Ronny Sutarto

Symmetry of charge order in cuprates

Charge-ordered ground states permeate the phenomenology of 3d-based transition metal oxides, and more generally represent a distinctive hallmark of strongly correlated states of matter. The recent discovery of charge order in various cuprate families has fuelled new interest into the role played by this incipient broken symmetry within the complex phase diagram of high-T(c) superconductors. Here, we use resonant X-ray scattering to resolve the main characteristics of the charge-modulated state in two cuprate families: Bi2Sr(2-x)La(x)CuO(6+δ) (Bi2201) and YBa2Cu3O(6+y) (YBCO). We detect no signatures of spatial modulations along the nodal direction in Bi2201, thus clarifying the inter-unit-cell momentum structure of charge order. We also resolve the intra-unit-cell symmetry of the charge-ordered state, which is revealed to be best represented by a bond order with modulated charges on the O-2p orbitals and a prominent d-wave character. These results provide insights into the origin and microscopic description of charge order in cuprates, and its interplay with superconductivity.

Extreme mobility enhancement of two-dimensional electron gases at oxide interfaces by charge-transfer-induced modulation doping.

Two-dimensional electron gases (2DEGs) formed at the interface of insulating complex oxides promise the development of all-oxide electronic devices. These 2DEGs involve many-body interactions that give rise to a variety of physical phenomena such as superconductivity, magnetism, tunable metal-insulator transitions and phase separation. Increasing the mobility of the 2DEG, however, remains a major challenge. Here, we show that the electron mobility is enhanced by more than two orders of magnitude by inserting a single-unit-cell insulating layer of polar La(1-x)Sr(x)MnO3 (x = 0, 1/8, and 1/3) at the interface between disordered LaAlO3 and crystalline SrTiO3 produced at room temperature. Resonant X-ray spectroscopy and transmission electron microscopy show that the manganite layer undergoes unambiguous electronic reconstruction, leading to modulation doping of such atomically engineered complex oxide heterointerfaces. At low temperatures, the modulation-doped 2DEG exhibits Shubnikov-de Haas oscillations and fingerprints of the quantum Hall effect, demonstrating unprecedented high mobility and low electron density.

Strain-induced spin states in atomically ordered cobaltites.

Epitaxial strain imposed in complex oxide thin films by heteroepitaxy is recognized as a powerful tool for identifying new properties and exploring the vast potential of materials performance. A particular example is LaCoO(3), a zero spin, nonmagnetic material in the bulk, whose strong ferromagnetism in a thin film remains enigmatic despite a decade of intense research. Here, we use scanning transmission electron microscopy complemented by X-ray and optical spectroscopy to study LaCoO(3) epitaxial thin films under different strain states. We observed an unconventional strain relaxation behavior resulting in stripe-like, lattice modulated patterns, which did not involve uncontrolled misfit dislocations or other defects. The modulation entails the formation of ferromagnetically ordered sheets comprising intermediate or high spin Co(3+), thus offering an unambiguous description for the exotic magnetism found in epitaxially strained LaCoO(3) films. This observation provides a novel route to tailoring the electronic and magnetic properties of functional oxide heterostructures.

Charge ordering in the electron-doped superconductor Nd2–xCexCuO4

Finding order in exotic superconductors Physicists can coax some copper-oxide compounds into becoming superconducting by chemically adding extra charge carriers: holes or electrons. Concentrating on hole-doped materials, researchers have found a host of different phases in the neighborhood of or co-existing with superconductivity. One such phase is a modulation in charge density [a charge density wave (CDW)] that appears to be ubiquitous in hole-doped families. Da Silva Neto et al. now show that a similar phase exists in the electron-doped material Nd2-xCexCuO4. As they cooled the material, the authors first detected the CDW at temperatures considerably higher than in the hole-doped copper-oxides. Science, this issue p. 282 Resonant x-ray scattering is used to detect ordering similar to that observed in hole-doped cuprates. In cuprate high-temperature superconductors, an antiferromagnetic Mott insulating state can be destabilized toward unconventional superconductivity by either hole or electron doping. In hole-doped (p-type) cuprates, a charge ordering (CO) instability competes with superconductivity inside the pseudogap state. We report resonant x-ray scattering measurements that demonstrate the presence of charge ordering in the n-type cuprate Nd2–xCexCuO4 near optimal doping. We find that the CO in Nd2–xCexCuO4 occurs with similar periodicity, and along the same direction, as in p-type cuprates. However, in contrast to the latter, the CO onset in Nd2–xCexCuO4 is higher than the pseudogap temperature, and is in the temperature range where antiferromagnetic fluctuations are first detected. Our discovery opens a parallel path to the study of CO and its relationship to antiferromagnetism and superconductivity.

Broken translational and rotational symmetry via charge stripe order in underdoped YBa2Cu3O6+y

Picking out the elusive stripes Copper-oxide superconductors have periodic modulations of charge density. Typically, the modulation is not the same for the whole crystal, but breaks up into small nanosized domains. Bulk experiments show that the density is modulated along both axes in the copper-oxide plane, but it is not clear whether this is true only on the scale of the whole crystal or also locally, for each domain. Comin et al. analyzed the charge order in the compound YBa2Cu3O6+y, using resonant x-ray scattering, and found that it was consistent with a local unidirectional, so-called stripy, ordering. Science, this issue p. 1335 Resonant x-ray scattering is used to distinguish between stripe and checkerboard orders in a cuprate family. After the discovery of stripelike order in lanthanum-based copper oxide superconductors, charge-ordering instabilities were observed in all cuprate families. However, it has proven difficult to distinguish between unidirectional (stripes) and bidirectional (checkerboard) charge order in yttrium- and bismuth-based materials. We used resonant x-ray scattering to measure the two-dimensional structure factor in the superconductor YBa2Cu3O6+y in reciprocal space. Our data reveal the presence of charge stripe order (i.e., locally unidirectional density waves), which may represent the true microscopic nature of charge modulation in cuprates. At the same time, we find that the well-established competition between charge order and superconductivity is stronger for charge correlations across the stripes than along them, which provides additional evidence for the intrinsic unidirectional nature of the charge order.

Element Specific Monolayer Depth Profiling

The electronic phase behavior and functionality of interfaces and surfaces in complex materials are strongly correlated to chemical composition profiles, stoichiometry and intermixing. Here a novel analysis scheme for resonant X-ray reflectivity maps is introduced to determine such profiles, which is element specific and non-destructive, and which exhibits atomic-layer resolution and a probing depth of hundreds of nanometers.

Facile synthesis of few-layer-thick carbon nitride nanosheets by liquid ammonia-assisted lithiation method and their photocatalytic redox properties

High-quality few-layer-thick graphitic carbon nitride (g-C3N4) nanosheets (NSs) were fabricated by a simple, highly efficient, and rapid method namely, liquid ammonia (LA)-assisted lithiation. Li intercalation occurred in less than half an hour, importantly, the degree of Li intercalation was indicated by the color change of LA solution from deep blue to colorless. The obtained products were carefully investigated by field-emission transmission electron microscopy, field-emission scanning electron microscopy, atomic force microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, Raman scattering spectrometry, UV-visible absorption spectrometry, photoluminescence, soft X-ray absorption and nonresonant soft X-ray emission spectroscopy, and X-ray absorption near-edge structure analyses. Because of the lack of high-temperature or high-energy treatment, high-yield few-layer-thick g-C3N4 NSs were produced with trace O2 impurity. Interestingly, while maintaining the similar crystal structure and chemical stoichiometric ratio relative to the parent bulk materials, the surface structure, electronic and optical properties were significantly varied. Moreover, compared to the bulk counterparts, the as-prepared g-C3N4 NSs show clearly enhanced photocatalytic redox activity with respect to both photocatalytic H2 evolution and hydroxyl radical generation. LA-assisted lithiation is a general method and could be easily extended to exfoliate diverse other layered materials such as molybdenum and tungsten sulfides.

Tailoring the electronic transitions of NdNiO3 films through (111)pc oriented interfaces

Bulk NdNiO3 and thin films grown along the pseudocubic (001)pc axis display a 1st order metal to insulator transition (MIT) together with a Neel transition at T = 200 K. Here, we show that for NdNiO3 films deposited on (111)pc NdGaO3, the MIT occurs at T = 335 K and the Neel transition at T = 230 K. By comparing transport and magnetic properties of layers grown on substrates with different symmetries and lattice parameters, we demonstrate a particularly large tuning when the epitaxy is realized on (111)pc surfaces. We attribute this effect to the specific lattice matching conditions imposed along this direction when using orthorhombic substrates.

Impact of quenched oxygen disorder on charge density wave order in YBa2Cu3O6+x.

The competition between superconductivity and charge density wave (CDW) order in underdoped cuprates has now been widely reported, but the role of disorder in this competition has yet to be fully resolved. A central question is whether disorder sets the length scale of the CDW order, for instance by pinning charge density fluctuations or disrupting an otherwise long-range order. Using resonant soft x-ray scattering, we investigate the sensitivity of CDW order in YBa2Cu3O6+x (YBCO) to varying levels of oxygen disorder. We find that quench cooling YBCO6.67 (YBCO6.75) crystals to destroy their o-V and o-VIII (o-III) chains decreases the intensity of the CDW superlattice peak by a factor of 1.9 (1.3), but has little effect on the CDW correlation length, incommensurability, and temperature dependence. This reveals that while quenched oxygen disorder influences the CDW order parameter, the spatial extent of the CDW order is insensitive to the level of quenched oxygen disorder and may instead be a consequence of competition with superconductivity.

Doping-dependent charge order correlations in electron-doped cuprates

Resonant x-ray scattering clarifies the link between charge order and magnetism/superconductivity in n-doped cuprates. Understanding the interplay between charge order (CO) and other phenomena (for example, pseudogap, antiferromagnetism, and superconductivity) is one of the central questions in the cuprate high-temperature superconductors. The discovery that similar forms of CO exist in both hole- and electron-doped cuprates opened a path to determine what subset of the CO phenomenology is universal to all the cuprates. We use resonant x-ray scattering to measure the CO correlations in electron-doped cuprates (La2−xCexCuO4 and Nd2−xCexCuO4) and their relationship to antiferromagnetism, pseudogap, and superconductivity. Detailed measurements of Nd2−xCexCuO4 show that CO is present in the x = 0.059 to 0.166 range and that its doping-dependent wave vector is consistent with the separation between straight segments of the Fermi surface. The CO onset temperature is highest between x = 0.106 and 0.166 but decreases at lower doping levels, indicating that it is not tied to the appearance of antiferromagnetic correlations or the pseudogap. Near optimal doping, where the CO wave vector is also consistent with a previously observed phonon anomaly, measurements of the CO below and above the superconducting transition temperature, or in a magnetic field, show that the CO is insensitive to superconductivity. Overall, these findings indicate that, although verified in the electron-doped cuprates, material-dependent details determine whether the CO correlations acquire sufficient strength to compete for the ground state of the cuprates.