Physics of Complex inorganic Nanomaterials

The research in the IMS workgroup headed by dr. Gertjan Koster focuses on three areas: manipulated oxide thin film growth and modeling, oxide thin film meso materials and in situ spectroscopy. The research is centered on the COMAT system; a UHV pulsed laser deposition (PLD) system with in situ spectroscopies and imaging techniques (XPS, UPS, XPD, STM, AFM, PFM). Manipulated Oxide thin film Growth and modeling: In materials science a connection is made between synthesis, structure/composition and materials properties. The type and conditions of synthesis determine the atomic arrangement and in turn, the microscopic structure and composition of a material determine the electronic response to the position of positive atomic core and thus its properties (e.g., transport, magnetic, dielectric etc). Using thin film deposition as synthesis method, it therefore means that in order to able to control the atomic arrangements in a thin film, one has to control the ordering processes that take place: nucleation and growth. In the following a brief overview of the techniques and studies to oxide thin film growth is given. Most existing thin film preparation techniques were developed with a specific group of materials in mind but are often used in a broader context for quick explorative research. The problem which usually arises is in the case of more complex compounds, is that one can less reliably extract information on the relationship between micro structure and macroscopic properties due to the lack of control of composition and phase formation. A newly explored realm of a deposition technique can be illustrated by looking at the typical deposition mode with pulsed laser deposition (PLD, extremely high deposition rate within one pulse). It has been shown that it can lead to imposed layer-by-layer growth resulting in sharp, well-defined interfaces. It is possible with PLD to impose a single level 2D growth mode or layer-by-layer growth mode for different complex oxides despite unfavorable deposition conditions with respect to mobility.

Another innovation came with the possibility of studying the epitaxial growth of oxide materials during deposition at relatively high pressures, so-called high pressure reflection high energy electron diffraction (RHEED), has significantly increased our ability to construct artificial layers and junctions. The main advantage of this high pressure (typically 10-50 Pa) is the stability of the deposited layers, as the chemical composition and structure are strongly dependent on

the pressure during growth. Furthermore, the background pressure can influence the growth mode significantly: SrTiO3 and SrRuO3 can be grown in a step-flow as well as layer-by-layer growth mode just by changing the oxygen pressure and deposition temperature.

Finally, a breakthrough in the investigation of surface kinetics of complex materials came with the introduction of a method to control the surface termination of substrates as well as deposited layers. In the case of complex materials this is a non-trivial problem and most of the time cannot be simply achieved by standard cleavage or annealing. Importantly, mixed terminated substrate surfaces lead to different growth behaviour, as shown even in the case of homoepitaxy of SrTiO3. If it would be possible to study transport through structures and interfaces which are well-characterized on an atomic scale, substantial progress might be made in understanding the factors governing electrical and magnetic transport phenomena. Ideally, one would like to have model systems analogous to the III-V semiconducting materials that can be grown epitaxially. Hybrid Pulsed Laser Deposition/Molecular Beam Synthesis (MBE) system for oxide growth with in situ XPS1, UPS2 and RHEED3: Unlike PLD, MBE growth requires rate control for the individual components of the materials (e.g., Sr and Ru and O in SrRuO3). The use of Electron Impact Emission Spectrometry was studied for such purposes as well as the generation of atomic oxygen. Epitaxially stabilized oxides with imposed crystal symmetries, such as CuO, which occurs as the monoclinic mineral tenorite in nature, but we have evidence now that CuO can assume higher crystal symmetry when grown on a suitable substrate. In a quite different approach we have monitored the crystallization of both YBa2Cu3O7 and YBa2Cu4O8 from dense glassy precursors using X-ray scattering and an ambient controlled hot stage (invited talk, SSRL user meeting, Menlo Park, 2004). This general method makes possible the growth of films from constituents which are too volatile or where the phase equilibrium is unfavorable. One of the topics that was studied with prof. T.H. Geballe at Stanford is a simple predictive method to select potentially interesting oxide materials based on an ionic approach (appeared in PRB).

Recent topics:

-Controlled peroskite single crystal surface termination; chemical treatment (appeared in Advanced Functional Materials) -Self-assembly of epitaxial nanowires; we study the diffusional processes on different oxide terminations by applying a Monte Carlo simulation, providing a confirmation of our kinetic model as well as giving direction in how to choose experimental parameters (submitted). Oxide thin film meso materials Our ability to control the composition, size, and shape of metal oxide-based nanostructures has progressed over the past decade to a level that we can now control the functional properties of these with a high degree of accuracy. In this research (funded under TOP-NWO) we want to make a leap forward in inorganic materials development, and design and assemble such objects to form larger, hierarchical structures. The aim is to develop strategies that combine material synthesis and (self-) assembly of nano-size building blocks (spheres, cubes, wires, rods, coreshell structures, etc.), into mesoscale architectures with 3D spatial control over the location of elements of the assembly. In such hierarchical structures, the traditional molecular length scale is far extended, and collective effects determine the property of the assembly. It is our goal to combine and develop techniques that allow the synthesis and organization of novel materials at multiple length scales in three spatial dimensions. The formation of such hierarchical assemblies from functional metal oxide building blocks with magnetic, optical, mechanical, electrical, or otherwise functional properties is a new approach. For example, we explore new methods to grow single crystalline complex oxide nanowires by self-organization. This is achieved by exploiting two unexpected particularities of the terminating atomical planes of single crystalline perovskite transition metal oxides: for example 1), we found that in the case of (110) DyScO3 the two possible terminating surfaces, DyO and ScO2, order into line-like patterns and 2) the difference in surface diffusivity of the deposited metallic and ferromagnetic SrRuO3 on the two terminations, driving the self organization process (submitted).

The SrRuO3 wires are metallic, yet electrically isolated from each other over macroscopic length scales, single crystalline and fully oriented, which could be

applied in cross-wire architectures or as a patterned electrode material in combination with ferroelectric oxides such as Pb(Zr,Ti)O3. In situ Spectroscopy

Hybrid Pulsed Laser Deposition/Molecular Beam Synthesis system for oxide growth with in situ XPS, UPS and RHEED (developed at the Geballe Laboratory for Advanced Materials at Stanford University) gives the opportunity to investigate intrinsic electronic properties of epitaxial systems by electron spectroscopy as well as take advantage of the two ways of generating particles for deposition, i.e., electron beam deposition and pulsed laser deposition. Because of both the in situ thin film synthesis, eliminating anomalies due to the interaction with ambient air, as well the fact that probing depth are of the order of the thin film thicknesses, a true comparison of electronic properties and transport properties are possible.

Current investigations, using the COMAT system at Twente, a UHV pulsed laser deposition (PLD) system with various in situ spectroscopies and imaging techniques (XPS, UPS, XPD, STM, AFM, PFM) inspired on the system at Stanford, are aimed for example at controlling the octaeader rotations by epitaxy and study their effect on properties of various magnetic perovskite-type oxides such as LaSrMnO3. Both in situ photoelectron spectroscopy as well in situ photoelectron diffraction are being employed and with a soon to be installed in situ nano-probe system based on scanning tunneling microscopy, transport measurements can simultaneously be performed on a local scale. Other examples of oxide systems that are being investigated using photoelectron spectroscopy are the itinerant ferromagnet SrRuO3 and the LaAlO3/SrTiO3 system (ongoing research, appeared in PRL and PRB). In a separate effort, in the MURI program for superconductor coated conductors a real time diagnostic procedure was demonstrated, which was made possible by Fourier Transform Infrared reflectometry (appeared in Applied Physics Letters). Not only does this technique monitor the exact temperature of the surface on which a film is growing, it was also found that the reflectivity spectra give useful information regarding the state of the growing film. For the case of high rate Electron-Beam deposition of YBa2Cu3O7

on metal tape it was discovered that the nucleation and growth of the superconducting phase are wildly dependent on the oxygen pressure and activity during and just after the deposition as revealed by FTIR. As a recent example, it is worth mentioning the study of epitaxially stabilized cubic CuO using in situ photoelectron spectroscopy and photoelectron diffraction. (appeared in PRB as editors choice)