Kwon Kiok, Suh Bong Lim, Park Kangho, Kim Jihan, Jung Hee-Tae
National Research Laboratory for Organic Optoelectronic Materials, Department of Chemical and Biomolecular Engineering (BK-21 Plus), Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141, Korea.
Department of Chemical and Biomolecular Engineering (BK-21 Plus), Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141, Korea.
Sci Rep. 2019 Mar 7;9(1):3885. doi: 10.1038/s41598-019-40363-6.
The fabrication of an ultra-dense, highly periodic nanoparticle array from a soft template is one of the most important issues in the fields of material science and nanotechnology. To date, block copolymer (BCP) structures have been primarily used as templates for fabricating highly periodic nanoparticle arrays with high areal densities. Herein, we demonstrate for the first time the use of a supramolecular dendrimer assembly for the formation of a highly ordered nanoparticle array with a high areal density of ~20 Tdot/in, four times larger than that of the currently reported BCP-based nanoparticle arrays. By the simple thermal annealing of a dendrimers containing a metal precursor between two flat, solid substrates, a hexagonal array of small gold nanoparticles (with a diameter of ~1.6 nm and center-to-center distance of ~5.3 nm), oriented normal to the bottom, was achieved. Density functional theory calculations demonstrated that the gold cation strongly bound to the head group of the dendrimer. This structure served as a building block for self-assembly into a stable cylindrical structure. We anticipate that this study will lead to the creation of a large family of supramolecular dendrimers that can be utilized as soft templates for creating periodic, ultra-dense nanoparticle arrays.
利用软模板制备超致密、高周期性的纳米颗粒阵列是材料科学和纳米技术领域最重要的问题之一。迄今为止,嵌段共聚物(BCP)结构主要被用作制备具有高面密度的高周期性纳米颗粒阵列的模板。在此,我们首次展示了使用超分子树枝状聚合物组装体来形成具有约20 Tdot/in高面密度的高度有序纳米颗粒阵列,这比目前报道的基于BCP的纳米颗粒阵列大四倍。通过在两个平坦的固体基板之间对含有金属前驱体的树枝状聚合物进行简单的热退火,实现了垂直于底部取向的小金纳米颗粒(直径约1.6 nm,中心距约5.3 nm)的六边形阵列。密度泛函理论计算表明,金阳离子与树枝状聚合物的头基强烈结合。这种结构作为自组装成稳定圆柱形结构的构建单元。我们预计这项研究将导致创建大量超分子树枝状聚合物家族,可作为制备周期性、超致密纳米颗粒阵列的软模板。