Revealing the growth of copper on polystyrene-block-poly(ethylene oxide) diblock copolymer thin films with in situ GISAXS.

Revealing the growth of copper on polystyrene-block-poly(ethylene oxide) diblock copolymer thin films with in situ GISAXS.
复制标题

利用原位 GISAXS 揭示铜在聚苯乙烯-嵌段-聚环氧乙烷二嵌段共聚物薄膜上的生长

DOI:
10.1039/d1nr01480c
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发表时间:
2021
期刊:
影响因子:
6.7
通讯作者:
P. Müller-Buschbaum
P. Müller-Buschbaum
中科院分区:
材料科学2区
文献类型:
--
作者:
S. J. Schaper;F. C. Löhrer;S. Xia;C. Geiger;M. Schwartzkopf;P. Pandit;J. Rubeck;B. Fricke;S. Frenzke;A. M. Hinz;N. Carstens;O. Polonskyi;T. Strunskus;F. Faupel;S. V. Roth;P. Müller-Buschbaum

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铜(Cu)作为优良的导电体和两亲性二嵌段共聚物聚苯乙烯-聚环氧乙烷(PS-b-PEO)作为聚合物电解质和离子导体可与活性材料结合用于聚合物锂离子电池(LIBs)的复合电极。由于界面是lib中的关键问题,采用原位掠入射小角x射线散射(GISAXS)技术研究了高PEO分数PS-b-PEO薄膜上Cu触点的溅射沉积,以实时跟踪Cu层的形成。我们观察到铜团簇的分层形态,形成更大的铜团簇。确定了PS-b-PEO微相分离和Cu簇的两个特征距离。铜团簇在PS畴上的选择性聚集解释了即使在达到完全表面覆盖后铜层仍然存在分层形态的起源。在溅射沉积的最初几纳米内生长的球状Cu团簇形成了一个高度多孔的Cu -聚合物界面。根据PS-b-PEO薄膜上Cu簇生长动力学的不同,将Cu簇生长分为4个阶段:(I)成核、(II)扩散驱动生长、(III)吸附驱动生长和(IV)晶粒生长。在有效铜层厚度为5.75 nm时实现了渗滤。
Copper (Cu) as an excellent electrical conductor and the amphiphilic diblock copolymer polystyrene-block-poly(ethylene oxide) (PS-b-PEO) as a polymer electrolyte and ionic conductor can be combined with an active material in composite electrodes for polymer lithium-ion batteries (LIBs). As interfaces are a key issue in LIBs, sputter deposition of Cu contacts on PS-b-PEO thin films with high PEO fraction is investigated with in situ grazing-incidence small-angle X-ray scattering (GISAXS) to follow the formation of the Cu layer in real-time. We observe a hierarchical morphology of Cu clusters building larger Cu agglomerates. Two characteristic distances corresponding to the PS-b-PEO microphase separation and the Cu clusters are determined. A selective agglomeration of Cu clusters on the PS domains explains the origin of the persisting hierarchical morphology of the Cu layer even after a complete surface coverage is reached. The spheroidal shape of the Cu clusters growing within the first few nanometers of sputter deposition causes a highly porous Cu–polymer interface. Four growth stages are distinguished corresponding to different kinetics of the cluster growth of Cu on PS-b-PEO thin films: (I) nucleation, (II) diffusion-driven growth, (III) adsorption-driven growth, and (IV) grain growth of Cu clusters. Percolation is reached at an effective Cu layer thickness of 5.75 nm.
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