Linear Hyperfine Tuning of Donor Spins in Silicon Using Hydrostatic Strain.

We experimentally study the coupling of group V donor spins in silicon to mechanical strain, and measure strain-induced frequency shifts that are linear in strain, in contrast to the quadratic dependence predicted by the valley repopulation model (VRM), and therefore orders of magnitude greater than that predicted by the VRM for small strains |ϵ|<10^{-5}. Through both tight-binding and first principles calculations we find that these shifts arise from a linear tuning of the donor hyperfine interaction term by the hydrostatic component of strain and achieve semiquantitative agreement with the experimental values. Our results provide a framework for making quantitative predictions of donor spins in silicon nanostructures, such as those being used to develop silicon-based quantum processors and memories. The strong spin-strain coupling we measure (up to 150 GHz per strain, for Bi donors in Si) offers a method for donor spin tuning-shifting Bi donor electron spins by over a linewidth with a hydrostatic strain of order 10^{-6}-as well as opportunities for coupling to mechanical resonators.

Acceptor doping in the proton conductor SrZrO3.

Perovskite zirconates such as SrZrO3 exhibit improved proton solubility and conductivity when doped with trivalent cations substituting at the Zr site. In this work, we present a detailed study of Sc and Y dopants in SrZrO3 based on first-principles, hybrid density-functional calculations. When substituting at the Zr site (ScZr, YZr), both dopants give rise to a single, deep acceptor level, where the neutral impurity forms a localized hole polaron state. The ε(0/-) charge transition levels are 0.60 eV and 0.58 eV above the valence-band maximum for ScZr and YZr, respectively. Under certain growth conditions, Sc and Y will form self-compensating donor species by substituting at the Sr site (ScSr, YSr), and this is detrimental to proton conductivity. Due to its larger ionic radius, Y exhibits a greater tendency than Sc to self-compensate at the Sr site. We also investigated the proton-dopant association. The binding energy of a proton to a negatively charged acceptor impurity is 0.41 eV for Sc and 0.31 eV for Y, indicating that proton transport is limited by trapping at impurity sites.

Ab initio study of hydrogenic effective mass impurities in Si nanowires.

The effect of B and P dopants on the band structure of Si nanowires is studied using electronic structure calculations based on density functional theory. At low concentrations a dispersionless band is formed, clearly distinguishable from the valence and conduction bands. Although this band is evidently induced by the dopant impurity, it turns out to have purely Si character. These results can be rigorously analyzed in the framework of effective mass theory. In the process we resolve some common misconceptions about the physics of hydrogenic shallow impurities, which can be more clearly elucidated in the case of nanowires than would be possible for bulk Si. We also show the importance of correctly describing the effect of dielectric confinement, which is not included in traditional electronic structure calculations, by comparing the obtained results with those of G0W0 calculations.

Surprising stability of neutral interstitial hydrogen in diamond and cubic BN.

In virtually all semiconductors and insulators, hydrogen interstitials ([Formula: see text]) act as negative-U centers, implying that hydrogen is never stable in the neutral charge state. Using hybrid density functional calculations, we find a different behavior for [Formula: see text] in diamond and cubic BN. In diamond, [Formula: see text] is a very strong positive-U center, and the [Formula: see text] charge state is stable over a Fermi-level range of more than 2 eV. In cubic BN, a III-V compound similar to diamond, we also find positive-U behavior, though over a much smaller Fermi-level range. These results highlight the unique behavior of [Formula: see text] in these covalent wide-band-gap semiconductors.

First-principles study of van der Waals interactions in MoS2 and MoO3.

Van der Waals interactions play an important role in layered materials such as MoS2 and MoO3. Within density functional theory, several methods have been developed to explicitly include van der Waals interactions. We compare the performance of several of these functionals in describing the structural and electronic properties of MoS2 and MoO3. We include functionals based on the local density or generalized gradient approximations, but also based on hybrid functionals. The coupling of the semiempirical Grimme D2 method with the hybrid functional HSE06 is shown to lead to a very good description of both structural and electronic properties.

Polarization-driven topological insulator transition in a GaN/InN/GaN quantum well.

Topological insulator (TI) states have been demonstrated in materials with a narrow gap and large spin-orbit interactions (SOI). Here we demonstrate that nanoscale engineering can also give rise to a TI state, even in conventional semiconductors with a sizable gap and small SOI. Based on advanced first-principles calculations combined with an effective low-energy k · p Hamiltonian, we show that the intrinsic polarization of materials can be utilized to simultaneously reduce the energy gap and enhance the SOI, driving the system to a TI state. The proposed system consists of ultrathin InN layers embedded into GaN, a layer structure that is experimentally achievable.

Hydrogenated cation vacancies in semiconducting oxides.

Using first-principles calculations we have studied the electronic and structural properties of cation vacancies and their complexes with hydrogen impurities in SnO(2), In(2)O(3) and ß-Ga(2)O(3). We find that cation vacancies have high formation energies in SnO(2) and In(2)O(3) even in the most favorable conditions. Their formation energies are significantly lower in ß-Ga(2)O(3). Cation vacancies, which are compensating acceptors, strongly interact with H impurities resulting in complexes with low formation energies and large binding energies, stable up to temperatures over 730 °C. Our results indicate that hydrogen has beneficial effects on the conductivity of transparent conducting oxides: it increases the carrier concentration by acting as a donor in the form of isolated interstitials, and by passivating compensating acceptors such as cation vacancies; in addition, it potentially enhances carrier mobility by reducing the charge of negatively charged scattering centers. We have also computed vibrational frequencies associated with the isolated and complexed hydrogen, to aid in the microscopic identification of centers observed by vibrational spectroscopy.

Quantum computing with defects.

Identifying and designing physical systems for use as qubits, the basic units of quantum information, are critical steps in the development of a quantum computer. Among the possibilities in the solid state, a defect in diamond known as the nitrogen-vacancy (NV(-1)) center stands out for its robustness--its quantum state can be initialized, manipulated, and measured with high fidelity at room temperature. Here we describe how to systematically identify other deep center defects with similar quantum-mechanical properties. We present a list of physical criteria that these centers and their hosts should meet and explain how these requirements can be used in conjunction with electronic structure theory to intelligently sort through candidate defect systems. To illustrate these points in detail, we compare electronic structure calculations of the NV(-1) center in diamond with those of several deep centers in 4H silicon carbide (SiC). We then discuss the proposed criteria for similar defects in other tetrahedrally coordinated semiconductors.

Mutual passivation of electrically active and isovalent impurities in dilute nitrides.

Using first-principles calculations we investigate the mutual passivation of shallow donor Si and isovalent N in dilute GaAsN alloys. Instead of the recently proposed pairing of Si and N on adjacent substitutional sites (Si(Ga)-N(As)) [K. M. Yu et al., Nat. Mater. 1, 185 (2002); J. Li et al., Phys. Rev. Lett. 96, 035505 (2006)] we find that N changes the behavior of Si in dilute nitride alloys in a more dramatic way. N and Si combine into a deep-acceptor split interstitial, where Si and N share an As site [(Si-N) (As)], with a significantly lower formation energy than that of the Si(Ga)-N(As) pair in n-type GaAs and dilute GaAsN alloys. The formation of (Si-N)(As) explains the GaAs band-gap recovery and the appearance of a photoluminescence peak at approximately 0.8 eV. This model can also be extended to Ge-doped GaAsN alloys, and correctly predicts the absence of mutual passivation in the case of column-VI dopants.

Computational studies of conductivity in wide-band-gap semiconductors and oxides.

The ability to control conductivity is essential for design and fabrication of (opto)electronic devices. Such conductivity control has traditionally been very difficult in wide-band-gap semiconductors, and native point defects have often been invoked to explain these problems. State-of-the-art first-principles calculations based on density functional theory have been used to elucidate these issues. Approaches for overcoming the 'band-gap problem', including the LDA+U method, allow more accurate comparisons and predictions of defect levels. The methodology is illustrated with the case of native point defects in zinc oxide. Computations reveal that the prevailing n-type conductivity cannot be attributed to native defects; it must thus be caused by impurities that are unintentionally incorporated. Hydrogen is shown to be an excellent candidate for such an impurity.

Effects of hydrogen on the electronic properties of dilute GaAsN alloys.

Nitrogen has profound effects on the electronic structure of GaAs, as only a few percent of N can drastically lower the band gap. It is, however, not recognized that the same amount of N can also qualitatively alter the electronic behavior of hydrogen: First-principles calculations reveal that, in GaAsN, a H atom bonds to N and can act as a donor in its own right, whereas in GaAs and GaN, H is amphoteric, causing passivation instead. At high Fermi energy and H concentration, a N complex with two H was found to have lower energy than the single-H configuration. By removing the effect of N, this electrically inactive complex restores the gap of GaAs.

Entropy-driven stabilization of a novel configuration for acceptor-hydrogen complexes in GaN.

We present a model for the microscopic structure of Mg-H complexes in GaN, explaining the unusual bond angle observed in recent vibrational spectroscopy studies. The structure is not the lowest-energy configuration at T = 0, but it is stabilized at elevated temperatures due to the large entropy associated with a set of low-energy rotational excitations. The rotational excitation spectrum is calculated using a quantum-mechanical model in which the hydrogen atom moves in a weak corrugation potential. Consequences for experiment are discussed.