Abstract The electrical and optical properties of thin films can be modulated by its supramolecular arrangement being this latter closely related to the fabrication method. Here, we are exploiting the impact of deposition techniques of nickel phthalocyanine (NiPc) and tetrasulfonated nickel phthalocyanine (NiTsPc) thin films on their supramolecular arrangement. Deposition techniques as Langmuir-Schaffer (LS), Langmuir-Blodgett (LB), physical vapor deposition (PVD), dipping- and spray-Layer-by-Layer (LbL) were applied for fabrication of the thin films. Linear growth was observed for all films indicating control of the amount of NiPc or NiTsPc deposited in each technique at nm scale. Fourier-transform infrared absorption spectroscopy (FTIR) and micro-Raman scattering confirmed the chemical stability of NiPc and NiTsPc concerning the deposition technique (water or heat). Besides, FTIR and X-ray diffraction data suggested that all thin films present isotropy in terms of molecular organization, with a predominance of the crystalline α-phase in the case of PVD, LB, and LS films. Atomic force microscopy images revealed irregularities at the surface for all thin film with the roughness/thickness ratio being 4.5% for PVD, 9% for both LB and LS films, and 18 and 35% for spray- and dipping-LbL films, respectively. The electrochemical behavior in both inert electrolyte and dopamine (DA) solution was directly dependent on the film morphology (molecular aggregates and surface roughness). The increase of the roughness in relation to thickness promoted films better electrochemical responses to DA oxidation. The dipping-LbL films showed the smaller potential of DA oxidation (0.114 V), even compared to the bare substrate (0.133 V). The deposition technique showed to be an suitable tool to tune the supramolecular arrangement of phthalocyanine forming thin films, which improve and/or change the electrochemical properties of the device.

中文翻译：

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镍酞菁的电化学性质：通过沉积技术调整薄膜形态的影响

摘要 薄膜的电学和光学性质可以通过其超分子排列来调节，后者与制备方法密切相关。在这里，我们正在利用镍酞菁 (NiPc) 和四磺化镍酞菁 (NiTsPc) 薄膜的沉积技术对其超分子排列的影响。沉积技术如 Langmuir-Schaffer (LS)、Langmuir-Blodgett (LB)、物理气相沉积 (PVD)、浸渍和喷涂逐层 (LbL) 用于制造薄膜。观察到所有薄膜的线性生长，表明在纳米尺度下控制在每种技术中沉积的 NiPc 或 NiTsPc 的量。傅里叶变换红外吸收光谱 (FTIR) 和微拉曼散射证实了 NiPc 和 NiTsPc 在沉积技术（水或热）方面的化学稳定性。此外，FTIR 和 X 射线衍射数据表明，所有薄膜在分子组织方面都表现出各向同性，在 PVD、LB 和 LS 薄膜的情况下，结晶 α 相占优势。原子力显微镜图像显示所有薄膜的表面不规则，PVD 的粗糙度/厚度比为 4.5%，LB 和 LS 膜的粗糙度/厚度比为 9%，喷涂和浸渍 LbL 膜的粗糙度/厚度比分别为 18% 和 35%。惰性电解质和多巴胺 (DA) 溶液中的电化学行为直接取决于膜形态（分子聚集体和表面粗糙度）。粗糙度相对于厚度的增加促进了薄膜对 DA 氧化的更好电化学响应。即使与裸基板 (0.133 V) 相比，浸渍 LbL 膜也显示出较小的 DA 氧化电位 (0.114 V)。沉积技术被证明是一种合适的工具，可以调整酞菁形成薄膜的超分子排列，从而改善和/或改变器件的电化学性能。