magnetron sputtering. These superlattices with bilayer periods ranging from 6 to 20 nm, exhibit a unique three-fold superstructure, confirmed by X-ray diffraction and reciprocal space mapping (RSM). Each constituent forms distinct 3D checkerboard superstructures, with a period of 7.5 {\AA} for HfN and 12.5 A for HfAlN. RSMs further reveal low mosaicity, high crystalline quality, and in-plane compressive strains, indicating well preserved coherence across interfaces. Mechanical testing shows that the superlattices maintain the high hardness of HfAlN (\~36 GPa) independent of bilayer period, while surpassing the softer HfN (~27 GPa), consistent with interface-driven Koehler strengthening. Micropillar compression shows brittle fracture on the {110}<110> system, yet with distributed cracking and faster mechanical recovery compared to monolithic films, suggesting improved toughness. Cube-corner indentation further corroborate this behavior, with pile-up and suppressed fracture events. These results demonstrate that epitaxial HfN/HfAlN superlattices uniquely combine high hardness with improved toughness, enabled by their three-fold superstructured architecture. Leveraging the intrinsic high-temperature stability of HfN-based materials, this design offers a robust pathway toward next-generation protective coatings capable of maintaining performance under extreme conditions.

cond-mat.mtrl-sci↗

arXiv2025

Growth Mechanisms and Mechanical Response of 3D Superstructured Cubic and Hexagonal Hf$_{1-x}$Al$_x$N Thin Films

Transition metal aluminum nitrides are a technologically important class of multifunctional ceramics, however, the HfAlN system remains largely unexplored. We investigate phase stability, nanostructure design, and mechanical behavior of Hf$_{1-x}$Al$_x$N$_y$ thin films deposited on MgO(001) substrates using ion-assisted reactive magnetron sputtering. Compared to growth temperature and ion assistance, backscattered Ar neutrals are shown to have a dominant influence on the film structure. The Al-rich (x > 0.41) films form a nanocrystalline morphology consisting of Hf- and Al-rich nanodomains in a wurtzite-hexagonal(h) 0001 fiber-texture exhibiting about 22 GPa hardness, considerably higher than that of a binary AlN. For low Al contents, x < 0.30, surface-driven spinodal decomposition by energetic Ar neutrals during deposition in combination with quenching of sub-surface diffusion results in an unusual - and unique for nitrides - three-dimensional checkerboard superstructure of AlN- and HfN-rich nanodomains in the single-crystal rocksalt-cubic (c) phase. Lattice-resolved scanning transmission electron microscopy complemented with x-ray and electron diffraction reveals that the superstructure periodicity extends along <100> directions and the size increases linearly from 9 to 13 A with rising Al content. Consequently, the nanoindentation hardness increases sharply from 26 GPa for HfN$_y$, to \~38 GPa for c-Hf$_{1-x}$Al$_x$N$_y$, due to dislocation pinning at the superstructure strain fields. Micropillar compression of c-Hf$_{0.93}$Al$_{0.07}$N$_{1.15}$ shows a considerably higher yield stress compared to HfN$_y$ and controlled brittle fracture occurs via {110}<011> slip systems, attributed to superstructure inhibited dislocation motion. In contrast, nanocrystalline h-Hf$_{0.59}$Al$_{0.41}$N$_{1.23}$ exhibits a high yield stress and limited plasticity before strain burst failure.

cond-mat.mtrl-sci↗

arXiv2020

Adaptive hard and tough mechanical response in single-crystal B1 VNx ceramics via control of anion vacancies

High hardness and toughness are generally considered mutually exclusive properties for single-crystal ceramics. Combining experiments and ab initio molecular dynamics (AIMD) atomistic simulations at room temperature, we demonstrate that both the hardness and toughness of single-crystal NaCl-structure VNx/MgO(001) thin films are simultaneously enhanced through the incorporation of anion vacancies. Nanoindentation results show that VN0.8, here considered as representative understoichiometric VNx system, is ~20% harder, as well as more resistant to fracture than stoichiometric VN samples. AIMD modeling of VN and VN0.8 supercells subjected to [001] and [110] elongation reveal that the tensile strengths of the two materials are similar. Nevertheless, while the stoichiometric VN phase systematically cleaves in a brittle manner at tensile yield points, the understoichiometric compound activates transformation-toughening mechanisms that dissipate accumulated stresses. AIMD simulations also show that VN0.8 exhibits an initially greater resistance to both {110}<1-10> and {111}<1-10> shear deformation than VN. However, for progressively increasing shear strains, the VN0.8 mechanical behavior gradually evolves from harder to more ductile than VN. The transition is mediated by anion vacancies, which facilitate {110}<1-10> and {111}<1-10> lattice slip by reducing activation shear stresses by as much as 35%. Electronic-structure analyses show that the two-regime hard/tough mechanical response of VN0.8 primarily stems from its intrinsic ability to transfer d electrons between 2nd-neighbor and 4th-neighbor (i.e., across vacancy sites) V-V metallic states. Our work offers a route for electronic-structure design of hard materials in which a plastic mechanical response is triggered with loading.

cond-mat.mtrl-sci↗

arXiv2019

Phase composition and transformations in magnetron-sputtered (Al,V)2O3 coatings

Coatings of (Al1-xVx)2O3, with x ranging from 0 to 1, were deposited by pulsed DC reactive sputter deposition on Si(100) at a temperature of 550 °C. XRD showed three different crystal structures depending on V-metal fraction in the coating: α-V2O3 rhombohedral structure for 100 at.% V, a defect spinel structure for the intermediate region, 63 - 42 at.% V. At lower V-content, 18 and 7 at.%, a gamma-alumina-like solid solution was observed, shifted to larger d-spacing compared to pure γ-Al2O3. The microstructure changes from large columnar faceted grains for α-V2O3 to smaller equiaxed grains when lowering the vanadium content toward pure γ-Al2O3. Annealing in air resulted in formation of V2O5 crystals on the surface of the coating after annealing to 500 °C for 42 at.% V and 700 °C for 18 at.% V metal fraction respectively. The highest thermal stability was shown for pure γ-Al2O3-coating, which transformed to α-Al2O3 after annealing to 1100° C. Highest hardness was observed for the Al-rich oxides, ~24 GPa. The latter decreased with increasing V-content, larger than 7 at.% V metal fraction. The measured hardness after annealing in air decreased in conjunction with the onset of further oxidation of the coatings.

cond-mat.mtrl-sci↗

arXiv2019

Tin+1Cn MXene with fully saturated and thermally stable Cl terminations

MXenes are a rapidly growing family of 2D materials that exhibit a highly versatile structure and composition, allowing for significant tuning of the material properties. These properties are, however, ultimately limited by the surface terminations, which are typically a mixture of species, including F and O that are inherent to the MXene processing. Other and robust terminations are lacking. Here, we apply high-resolution scanning transmission electron microscopy (STEM), corresponding image simulations and first-principles calculations to investigate the surface terminations on MXenes synthesized from MAX phases through Lewis acidic melts. The results show that atomic Cl terminates the synthesized MXenes, with mere residual presence of other termination species. Furthermore, in situ STEM-electron energy loss spectroscopy (EELS) heating experiments show that the Cl terminations are stable up to 750 °C. Thus, we present an attractive new termination that widely expands the MXenes functionalization space and enable new applications.

cond-mat.mtrl-sci↗

arXiv2017

Effects of surface vibrations on interlayer mass-transport: ab initio molecular dynamics investigation of Ti adatom descent pathways and rates from TiN/TiN(001) islands

We carry out density-functional ab initio molecular dynamics (AIMD) simulations of Ti adatom (Tiad) migration on, and descent from, TiN <100>-faceted epitaxial islands on TiN(001) at temperatures T ranging from 1200 to 2400 K. Adatom-descent energy-barriers determined via ab initio nudged-elastic-band calculations at 0 Kelvin suggest that Ti interlayer transport on TiN(001) occurs essentially exclusively via direct hopping onto a lower layer. However, AIMD simulations reveal comparable rates for Tiad descent via direct-hopping vs. push-out/exchange with a Ti island edge atom for T >= 1500 K. We demonstrate that the effect is due to surface vibrations, which yield considerably lower activation energies at finite temperatures by significantly modifying the adatom push/out-exchange reaction pathway.

cond-mat.mtrl-sci↗

arXiv2017

Multi-Grid Detector for Neutron Spectroscopy: Results Obtained on Time-of-Flight Spectrometer CNCS

The Multi-Grid detector technology has evolved from the proof-of-principle and characterisation stages. Here we report on the performance of the Multi-Grid detector, the MG.CNCS prototype, which has been installed and tested at the Cold Neutron Chopper Spectrometer, CNCS at SNS. This has allowed a side-by-side comparison to the performance of $^3$He detectors on an operational instrument. The demonstrator has an active area of 0.2 m$^2$. It is specifically tailored to the specifications of CNCS. The detector was installed in June 2016 and has operated since then, collecting neutron scattering data in parallel to the He-3 detectors of CNCS. In this paper, we present a comprehensive analysis of this data, in particular on instrument energy resolution, rate capability, background and relative efficiency. Stability, gamma-ray and fast neutron sensitivity have also been investigated. The effect of scattering in the detector components has been measured and provides input to comparison for Monte Carlo simulations. All data is presented in comparison to that measured by the $^3$He detectors simultaneously, showing that all features recorded by one detector are also recorded by the other. The energy resolution matches closely. We find that the Multi-Grid is able to match the data collected by $^3$He, and see an indication of a considerable advantage in the count rate capability. Based on these results, we are confident that the Multi-Grid detector will be capable of producing high quality scientific data on chopper spectrometers utilising the unprecedented neutron flux of the ESS.

physics.ins-det↗

arXiv2015

Investigation of background in large-area neutron detectors due to alpha emission from impurities in aluminium

Thermal neutron detector based on films of $^{10}$B$_4$C have been developed as an alternative to $^3$He detectors. In particular, The Multi-Grid detector concept is considered for future large area detectors for ESS and ILL instruments. An excellent signal-to-background ratio is essential to attain expected scientific results. Aluminium is the most natural material for the mechanical structure of of the Multi-Grid detector and other similar concepts due to its mechanical and neutronic properties. Due to natural concentration of $α$ emitters, however, the background from $α$ particles misidentified as neutrons can be unacceptably high. We present our experience operating a detector prototype affected by this issue. Monte Carlo simulations have been used to confirm the background as $α$ particles. The issues have been addressed in the more recent implementations of the Multi-Grid detector by the use of purified aluminium as well as Ni-plating of standard aluminium. The result is the reduction in background by two orders of magnitude. A new large-area prototype has been built incorporating these modifications.

physics.ins-det↗

arXiv2015

First-principles study of configurational disorder in B$_{4}$C using a superatom-special quasirandom structure method

Configurationally disordered crystalline boron carbide, B$_{4}$C, is studied using first-principles calculations. We investigate both dilute and high concentrations of carbon-boron substitutional defects. For the latter purpose, we suggest a superatom's picture of the complex structure and combine it with a special quasi-random structure approach for disorder. In this way, we model a random distribution of high concentrations of the identified low-energy defects: 1) Bipolar defects and 2) Rotation of icosahedral carbon among the three polar-up sites. Additionally, the substitutional disorder of the icosahedral carbon at all six polar sites, as previously discussed in the literature, is also considered. Two configurational phase transitions from the ordered to the disordered configurations are predicted to take place upon increasing temperature using a mean-field approximation for the entropy. The first transition, at 870 K, induces substitutional disorder of the icosahedral carbon atoms among the three polar-up sites, meanwhile the second transition, at 2325 K, reveals the random substitution of the icosahedral carbon atoms at all six polar sites coexisting with bipolar defects. Already the first transition removes the monoclinic distortion existing in the ordered ground state configuration and restore the rhombohedral system (R3m). The restoration of inversion symmetry yielding the full rhombohedral symmetry (R-3m) on average, corresponding to what is reported in the literature, is achieved after the second transition. The electronic density of states, obtained from the disordered phases indicates a sensitivity of band gap to the degree of configurational disorder in B$_{4}$C.

cond-mat.mtrl-sci↗

arXiv2015

Configurational order-disorder induced metal-nonmetal transition in B$_{13}$C$_{2}$ studied with first-principles superatom-special quasirandom structure method

Due to a large discrepancy between theory and experiment, the electronic character of crystalline boron carbide B$_{13}$C$_{2}$ has been a controversial topic in the field of icosahedral boron-rich solids. We demonstrate that this discrepancy is removed when configurational disorder is accurately considered in the theoretical calculations. We find that while ordered ground state B$_{13}$C$_{2}$ is metallic, configurationally disordered B$_{13}$C$_{2}$, modeled with a superatom-special quasirandom structure method, goes through a metal to non-metal transition as the degree of disorder is increased with increasing temperature. Specifically, one of the chain-end carbon atoms in the CBC chains substitutes a neighboring equatorial boron atom in a B$_{12}$ icosahedron bonded to it, giving rise to a B$_{11}$C$^{e}$(BBC) unit. The atomic configuration of the substitutionally disordered B$_{13}$C$_{2}$ thus tends to be dominated by a mixture between B$_{12}$(CBC) and B$_{11}$C$^{e}$(BBC). Due to splitting of valence states in B$_{11}$C$^{e}$(BBC), the electron deficiency in B$_{12}$(CBC) is gradually compensated.

cond-mat.mtrl-sci↗

arXiv2013

A 10B-based neutron detector with stacked Multiwire Proportional Counters and macrostructured cathodes

We present the results of the measurements of the detection efficiency for a 4.7 Å neutron beam incident upon a detector incorporating a stack of up to five MultiWire Proportional Counters (MWPC) with Boron-coated cathodes. The cathodes were made of Aluminum and had a surface exhibiting millimeter-deep V-shaped grooves of 45°, upon which the thin Boron film was deposited by DC magnetron sputtering. The incident neutrons interacting with the converter layer deposited on the sidewalls of the grooves have a higher capture probability, owing to the larger effective absorption film thickness. This leads to a higher overall detection efficiency for the grooved cathode when compared to a cathode with a flat surface. Both the experimental results and the predictions of the GEANT4 model suggests that a 5-counter detector stack with coated grooved cathodes has the same efficiency as a 7-counter stack with flat cathodes. The reduction in the number of counters in the stack without altering the detection efficiency will prove highly beneficial for large-area position-sensitive detectors for neutron scattering applications, for which the cost-effective manufacturing of the detector and associated readout electronics is an important objective. The proposed detector concept could be a technological option for one of the new chopper spectrometers and other instruments planned to be built at the future European Spallation Source in Sweden. These results with macrostructured cathodes generally apply not just to MWPCs but to other gaseous detectors as well.

physics.ins-det↗

arXiv2012

Effects of configurational disorder on adatom mobilities on TiAlN(001) surfaces

We use metastable NaCl-structure Ti0.5Al0.5N alloys to probe effects of configurational disorder on adatom surface diffusion dynamics which control phase stability and nanostructural evolution during film growth. First-principles calculations were employed to obtain potential energy maps of Ti and Al adsorption on an ordered TiN(001) reference surface and a disordered Ti0.5Al0.5N(001) solid-solution surface. The energetics of adatom migration on these surfaces are determined and compared in order to isolate effects of configurational disorder. The results show that alloy surface disorder dramatically reduces Ti adatom mobilities. Al adatoms, in sharp contrast, experience only small disorder-induced differences in migration dynamics.

cond-mat.mtrl-sci↗

arXiv2011

Electronic structure investigation of Ti3AlC2, Ti3SiC2, and Ti3GeC2 by soft-X-ray emission spectroscopy

The electronic structures of epitaxially grown films of Ti3AlC2, Ti3SiC2 and Ti3GeC2 have been investigated by bulk-sensitive soft X-ray emission spectroscopy. The measured high-resolution Ti L, C K, Al L, Si L and Ge M emission spectra are compared with ab initio density-functional theory including core-to-valence dipole matrix elements. A qualitative agreement between experiment and theory is obtained. A weak covalent Ti-Al bond is manifested by a pronounced shoulder in the Ti L-emission of Ti3AlC2. As Al is replaced with Si or Ge, the shoulder disappears. For the buried Al and Si-layers, strongly hybridized spectral shapes are detected in Ti3AlC2 and Ti3SiC2, respectively. As a result of relaxation of the crystal structure and the increased charge-transfer from Ti to C, the Ti-C bonding is strengthened. The differences between the electronic structures are discussed in relation to the bonding in the nanolaminates and the corresponding change of materials properties.

cond-mat.mtrl-sci↗

arXiv2011

Electronic structure and chemical bonding in Ti4SiC3 investigated by soft x-ray emission spectroscopy and first principle theory

The electronic structure in the new transition metal carbide Ti4SiC3 has been investigated by bulk-sensitive soft x-ray emission spectroscopy and compared to the well-studied Ti3SiC2 and TiC systems. The measured high-resolution Ti L, C K and Si L x-ray emission spectra are discussed with ab initio calculations based on density-functional theory including core-to-valence dipole matrix elements. The detailed investigations of the Ti-C and Ti-Si chemical bonds provide increased understanding of the physical properties of these nanolaminates. A strongly modified spectral shape is detected for the buried Si monolayers due to Si 3p hybridization with the Ti 3d orbitals. As a result of relaxation of the crystal structure and the charge-transfer from Ti (and Si) to C, the strength of the Ti-C covalent bond is increased. The differences between the electronic and crystal structures of Ti4SiC3 and Ti3SiC2 are discussed in relation to the number of Si layers per Ti layer in the two systems and the corresponding change of materials properties.

cond-mat.mtrl-sci↗

arXiv2011

Bonding mechanism in the nitrides Ti2AlN and TiN: an experimental and theoretical investigation

The electronic structure of nanolaminate Ti2AlN and TiN thin films has been investigated by bulk-sensitive soft x-ray emission spectroscopy. The measured Ti L, N K, Al L1 and Al L2,3 emission spectra are compared with calculated spectra using ab initio density-functional theory including dipole transition matrix elements. Three different types of bond regions are identified; a relatively weak Ti 3d - Al 3p bonding between -1 and -2 eV below the Fermi level, and Ti 3d - N 2p and Ti 3d - N 2s bonding which are deeper in energy observed at -4.8 eV and -15 eV below the Fermi level, respectively. A strongly modified spectral shape of 3s states of Al L2,3 emission from Ti2AlN in comparison to pure Al metal is found, which reflects the Ti 3d - Al 3p hybridization observed in the Al L1 emission. The differences between the electronic and crystal structures of Ti2AlN and TiN are discussed in relation to the intercalated Al layers of the former compound and the change of the materials properties in comparison to the isostructural carbides.

cond-mat.mtrl-sci↗

arXiv2011

Electronic structure and chemical bonding anisotropy investigation of wurtzite AlN

The electronic structure and the anisotropy of the Al - N π and σ chemical bonding of wurtzite AlN has been investigated by bulk-sensitive total fluorescence yield absorption and soft x-ray emission spectroscopies. The measured N K, Al L1, and Al L2,3 x-ray emission and N 1s x-ray absorption spectra are compared with calculated spectra using first principles density-functional theory including dipole transition matrix elements. The main N 2p - Al 3p hybridization regions are identified at -1.0 to -1.8 eV and -5.0 to -5.5 eV below the top of the valence band. In addition, N 2s - Al 3p and N 2s - Al 3s hybridization regions are found at the bottom of the valence band around -13.5 eV and -15 eV, respectively. A strongly modified spectral shape of Al 3s states in the Al L2,3 emission from AlN in comparison to Al metal is found, which is also reflected in the N 2p - Al 3p hybridization observed in the Al L1 emission. The differences between the electronic structure and chemical bonding of AlN and Al metal are discussed in relation to the position of the hybridization regions and the valence band edge influencing the magnitude of the large band gap.

cond-mat.mtrl-sci↗

arXiv2010

A unified cluster expansion method applied to the configurational thermodynamics of cubic TiAlN

We study the thermodynamics of cubic Ti1-xAlxN using a unified cluster expansion approach for the alloy problem. The purely configurational part of the alloy Hamiltonian is expanded in terms of concentration and volume dependent effective cluster interactions. By separate expansions of the chemical fixed-lattice, and local lattice relaxation terms of the ordering energies, we demonstrate how the screened generalized perturbation method can be fruitfully combined with a concentration dependent Connolly-Williams cluster expansion method. Utilising the obtained Hamiltonian in Monte Carlo simulations we access the free energy of Ti1-xAlxN alloys and construct the isostructural phase diagram. The results show surprising similarities with the previously obtained mean-field results: The metastable c-TiAlN is subject to coherent spinodal decomposition over a larger part of the concentration range, e.g. from x >= 0.33 at 2000 K.

cond-mat.stat-mech↗