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At least 757 records · Page 42

Electron–Hole Dimers in the Parent Phase of Quasi–2D Cuprates

The key feature of parent cuprates of the La{sub 2}CuO{sub 4} type, in addition to their high ionic polarizability and closeness to polarization catastrophe, is identified as their instability against charge transfer that is accompanied by the formation of a system of metastable dipole-active Mott–Hubbard excitons, i.e., electron–hole (EH) dimers. This feature determines the behavior of cuprates upon nonisovalent substitution. Within the simplest model equivalent to a system of composite bosons, nonisovalent substitution shifts the phase equilibrium toward condensation of EH dimers and the formation of inhomogeneous EH liquid. To describe the electronic state of doped cuprates effectively, we propose to use the pseudospin S = 1 formalism. It enables us to treat cardinally new charged states such as Anderson’s RVB phases. Recombination of EH dimers at a critically low energy of local and nonlocal correlations drives the system into the state of a Fermi liquid.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Development and Characterization of High Performance and Robust Mixed Conducting Cathodes Supportive of Lower Cost Solid Oxide Fuel Cells (Final Report)

The objective of the proposed research is to advance an existing partnership between the University of South Carolina (USC) and LG Fuel Cell Systems, Inc. (LGFCS) to research and develop mixed electronic and ionic conducting cathode materials for durable and robust low-cost solid oxide fuel cells (SOFCs). The first task is to develop mixed ionic and electronic conducting doped (Pr,Nd)NiO 4 (PNNO)-based cathodes. This task is built on a prior collaborative work with LG Fuel Cell System, which showed that doped PNNO could exhibit phase stability at high temperatures. The initial focus will be on investigating the durability and endurance of its electrochemical performance and the temporal evolution of microstructures. In-situ high temperature neutron diffraction and x-ray diffraction will be used to study the structures of these phase stable compounds. PNNO doped with Ca and transition metal elements will be synthesized. Physical properties of these materials with respect to coefficient of thermal expansion, electrical conductivity, diffusion coefficient, and nonstoichiometry will be measured. The benefits of dense versus porous barriers will be studied and the role of barrier layer will be identified and a guideline will be provided to choose the maximum porosity for durable and robust cathode performance with co-doped PNNO as the cathodes. LSCF6428 will be used to compare its power density with that of co-doped PNNO in the absence of Cr, but some studies comparing Cr tolerance will be performed towards the end of the project. The conditions at which preferred nickelate phases are stable will be defined, including sintering temperature, operating temperature, and composition range. The second task will focus on the investigation of the location of degradation by using differential relaxation time (DRT) analysis, coupled with least squares fitting and systematical post analyses. DRT analysis can provide (1) a direct access to the kinetic parameters of the underlying processes in both cathode and anode, and (2) a clearer picture of SOFC operation, which allows loss factors to the changes of microstructures or activities of either electrode to be distinguished, and a better target fuel cell development to be enabled. The third task aims at applying the accelerated testing protocol to investigate the microstructural evolution of the cathode candidates identified in this research. Technical approaches will be developed to mitigate and improve the durability of cathode materials by choosing the right chemistry and tuning cathode microstructures.

36 MATERIALS SCIENCE↗

High-field/high-frequency electron spin resonances of Fe-doped β − Ga 2 O 3 by terahertz generalized ellipsometry: Monoclinic symmetry effects

We demonstrate detection and measurement of electron paramagnetic spin resonances (EPR) of iron defects in β − Ga 2 O 3 utilizing generalized ellipsometry at frequencies between 110 and 170 GHz. The experiments are performed on an Fe-doped single crystal in a free-beam configuration in reflection at 45 ∘ and magnetic fields between 3 and 7 T. In contrast with low-field, low-frequency EPR measurements, we observe all five transitions of the s = 5 / 2 high-spin state Fe 3 + simultaneously. We confirm that ferric Fe 3 + is predominantly found at octahedrally coordinated Ga sites. We obtain the full set of fourth-order monoclinic zero-field splitting parameters for both octahedrally and tetrahedrally coordinated sites by employing measurements at multiple sample azimuth rotations. The capability of high-field EPR allows us to demonstrate that simplified second-order orthorhombic spin Hamiltonians are insufficient, and fourth-order terms as well as consideration of the monoclinic symmetry are needed. These findings are supported by computational approaches based on density-functional theory for second-order and on ligand-field theory for fourth-order parameters of the spin Hamiltonian. Terahertz ellipsometry is a way to measure spin resonances in a cavity-free setup. Its possibility of varying the probe frequency arbitrarily without otherwise changing the experimental setup offers unique means of truly disentangling different components of highly anisotropic spin Hamiltonians. Published by the American Physical Society 2024

Materials Science↗

Charge partitioning and anomalous hole doping in Rh-doped Sr 2 IrO 4

The simultaneous presence of sizable spin-orbit interactions and electron correlations in iridium oxides has led to predictions of novel ground states including Dirac semimetals, Kitaev spin liquids, and superconductivity. Electron and hole doping studies of spin-orbit assisted Mott insulator Sr 2 IrO 4 are being intensively pursued due to extensive parallels with the La 2 CuO 4 parent compound of cuprate superconductors. In particular, the mechanism of charge doping associated with replacement of Ir with Rh ions remains controversial with profound consequences for the interpretation of electronic structure and transport data. Using x-ray absorption near edge structure measurements at the Rh L, K, and Ir L edges we observe anomalous evolution of charge partitioning between Rh and Ir with Rh doping. The partitioning of charge between Rh and Ir sites progresses in a way that holes are initially doped into the J eff = 1/2 band at low x only to be removed from it at higher x values. Furthermore, this anomalous hole doping naturally explains the reentrant insulating phase in the phase diagram of Sr 2 Ir 1–x Rh x O 4 and ought to be considered when searching for superconductivity and other emergent phenomena in iridates doped with 4d elements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Role of dopants in LiF:Mg,Cu, LiF:Mg,P and LiF:Mg,Cu,P detectors

In this study, electronic structure of LiF crystal doped with Mg,Cu,P impurities was studied with WIEN2k code on the basis of FPLAPW+lo method. Results show that in Mg-doped LiF composition, an electronic trap was created with impurity concentration of 1.56% and 3.125%. In this condition, the electronic trap with increasing the percentage of the impurities up to 4.687% is annihilated. It was found, that by doping of Mg and Cu or P simultaneously, a hole-trap is created in valence band. It was realized that in LiF:Mg,Cu, LiF:Mg,P and LiF:Mg,Cu,P, Cu impurity and Li atom, have a key role in creation of levels which lead to create electronic and hole traps. Mg impurity and F atom, only have a role in creation of electronic traps. In addition, P impurity has a main role in creation of the electronic and hole traps in LiF:Mg,Cu,P. The activation energy of electronic and hole trap in LiF:Mg,Cu, LiF:Mg,P and LiF:Mg,Cu,P crystalline lattice were obtained as 0.3 and 5.5 eV, 0.92 and 3.4 eV and 0.75 and 3.1 eV, respectively. - Graphical abstract: Figure (a) and (b) shows changes in electronic structure and band gap energy of LiF crystal due to presence of Mg and Cu, Mg and P ions respectively. - Highlights: • Electronic structure of LiF, LiF:Mg,Cu, LiF:Mg,P and LiF:Mg,Cu,P materials were studied with WIEN2K code. • In LiF:Mg,Cu and LiF:Mg,Cu,P, Li atom and Cu impurity have a key role in creation of levels. • F atom and Mg impurity only have a role in creation of electronic traps. • In LiF:Mg,Cu,P, P impurity has a main role in creation of electronic and hole traps.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First-principles investigation of metal-doped cubic BaTiO{sub 3}

Highlights: • Electronic properties of metal-doped cubic BaTiO{sub 3} are studied by DFT calculations. • Most transition-metal doping can effectively reduce the band gap of BaTiO{sub 3}. • The effective mass can be reduced by doping BaTiO{sub 3} with metals. • Substituting Ti with Fe or Mo could improve the photoelectric properties of BaTiO{sub 3}. - Abstract: The electronic properties of metal-doped cubic BaTiO{sub 3} have been investigated using first-principles calculations. Through systematic analysis on effects of various metals doping through substituting Ti with the main group, 3d and 4d transitions metal atoms, we show that most transition metal doping can effectively reduce the band gap of BaTiO{sub 3}. The partial density of states analysis indicates that different doping elements have different effects on the band-gap engineering. The effective mass of BaTiO{sub 3} before and after doping was further analyzed. And we found that the hole effective mass apparently decrease after Fe, Cu, Zn, Mo, and Ag doping, which could lead to increase of hole mobility and charge transfer enhancement. The calculation results showed that substituting Ti with Fe or Mo would be more effective for improving the photoelectric property of BaTiO{sub 3}. Our theoretical calculations provide useful insights and beneficial guidance into experimental study of BaTiO{sub 3} in the photoelectric applications.

36 MATERIALS SCIENCE↗

Blue phosphorescent organic light-emitting devices utilizing cesium–carbonate-doped 2,4,6-tris(2',4'-difluoro-[1,1'- biphenyl]-4-yl)-1,3,5-triazine

We report an alternative, high yielding synthesis for the known compound 2,4,6-tris(2',4'-difluoro-[1,1'-biphenyl]-4-yl)-1,3,5-triazine, (tris-(dFB)Tz). The lowest occupied molecular orbital energy for tris-(dFB)Tz is calculated to be -3.5 eV via electrochemical characterization. The deep ELUMO of tris-(dFB)Tz affords a material with excellent electron acceptor characteristics for use in n-doped electron transport layers. Tris-(dFB)Tz shows a four order of magnitude increase in the number of carriers upon doping with 8 wt.% Cs2CO3. Enhanced electron injection was also observed upon doping with Cs2CO3, eliminating the need for a LiF injection layer. Blue phosphorescent OLEDs were fabricated using n-doped tris-(dFB)Tz electron transport layers. OLEDs with thick (700Å) Cs2CO3 doped tris-(dFB)Tz electron transport layers had lower operating voltage than OLEDS with an undoped electron transport layer of bis(diphenylphosphoryl)dibenzothiophene (PO15), which has previously been used in low voltage, high efficiency OLEDs. The tris-(dFB)Tz results indicate that aromatic substituted triazines may be promising materials for use as electron acceptors in n-doped organic electronic systems.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Electron and hole gas in modulation-doped GaAs/Al{sub 1-x}Ga{sub x}As radial heterojunctions

We perform self-consistent Schroedinger-Poisson calculations with exchange and correlation corrections to determine the electron and hole gas in a radial heterojunction formed in a GaAs/AlGaAs core-multi-shell nanowire, which is either n- or p-doped. We show that the electron and hole gases can be tuned to different localizations and symmetries inside the core as a function of the doping density/gate potential. Contrary to planar heterojunctions, conduction electrons do not form a uniform 2D electron gas (2DEG) localized at the GaAs/AlGaAs interface, but rather show a transition between an isotropic, cylindrical distribution deep in the GaAs core (low doping) and a set of six tunnel-coupled quasi-1D channels at the edges of the interface (high doping). Holes, on the other hand, are much more localized at the GaAs/AlGaAs interface. At low doping, they present an additional localization pattern with six separated 2DEGs strips. The field generated by a back-gate may easily deform the electron or hole gas, breaking the sixfold symmetry. Single 2DEGs at one interface or multiple quasi-1D channels are shown to form as a function of voltage intensity, polarity, and carrier type.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Direct observation of the electronic structure in thermoelectric half-Heusler alloys Zr{sub 1−x}M{sub x}NiSn (M = Y and Nb)

This study investigates the electronic and local crystal structures of the hole-doped Zr{sub 1−x}Y{sub x}NiSn and electron-doped Zr{sub 1−x}Nb{sub x}NiSn alloys using synchrotron radiation photoemission spectroscopy (SR-PES) and synchrotron radiation X-ray powder diffraction (SR-XRD) measurements, thereby clarifying the mechanisms underlying the thermoelectric performance of the p- and n-type alloys. SR-XRD analysis reveals an interstitial Ni disorder in the half-Heusler structure and the substitution of the dopant Y and Nb atoms at the Zr site. SR-PES result shows that the variation in the electronic structure of the alloys due to doping can be explained on the basis of the rigid band model. The asymmetric pseudo-gap near the Fermi level, which is rather unexpected from the band structure calculation because of the presence of the interstitial Ni disorder, could possibly be the reason underlying poor thermoelectric performance of p-type half-Heusler ZrNiSn alloys when compared with the n-type counterparts.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Extremely large anisotropic transport caused by electronic phase separation in Ti-doped Ca 3 Ru 2 O 7

In this paper, we reported an extremely large out-of-plane/in-plane anisotropic transport (${{\rho}_{c}}/{{\rho}_{ab}}$ ~ 10 9 ) in double layer ruthenates. The mechanism that may be responsible for this phenomenon is also explored here. Distinct from previously well studied layered materials which show large out-of-plane/in-plane electronic anisotropy (10 3 –10 6 ), the Ti-doped Ca 3 Ru 2 O 7 single crystals not only form quasi-2D layered structure, but also show phase separation within the layers. We found that Ti doping in Ca 3 Ru 2 O 7 induced electronic phase separation between the insulating phase and weak localized phase. The ratio of these two phases is very sensitive to the Ti concentration. At typical concentration, the weak localized phase may form a channel on the background of the insulating phase within the ab plane. However, the small volume of weak localized phase makes it less likely to overlap in different layers. This results in a much larger electronic anisotropy ratio than pristine compound Ca 3 Ru 2 O 7 . Furthermore, this new mechanism provides a route for further increase electronic anisotropy, which will remarkably reduce current leak and power consumption in electronic devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Boron concentration profiling by high angle annular dark field-scanning transmission electron microscopy in homoepitaxial δ-doped diamond layers

To develop further diamond related devices, the concentration and spatial location of dopants should be controlled down to the nanometer scale. Scanning transmission electron microscopy using the high angle annular dark field mode is shown to be sensitive to boron doping in diamond epilayers. An analytical procedure is described, whereby local boron concentrations above 10{sup 20} cm{sup −3} were quantitatively derived down to nanometer resolution from the signal dependence on thickness and boron content. Experimental boron local doping profiles measured on diamond p{sup −}/p{sup ++}/p{sup −} multilayers are compared to macroscopic profiles obtained by secondary ion mass spectrometry, avoiding reported artefacts.

36 MATERIALS SCIENCE↗

Effects of Mn dopant locations on the electronic bandgap of PbS quantum dots

Dilute magnetic semiconductors (DMSs) are typically made by doping semiconductors with magnetic transition metal elements. Compared to the well-understood bulk and thin film DMS, the understanding of the magnetic element doping effects in semiconducting quantum dots (QDs) is relatively poor. In particular, the influence of the dopant locations is rarely explored. Here, we present a comprehensive study of the effects of Mn doping on the electronic density of states of PbS QDs. Based on the results observed by scanning tunneling microscopy, X-ray diffraction, electron paramagnetic resonance, and density functional theory calculations, it is found that the Mn doping causes a broadening of the electronic bandgap in the PbS QDs. The sp-d hybridization between the PbS host material and Mn dopants is argued to be responsible for the bandgap broadening. Moreover, the locations of the Mn dopants, i.e., on the surface or inside the QDs, have been found to play an important role in the strength of the sp-d hybridization, which manifests as different degrees of the bandgap change.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Atomic scale studies of doped-hole distributions, self-organized electronic nano-domains, and electron-boson coupling in high Tc-cuprates

Progress is reported in these areas (titles and abstracts of journal articles produced for the contract): Exotic Density Wave in Underdoped Cuprates; Varying the inter-atomic distances within individual crystal unit-­cells of cuprates; Truncated Momentum Space Electronic Structure of Underdoped Bi 2 Sr 2 CaCu 2 O 8+δ ; and, Visualizing Phase Fluctuating d-Wave Superconductivity in the Cuprate Pseudogap State.

36 MATERIALS SCIENCE↗

Electronic structure of Al- and Ga-doped ZnO films studied by hard X-ray photoelectron spectroscopy

Al- and Ga-doped sputtered ZnO films (AZO, GZO) are semiconducting and metallic, respectively, despite the same electronic valence structure of the dopants. Using hard X-ray photoelectron spectroscopy we observe that both dopants induce a band in the electronic structure near the Fermi level, accompanied by a narrowing of the Zn 3d/O 2p gap in the valence band and, in the case of GZO, a substantial shift in the Zn 3d. Ga occupies substitutional sites, whereas Al dopants are in both substitutional and interstitial sites. The latter could induce O and Zn defects, which act as acceptors explaining the semiconducting character of AZO and the lack of variation in the optical gap. By contrast, mainly substitutional doping is consistent with the metallic-like behavior of GZO.

36 MATERIALS SCIENCE↗

Eu 2+ –Eu 3+ valence transition in double, Eu-, and Na-doped PbSe from transport, magnetic, and electronic structure studies

The Eu atoms in Pb 1-x Eu x Se have long been assumed to be divalent. We show that p-type doping of this magnetic semiconductor alloy with Na can modify the effective Eu valence: a mixed, Eu 2+ –Eu 3+ state appears in Pb 1-x-y Eu x Na y Se at particular values of y. Magnetization, carrier concentration, resistivity, and thermopower of Pb 1-x-y Eu x Na y Se are reported for a number of samples with different x and y. A pronounced increase in thermopower at a given carrier concentration was identified and attributed to the presence of enhanced ionized impurity scattering. A strong decrease in the hole concentration is observed in Pb1-yNaySe when Eu is added to the system, which we attribute to a Eu 2+ –Eu 3+ self-ionization process. This is evidenced by magnetization measurements, which reveal a significant reduction of the magnetic moment of Pb 1-x Eu x Se upon alloying with Na. Further, a deviation of magnetization from a purely paramagnetic state, described by a Brillouin function, identifies antiferromagnetic interactions between the nearest-neighbor Eu atoms: a value of J ex /k B = -0.35 K was found for the exchange coupling parameter. The conclusion of a Eu 2+ –Eu 3+ self-ionization process being in effect is supported further by the electronic structure calculations, which show that an instability of the 4f 7 configuration of the Eu 2+ ion appears with Na doping. In conclusion, schematically, it was found that the Eu 4f levels form states near enough to the Fermi energy that hole doping can lower the Fermi energy and trigger a reconfiguration of a 4f electronic shell.

36 MATERIALS SCIENCE↗

Charge Carriers Modulate the Bonding of Semiconductor Nanoparticle Dopants As Revealed by Time-Resolved X-ray Spectroscopy

Understanding the electronic structure of doped semiconductors is essential to realize advancements in electronics and in the rational design of nanoscale devices. Here, we report the results of time-resolved X-ray absorption studies on copper-doped cadmium sulfide nanoparticles that provide an explicit description of the electronic dynamics of the dopants. The interaction of a dopant ion and an excess charge carrier is unambiguously observed via monitoring the oxidation state. The experimental data combined with DFT calculations demonstrate that dopant bonding to the host matrix is modulated by its interaction with charge carriers. Additionally, the transient photoluminescence and the kinetics of dopant oxidation reveal the presence of two types of surface-bound ions that create mid-gap states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗