4D Printing at the Microscale

3D printing of adaptive and dynamic structures, also known as 4D printing, is one of the key challenges in contemporary materials science. The additional dimension refers to the ability of 3D printed structures to change their properties—for example, shape—over time in a controlled fashion as the result of external stimulation. Within the last years, significant efforts have been undertaken in the development of new responsive materials for printing at the macroscale. However, 4D printing at the microscale is still in its early stages. Thus, this progress report will focus on emerging materials for 4D printing at the microscale as well as their challenges and potential applications. Hydrogels and liquid crystalline and composite materials have been identified as the main classes of materials representing the state of the art of the growing field. For each type of material, the challenges and critical barriers in the material design and their performance in 4D microprinting are discussed. Importantly, further necessary strategies are proposed to overcome the limitations of the current approaches and move toward their application in fields such as biomedicine, microrobotics, or optics.     

基于湿度刺激响应水凝胶的飞秒激光四维打印研究

开发了一种具备湿度刺激响应的复合水凝胶前驱体,并利用飞秒激光双光子聚合技术,对该智能响应水凝胶材料进行三维微纳成形制造。系统研究了激光功率和直写速度对该水凝胶材料成形中的线宽、墙高、溶胀度以及机械模量的影响规律,进一步通过对双层结构的有限元仿真和直写结构的设计,实现了三维微纳结构在外界环境刺激下的可控形变。理论计算和实验结果表明,激光功率和直写速度能实现对智能水凝胶材料三维成形和结构性能的精确调制,实现了双层水凝胶微结构的自主可编程形状转换,推动了微纳软体机器人和精细组织工程的发展。     

利用飞秒激光直写技术制备钙钛矿微盘激光器

利用溶液法制备的钙钛矿微/纳米晶虽然可以得到性能良好的微型激光器,但是其所需生长周期较长且缺乏重复性.为了解决这一问题,提出了利用飞秒激光直写技术制备高重复性钙钛矿微盘激光器的新方法.首先使用双源共蒸的方法在石英玻璃衬底上沉积FAPbI3钙钛矿薄膜,然后采用飞秒激光直写技术在FAPbI3钙钛矿薄膜上制备不同直径的微盘激...     

飞秒激光组装一维纳米材料及其应用

一维纳米材料具有众多优异的特性,是构建微纳米功能性器件的基石。实现一维纳米材料在二维和三维空间的高精度和高定向组装是充分发挥其应用潜力的关键,同时也是制造难点。在众多纳米材料组装技术中,飞秒激光直写诱导组装技术具有独特优势,可实现一维纳米材料在任意三维结构中的可设计、高定向及高精度的组装。首先简要介绍了一维纳米材料组装研究的背景,并总结了非激光直写组装技术的研究现状和存在的挑战,然后较详细介绍了飞秒激光直写技术在一维纳米材料组装研究中的进展,重点回顾了金属(包括Au和Ag纳米线)、半导体(包括CNTs和ZnO)一维纳米材料的飞秒激光直写组装及微纳光电子功能器件的制造。并讨论了诱导一维纳米材料定向排布的光学力和非光学力(包括剪切力、体积收缩应力和空间限制)的作用机理,理论计算和实验研究结果验证了飞秒激光诱导的非光学力作用是导致一维纳米材料定向排布的主要原因。最后探讨了目前飞秒激光组装技术面临的一些问题和未来在高精度纳米材料组装和三维功能器件集成方面的发展趋势。     

Botanical‐Inspired 4D Printing of Hydrogel at the Microscale

Botanical systems have evolved the intriguing ability to respond to diverse stimuli due to long‐term survival competition. Mimicking these dynamic behaviors has greatly advanced the developments in wide fields ranging from soft robotics, precision sensors to drug delivery and biomedical devices. However, realization of stimuli‐responsive components at the microscale with high response speed still remains a significant challenge. Herein, the miniature biomimetic 4D printing of pH‐responsive hydrogel is reported in spatiotemporal domain by femtosecond laser direct writing. The dimension of the printed architectures is at the microscale (<10² µm) and the response speed is reduced down to subsecond level (<500 ms). Shape transformation with multiple degrees of freedom is accomplished by taking advantage of pH‐triggered expansion, contraction, and torsion. Biomimetic complex shape‐morphing is enabled by adopting flexible scanning strategies. In addition, application of this 4D‐printed micro‐architecture in selective micro‐object trapping and releasing is demonstrated, showcasing its possibilities in micromanipulation, single‐cell analysis, and drug delivery.     

Shape-Memory Balloon Structures by Pneumatic Multi-material 4D Printing

4D printing is an attractive approach for manufacturing structures that can adopt new shapes or functionalities after printing. However, 4D printing methods and materials that can be used to achieve structures with complex shapes and excellent mechanical properties simultaneously are still lacking. Here, a novel 4D printing is developed where multi-material digital light process 3D printing of shape memory polymers (SMPs) fabricates a structure that is later transformed into a complex 3D shape with robust mechanical properties by pneumatic manipulation. In this method, the shape change is controlled by the spatial distributions of SMPs, which is designed by finite element analysis. Experimental investigations are carried out to print various structured balloons with predefined intricate shapes, including a structure in dog-like shape and a surface with the human face contour. These structures are also endowed with robust mechanical stiffness and lightweight features, which allow this new 4D printing approach for potential applications in biomedical devices, reconfigurable structures, and metamaterials.     

Advances in 4D Printing: Materials and Applications

4D printing has attracted tremendous interest since its first conceptualization in 2013. 4D printing derived from the fast growth and interdisciplinary research of smart materials, 3D printer, and design. Compared with the static objects created by 3D printing, 4D printing allows a 3D printed structure to change its configuration or function with time in response to external stimuli such as temperature, light, water, etc., which makes 3D printing alive. Herein, the material systems used in 4D printing are reviewed, with emphasis on mechanisms and potential applications. After a brief overview of the definition, history, and basic elements of 4D printing, the state‐of‐the‐art advances in 4D printing for shape‐shifting materials are reviewed in detail. Both single material and multiple materials using different mechanisms for shape changing are summarized. In addition, 4D printing of multifunctional materials, such as 4D bioprinting, is briefly introduced. Finally, the trend of 4D printing and the perspectives for this exciting new field are highlighted.     

Direct 3D Printing of Ultralight Graphene Oxide Aerogel Microlattices

Graphene aerogel microlattices (GAMs) hold great prospects for many multifunctional applications due to their low density, high porosity, designed lattice structures, good elasticity, and tunable electrical conductivity. Previous 3D printing approaches to fabricate GAMs require either high content of additives or complex processes, limiting their wide applications. Here, a facile ion‐induced gelation method is demonstrated to directly print GAMs from graphene oxide (GO) based ink. With trace addition of Ca²⁺ ions as gelators, aqueous GO sol converts to printable gel ink. Self‐standing 3D structures with programmable microlattices are directly printed just in air at room temperature. The rich hierarchical pores and high electrical conductivity of GAMs bring admirable capacitive performance for supercapacitors. The gravimetric capacitance (C_s) of GAMs is 213 F g^?1 at 0.5 A g^?1 and 183 F g^?1 at 100 A g^?1, and retains over 90% after 50 000 cycles. The facile, direct 3D printing of neat graphene oxide can promote wide applications of GAMs from energy storage to tissue engineering scaffolds.     

飞秒激光在生物学领域的应用

生物技术与激光技术在20世纪发展迅速。飞秒激光与其他长脉冲激光相比具有以下明显的特征:1)由于能量淀积时间短,在激光加工时,可以实现热效应可以忽略的超精细加工;2)聚焦时焦点附近的光子密度大,可以实现基于高度非线性过程的有空间选择的微观结构操控。因此,飞秒激光问世以来,其优越的特性引起了科学家,包括生物学家的普遍关注。本文综述了飞秒在现代生物学领域中的一些应用,包括基于多光子和二阶以及三阶光学非线性的生物三维成像、研究化学反应和生物学动力学过程、活细胞操纵以及生物材料的微处理和纳米尺度生物结构的切割等。     

Fabrication of Glass-Ceramic 3D Micro-Optics by Combining Laser Lithography and Calcination

This perspective is an overview of a recent direction in optical 3D printing, where polymerization of crosslinkable materials and nanomaterial fillers can be guided to the final structures and new composites via high temperature annealing (HTA). Defining 3D nano/micro-structures by ultrafast laser direct writing and tailoring their precursor composition with subsequent tunability of the final properties during 750–1500 °C HTA step takes place at the large surface-to-volume ratio conditions favoring efficient pyrolysis and calcination, which are required for exchange of chemical materials/gases between glass/ceramic phase and surrounding. Previously, unexplored inorganic material formation conditions in terms of fast thermal quenching, composition mixing and surface tension guided formation can be harnessed by glass making for creation of new materials endowed with preferable technical properties. An immediate application perspective for a high durability, integrated, and active 3D micro-optics is foreseen.     

In Situ Electrical Network Activation and Deactivation in Short Carbon Fiber Composites via 3D Printing

Prior studies on carbon-filler based, conductive polymer composites have mainly investigated how conductive filler morphology and concentration can tailor a material's electrical conductivity and overlooks the effects of filler alignment due to the difficulty to control and quickly quantify the filler alignment. Here, direct ink write 3D printing's unique ability is utilized to control carbon fiber alignment with a single process parameter, velocity ratio, to instantaneously activate or deactivate the electrical network in composites. Maximum electrical conductivity is achieved by randomly aligning carbon fibers that enhances the chance of direct fiber-to-fiber contact and, thus, activating the electrical network. However, aligning the fibers by increasing the velocity ratio disrupts the electrical network by minimizing fiber-to-fiber contact that resulted in a drastic decrease in electrical conductivity by as much as five orders of magnitude in both short and long carbon fiber composites. With this study, this study demonstrates that electrically conductive or insulative composites can be fabricated sequentially with a single ink. This novel ability to instantaneously control the electrical conductivity of carbon fiber reinforced composites allow to directly embed conductive pathways into designs to 3D print multifunctional composites that are capable of localized heating and self-sensing.     

飞秒激光脉冲技术的新进展

本文评述了飞秒激光产生与放大技术的新进展。     

全固态近红外、蓝光飞秒激光系统的实验研究

利用棱镜对引进频谱空间啁啾来补偿飞秒激光二次谐波产生中的相位失配,提高了倍频效率.建立了一套全固态、多波长(1064 nm,532 nm,823 nm,402 nm)飞秒脉冲激光系统.NdYVO4激光器输出的1064 nm激光功率可达10 W;532 nm绿光激光最高功率可达5.6 W.当用2.5 W绿光激光泵浦时,从钛宝石激光器及经BBO倍频可分别输出中心波长为823.1 nm和402 nm、平均功率300mW和73 mW、谱宽32.3 nm和5.1 nm、脉宽22fs和33.3fs、重复率108 MHz的近红外和蓝光飞秒激光.整个系统具有结构紧凑、倍频效率高、运行稳定的特点.     

飞秒放大激光脉冲的单次测量

在未加任何色散补偿的情况下，用相关方法直接测量得到了脉冲宽度为３９ｆｓ的单次放大激光脉冲。为实时测量低重复频率的超短强激光脉冲提供了可靠的手段。     

飞秒激光诱发直接带隙半导体瞬态漂白效应建模

在建立瞬态光谱吸收系数模型的基础上,结合超快载流子动力学机制,建立了可以描述飞秒激光诱发直接带隙半导体瞬态漂白机制的理论模型,对飞秒激光诱发直接带隙半导体的瞬态漂白特性进行了数值仿真研究。结果表明,飞秒激光不仅可以诱发对应波长的瞬态漂白,还能导致激发波长到半导体长波限的宽光谱范围的瞬态漂白,且波长越长漂白现象越明显,甚至会引发能带底部出现负吸收现象。     

Temperature Tunable 4D Polymeric Photonic Crystals

Photonic crystals owe their multitude of optical properties to the way their structure creates interference effects. It is therefore possible to influence the photonic response by acting on their physical structure. In this article, tunable photonic crystals made by elastic polymers that respond to their environment are explored, in particular with a physical deformation under temperature variation. This creates a feedback process in which the photonic response depends on its physical structure, which itself is influenced by the environmental changes. By using a multi-photon polymerization process specifically optimized for soft responsive polymers such as Liquid Crystalline Networks, highly resolved, reproducible, and mechanically self-standing photonic crystals are fabricated. The physical structure of the 3D woodpile can be tuned by an external temperature variation creating a reversible spectral tuning of 50 nm in the telecom wavelength range. By comparing these results with finite element calculations and temperature induced shape-change, it is confirmed that the observed tuning is due to an elastic deformation of the structure. The achieved nanometric patterning of tunable anisotropic photonic materials will further foster the development of reconfigurable photonic crystals with point defects acting as tunable resonant cavities and, more in general, of 4D nanostructures.     

飞秒激光烧蚀研究进展

介绍飞秒激光烧蚀材料的机理论模型，阐述飞秒激光烧蚀的特性，揭示飞秒激光烧蚀的广泛应用前景。     

飞秒激光脉冲刻写光纤布拉格光栅的研究进展

介绍了利用飞秒激光器刻写光纤布拉格光栅的三种基本方法:全息干涉法、相位掩模板法、直接逐点刻写法.讨论了飞秒激光制作光纤布拉格光栅的主要作用机制.详细论述了这三种方法的特点、规律及最新研究进展,并总结了飞秒激光制作的光纤布拉格光栅呈现出来的独特性质.     

飞秒激光加工微光学元件的研究

利用低功率飞秒激光振荡器进行材料表面加工的研究并将其应用于微光学元件的加工制作领域;对飞秒激光倍频光以及飞秒激光与光刻胶材料相互作用进行了实验;以光刻胶作为牺牲层进行表面加工获得了各种玻璃光栅及光掩模板;利用光学显微镜和原子力显微镜(AFM)对实验结果进行检测,得到微米量级的特征线宽;所得光栅的光学性能通过He-Ne激光器进行检测,实验结果与理论值一致。该研究为微光学元件的加工制作提供了新的方法。