The increasingly complex nanoscale three-dimensional and multilayered structures utilized in nanoelectronic, catalytic, and energy conversion/storage devices necessitate novel substrate-selective material deposition approaches featuring bottom-up and self-aligned precision processing. Here, we demonstrate the area-selective atomic layer deposition (AS-ALD) of two noble metals, Pt and Pd, by using a plasma-polymerized fluorocarbon layer as growth inhibition surfaces. The contact angle, x-ray photoelectron spectroscopy (XPS), and scanning electron microscopy measurements were performed to investigate the blocking ability of polymerized fluorocarbon (CF_x) layers against ALD-grown metal films. Both Pt and Pd showed significant nucleation delays on fluorocarbon surfaces. Self-aligned film deposition is confirmed using this strategy by growing Pt and Pd on the microscale lithographically patterned CF_x/Si samples. CF_x blocking layer degradation during ozone exposure was analyzed using XPS measurements, which confirmed the oxygen physisorption as the main responsible surface reaction with further hydroxyl group formation on the CF_x surface. Our work reveals that the CF_x layer is compatible with an ozone coreactant until the blocking polymer cannot withstand oxygen physisorption. Our results could potentially be used to investigate and develop radical-assisted AS-ALD processes for a wider selection of materials.

中文翻译：

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贵金属的区域选择性原子层沉积：聚合的碳氟化合物层可作为有效的生长抑制剂

在纳米电子，催化和能量转换/存储设备中使用的越来越复杂的纳米级三维多层结构，需要采用自底向上和自对准精确处理的新型衬底选择性材料沉积方法。在这里，我们通过使用等离子体聚合的碳氟化合物层作为生长抑制表面，展示了两种贵金属Pt和Pd的区域选择性原子层沉积（AS-ALD）。进行接触角，X射线光电子能谱（XPS）和扫描电子显微镜测量以研究聚合碳氟化合物（CF _x）层，以防止ALD生长的金属膜。Pt和Pd均在碳氟化合物表面上显示出明显的成核延迟。使用这种策略通过在微型光刻图案化的CF _x / Si样品上生长Pt和Pd来确认自对准膜沉积。使用XPS测量分析了在臭氧暴露过程中CF _x阻挡层的降解，这证实了氧的物理吸附是主要的表面反应，并在CF _x表面进一步形成了羟基。我们的工作表明CF _x该层与臭氧共反应物相容，直到封闭聚合物不能承受氧的物理吸附。我们的结果可能会被用于研究和开发自由基辅助的AS-ALD工艺，以用于更多的材料选择。