Hybridization between the conduction band and 3d orbitals in the oxide-based diluted magnetic semiconductor In$_{2-x}$V$_x$O$_3$
M. Kobayashi, Y. Ishida, J. I. Hwang, G. S. Song, M. Takizawa, A. Fujimori, Y. Takeda, T. Ohkochi, T. Okane, Y. Saitoh, H. Yamagami, Amita Gupta, H. T. Cao, K. V. Rao
The electronic structure of In$_{2-x}$V$_x$O$_3$ ($x=0.08$) has been investigated using photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS). The V $2p$ core-level PES and XAS spectra revealed trivalent electronic state of the V ion, consistent with the substitution of the V ion for the In site. The V 3d partial density of states obtained by the resonant PES technique showed a sharp peak above the O $2p$ band. While the O $1s$ XAS spectrum of In$_{2-x}$V$_x$O$_3$ was similar to that of In$_2$O$_3$, there were differences in the In $3p$ and 3d XAS spectra between V-doped and pure In$_2$O$_3$. The observations give clear evidence for hybridization between the In conduction band and the V 3d orbitals in In$_{2-x}$V$_x$O$_3$.
We have studied the critical temperature of Diluted Magnetic Semiconductors by means of Monte Carlo simulations and Coherent-Potential-Approximation (CPA) calculations. In our model for this syste m, the magnetic ions couple with the carriers through an antiferromagnetic exchange interaction, $J$, and an electrostatic interaction $W$. The effective impurity potential $J-W$ controls the hybridization between the magnetic impurities and the hole charge on the dopants. We find that the critical temperature depends substantially on the hole charge on the magnetic impurities. The CPA critical tempe…
The electronic structure of the new diluted magnetic semiconductor Ba$_{1-x}$K$_{x}$(Zn$_{1-y}$Mn$_{y}$)$_{2}$As$_{2}$ ($x=0.30$, $y=0.15$) in single crystal form has been investigated by angle-resolved photoemission spectroscopy (ARPES). %High density of states of nondispersive bands composed of the Zn $3d$ orbitals are observed with ultraviolet incident light. Measurements with soft x-rays clarify the host valence-band electronic structure primarily composed of the As $4p$ states. Two hole pockets around the $Γ$ point, a hole corrugated cylinder surrounding the $Γ$ and Z points, and an elect…
Here we report the synthesis of a bulk oxide diluted magnetic semiconductor (DMS) system La1-xSrxCu0.925Mn0.075SO (x=0, 0.025, 0.05, 0.075, and 0.1). As a wide band gap p-type oxide semiconductor, LaCuSO satisfies all the conditions forecasted theoretically to be a room temperature DMS. The Curie temperature (TC) is around 200K as x>0.05, which is among the highest TC record of known bulk DMS materials up to now. The system provides a rare example of oxide DMS system with p-type conduction, which is important for formation of high temperature spintronic devices.
Here we report the successful synthesis of a spin- & charge-decoupled diluted magnetic semiconductor (Ca,Na)(Zn,Mn)2As2, crystallizing into the hexagonal CaAl2Si2 structure. The compound shows a ferromagnetic transition with a Curie temperature up to 33 K with 10% Na doping, which gives rise to carrier density of np~10^20 cm^-3. The new DMS is a soft magnetic material with HC<400 Oe. The anomalous Hall effect is observed below the ferromagnetic ordering temperature. With increasing Mn doping, ferromagnetic order is accompanied by an interaction between the local spin and mobile charge, giving …
A key issue in heavy fermion research is how subtle changes in the hybridization between the 4$f$ (5$f$) and conduction electrons can result in fundamentally different ground states. CeRhIn$_5$ stands out as a particularly notable example: replacing Rh by either Co or Ir, located above or below Rh in the periodic table, antiferromagnetism gives way to superconductivity. In this photoemission study of CeRhIn$_5$, we demonstrate that the use of resonant ARPES with polarized light allows to extract detailed information on the 4$f$ crystal field states and details on the 4$f$ and conduction electr…
Chemical pressure is an effective method to tune physical properties, particularly for diluted magnetic semiconductors (DMS) of which ferromagnetic ordering is mediated by charge carriers. Via substitution of smaller Ca for larger Sr, we introduce chemical pressure on (Sr,Na)(Cd,Mn)2As2 to fabricate a new DMS material (Ca,Na)(Cd,Mn)2As2. Carriers and spins are introduced by substitutions of (Ca,Na) and (Cd,Mn) respectively. The unit cell volume reduces by 6.2% after complete substitution of Ca for Sr, suggesting a subsistent chemical pressure. Importantly the local geometry of [Cd/MnAs4] tetra…
A direct observation of the giant Zeeman splitting of the free excitons in (Ga,Fe)N is reported. The magnetooptical and magnetization data imply the ferromagnetic sign and a reduced magnitude of the effective p-d exchange energy governing the interaction between Fe^{3+} ions and holes in GaN, N_0 beta^(app) = +0.5 +/- 0.2 eV. This finding corroborates the recent suggestion that the strong p-d hybridization specific to nitrides and oxides leads to significant renormalization of the valence band exchange splitting.
We report the ultrafast optical pump-probe spectroscopy measurements on the recently discovered quantum critical ferromagnet CeRh$_6$Ge$_4$. Our experimental results reveal the two-stage development of the hybridization between localized $f$ moments and conduction electrons with lowering temperature, as evidenced by (1) the presence of hybridization fluctuation for temperatures from $\sim$85 K ($T^*$) to $\sim$140 K ($T^\dagger$), and (2) the emergence of collective hybridization below the coherence temperature, $T^*$, marked by the opening of an indirect gap of 2$Δ$ $\approx$12 meV. We also o…
The RKKY interaction between substitutional Mn local moments in GaAs is both spin-direction-dependent and spatially anisotropic. In this Letter we address the strength of these anisotropies using a semi-phenomenological tight-binding model which treats the hybridization between Mn d-orbitals and As p-orbitals perturbatively and accounts realistically for the non-local exchange interaction between their spins. We show that exchange non-locality, valence-band spin-orbit coupling, and band-structure anisotropy all play a role in determining the strength of both effects. We use these results to es…
We investigate the effect of quantum confinement on the ferromagnetism of diluted magnetic semiconductor Ga$_{1-x}$Mn$_x$As using a combination of tight-binding and density functional methods. We observe strong majority-spin Mn $d$-As $p$ hybridization, as well as half metallic behavior, down to sizes as small as 20 Åin diameter. Below this critical size, the doped holes are self-trapped by the Mn-sites, signalling both valence and electronic transitions. Our results imply that magnetically doped III-V nanoparticles will provide a medium for manipulating the electronic structure of dilute magn…
We have calculated the chemical trend of magnetic exchange parameters ($J_{dd}$, $N α$, and $N β$) of Zn-based II-VI semiconductors ZnA (A=O, S, Se, and Te) doped with Co or Mn. We show that a proper treatment of electron correlations by the LSDA+$U$ method leads to good agreement between experimental and theoretical values of the nearest-neighbor exchange coupling $J_{dd}$ between localized 3$d$ spins in contrast to the LSDA method. The exchange couplings between localized spins and doped electrons in the conduction band $N α$ are in good agreement with experiment as well. But the values for …
Spin polarized current is the main ingredient of diluted magnetic oxides due to its potential manipulation in spintronic devices. However, most research has focused on ferromagnetic properties rather than polarization of electric current, because direct measurements were difficult and the origin of spin polarized currents has yet to be fully understood. The method to increase the spin polarized current percentage is beyond practical consideration at the present status. To target this problem, we focus on the role of oxygen vacancies and nano grain size on the spin polarized current, which are …
By using first-principles electronic structure calculations, we have studied the magnetic interactions in a proposed BaZn$_2$P$_2$-based diluted magnetic semiconductor (DMS). For a typical compound Ba(Zn$_{0.944}$Mn$_{0.056}$)$_2$P$_2$ with only spin doping, due to the superexchange interaction between Mn atoms and the lack of itinerant carriers, the short-range antiferromagnetic coupling dominates. Partially substituting K atoms for Ba atoms, which introduces itinerant hole carriers into the $p$ orbitals of P atoms so as to link distant Mn moments with the spin-polarized hole carriers via the…
In heavy fermions the relaxation dynamics of photoexcited carriers has been found to be governed by the low energy indirect gap, E$_{g}$, resulting from hybridization between localized moments and conduction band electrons. Here, carrier relaxation dynamics in a prototype Kondo insulator YbB${}_{12}$ is studied over large range of temperatures and over three orders of magnitude. We utilize the intrinsic non-linearity of dynamics to quantitatively determine microscopic parameters, such as electron-hole recombination rate. The extracted value reveals that hybridization is accompanied by a strong…
We address the problem of hybridization between topological surface states and a non-topological flat bulk band. Our model, being a mixture of three-dimensional Bernevig-Hughes-Zhang and two-dimensional pseudospin-1 Hamiltonian, allows explicit treatment of the topological surface state evolution by continuously changing the hybridization between the inverted bands and an additional "parasitic" flat band in the bulk. We show that the hybridization with a flat band lying below the edge of conduction band converts the initial Dirac-like surface states into a branch below and one above the flat b…
The electronic structure of doped Mn in (Ga,Mn)As is studied by resonant inelastic X-ray scattering (RIXS). From configuration-interaction cluster-model calculations, the line shapes of the Mn $L_3$ RIXS spectra can be explained by $d$-$d$ excitations from the Mn$^{3+}$ ground state, dominated by charge-transferred states, rather than a Mn$^{2+}$ ground state. Unlike archetypical $d$-$d$ excitation, the peak widths are broader than the experimental energy resolution. We attribute the broadening to a finite lifetime of the $d$-$d$ excitations, which decay rapidly to electron-hole pairs in the h…
Considering a general situation where a semiconductor is doped by magnetic impurities leading to a carrier-induced ferromagnetic exchange coupling between the impurity moments, we show theoretically the possible generic existence of three ferromagnetic transition temperatures, T_1 > T_2 > T_3, with two distinct ferromagnetic regimes existing for T_1 > T > T_2 and T < T_3. Such an intriguing re-entrant ferromagnetism, with a paramagnetic phase (T_2 > T > T_3) between two ferromagnetic phases, arises from a subtle competition between indirect exchange induced by thermally activated carriers in a…
The electronic structure of the Cr ions in the diluted ferromagnetic semiconductor Zn$_{1-x}$Cr$_x$Te ($x=0.03$ and 0.15) thin films has been investigated using x-ray magnetic circular dichroism (XMCD) and photoemission spectroscopy (PES). Magnetic-field ($H$) and temperature ($T$) dependences of the Cr $2p$ XMCD spectra well correspond to the magnetization measured by a SQUID magnetometer. The line shape of the Cr $2p$ XMCD spectra is independent of $H$, $T$, and $x$, indicating that the ferromagnetism is originated from the same electronic states of the Cr ion. Cluster-model analysis indicat…
The magnetic circular dichroism of III-V diluted magnetic semiconductors, calculated within a theoretical framework suitable for highly disordered materials, is shown to be dominated by optical transitions between the bulk bands and an impurity band formed from magnetic dopant states. The theoretical framework incorporates real-space Green's functions to properly incorporate spatial correlations in the disordered conduction band and valence band electronic structure, and includes extended and localized electronic states on an equal basis. Our findings reconcile unusual trends in the experiment…
Guided by the internal-reference rule and the known band offsets in III-V and II-VI diluted magnetic semiconductors, we discuss the feasibility of obtaining p-type conductivity, required for the carrier-induced ferromagnetism, as well as the cases for which the doping by shallow impurities may lead to the ferromagnetism driven by the double exchange. We consider the dependence of kinetic exchange on the p-d hybridization, on the electronic configurations of the magnetic ions, and on the energies of the charge transfer between the valence band of host materials and the magnetic ions. In the cas…
We have used an eight band model to investigate the electronic structures and to calculate the optical matrix elements of InAs-GaSb broken gap semiconductor heterostructures. The unusual hybridization of the conduction band states in InAs layers with the valence band states in GaSb layers has been analyzed in details. We have studied the dependence of optical matrix elements on the degree of conduction-valence hybridization, the tuning of hybridization by varying the width of the GaSb layers and/or InAs layers, and the sensitivity of quantized levels to this tuning. Large spin-orbit splitting …
In the series R2PdSi3, Nd2PdSi3 is an anomalous compound in the sense that it exhibits ferromagnetic order unlike other members in this family. The magnetic ordering temperature is also unusually high compared to the expected value for a Nd-based system, assuming 4f localization. Here, we have studied the electronic structure of single crystalline Nd2PdSi3 employing high resolution photoemission spectroscopy and ab initio band structure calculations. Theoretical results obtained for the effective electron correlation strength of 6 eV corroborate well with the experimental valence band spectra.…
The muffin-tin model of an effective-mass electron interacting with magnetic ions in semiconductors is extended to incorporate electrostatic potentials that are present in the case of Mn-based III-V compounds (${Ga}_{1-x} {Mn}_x {N}$, ${Ga}_{1-x} {Mn}_x {As}$). Since the conduction band electron is repelled from negatively charged magnetic ions and attracted by compensating donors, the \emph{apparent} value of the s-d exchange coupling $N_0 α$ is reduced. It is shown that the magnitude of this effect increases when x diminishes. Our model may explain an unusual behavior of electron spin splitt…
As an exemplary Kondo insulator, SmB6 has been studied for several decades; however, direct evidence for the development of the Kondo coherent state and the evolution of the electronic structure in the material has not been obtained due to the rather complicated electronic and thermal transport behavior. Recently, these open questions attracted increasing attention as the emergence of a time-reversal invariant topological surface state in the Kondo insulator has been suggested. Here, we use point-contact spectroscopy to reveal the temperature dependence of the electronic states in SmB6. We dem…
Wurtzite GaN:Mn films on sapphire substrates were successfully grown by use of the molecular beam epitaxy (MBE) system. The film has an extremely high Curie temperature of around 940 K, although the Mn concentration is only about 3 ~ 5 %. Magnetization measurements were carried out in magnetic fields parallel to the film surface up to 7 T. The magnetization process shows the coexistence of ferromagnetic and paramagnetic contributions at low temperatures, while the typical ferromagnetic magnetization process is mainly observed at high temperatures because of the decrease of the paramagnetic con…
A new LDA+U band calculation is performed on the Kondo insulator material YbB$_{12}$ and an energy gap of about 0.001Ryd is obtained. Based on this, a simple tight-binding model with 5d$ε$ and 4f $Γ_8$ orbitals on Yb atoms and the nearest neighbor $σ$-bonds between them is constructed with a good agreement to the above the LDA+U calculation near the gap. The density of states is also calculated and the shape is found to be very asymmetric with respect to the gap. A formation mechanism of the gap is clarified for the first time in a realistic situation with the orbital degeneracies in both cond…
We study how a finite hybridization between a narrow correlated band and a wide conduction band affects the Mott transition. At zero temperature, the hybridization is found to be a relevant perturbation, so that the Mott transition is suppressed by Kondo screening. In contrast, a first-order transition remains at finite temperature, separating a local moment phase and a Kondo- screened phase. The first-order transition line terminates in two critical endpoints. Implications for experiments on f-electron materials such as the Cerium alloy Ce$_{0.8}$La$_{0.1}$Th$_{0.1}$ are discussed.
We present the cationic impurity assisted band offset phenomena in NixCd1-xO (x= 0, 0.02, 0.05, 0.1, 0.2, 0.4, 0.8, 1) thin films and further discussed in the light of orbital hybridization modification. Compositional and structural studies revealed that cationic substitution of Cd2+ by Ni2+ ions leads to a monotonic shift in (220) diffraction peak, indicating the suppression of lattice distortion while evolution of local strain with increasing Ni concentration mainly associated to the mismatch in electro-negativity of Cd2+ and Ni2+ ion. In fact, Fermi level pinning towards conduction band min…
We report the realization of a new multi-band-gap semiconductor. The highly mismatched alloy Zn1-yMnyOxTe1-x has been synthesized using the combination of oxygen ion implantation and pulsed laser melting. Incorporation of small quantities of isovalent oxygen leads to the formation of a narrow, oxygen-derived band of extended states located within the band gap of the Zn1-yMnyTe host. When only 1.3% of Te atoms is replaced with oxygen in a Zn0.88Mn0.12Te crystal (with band gap of 2.32 eV) the resulting band structure consists of two direct band gaps with interband transitions at ~1.77 eV and 2.7…
A particularly promising pathway to enhance the efficiency of thermoelectric materials lies in the use of resonant states, as suggested by experimentalists and theorists alike. In this paper, we go over the mechanisms used in the literature to explain how resonant levels affect the thermoelectric properties, and we suggest that the effects of hybridization are crucial yet ill-understood. In order to get a good grasp of the physical picture and to draw guidelines for thermoelectric enhancement, we use a tight-binding model containing a conduction band hybridized with a flat band. We find that t…
The local electronic structure of N atoms in a diluted GaAs1-xNx (x=3%) alloy, in view of applications in optoelectronics, is determined for the first time using soft-X-ray absorption (SXA) and emission (SXE). Deviations from crystalline GaN, in particular in the conduction band, are dramatic. Employing the orbital character and elemental specificity of the SXE/SXA spectroscopies, we identify a charge transfer from the N atoms at the valence band maximum, reducing the overlap with the wavefunction in conduction band minimum, as the main factor limiting the optical efficiency of GaAs1-xNx alloy…
Taking Mn doped Germanium as an example, we evoke the consideration of a two-band-like conduction in diluted ferromagnetic semiconductor (FMS). The main argument for claiming Ge:Mn as a FMS is the occurrence of the anomalous Hall effect (AHE). Usually, the reported AHE (1) is observable at temperatures above 10 K, (2) exhibits no hysteresis, and (3) changes the sign of slope. We observed a similar Hall resistance in Mn implanted Ge with the Mn concentration as low as 0.004%. We show that the puzzling AHE features can be explained by considering a two-band-like conduction in Ge:Mn.
The electronic properties of aluminum-doped graphenes enriched by multi-orbital hybridizations are investigated using first-principles calculations. The feature-rich electronic structures exhibit the quasi-rigid red shifts of the carbon-created energy bands, the Al-dominated valence and conduction bands, and many free electrons in the conduction Dirac cone. These are directly reflected in the special structures of density of states (DOS). The Al- and alkali-induced high free carrier densities are almost the same. There exist certain important differences among the Al-, alkali- and halogen-dope…
Surface of quantum materials often exhibits significantly different behavior than the bulk due to changed topologies and symmetry protections. The outstanding problem is to find out if the exoticity of a material is linked to the changed topology at the surface or it is a bulk property. Hard x-ray photoemission spectroscopy (HAXPES) is a significantly bulk sensitive technique (escape depth of valence electrons is about 40 Å for 6 keV photon energy) and the probing depth can be tuned by changing the electron emission angle. Therefore, HAXPES is often used to reveal the surface-bulk differences …
Metalated phthalocyanines (Pc's) are robust and versatile molecular complexes, whose properties can be tuned by changing their functional groups and central metal atom. The electronic structure of magnesium Pc (MgPc) - structurally and electronically similar to chlorophyll - adsorbed on the Ag(100) surface is investigated by low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS), non-contact atomic force microscopy (ncAFM) and density functional theory (DFT). Single, isolated MgPc's exhibit a flat, four-fold rotationally symmetric morphology, with doubly degenerate, partial…
: n-type Ge/SiGe asymmetric-coupled quantum wells represent the building block of a variety of nanoscale quantum devices, including recently proposed designs for a silicon-based THz quantum cascade laser. In this paper, we combine structural and spectroscopic experiments on 20-module superstructures, each featuring two Ge wells coupled through a Ge-rich tunnel barrier, as a function of the geometry parameters of the design and the P dopant concentration. Through the comparison of THz spectroscopic data with numerical calculations of intersubband optical absorption resonances, we demonstrated t…
The electronic band structure of Ga(PAsN) with a few percent of nitrogen is calculated in the whole composition of Ga(PAs) host using the state-of-the-art density functional methods including the modified Becke-Johnson functional to correctly reproduce the band gap, and band unfolding to reveal the character of the bands within the entire Brillouin zone. As expected, relatively small amounts of nitrogen introduced to Ga(PAs) lead to formation of an intermediate band below the conduction band which is consistent with the band anticrossing model, widely used to describe the electronic band struc…
