Centre for Nano and Soft Matter Sciences, Jalahalli, Bengaluru 560013, India.
Phys Chem Chem Phys. 2019 Oct 24;21(41):22955-22965. doi: 10.1039/c9cp03873f.
The structural organization and its effect on conducting pathways in lead phthalocyanine (PbPc) thin films, a nonplanar phthalocyanine, deposited on Si and highly oriented pyrolytic graphite (HOPG) substrates in the presence of iodine and ammonia vapors are presented. Two-dimensional grazing incidence X-ray diffraction studies reveal that the crystalline ordering in pristine PbPc films on Si and HOPG substrates undergoes a drastic molecular rearrangement and surface reconstruction upon iodine doping. The structural rearrangement leads to morphological changes and higher surface roughness in iodine doped PbPc (I-PbPc) films. The obvious enhancement in the current values of I-PbPc is attributed to the introduction of holes as charge carriers. Nanoscale current mapping reveals the presence of percolation pathways in I-PbPc films, on both Si and HOPG substrates, being responsible for the observed high conductance in contrast to the isolated conducting domains in the pristine PbPc system. The broad distribution of current values across various conducting domains on Si is attributed to a mixture of crystalline phases and disordered fractions of I-PbPc, while the narrow distribution of current values observed in the case of HOPG arises from the majorly disordered PbPc molecules. These films also show enhanced sensitivity towards ammonia that is almost four times higher in magnitude than for pristine PbPc films. The current maps show that the adsorption of ammonia molecules disrupts the iodine percolation pathways, thereby imposing a detrimental effect on the conductivity of the PbPc films.
本文介绍了在碘和氨蒸气存在的情况下,沉积在 Si 和高取向热解石墨(HOPG)衬底上的非平面酞菁铅(PbPc)薄膜的结构组织及其对导电路径的影响。二维掠入射 X 射线衍射研究表明,在 Si 和 HOPG 衬底上的原始 PbPc 薄膜的晶体有序性在碘掺杂后经历了剧烈的分子重排和表面重构。结构重排导致碘掺杂 PbPc(I-PbPc)薄膜的形貌变化和表面粗糙度增加。I-PbPc 中电流值的明显增强归因于作为载流子的空穴的引入。纳米级电流映射揭示了在 Si 和 HOPG 衬底上的 I-PbPc 薄膜中存在渗流路径,这是观察到的高电导率的原因,与原始 PbPc 系统中孤立的导电畴形成对比。在 Si 上各种导电畴的电流值的广泛分布归因于 I-PbPc 的结晶相和无序分数的混合物,而在 HOPG 情况下观察到的电流值的窄分布则是由于主要无序的 PbPc 分子。这些薄膜对氨也表现出增强的敏感性,其幅度比原始 PbPc 薄膜高近四倍。电流图表明,氨分子的吸附破坏了碘的渗流路径,从而对 PbPc 薄膜的导电性产生了不利影响。