Growth control of oxygen stoichiometry in homoepitaxial SrTiO3 films by pulsed laser epitaxy in high vacuum

In many transition metal oxides (TMOs), oxygen stoichiometry is one of the most critical parameters that plays a key role in determining the structural, physical, optical, and electrochemical properties of the material. However, controlling the growth to obtain high quality single crystal films having the right oxygen stoichiometry, especially in a high vacuum environment, has been viewed as a challenge. In this work, we show that through proper control of the plume kinetic energy, stoichiometric crystalline films can be synthesized without generating oxygen defects, even in high vacuum. We use a model homoepitaxial system of SrTiO3 (STO) thin films on single crystal STO substrates. Physical property measurements indicate that oxygen vacancy generation in high vacuum is strongly influenced by the energetics of the laser plume, and it can be controlled by proper laser beam delivery. Therefore, our finding not only provides essential insight into oxygen stoichiometry control in high vacuum for understanding the fundamental properties of STO-based thin films and heterostructures, but expands the utility of pulsed laser epitaxy of other materials as well

Growth Control of Oxygen Stoichiometry in Homoepitaxial SrTiO\u3csub\u3e3\u3c/sub\u3e Films by Pulsed Laser Epitaxy in High Vacuum

In many transition metal oxides, oxygen stoichiometry is one of the most critical parameters that plays a key role in determining the structural, physical, optical, and electrochemical properties of the material. However, controlling the growth to obtain high quality single crystal films having the right oxygen stoichiometry, especially in a high vacuum environment, has been viewed as a challenge. In this work, we show that, through proper control of the plume kinetic energy, stoichiometric crystalline films can be synthesized without generating oxygen defects even in high vacuum. We use a model homoepitaxial system of SrTiO3 (STO) thin films on single crystal STO substrates. Physical property measurements indicate that oxygen vacancy generation in high vacuum is strongly influenced by the energetics of the laser plume, and it can be controlled by proper laser beam delivery. Therefore, our finding not only provides essential insight into oxygen stoichiometry control in high vacuum for understanding the fundamental properties of STO-based thin films and heterostructures, but expands the utility of pulsed laser epitaxy of other materials as well

Alleviating Polarity-Conflict at the Heterointerfaces of KTaO\u3csub\u3e3\u3c/sub\u3e/GdScO\u3csub\u3e3\u3c/sub\u3e Polar Complex-Oxides

We have synthesized and investigated the heterointerfaces of KTaO3 (KTO) and GdScO3 (GSO), which are both polar complex-oxides along the pseudo-cubic [001] direction. Since their layers have the same, conflicting net charges at interfaces, i.e., KO(−1)/ScO2(−1) or TaO2(+1)/GdO(+1), forming the heterointerface of KTO/GSO should be forbidden due to strong Coulomb repulsion, the so-called polarity conflict. However, we have discovered that atomic reconstruction occurs at the heterointerfaces between KTO thin-films and GSO substrates, which effectively alleviates the polarity conflict without destroying the hetero-epitaxy. Our result demonstrates one of the important ways to create artificial heterostructures from polar complex-oxides

Conducting LaAlO\u3csub\u3e3\u3c/sub\u3e/SrTiO\u3csub\u3e3\u3c/sub\u3e Heterointerfaces on Atomically-Flat Substrates Prepared by Deionized-Water

We have investigated how the recently-developed water-leaching method for atomically-flat SrTiO3 (STO) substrates affects the transport properties of LaAlO3 (LAO) and STO heterointerfaces. Using pulsed laser deposition at identical growth conditions, we have synthesized epitaxial LAO thin-films on two different STO substrates, which are prepared by water-leaching and buffered hydrofluoric acid (BHF) etching methods. The structural, transport, and optical properties of LAO/STO heterostructures grown on water-leached substrates show the same high-quality as the samples grown on BHF-etched substrates. These results indicate that the water-leaching method can be used to grow complex oxide heterostructures with atomically well-defined heterointerfaces without safety concerns

Transparent Conducting Oxides: A δ-Doped Superlattice Approach

Metallic states appearing at interfaces between dissimilar insulating oxides exhibit intriguing phenomena such as superconductivity and magnetism. Despite tremendous progress in understanding their origins, very little is known about how to control the conduction pathways and the distribution of charge carriers. Using optical spectroscopic measurements and density-functional theory (DFT) simulations, we examine the effect of SrTiO3 (STO) spacer layer thickness on the optical transparency and carrier distribution in La δ-doped STO superlattices. We experimentally observe that these metallic superlattices remain highly transparent to visible light; a direct consequence of the appropriately large gap between the O 2p and Ti 3d states. In superlattices with relatively thin STO layers, we predict that three-dimensional conduction would occur due to appreciable overlap of quantum mechanical wavefunctions between neighboring δ-doped layers. These results highlight the potential for using oxide heterostructures in optoelectronic devices by providing a unique route for creating novel transparent conducting oxides

Investigations of Metastable Ca\u3csub\u3e2\u3c/sub\u3eIrO\u3csub\u3e4\u3c/sub\u3e Epitaxial Thin-Films: Systematic Comparison with Sr\u3csub\u3e2\u3c/sub\u3eIrO\u3csub\u3e4\u3c/sub\u3e and Ba\u3csub\u3e2\u3c/sub\u3eIrO\u3csub\u3e4\u3c/sub\u3e

We have synthesized thermodynamically metastable Ca2IrO4 thin-films on YAlO3 (110) substrates by pulsed laser deposition. The epitaxial Ca2IrO4 thin-films are of K2NiF4-type tetragonal structure. Transport and optical spectroscopy measurements indicate that the electronic structure of the Ca2IrO4 thin-films is similar to that of Jeff = 1/2 spin-orbit-coupled Mott insulator Sr2IrO4 and Ba2IrO4, with the exception of an increased gap energy. The gap increase is to be expected in Ca2IrO4 due to its increased octahedral rotation and tilting, which results in enhanced electron-correlation, U/W. Our results suggest that the epitaxial stabilization growth of metastable-phase thin-films can be used effectively for investigating layered iridates and various complex-oxide systems

Tuning Electronic Structure via Exipatial Strain in Sr\u3csub\u3e2\u3c/sub\u3eIrO\u3csub\u3e4\u3c/sub\u3e Thin Films

We have synthesized epitaxial Sr2IrO4 thin-films on various substrates and studied their electronic structure as a function of lattice-strain. Under tensile (compressive) strain, increased (decreased) Ir-O-Ir bond-angle is expected to result in increased (decreased) electronic bandwidth. However, we have observed that the two optical absorption peaks near 0.5 eV and 1.0 eV are shifted to higher (lower) energies under tensile (compressive) strain, indicating that the electronic-correlation energy is also affected by in-plane lattice-strain. The effective tuning of electronic structure under lattice-modification provides an important insight into the physics driven by the coexisting strong spin-orbit coupling and electronic correlation

Selective Growth of Epitaxial Sr\u3csub\u3e2\u3c/sub\u3eIrO\u3csub\u3e4\u3c/sub\u3e by Controlling Plume Dimensions in Pulsed Laser Deposition

We report that epitaxial Sr2IrO4 thin-films can be selectively grown using pulsed laser deposition (PLD). Due to the competition between the Ruddlesden-Popper phases of strontium iridates (Srn+1IrnO3n+1), conventional PLD methods often result in mixed phases of Sr2IrO4 (n = 1), Sr3Ir2O7 (n = 2), and SrIrO3 (n = ∞). We have discovered that reduced PLD plume dimensions and slow deposition rates are the key for stabilizing pure Sr2IrO4 phase thin-films, identified by real-time in-situ monitoring of their optical spectra. The slow film deposition results in a thermodynamically stable TiO2\\SrO\IrO2\SrO\SrO configuration at an interface rather than TiO2\\SrO\SrO\IrO2\SrO between a TiO2-terminated SrTiO3 substrate and a Sr2IrO4 thin film, which is consistent with other layered oxides grown by molecular beam epitaxy. Our approach provides an effective method for using PLD to achieve pure phase thin-films of layered materials that are susceptible to several energetically competing phases

Electronic and Optical Properties of La-Doped Sr\u3csub\u3e3\u3c/sub\u3eIr\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e7\u3c/sub\u3e Epitaxial Thin Films

We have investigated structural, transport, and optical properties of tensile strained (Sr1−xLax)3Ir2O7 (x = 0, 0.025, 0.05) epitaxial thin films. While high-Tc superconductivity is predicted theoretically in the system, we have observed that all of the samples remain insulating with finite optical gap energies and Mott variable-range hopping characteristics in transport. Cross-sectional scanning transmission electron microscopy indicates that structural defects such as stacking faults appear in this system. The insulating behavior of the La-doped Sr3Ir2O7 thin films is presumably due to disorder-induced localization and ineffective electron doping of La, which brings to light the intriguing difference between epitaxial thin films and bulk single crystals of the iridates

Electronic Structure and Insulating Gap in Epitaxial VO\u3csub\u3e2\u3c/sub\u3e Polymorphs

Determining the origin of the insulating gap in the monoclinic VO2(M1) is a long-standing issue. The difficulty of this study arises from the simultaneous occurrence of structural and electronic transitions upon thermal cycling. Here, we compare the electronic structure of the M1 phase with that of single crystalline insulating VO2(A) and VO2(B) thin films to better understand the insulating phase of VO2. As these A and B phases do not undergo a structural transition upon thermal cycling, we comparatively study the origin of the gap opening in the insulating VO2 phases. By x-ray absorption and optical spectroscopy, we find that the shift of unoccupied t2g orbitals away from the Fermi level is a common feature, which plays an important role for the insulating behavior in VO2 polymorphs. The distinct splitting of the half-filled t2g orbital is observed only in the M1 phase, widening the bandgap up to ∼0.6 eV. Our approach of comparing all three insulating VO2 phases provides insight into a better understanding of the electronic structure and the origin of the insulating gap in VO2