Dressick Walter J, Soto Carissa M, Fontana Jake, Baker Colin C, Myers Jason D, Frantz Jesse A, Kim Woohong
Center for Bio/Molecular Science & Engineering, United States Naval Research Laboratory, Washington, District of Columbia, United States of America.
Optical Sciences Division, United States Naval Research Laboratory, Washington, District of Columbia, United States of America.
PLoS One. 2014 Jun 18;9(6):e100203. doi: 10.1371/journal.pone.0100203. eCollection 2014.
We present a method of Cu(In,Ga)S2 (CIGS) thin film formation via conversion of layer-by-layer (LbL) assembled Cu-In-Ga oxide (CIGO) nanoparticles and polyelectrolytes. CIGO nanoparticles were created via a novel flame-spray pyrolysis method using metal nitrate precursors, subsequently coated with polyallylamine (PAH), and dispersed in aqueous solution. Multilayer films were assembled by alternately dipping quartz, Si, and/or Mo substrates into a solution of either polydopamine (PDA) or polystyrenesulfonate (PSS) and then in the CIGO-PAH dispersion to fabricate films as thick as 1-2 microns. PSS/CIGO-PAH films were found to be inadequate due to weak adhesion to the Si and Mo substrates, excessive particle diffusion during sulfurization, and mechanical softness ill-suited to further processing. PDA/CIGO-PAH films, in contrast, were more mechanically robust and more tolerant of high temperature processing. After LbL deposition, films were oxidized to remove polymer and sulfurized at high temperature under flowing hydrogen sulfide to convert CIGO to CIGS. Complete film conversion from the oxide to the sulfide is confirmed by X-ray diffraction characterization.
我们提出了一种通过逐层（LbL）组装的铜铟镓氧化物（CIGO）纳米颗粒和聚电解质的转化来形成铜铟镓硫（Cu(In,Ga)S2，CIGS）薄膜的方法。CIGO纳米颗粒是通过一种使用金属硝酸盐前驱体的新型火焰喷雾热解方法制备的，随后用聚烯丙胺（PAH）包覆，并分散在水溶液中。通过将石英、硅和/或钼基板交替浸入聚多巴胺（PDA）或聚苯乙烯磺酸盐（PSS）溶液中，然后再浸入CIGO-PAH分散液中，组装多层膜，以制备厚度达1-2微米的薄膜。发现PSS/CIGO-PAH薄膜不合适，因为其对硅和钼基板的附着力弱，硫化过程中颗粒扩散过度，以及机械柔软性不适合进一步加工。相比之下，PDA/CIGO-PAH薄膜在机械性能上更坚固，对高温加工的耐受性更强。在逐层沉积后，将薄膜氧化以去除聚合物，并在流动的硫化氢气氛下高温硫化，将CIGO转化为CIGS。通过X射线衍射表征证实了薄膜从氧化物到硫化物的完全转化。
