从大自然中神奇景观钟乳石的形成到生活中常见的现象咖啡渍图案，都离不开蒸发诱导自组装的作用。随着表面结构制备的要求越来越高，受限液体蒸发诱导自组装显示出了重要的学术研究意义和广阔的实际应用前景。特别是在喷墨打印、生物医药、材料科学、纳/微电子机械系统等具有外部环境限制下的实际制造领域中，受限液体蒸发诱导自组装更是体现出了巨大的应用价值。针对受限液体蒸发诱导自组装中的三个关键科学问题：液体蒸发和固体自组装之间的耦合、三相接触线移动和颗粒沉积之间的耦合、受限液体蒸发诱导自组装的尺寸效应，本文采用以实验和理论为主，模拟为辅的方法开展研究，主要内容如下：

疏水固体表面上球冠状液滴蒸发诱导离子结晶自组装。针对盐结晶在微观尺度上各向异性生长和不同的界面性质导致在宏观尺度上很难获得完美晶体结构的难题，开展了氯化钠溶液液滴在疏水基底上的蒸发诱导结晶自组装实验，探索了使用微量水溶性聚合物对结晶行为的调控作用，提出了“蒸发诱导结晶自组装”的概念，通过液-气界面的受限作用成功诱导氯化钠有序结晶、生长，最终自组装形成壳体和空心管状的三维结构。建立了自组装晶体结构分区相图，分析壳体外/内表面和空心管状结构对组分浓度的依赖性，从实验上直接观察到了多孔受限结构对结晶物自发抬升的作用。理论上，发展了多元组分溶液的三维格点模型，得到了初始状态下溶液混合自由能，初始能量越低，蒸发诱导结晶自组装过程越稳定，揭示了自组装晶体结构的形成和演化机理。通过拟合溶液初始混合自由能和蒸发速率的关系，反演了自组装结构的形成对液体蒸发过程施加的受限作用。希望可以为矿物结垢处理和单晶纤维材料制备等应用提供设计参考和理论指导。

圆柱管中受限液体蒸发诱导纳米颗粒沉积自组装。开展了受限在圆柱管中纳米颗粒水悬浮液的蒸发诱导沉积自组装实验，探索了受限空间的几何效应和基底的温度效应对沉积图案形成，发现了蜂窝状、多环、岛状和两种过渡态沉积图案。通过建立沉积图案分区相图，厘清了几何效应和温度效应对沉积图案形成和演化的影响，找到了规则、有序的多环图案形成的最优实验条件。针对多环沉积图案，实验上直接观察到了三相接触线钉扎/去钉扎的周期性运动；理论上，基于 Onsager 变分原理，推导了在蒸发过程中受限液体的几何形状随时间的演化方程，厘清了接触线半径和接触角随时间的演化规律，接触线半径呈阶梯状上升演化，对应的接触角呈锯齿状振荡演化；定量化地阐明了接触线移动能力、蒸发效应和界面张力在颗粒沉积过程中的作用，揭示了多环沉积图案的形成机理。通过对成环位置和环间距变化的定量分析，理论预测很好地再现了实验结果。

固体表面受限薄膜蒸发去润湿诱导分形沉积自组装。开展了溶解有布洛芬小分子的乙醇液滴在硅片上的蒸发诱导沉积自组装实验，提出了“蒸发诱导分形图案”的概念，在同一实验模型下实现了三种沉积图案的构建，并通过跨尺度理论模型进行了验证。在蒸发效应的作用下，混合液滴首先在硅片上铺展，达到最大铺展半径后去润湿，在基底上留下一层均匀的薄膜，最后薄膜去润湿，布洛芬小分子团聚形成颗粒进行沉积。定量化地分析了混合液滴在硅片表面上丰富的流体动力学行为；通过调整初始布洛芬浓度，制备了从微观到宏观尺度一系列厚度的薄膜；基于薄膜去润湿构造了均匀、多边形和咖啡环沉积图案，并通过分形维数将这一系列沉积图案之间建立了几何上的联系。理论上，发展了膜厚演化动力学方程，并考虑了 van der Waals 力、表面张力和重力在薄膜中的作用，揭示了沉积图案的形成机理和演化规律。

本文以实验为基础，可视化、定量化地开展了三个典型受限液体（疏水固体表面球冠状液滴、圆柱管中受限液体和固体表面受限薄膜）的蒸发诱导自组装研究，通过探索受限液体蒸发过程和自组装结构对浓度、温度、几何等因素的依赖性，发现了结晶物可以自发抬升基底表面等新现象，并解释了其成因和规律；利用跨尺度数值模拟，补充实验手段中难以测试到的数据，进一步支撑了实验现象；在实验和模拟的基础上，建立理论模型，重现实验现象，阐明了自组装结构的形成过程，并揭示了其中的能量和力学调控机理。希望可以帮助对于受限液体蒸发诱导自组装背后深刻物理内涵的认识，以及对于矿物结垢污染处理和单晶纤维材料制备等应用提供理论指导。

From the formation of stalactites in the magical landscape of nature to the common phenomenon of coffee stain patterns in life, the role of evaporation-induced self-assembly (EISA) is inseparable. With the increasing demand for the preparation of surface structure, EISA of confined liquid has shown significant academic research significance and broad practical application prospects. Especially in the practical manufacturing fields with external constraints such as inkjet printing, biomedicine, material science and nano/micro electro-mechanical systems (NEMS/MEMS), EISA of confined liquid has demonstrated great application value. Focusing on three key scientific problems: coupling between liquid evaporation and solid self-assembly, coupling between three-phase contact line movement and particle deposition, and size effect of EISA, this dissertation adopts a combined approach of mainy experimental and theoretical methods with simulation as a supplement to carry out the research, with the main contents as follows:

Crysatllization self-assembly of ions induced by the spherical crown drop evaporation on hydrophobic substrate. To address the challenge that the anisotropic growth of salt crystals at microscale and the different interfacial properties make it difficult to obtain perfect crystal structures at macroscale, evaporation and crystallization experiments are conducted using a sodium chloride solution drop on a hydrophobic substrate. In this study, the effect of trace water-soluble polymers on the crystallization behavior are explored. The concept of evaporation-induced crystal self-assembly (EICSA) is proposed, which successfully helps NaCl to crystal and grow orderly through the limting of liquid-vapor interface, and finally self-assembles into a three-dimensional structure of shell and hollow tube. A crystal structure partition phase diagram is established to analyze its dependence on the component concentration. The role of porous confined structure on the spontaneous lifting of crystals has been directly observed from experiments. A three-dimensional lattice model of multi-component solution is theoretically developed to obtain the initial mixed free energy of the solution, revealing the formation mechanism of the crystal structure. And the lower the initial energy, the more stable the EICSA. By fitting the relationship between the initial mixed free energy of the solution and the evaporation rate, the confined effect of self-assembly structure formation on the evaporation process is inferred conversely. Hopelly, these results can provide design reference and theoretical guidance for applications such as mineral fouling treatment and single crystal fiber materials preparation.

Deposition self-assembly of nanoparticles induced by the confined liquid evaporation in a cylindrical tube. Evaporation and deposition experiments are conducted using aqueous suspension containing nanoparticles in a confined cylindrical tube, exploring the effects of confined geometry and substrate temperature on the formation of deposition patterns. Honeycomb, multi-ring, island, and two transitional patterns are discovered. By establishing a phase diagram of deposition patterns, the formation and evolution laws of deposition patterns are clarified, and the optimal experimental conditions for the formation of regular and ordered multi-ring patterns are found. In addition, for multi-ring deposition patterns. In experiment, the periodic pinned/depinned movement of three-phase contact line is directly observed. In theory, based on the Onsager variational principle, the evolution equation of the confined liquid shape is derived, clarifying the temporal evolution of the contact line and contact angle, i.e., a staircase manner of contact line and an oscillation mode of contact angle, quantitatively elucidating the roles of contact line mobility, evaporation effect, and interfacial tension in the process of particle deposition, and finally revealing the formation mechanism of multi-ring deposition pattern. Furthermore, the theoretical predictions well reproduce the experimental results by quantitative analysis of ring positions and spacing variations.

Self-assembly of fractal deposition induced by the evaporating dewetting of thin films confined to the solid seuface. Evaporation and deposition experiments are conducted using an ethanol drop dissolved with ibuprofen molecules on a silicon wafer, and the concept of evaporation-induced fractal patterns (EIFP) is proposed. The construction of three types of deposition patterns is achieved using the same experimental model, and verified by a cross scale theoretical model. Under the effect of evaporation, the mixed drop first spreads on the substrate and reaches the maximum spreading radius before dewetting, leaving a uniform thin film on the substrate. Finally, particles formed by the aggregation of small molecules are deposited based on the film dewetting. The rich hydrodynamics behaviors of the mixed drop on the silicon wafer is quantitatively analyzed. By adjusting the initial ibuprofen concentration, a series of thin films with thickness ranging from microscale to macroscale are prepared in experiments. Uniform, polygonal and coffee ring patterns are constructed based on film dewetting, and a geometric relationship among these deposition patterns is established through the calculation of fractal dimension. In theory, the dynamic equation for film thickness evolution is developed, and the roles of van der Waals force, surface tension, and gravity on the film are considered, revealing the formation mechanism and evolution laws of depositon patterns.

Based on experiments, this dissertation visually and quantitatively studies the evaporation-induced self-assembly process of three typical confined liquids (spherical crown drop on hydrophobic substrate, confined liquid in a cylindrical tube, and thin film confined to the solid surface). By exploring the dependence of confined liquid evaporation and self-assembly structure on concentration, temperature, geometry, and other factors, some new phenomena are discovered, such as the spontaneous lifting of crystals, and their causes and laws are explained. To supplement the experimental data that are difficult to test through experiments, cross-scale numerical simulations are utilized. Furthermore, theoretical models are established to reproduce the experimental phenomena, clarify the formation of self-assembly structures, and reveal the energy and mechanics mechanisms involved. Overall, this dissertation provides a deeper understanding of the profound physical connotations behind EISA of confined liquid, and hope to provide theoretical guidance for applications such as mineral fouling treatment and single crystal fiber materials preparation.