Marian Smoluchowski Institute of Physics, Jagiellonian University, 30-348 Krakow, Poland.
Nanoscale. 2018 Dec 20;11(1):89-97. doi: 10.1039/c8nr04545c.
Reduced titanium oxide structures are regarded as promising materials for various catalytic and optoelectronic applications. There is thus an urgent need for developing methods of controllable formation of crystalline nanostructures with tunable oxygen nonstoichiometry. We introduce the Extremely Low Oxygen Partial Pressure (ELOP) method, employing an oxygen getter in close vicinity to an oxide during thermal reduction under vacuum, as an effective bottom-up method for the production of nanowires arranged in a nanoscale metallic network on a SrTiO3 perovskite surface. We demonstrate that the TiO nanowires crystallize in a highly ordered cubic phase, where single nanowires are aligned along the main crystallographic directions of the SrTiO3 substrate. The dimensions of the nanostructures are easily tunable from single nanometers up to the mesoscopic range by varying the temperature of reduction. The interface between TiO and SrTiO3 (metal and insulator) was found to be atomically sharp providing the unique possibility of the investigation of electronic states, especially since the high conductivity of the TiO nanostructures is maintained after room temperature oxidation. According to the growth model we propose, TiO nanowire formation is possible due to the incongruent sublimation of strontium and crystallographic shearing, triggered by the extremely low oxygen partial pressure (ELOP). The controlled formation of conductive nanowires on a perovskite surface holds technological potential for implementation in memristive devices, organic electronics, or for catalytic applications, and provides insight into the mechanism of nanoscale phase transformations in metal oxides. We believe that the ELOP mechanism of suboxide formation is suitable for the formation of reduced suboxides on other perovskite oxides and for the broader class of transition metal oxides.
还原氧化钛结构被认为是各种催化和光电应用的有前途的材料。因此,迫切需要开发可控形成具有可调氧非化学计量比的结晶纳米结构的方法。我们引入了超低氧分压 (ELOP) 方法,即在真空下热还原过程中,在氧化物附近使用吸氧剂,作为在 SrTiO3 钙钛矿表面上形成纳米尺度金属网络排列的纳米线的有效自下而上的方法。我们证明 TiO 纳米线在高度有序的立方相中结晶,其中单根纳米线沿着 SrTiO3 衬底的主要晶向排列。通过改变还原温度,很容易将纳米结构的尺寸从单纳米尺寸调谐到介观范围。TiO 和 SrTiO3(金属和绝缘体)之间的界面是原子级锐利的,这为研究电子态提供了独特的可能性,特别是因为 TiO 纳米结构的高导电性在室温氧化后得以保持。根据我们提出的生长模型,由于锶的不一致升华和极低氧分压 (ELOP) 触发的晶面剪切,TiO 纳米线的形成成为可能。在钙钛矿表面上可控形成的导电纳米线在阻变器件、有机电子学或催化应用中具有技术潜力,并深入了解了金属氧化物中纳米尺度相转变的机制。我们相信,亚氧化物形成的 ELOP 机制适用于其他钙钛矿氧化物和更广泛的过渡金属氧化物上还原亚氧化物的形成。