Controllable fabrication of Cu_2O porous nanostructured films by negative bias deposition method
- 物理技术－已发表论文 
由于具有低成本、无毒、铜源丰富等优点,以及在气敏传感器、太阳能电池、光催化等领域的潜在应用前景,; Cu_2O薄膜引起了人们的广泛关注.采用射频平衡磁控溅射镀膜系统,在薄膜沉积过程中通过施加不同衬底负偏压可控制备了Cu_2O多孔纳米结构薄膜.研; 究发现,所得Cu_2O薄膜具有灵活可调的孔隙度和纳米构筑单元形貌特征,并且它们与衬底负偏压的大小密切相关;薄膜沿衬底法线方向呈柱状生长且具有显著; 的(111)择优取向;禁带宽度在2.0~2.35; eV之间可调.很明显地,传统的溅射离子轰击、再溅射理论并不适合用来解释上述负偏压效应,因此在此基础上提出了一种负偏置沉积过程中材料原子或分子在薄; 膜表面选择性优先沉积机制.As one of the most common two kinds of copper oxides, cuprous oxide; (Cu_2O) is an important p-type transition metal oxide semiconductor; material. Due to the advantages of low-cost, non-toxicity and abundant; copper sources and the potential applications in the fields of gas; sensors, solar cells and photocatalysts, thin films of Cu_2O have; attracted great interest of researchers. To enhance the performances of; the above Cu_2O-based surface-sensitive devices and materials, the; researchers tend to prepare Cu_2O thin films of porous or even; nanoporous structures. However, there is still no effective method; available for the controllable fabrication of Cu_2O porous; nanostructured films (or porous nanostructure-films, short for PNFs),; which owns not only the common features of porous thin films but also; the unique properties of nanosize building units. By using a; radiofrequency balanced magnetron sputtering (MS) deposition system, in; this paper, Cu_2O PNFs were prepared on clean glass slides by applying; different negative bias voltage during film deposition. After the; preparation, a field-emission scanning electron microscope (FESEM), a; grazing-incidence X-ray diffractometer (GIXRD) and an; ultraviolet-visible (UV-Vis) spectrophotometer were applied subsequently; for the detailed characterizations of surface morphology, texture and; optical property respectively. It was observed that the as-prepared; Cu_2O PNFs exhibited flexible porosities and nanosize building units,; which were greatly dependent on the substrate negative bias voltage. In; particular, when the substrate bias voltage was kept at -50 or -150 V,; the as-prepared Cu_2O PNFs both demonstrated intriguing triangular; pyramid-like nanostructures with distinct edges and corners on the; porous film surface. Further, the side view FESEM images and the; out-of-plane GIXRD spectra demonstrated a columnar growth of the Cu_2O; PNFs with a notable preferential orientation of (111). The optical; testing results showed that the band gap of the Cu_2O PNFs obtained at; different negative bias voltages was tunable between 2.0 and 2.35 eV,; which demonstrated a little red or blue shift relative to that of bulk; Cu_2O (2.17 eV). It is expected that the traditional ion bombardment and; re-sputtering theories are not suitable for the explanation of the above; bias voltage effects. This is because the traditional ion bombardment; and re-sputtering theories were proposed to account for the bias; deposition in an unbalanced magnetron sputtering (MS) system rather than; the present balanced MS system. Further, the experimentally observed; non-linearly changed density or porosity of the Cu_2O PNFs with the bias; voltage at relatively low values and the common even surface at; relatively high values confirmed this viewpoint. Based on the above; findings and analysis, a selectively preferential deposition of material; atoms or molecules on the film surface during the negative bias; deposition was proposed. That is, when the substrate is negatively; biased, the tipcharging effect of electrons would occur on the nanoscale; rough surface of the substrate or the depositing film. The resulting; electric field near the substrate or film surface is non-uniform and; could be regarded as an assembly of many electric fields of particle or; tip charges.