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1.
iScience ; 23(6): 101196, 2020 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-32516720

RESUMO

The charge states of elements dictate the behavior of electrons and phonons in a lattice, either directly or indirectly. Here, we report the discovery of an anomalous charge state evolution in the superconducting M3Al2C (M = Mo, W) system, where electron doping can be achieved through "oxidation." Specifically, with the continuous removal of electron donor (Al) from the structure, we found an electron doping effect in the negatively charged transition metals. Over a certain threshold, the charge state of transition metals goes through a sudden reversion from negative to positive, which leads to a subsequent structure collapse. Concomitantly, the previous robust superconducting transition temperatures (Tcs) can be flexibly modulated. Detailed analysis reveals the origin of the superconductivity and the intimate relationship between the charge state and the electron-phonon coupling constant. The peculiar charge state in M3Al2C plays an important role in both its structure and superconductivity.

2.
Artigo em Inglês | MEDLINE | ID: mdl-32460482

RESUMO

Owing to the recent discovery of the current-induced metal-insulator transition and unprecedented electronic properties of the concomitant phases of calcium ruthenate Ca2RuO4, it is emerging as an important material. To further explore the properties, the growth of epitaxial thin films of Ca2RuO4 is receiving more attention, as high current densities can be applied to thin-film samples and the amount can be precisely controlled in an experimental environment. However, it is difficult to grow high-quality thin films of Ca2RuO4 due to the easy formation of the crystal defects originating from the sublimation of RuO4; therefore, the metal-insulator transition of Ca2RuO4 is typically not observed in the thin films. Herein, a stable current-induced metal-insulator transition is achieved in the high-quality thin films of Ca2RuO4 grown by solid-phase epitaxy under high growth temperatures and pressures. In the Ca2RuO4 thin films grown by ex situ annealing at >1200 °C and 1.0 atm, continuous changes in the resistance of over 2 orders of magnitude are induced by currents with a precise dependence of the resistance on the current amplitude. A hysteretic, abrupt resistive transition is also observed in the thin films from the resistance-temperature measurements conducted under constant-voltage (variable-current) conditions with controllability of the transition temperature. A clear resistive switching by the current-induced transition is demonstrated in the current-electric-field characteristics, and the switching currents and fields are shown to be very stable. These results represent a significant step toward understanding the high-current-density properties of Ca2RuO4 and the future development of Mott-electronic devices based on electricity-driven transitions.

3.
Inorg Chem ; 58(17): 11819-11827, 2019 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-31415158

RESUMO

Among the intermetallics and alloys, YCu is an unusual material because it displays negative thermal expansion without spin ordering. The mechanism behind this behavior that is caused by the structural phase transition of YCu has yet to be fully understood. To gain insight into this mechanism, we experimentally examined the crystal structure of the low-temperature phase of YCu and discuss the origin of the phase transition with the aid of thermodynamics calculations. The result shows that the high-temperature (cubic CsCl-type) to low-temperature (orthorhombic FeB-type) structural phase transition is driven by the rearrangement of three covalent bonds, namely, Y-Cu, Y-Y, and Cu-Cu, which compete for the bonding energy and phonon entropy. At low temperatures, the mixing of Y and Cu does not take place easily because of the weak attractive force between these atoms expected from the small negative mixing enthalpy. This causes all three interactions to take part in the bonding, and Y and Cu are segregated to form an FeB-type structure, which is stabilized by internal energy. At higher temperatures, Cu ions are bound loosely with Y ions due to the large Y-Cu distance (3.01 Å), which results in large vibration entropy and stabilizes a CsCl-type crystal structure. In addition, the CsCl-type structure is reinforced by the Y-Y interaction between next-nearest neighbors, resulting in a smaller unit cell volume. The crystal structure has the simple cubic framework of Y containing Cu ions bound loosely at the cavity sites. The calculated frequency of the Y-like phonon modes is much higher than that of the Cu-like modes, indicating the presence of Y-Y covalent interactions in the CsCl-type phase.

4.
ACS Appl Mater Interfaces ; 11(38): 35132-35137, 2019 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-31456393

RESUMO

Oxide semiconductor thin-film transistors (TFTs) are currently used as the fundamental building blocks in commercial flat-panel displays because of the excellent performance of n-channel TFTs. However, except for a few materials, their p-channel performances have not been acceptable. Although some p-type oxide semiconductors exhibit superior hole transport properties, their TFT performances are greatly deteriorated, which is a major obstacle in the development of complementary metal-oxide-semiconductor (CMOS) circuits. Herein, an ionic nitride semiconductor, copper nitride (Cu3N), composed of environmentally benign elements is shown to exhibit highly symmetric hole and electron transport, indicating its suitability for application in CMOS circuits. We performed a two-step investigation. The first step was to examine the ultimate potential of Cu3N using an electric-double-layer transistor structure with epitaxial Cu3N channels measured at 220 K, which exhibited ambipolar operation with hole and electron mobilities of ∼5 and ∼10 cm2 V-1 s-1, respectively, and a high on/off ratio of ∼105. The second step is to demonstrate the feasibility of TFT circuits with a polycrystalline channel on non-single-crystal (SiO2/Si) substrates. CMOS-like inverters composed of two polycrystalline Cu3N ambipolar TFTs on a SiO2/Si substrate exhibited a high voltage gain of ∼100.

5.
Phys Chem Chem Phys ; 20(32): 20952-20956, 2018 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-30069569

RESUMO

Hydrogen (H) plays critical roles in the electrical properties of semiconductor materials and devices. In this work, we report multiple states and roles of H in SnS by H plasma treatment and density functional theory (DFT) calculations. The as-deposited SnS films include impurity H at 2.3 × 1019 cm-3, four orders of magnitude larger than the hole density. The DFT calculations reveal that H exists in multiple states at the equilibrium mainly at the interstitial and the Sn-substitutional sites, which have formation enthalpies lower than those for the intrinsic defects. These H states work as donors and acceptors, respectively, and strongly pin the Fermi level in the p-type region. The native p-type conduction in the actual SnS semiconductors is caused mainly by the H-on-Sn (HSn) acceptors, rather than the previously reported Sn vacancies (VSn) for pure SnS. It is also confirmed that even stronger H doping with larger H chemical potentials cannot convert SnS to an n-type conductor because it reduces SnS to Sn metal.

6.
Inorg Chem ; 57(8): 4502-4509, 2018 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-29578339

RESUMO

We report the synthesis and characterizations of a new FeSe-based compound CsFe4-δSe4, which is closely related to alkali intercalated FeSe superconductors while exhibits distinct features. It does not undergo phase separation and antiferromagnetic transition. Powder neutron diffractions, electron microscopy and high-angle annular-dark-field images confirm that CsFe4-δSe4 possesses an ordered Cs arrangement as √2 × âˆš2 superstructure, evidencing a B-centered orthorhombic lattice with a space group of Bmmm. The temperature-dependent powder neutron diffractions indicate no structural and magnetic transition from 320 to 5 K. In contrast to the symmetry-breaking in FeSe, this phase naturally possesses the orthorhombic symmetry even at room temperature. DFT calculations and transport measurements reveal a novel Fermi surface geometry with two electron-like sheets centered on Γ point and intermediate density of states at the Fermi level comparing with the value of FeSe and the superconducting A xFe2Se2.

7.
J Phys Chem Lett ; 9(1): 43-48, 2018 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-29231743

RESUMO

Over the past few years, the development of lead-free and stable perovskite absorbers with excellent performance has attracted extensive attention. Much effort has been devoted to screening and synthesizing this type of solar cell absorbers. Here, we present a general design strategy for designing the layered halide double perovskites Cs3+nM(II)nSb2X9+3n (M = Sn, Ge) with desired photovoltaic-relevant properties by inserting [MX6] octahedral layers, based on the principles of increased electronic dimensionality. Compared to Cs3Sb2I9, more suitable band gaps, smaller carrier effective masses, larger dielectric constants, lower exciton binding energies, and higher optical absorption can be achieved by inserting variable [SnI6] or [GeI6] octahedral layers into the [Sb2I9] bilayers. Moreover, our results show that adjusting the thickness of inserted octahedral layers is an effective approach to tune the band gaps and carrier effective masses in a large range. Our work provides useful guidance for designing the promising layered antimony halide double perovskite absorbers for photovoltaic applications.

8.
Chemistry ; 24(10): 2305-2316, 2018 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-29205559

RESUMO

The bandgap is the most important physical property that determines the potential of semiconductors for photovoltaic (PV) applications. This Minireview discusses the parameters affecting the bandgap of perovskite semiconductors that are being widely studied for PV applications, and the recent progress in the optimization of the bandgaps of these materials. Perspectives are also provided for guiding future research in this area.

9.
J Phys Chem Lett ; 9(1): 258-262, 2018 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-29280377

RESUMO

Although metal halide double perovskites A2B(I)B(III)X6 are expected as nontoxic alternatives for lead halide perovskites, recent studies have shown that only Tl(I)-Bi(III) and In(I)-Bi(III) bromides are thermodynamically stable and possess optoelectronic properties suitable for photovoltaic absorbers. Here, we show, through density functional theory calculations, that Tl-Bi and In-Bi bromide double perovskites exhibit significantly different semiconducting behaviors due to the different energy levels of the highest-occupied pseudoclosed s2 orbitals of Tl(I) and In(I). While Tl-Bi double perovskites can exhibit semiconducting p-type properties, In-Bi bromide double perovskites exhibit metallic p-type ones regardless of the synthesis condition due to the extremely low formation energy of In vacancy. Such difference makes Tl-Bi bromide double perovskites suitable for optoelectronic applications, but not In-Bi bromide double perovskites. Furthermore, there is a high probability for In to substitute a Bi site, forming a local In-In bromide double perovskite structure with a lower local conduction band minimum, detrimentally affecting the open circuit voltage of In-Bi bromide double perovskite-based thin film solar cells.

10.
Inorg Chem ; 56(17): 10535-10542, 2017 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-28812880

RESUMO

The electronic structures of 35 A2+B4+O3 ternary cubic perovskite oxides, including their hypothetical chemical compositions, were calculated by a hybrid functional method with the expectation that peculiar electronic structures and unique carrier transport properties suitable for semiconductor applications would be hidden in high-symmetry cubic perovskite oxides. We found unique electronic structures of Si-based oxides (A = Mg, Ca, Sr, and Ba, and B = Si). In particular, the unreported cubic BaSiO3 has a very narrow band gap (4.1 eV) compared with conventional nontransition-metal silicates (e.g., ∼9 eV for SiO2 and the calculated value of 7.3 eV for orthorhombic BaSiO3) and a small electron effective mass (0.3m0, where m0 is the free electron rest mass). The narrow band gap is ascribed to the nonbonding state of Si 3s and the weakened Madelung potential. The existence of the predicted cubic perovskite structure of BaSiO3 was experimentally verified by applying a high pressure of 141 GPa. The present finding indicates that it could be possible to develop a new transparent oxide semiconductor of earth abundant silicates if the symmetry of its crystal structure is appropriately chosen. Cubic BaSiO3 is a candidate for high-performance oxide semiconductors if this phase can be stabilized at room temperature and ambient pressure.

11.
Angew Chem Int Ed Engl ; 56(34): 10135-10139, 2017 08 14.
Artigo em Inglês | MEDLINE | ID: mdl-28467629

RESUMO

The electronic structures of the antifluorite-type compound Mg2 Si is described in which a sublattice of short cation-cation contacts creates a very low conduction band minimum. Since Mg2 Si shows n-type conductivity without intentional carrier doping, the present result indicates that the cage defined by the cations plays critical roles in carrier transport similar to those of inorganic electrides, such as 12 CaO⋅7 Al2 O3 :e- and Ca2 N. A distinct difference in the location of conduction band minimum between Mg2 Si and the isostructural phase Na2 S is explained in terms of factors such as the differing interaction strengths of the Si/S 3s orbitals with the cation levels, with the more core-like character of the S 3s leading to a relatively low conduction band energy at the Γ point. Based on these results and previous research on electrides, approaches can be devised to control the energy levels of cation sublattices in semiconductors.

12.
Proc Natl Acad Sci U S A ; 114(2): 233-238, 2017 01 10.
Artigo em Inglês | MEDLINE | ID: mdl-28028243

RESUMO

Efficient electron transfer between a cathode and an active organic layer is one key to realizing high-performance organic devices, which require electron injection/transport materials with very low work functions. We developed two wide-bandgap amorphous (a-) oxide semiconductors, a-calcium aluminate electride (a-C12A7:e) and a-zinc silicate (a-ZSO). A-ZSO exhibits a low work function of 3.5 eV and high electron mobility of 1 cm2/(V · s); furthermore, it also forms an ohmic contact with not only conventional cathode materials but also anode materials. A-C12A7:e has an exceptionally low work function of 3.0 eV and is used to enhance the electron injection property from a-ZSO to an emission layer. The inverted electron-only and organic light-emitting diode (OLED) devices fabricated with these two materials exhibit excellent performance compared with the normal type with LiF/Al. This approach provides a solution to the problem of fabricating oxide thin-film transistor-driven OLEDs with both large size and high stability.

13.
Sci Rep ; 6: 36828, 2016 11 11.
Artigo em Inglês | MEDLINE | ID: mdl-27833118

RESUMO

Thin films of the iron-based superconductor BaFe2(As1-xPx)2 (Ba122:P) were fabricated on polycrystalline metal-tape substrates with two kinds of in-plane grain boundary alignments (well aligned (4°) and poorly aligned (8°)) by pulsed laser deposition. The poorly aligned substrate is not applicable to cuprate-coated conductors because the in-plane alignment >4° results in exponential decay of the critical current density (Jc). The Ba122:P film exhibited higher Jc at 4 K when grown on the poorly aligned substrate than on the well-aligned substrate even though the crystallinity was poorer. It was revealed that the misorientation angles of the poorly aligned samples were less than 6°, which are less than the critical angle of an iron-based superconductor, cobalt-doped BaFe2As2 (~9°), and the observed strong pinning in the Ba122:P is attributed to the high-density grain boundaries with the misorientation angles smaller than the critical angle. This result reveals a distinct advantage over cuprate-coated conductors because well-aligned metal-tape substrates are not necessary for practical applications of the iron-based superconductors.

14.
Proc Natl Acad Sci U S A ; 113(15): 3986-90, 2016 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-27035956

RESUMO

It is thought that strong electron correlation in an insulating parent phase would enhance a critical temperature (Tc) of superconductivity in a doped phase via enhancement of the binding energy of a Cooper pair as known in high-Tc cuprates. To induce a superconductor transition in an insulating phase, injection of a high density of carriers is needed (e.g., by impurity doping). An electric double-layer transistor (EDLT) with an ionic liquid gate insulator enables such a field-induced transition to be investigated and is expected to result in a high Tc because it is free from deterioration in structure and carrier transport that are in general caused by conventional carrier doping (e.g., chemical substitution). Here, for insulating epitaxial thin films (∼10 nm thick) of FeSe, we report a high Tc of 35 K, which is 4× higher than that of bulk FeSe, using an EDLT under application of a gate bias of +5.5 V. Hall effect measurements under the gate bias suggest that highly accumulated electron carrier in the channel, whose area density is estimated to be 1.4 × 10(15) cm(-2) (the average volume density of 1.7 × 10(21) cm(-3)), is the origin of the high-Tc superconductivity. This result demonstrates that EDLTs are useful tools to explore the ultimate Tc for insulating parent materials.

15.
J Phys Chem Lett ; 6(24): 4966-71, 2015 Dec 17.
Artigo em Inglês | MEDLINE | ID: mdl-26618554

RESUMO

Electrides are characteristic of anionic electrons trapped at the structural voids in the host lattice. Electrides are potentially useful in various technological applications; however, electrides, particularly their inorganic subgroup, have been discovered only in limited material systems, notably zero-dimensional [Ca24Al28O64](4+):4e(-) and two-dimensional [Ca2N](+):e(-) and [Y2C](1.8+):1.8e(-). Here, on the basis of density functional theory calculations, we report the first one-dimensional (1D) electride with a [La8Sr2(SiO4)6](4+):4e(-) configuration, in which the four anionic electrons are confined in the channel spaces of the host material. According to this theoretical prediction, an insulator-semiconductor transition originating from electron confinement in the crystallographic channel sites was demonstrated experimentally, where 10.5% of the channel oxygen was removed by reacting an oxygen stoichiometric La8Sr2(SiO4)6O2 precursor with Ti metal at a high temperature. This study not only adds an unprecedented role to silicate apatite as a parent phase to a new 1D electride, but also, and more importantly, demonstrates an effective approach for developing new electrides with the assistance of computational design.

16.
Phys Chem Chem Phys ; 17(29): 18900-3, 2015 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-26144220

RESUMO

Cs2SnI6, a rarely studied perovskite variant material, is recently gaining a lot of interest in the field of photovoltaics owing to its nontoxicity, air-stability and promising photovoltaic properties. In this work, we report intrinsic defects in Cs2SnI6 using first-principles density functional theory calculations. It is revealed that iodine vacancy and tin interstitial are the dominant defects that are responsible for the intrinsic n-type conduction in Cs2SnI6. Tin vacancy has a very high formation energy (>3.6 eV) due to the strong covalency in the Sn-I bonds and is hardly generated for p-type doping. All the dominant defects in Cs2SnI6 have deep transition levels in the band gap. It is suggested that the formation of deep defects can be suppressed significantly by employing an I-rich synthesis condition, which is inevitable for photovoltaic and other semiconductor applications.

17.
Sci Rep ; 5: 10428, 2015 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-26020855

RESUMO

Tin monosulfide (SnS) is a naturally p-type semiconductor with a layered crystal structure, but no reliable n-type SnS has been obtained by conventional aliovalent ion substitution. In this work, carrier polarity conversion to n-type was achieved by isovalent ion substitution for polycrystalline SnS thin films on glass substrates. Substituting Pb(2+) for Sn(2+) converted the majority carrier from hole to electron, and the free electron density ranged from 10(12) to 10(15) cm(-3) with the largest electron mobility of 7.0 cm(2)/(Vs). The n-type conduction was confirmed further by the position of the Fermi level (EF) based on photoemission spectroscopy and electrical characteristics of pn heterojunctions. Density functional theory calculations reveal that the Pb substitution invokes a geometrical size effect that enlarges the interlayer distance and subsequently reduces the formation energies of Sn and Pb interstitials, which results in the electron doping.

18.
Cancer Immunol Immunother ; 64(7): 791-804, 2015 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-25835542

RESUMO

Wilms' tumor gene 1 (WT1) protein is a promising tumor-associated antigen for cancer immunotherapy. We have been performing WT1 peptide vaccination with good clinical responses in over 750 patients with leukemia or solid cancers. In this study, we generated single-cell gene-expression profiles of the effector memory (EM) subset of WT1-specific cytotoxic T lymphocytes (CTLs) in peripheral blood of nine acute myeloid leukemia patients treated with WT1 peptide vaccine, in order to discriminate responders (WT1 mRNA levels in peripheral blood decreased to undetectable levels, decreased but stayed at abnormal levels, were stable at undetectable levels, or remained unchanged from the initial abnormal levels more than 6 months after WT1 vaccination) from non-responders (leukemic blast cells and/or WT1 mRNA levels increased relative to the initial state within 6 months of WT1 vaccination) prior to WT1 vaccination. Cluster and principal component analyses performed using 83 genes did not discriminate between responders and non-responders prior to WT1 vaccination. However, these analyses revealed that EM subset of WT1-specific CTLs could be divided into two groups: the "activated" and "quiescent" states; in responders, EM subset of the CTLs shifted to the "quiescent" state, whereas in non-responders, those shifted to the "activated" state following WT1 vaccination. These results demonstrate for the first time the existence of two distinct EM states, each of which was characteristic of responders or non-responders, of WT1-specific CTLs in AML patients, and raises the possibility of using advanced gene-expression profile analysis to clearly discriminate between responders and non-responders prior to WT1 vaccination.


Assuntos
Antígenos de Neoplasias/imunologia , Memória Imunológica/imunologia , Leucemia Mieloide Aguda/imunologia , Linfócitos T Citotóxicos/imunologia , Proteínas WT1/imunologia , Adulto , Idoso , Antígenos de Neoplasias/genética , Vacinas Anticâncer/imunologia , Vacinas Anticâncer/uso terapêutico , Feminino , Perfilação da Expressão Gênica , Humanos , Imunoterapia/métodos , Leucemia Mieloide Aguda/terapia , Masculino , Pessoa de Meia-Idade , Análise de Componente Principal , RNA Mensageiro/sangue , RNA Mensageiro/genética , Linfócitos T Citotóxicos/citologia , Vacinas de Subunidades/imunologia , Vacinas de Subunidades/uso terapêutico , Proteínas WT1/genética
20.
Biochem Biophys Res Commun ; 456(2): 573-9, 2015 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-25478641

RESUMO

Adenosine A2A receptor (A2AR) heteromerizes with dopamine D2 receptor (D2R). However, these class A G protein-coupled receptor (GPCR) dimers are not fully formed, but depend on the equilibrium between monomer and dimer. In order to stimulate the heteromerization, we have previously shown a successful design for a fusion receptor, single-polypeptide-chain (sc) heterodimeric A2AR/D2R complex. Here, using whole cell binding assay, six more different scA2AR/D2R constructs were examined. Not only in scA2AR/D2R 'liberated' with longer spacers between the two receptors, which confer the same configuration as the prototype, the A2AR-odr4TM-D2LR, but differ in size (Forms 1-3), but also in scA2AR/D2LR (Form 6) fused with a transmembrane (TM) of another type II TM protein, instead of odr4TM, neither of their fixed stoichiometry (the apparent ratios of A2AR to D2R binding sites) was 1, suggesting their compact folding. This suggests that type II TM, either odr4 or another, facilitates the equilibrial process of the dimer formation between A2AR and D2LR, resulting in the higher-order oligomer formation from monomer of scA2AR/D2LR itself. Also, in the reverse type scA2AR/D2LR, i.e., the D2LR-odr4TM-A2AR, counter agonist-independent binding cooperativity (cooperative folding) was found to occur (Forms 4 and 5). In this way, the scA2AR/D2LR system has unveiled the cellular phenomenon as a snapshot of the molecular behavior in A2AR/D2LR dimer. Thus, these results indicate that the various designed types of functional A2AR/D2R exist even in living cells and that this fusion expression system would be useful to analyze as a model of the interaction between class A GPCRs.


Assuntos
Receptor A2A de Adenosina/química , Receptores de Dopamina D2/química , Sítio Alostérico , Sequência de Aminoácidos , Células HEK293 , Humanos , Dados de Sequência Molecular , Peptídeos/química , Ligação Proteica , Multimerização Proteica , Ensaio Radioligante
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