Raj Vidur, Lu Teng, Lockrey Mark, Liu Rong, Kremer Felipe, Li Li, Liu Yun, Tan Hark Hoe, Jagadish Chennupati
Secondary Ion Mass Spectrometry Facility, Office of the Deputy Vice-Chancellor (R&D) , Western Sydney University , Penrith , New South Wales 2751 , Australia.
ACS Appl Mater Interfaces. 2019 Jul 10;11(27):24254-24263. doi: 10.1021/acsami.9b05566. Epub 2019 Jun 28.
The challenges of making high-performance, low-temperature processed, p-type transparent conductors (TCs) have been the main bottleneck for the development of flexible transparent electronics. Though a few p-type transparent conducting oxides (TCOs) have shown promising results, they need high processing temperature to achieve the required conductivity which makes them unsuitable for organic and flexible electronic applications. Copper iodide is a wide band gap p-type semiconductor that can be heavily doped at low temperature (<100 °C) to achieve conductivity comparable or higher than many of the well-established p-type TCOs. However, as-processed CuI loses its transparency and conductivity with time in an ambient condition which makes them unsuitable for long-term applications. Herein, we propose CuI-TiO composite thin films as a replacement of pure CuI. We show that the introduction of TiO in CuI makes it more stable in ambient conditions while also improving its conductivity and transparency. A detailed comparative analysis between CuI and CuI-TiO composite thin films has been performed to understand the reasons for improved conductivity, transparency, and stability of CuI-TiO samples in comparison to pure CuI samples. The enhanced conductivity in CuI-TiO stems from the highly conductive space-charge layer formation at the CuI-TiO interface, whereas the improved transparency is due to reduced CuI grain growth mobility in the presence of TiO. The improved stability of CuI-TiO in comparison to pure CuI is a result of inhibited recrystallization and grain growth, reduced loss of iodine, and limited oxidation of the CuI phase in the presence of TiO. For optimized fraction of TiO, an average transparency of ∼78% (in 450-800 nm region) and a resistivity of 14 mΩ·cm are achieved, while maintaining a relatively high mobility of ∼3.5 cm V s with hole concentration reaching as high as 1.3 × 10 cm. Most importantly, this work opens up the possibility to design a new range of p-type transparent conducting materials using the CuI/insulator composite system such as CuI/SiO, CuI/AlO, CuI/SiN, and so forth.
制备高性能、低温处理的p型透明导体(TCs)所面临的挑战一直是柔性透明电子器件发展的主要瓶颈。尽管一些p型透明导电氧化物(TCOs)已显示出有前景的结果,但它们需要高温处理才能达到所需的电导率,这使得它们不适用于有机和柔性电子应用。碘化铜是一种宽带隙p型半导体,可在低温(<100°C)下进行重掺杂,以实现与许多成熟的p型TCOs相当或更高的电导率。然而,加工后的CuI在环境条件下会随时间失去透明度和电导率,这使其不适用于长期应用。在此,我们提出用CuI-TiO复合薄膜替代纯CuI。我们表明,在CuI中引入TiO使其在环境条件下更稳定,同时还提高了其电导率和透明度。已对CuI和CuI-TiO复合薄膜进行了详细的对比分析,以了解与纯CuI样品相比,CuI-TiO样品电导率、透明度和稳定性提高的原因。CuI-TiO中增强的电导率源于在CuI-TiO界面形成的高导电空间电荷层,而透明度的提高是由于在TiO存在下CuI晶粒生长迁移率降低。与纯CuI相比,CuI-TiO稳定性的提高是抑制再结晶和晶粒生长、减少碘损失以及在TiO存在下CuI相氧化受限的结果。对于优化的TiO含量,在450-800nm区域平均透明度约为78%,电阻率为14mΩ·cm,同时保持相对较高的迁移率约为3.5cm² V⁻¹ s⁻¹,空穴浓度高达1.3×10²⁰ cm⁻³。最重要的是,这项工作开启了使用CuI/绝缘体复合系统设计一系列新型p型透明导电材料的可能性,如CuI/SiO₂、CuI/Al₂O₃、CuI/SiN等。