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The discovery of the extremely shallow amorphous boron-crystalline silicon heterojunction occurred during the development of highly sensitive, hard and robust detectors for low-penetration-depth ionizing radiation, such as ultraviolet photons and low-energy electrons (below 1 keV). For many years it was believed that the junction created by the chemical vapor deposition of amorphous boron on n-type crystalline silicon was a shallow p-n junction, although experimental results could not provide evidence for such a conclusion. Only recently, quantum-mechanics based modelling revealed the unique nature and the formation mechanism of this new junction. Here, we review the initiation and the history of understanding the a-B/c-Si interface (henceforth called the “boron-silicon junction”), as well as its importance for the microelectronics industry, followed by the scientific perception of the new junctions. Future developments and possible research directions are also discussed.

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A new generation of radiation detectors relies on the crystalline Si and amorphous B (c-Si/a-B) junctions that are prepared through chemical vapor deposition of diborane (B₂H₆) on Si at low temperature (∼400 C). The Si wafer surface is dominated by the Si{0 0 1}3 1 domains that consist of two different Si species at low temperature. Here we investigate the geometry, stability and electronic properties of the hydrogen passivated Si{0 0 1}3 1 surfaces with deposited BH_n (n = 0 to 3) radicals using parameter-free first-principles approaches. Ab initio molecular dynamics simulations using the density functional theory (DFT) including van der Waals interaction reveal that in the initial stage the BH₃ molecules/radicals deposit on the Si(-H), forming (-Si)BH₄ radicals which then decompose into (-Si)BH₂ with release of H₂ molecules. Structural optimizations provide strong local relaxation and reconstructions at the deposited Si surface. Electronic structure calculations reveal the formation of various defect states in the forbidden gap. This indicates limitations of the presently used rigid electron-counting and band-filling models. The attained information enhances our understanding of the initial stage of the PureB process and the electric properties of the products.

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Abstract Deposition of a thin B layer via decomposition of B2H6 on Si (PureB process) produces B-Si junctions which exhibit unique electronic and optical properties. Here we present the results of our systematic first-principles study of BHn (n=0-3) radicals on Si(100)2x1:H surfaces, the initial stage of the PureB process. The calculations reveal an unexpectedly high stability of BH2 and BH3 radicals on the surface and a plausible atomic exchange mechanism of surface Si atoms with B atoms from absorbed BHn radicals. The calculations show strong local structural relaxation and reconstructions, as well as strong chemical bonding between the surface Si and the BHn radicals. Electronic structure calculations show various defect states in the energy gap of Si due to the BHn absorption. These results shed light on the initial stages of the complicated PureB process and also rationalize the unusual electronic, optical and electrical properties of the deposited Si surfaces.@en

Nb12O29 is a 4d transition metal oxide that occurs in two forms with different symmetries, monoclinic (m) and orthorhombic (o). The monoclinic form has unusual magnetic properties; below a temperature of 12 K, it exhibits both metallic conductivity and antiferromagnetic ordering. Here, first-principles densityfunctional theory calculations are used to study the structure, relative stability and electronic properties of Nb12O29. The optimized crystal structures are in good agreement with experimental observations and total energy calculations show similar stability of the two phases, while a magnetic electronic state is slightly favoured for m-Nb12O29. The unusual magnetism of the monoclinic phase originates from a Stoner instability that can be attributed to the Nb atoms with valence states close to Nb5+, i.e., the atoms with an electronic configuration of similar to d(0). This is in clear contradiction to current models in which the magnetism is attributed to the presence of localized Nb4+ ions with a formal d(1) configuration. Our study demonstrates that in complex structures, magnetic properties are best not inferred from ionic models, but require a full quantum mechanical calculation over the whole unit cell.@en

A set of interatomic pair potentials is developed for ZnO based on the partially charged rigid ion model (PCRIM). The derivation of the potentials combines lattice inversion, empirical fitting, and ab initio energy surface fitting. We show that, 0 despite the low number of parameters in this model (8), a wide range of physical properties is accurately reproduced using the new potential model. The calculated lattice parameters and elastic constants of ZnO in the wurtzite (WZ) phase, as well as the lattice parameters and stabilities of ZnO in other high-pressure and metastable phases, agree well with experiments and with density functional theory (DFT) calculations. The calculated transition pressure of the wurtzite-to-rocksalt (WZ-to-RS) transition is 12.3 GPa. A wurtzite-to-honeycomb (WZ-to-HC) phase transition induced by uniaxial pressure along the c-axis is simulated by means of molecular dynamics (MD) simulations. The WZ-to-HC transition takes place at an uniaxial pressure of 8.8 GPa while the reverse transition takes place at 2.9 GPa, which is consistent with DFT calculations. Other physical properties, including phonon dispersion, phonon density of states, and melting point calculated using our ZnO potential model are in good agreement with experimental and DFT data. Limitations of the novel ZnO potential model are also discussed.@en

Here, we show a novel solid-solid-vapor (SSV) growth mechanism whereby epitaxial growth of heterogeneous semiconductor nanowires takes place by evaporation-induced cation exchange. During heating of PbSe-CdSe nanodumbbells inside a transmission electron microscope (TEM), we observed that PbSe nanocrystals grew epitaxially at the expense of CdSe nanodomains driven by evaporation of Cd. Analysis of atomic-resolution TEM observations and detailed atomistic simulations reveals that the growth process is mediated by vacancies.@en

The eta-1-M(6)C, gamma-M(23)C(6), and pi-M(11)C(2) phases (M = Cr, Mn and Fe) have complex cubic lattices with lattice parameters of approximately 1.0 nm. They belong to the CFCC-TmC family (complex face-centered cubic transition metal carbides), display a rich variety of crystal structures, and play in important role in iron alloys and steels. Here we show that first-principles calculations predict high stability for the gamma-M(23)C(6) and eta-M(6)C phases, and instability for the pi-M(11)C(2) phases, taking into account various compositional and structural possibilities. The calculations also show a wide variety in magnetic properties. The Cr-containing phases were found to be non-magnetic and the Fe-phases to be ferromagnetic, while the Mn-containing phases were found to be either ferrimagnetic or non-magnetic. Details of the local atomic structures, and the formation and stability of these precipitates in alloys are discussed.@en

Iron carbides play a crucial role in steel manufacturing and processing and to a large extent determine the physical properties of steel products. The modified embedded atom method (MEAM) in combination with Lee's Fe-C potential is a good candidate for molecular dynamics simulations on larger Fe-C systems. Here, we investigate the stability and crystal structures of pure iron and binary iron carbides using MEAM and compare them with the experimental data and quantum-mechanical density functional theory calculations. The analysis shows that the Fe-C potential gives reasonable results for the relative stability of iron and iron carbides. The performance of MEAM for the prediction of the potential energy and the calculated lattice parameters at elevated temperature for pure iron phases and cementite are investigated as well. The conclusion is that Lee's MEAM Fe-C potential provides a promising basis for further molecular dynamics simulations of Fe-C alloys and steels at lower temperatures (up to 800 K).@en

A systematic first-principles study was conducted on the stability of binary iron carbides. The calculations showed that all the binary iron carbides are unstable relative to the elemental solids (¿-Fe and graphite). Apart from a cubic Fe23C6 phase, the energetically most favorable carbides exhibit hexagonal close-packed (hcp) Fesublattices. Structural relaxation of the hcp iron carbides was analyzed and discussed together with their relative thermodynamically stability. Finite-temperature analysis showed that contributions from lattice vibration and anomalous magnetic ordering (Curie-Weiss behavior), rather than from the conventional lattice mismatch with the matrix, are the origin of the high stability and predominance of cementite among the iron carbides in steels.@en

We demonstrate that electron irradiation of colloidal CdS nanorods carrying Au domains causes their evolution into AuS/Cd core/shell nanoparticles as a result of a concurrent chemical and morphological transformation. The shrinkage of the CdS nanorods and the growth of the Cd shell around the Au tips are imaged in real time, while the displacement of S atoms from the CdS nanorod to the Au domains is evidenced by high-sensitivity energy-dispersive X-ray (EDX) spectroscopy. The various nanodomains display different susceptibility to the irradiation, which results in nanoconfigurations that are very different from those obtained after thermal annealing. Such physical manipulations of colloidal nanocrystals can be exploited as a tool to access novel nanocrystal heterostructures.@en

Multiphase steels utilising composite strengthening may be further strengthened via grain refinement or precipitation by the addition of microalloying elements. In this study a Nb microalloyed steel comprising martensite, bainite and retained austenite has been studied. By means of transmission electron microscopy (TEM) we have investigated the size distribution and the structural properties of (Nb, Ti)N and NbC precipitates, their occurrence in the various steel phases, and their relationship with the Fe matrix. (Nb, Ti)N precipitates were found in ferrite, martensite, and bainite, while NbC precipitates were found only in ferrite. All NbC precipitates were found to be small (5-20 nm in size) and to have a face centred cubic (fcc) crystal structure with lattice parameter a = 4.36 +/- 0.05 angstrom. In contrast, the (Nb, Ti)N precipitates were found to have a broader size range (5-150 nm) and to have a fcc crystal structure with lattice parameter a = 8.09 +/- 0.05 angstrom. While the NbC precipitates were found to be randomly oriented, the (Nb, Ti)N precipitates have a welldefined Nishiyama Wasserman orientation relationship with the ferrite matrix. An analysis of the lattice mismatch suggests that the latter precipitates have a high potential for effective strengthening. Density functional theory calculations were performed for various stoichiometries of NbC(x) and Nb(x)Ti(y)N(z) phases and the comparison with experimental data indicates that both the carbides and nitrides are deficient in C and N content.@en

First-principles calculations were performed for the c-phases and other iron carbides/nitrides with hexagonal close-packed Fe sublattices. Although these nitrides/carbides have similar crystal structures, they exhibit different chemical and physical properties. Relative to alpha-Fe, graphite and N(2), all the epsilon-type nitrides are stable, while all the carbides are metastable. The lattice parameters of the epsilon-iron nitrides vary differently from those of the epsilon-carbides, as a function of the concentration of X (X=N, C). The structural relationships of epsilon-Fe(2)X with eta-Fe(2)X and zeta-Fe(2)X are discussed@en

First-principles calculations were performed for the c-phases and other iron carbides/nitrides with hexagonal close-packed Fe sublattices. Although these nitrides/carbides have similar crystal structures, they exhibit different chemical and physical properties. Relative to alpha-Fe, graphite and N-2, all the epsilon-type nitrides are stable, while all the carbides are metastable. The lattice parameters of the epsilon-iron nitrides vary differently from those of the epsilon-carbides, as a function of the concentration of X (X=N, C). The structural relationships of epsilon-Fe2X with eta-Fe2X and zeta-Fe2X are discussed.@en

Although Fe(2)C and Fe(2)N are technologically important materials, the exact nature of the chemical bonding of C and N atoms and the related impact on the electronic properties are at present unclear. Here, results of first-principles electronic structure calculations for Fe(2)X (X = C, N) phases are presented. The electronic structure calculations show that the roles of N and C in iron nitrides and carbides are comparable, and that the X-X interactions have significant impact on electronic properties. Accurate analysis of the spatially resolved differences in electron densities reveals a subtle distinction between the chemical bonding and charge transfer of N and C ions.@en

Fe2C plays a crucial role in the precipitation of iron carbides. Jack's structural models for epsilon-Fe2C, and non-stoichiometric epsilon-Fe2.4C, are analyzed using first-principles calculations. Several new configurations of epsilon-Fe2C with even higher stability are found. We show how epsilon-Fe2C transforms into eta-Fe2C, and address the structural relationships with the chi-Fe5C2, theta-Fe3C and Fe7C3 phases. The relative occurrence of these phases in steel, as well as their probable evolution during tempering of quenched steels, is discussed.@en

First-principles' calculations of GGA and GGA - U type have been performed for gamma-Fe23C6, a complex iron carbide with 116 atom in the unit cell GGA results were found to be in better agreement with experimental data than GGA + U results Various occupancies for Wyckoff positions and corresponding magnetic orderings have been explored Our calculations reveal that the crystal structure is composed of a framework of strongly linked Fe atoms, and additional stabilizing Fe and C atoms positioned in cavities The local electronic and magnetic properties vary strongly among the non-equivalent Fe sites in gamma-Fe23C6 The lattice parameters of gamma-Fe23C6 match those of austenite well Surprisingly, pure gamma-Fe23C6 is found to be more stable than commonly occurring theta-Fe3C cementite Moreover, the calculations show low vacancy energy (about 0 37 eV) for Fe at 4a sites in gamma-Fe23C6 Conditions of formation and factors hampering the formation of gamma-Fe23C6 in steel manufacturing processes are discussed@en

Surface energies of the distinct facets of nanocrystals are an important factor in the free energy and hence determine the nanocrystal morphology, chemical and physical properties, and even interparticle dipole interactions. Here we investigate the stability and atomic structure of polar and nonpolar PbSe surfaces by combining first-principles calculations with high-resolution transmission electron microscopy ITEM). For uncapped surfaces, the calculations predict that the nonpolar {100} surface Is the most stable with a surface energy of 0.184 J m(-2), while the nonpolar {110} and reconstructed {111}-Pb surfaces have surface energies of 0.318 J m(-2) and 0.328 J m(-2), respectively, Fully polar {111} surfaces are structurally unstable upon relaxation. These findings are in good agreement with TEM observations showing that capped nanocrystals have a nearly spherical, multifaceted morphology, while cubical shapes with predominantly {100} facets are obtained when the capping molecules are removed through heating in vacuum. During this process, however, also multipolar surfaces can temporarily exist just after the removal of the surfactants. These metastable {111} surfaces consist of ribbon-like nanodomains, whereby the ribbons are alternating in polarity. The calculations confirm that these multipolar surfaces are energetically more favorable than fully polar surfaces. The consequences for capped nanocrystals (a dominant Pb-oleate termination) and nanocrystal fusion (a shorter interaction range of dipole interactions) are discussed.@en