Department of Chemical & Biomolecular Engineering, University of Illinois at Urbana-Champaign , 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign , 1304 W. Green St., Urbana, Illinois 61801, United States.
Acc Chem Res. 2016 Dec 20;49(12):2756-2764. doi: 10.1021/acs.accounts.6b00445. Epub 2016 Nov 29.
The solution printability of organic semiconductors (OSCs) represents a distinct advantage for materials processing, enabling low-cost, high-throughput, and energy-efficient manufacturing with new form factors that are flexible, stretchable, and transparent. While the electronic performance of OSCs is not comparable to that of crystalline silicon, the solution processability of OSCs allows them to complement silicon by tackling challenging aspects for conventional photolithography, such as large-area electronics manufacturing. Despite this, controlling the highly nonequilibrium morphology evolution during OSC printing remains a challenge, hindering the achievement of high electronic device performance and the elucidation of structure-property relationships. Many elegant morphological control methodologies have been developed in recent years including molecular design and novel processing approaches, but few have utilized fluid flow to control morphology in OSC thin films. In this Account, we discuss flow-directed crystallization as an effective strategy for controlling the crystallization kinetics during printing of small molecule and polymer semiconductors. Introducing the concept of flow-directed crystallization to the field of printed electronics is inspired by recent advances in pharmaceutical manufacturing and flow processing of flexible-chain polymers. Although flow-induced crystallization is well studied in these areas, previous findings may not apply directly to the field of printed electronics where the molecular structures (i.e., rigid π-conjugated backbone decorated with flexible side chains) and the intermolecular interactions (i.e., π-π interactions, quadrupole interactions) of OSCs differ substantially from those of pharmaceuticals or flexible-chain polymers. Another critical difference is the important role of solvent evaporation in open systems, which defines the flow characteristics and determines the crystallization kinetics and pathways. In other words, flow-induced crystallization is intimately coupled with the mass transport processes driven by solvent evaporation during printing. In this Account, we will highlight these distinctions of flow-directed crystallization for printed electronics. In the context of solution printing of OSCs, the key issue that flow-directed crystallization addresses is the kinetics mismatch between crystallization and various transport processes during printing. We show that engineering fluid flows can tune the kinetics of OSC crystallization by expediting the nucleation and crystal growth processes, significantly enhancing thin film morphology and device performance. For small molecule semiconductors, nucleation can be enhanced and patterned by directing the evaporative flux via contact line engineering, and defective crystal growth can be alleviated by enhancing mass transport to yield significantly improved coherence length and reduced grain boundaries. For conjugated polymers, extensional and shear flow can expedite nucleation through flow-induced conformation change, facilitating the control of microphase separation, degree of crystallinity, domain alignment, and percolation. Although the nascent concept of flow-directed solution printing has not yet been widely adopted in the field of printed electronics, we anticipate that it can serve as a platform technology in the near future for improving device performance and for systematically tuning thin film morphology to construct structure-property relationships. From a fundamental perspective, it is imperative to develop a better understanding of the effects of fluid flow and mass transport on OSC crystallization as these processes are ubiquitous across all solution processing techniques and can critically impact charge transport properties.
有机半导体(OSC)的溶液可印刷性代表了材料加工的显著优势,它能够以低成本、高通量和节能的方式制造具有新形态因子的设备,这些新形态因子具有灵活性、可拉伸性和透明性。尽管 OSC 的电子性能无法与晶体硅相媲美,但 OSC 的溶液可加工性允许它们通过解决传统光刻的挑战性方面来补充硅,例如大面积电子制造。尽管如此,控制 OSC 印刷过程中高度非平衡形态演变仍然是一个挑战,这阻碍了实现高电子器件性能和阐明结构-性能关系。近年来已经开发了许多优雅的形态控制方法,包括分子设计和新型处理方法,但很少有利用流体流动来控制 OSC 薄膜中的形态。在本报告中,我们讨论了在小分子和聚合物半导体印刷过程中,利用流场控制结晶作为控制结晶动力学的有效策略。将流场控制结晶的概念引入印刷电子领域的灵感来自于制药制造和柔性链聚合物的流加工领域的最新进展。尽管在这些领域对流诱导结晶进行了深入研究,但以前的发现可能不适用于印刷电子领域,因为 OSC 的分子结构(即带有柔性侧链的刚性π-共轭主链)和分子间相互作用(即π-π相互作用、四极相互作用)与药物或柔性链聚合物有很大的不同。另一个关键区别是溶剂蒸发在开放系统中的重要作用,它决定了流动特性并确定了结晶动力学和途径。换句话说,流场诱导结晶与印刷过程中溶剂蒸发驱动的传质过程密切相关。在本报告中,我们将突出展示这些印刷电子领域中流场控制结晶的区别。在 OSC 的溶液印刷中,流场控制结晶解决的关键问题是结晶和印刷过程中各种传输过程之间的动力学不匹配。我们表明,通过控制溶剂蒸发,可以通过加快成核和晶体生长过程来调整 OSC 结晶的动力学,从而显著提高薄膜形态和器件性能。对于小分子半导体,可以通过接触线工程引导蒸发通量来增强成核并对其进行图案化,通过增强传质可以缓解有缺陷的晶体生长,从而获得明显改善的相干长度和减少晶界。对于共轭聚合物,拉伸和剪切流可以通过流诱导构象变化来加速成核,从而促进微相分离、结晶度、畴排列和渗流的控制。尽管流场导向溶液印刷的新概念尚未在印刷电子领域得到广泛应用,但我们预计它将在不久的将来成为提高器件性能和系统地调整薄膜形态以构建结构-性能关系的平台技术。从基础的角度来看,必须更好地了解流体流动和传质对 OSC 结晶的影响,因为这些过程在所有溶液处理技术中都普遍存在,并可能对电荷输运性能产生关键影响。