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摘要:
硬脆材料由于具有稳定的机械和化学性能、优良的光电特性等优势，在航空航天、光电工业等领域具有广泛的应用。激光加工由于具有高精度、高能量、非接触式加工等特点，是实现硬脆材料加工的理想技术。为了实现硬脆材料的去除加工，通常需要较高的激光能量，使得加工的结构精度较低，而且表面质量较差。本综述介绍了液体辅助激光加工技术在硬脆材料加工方面的研究进展，分别介绍了液相激光烧蚀、激光诱导背部湿法刻蚀和刻蚀辅助激光改性等三种液体辅助激光加工技术的原理，对比了各自的优势和不足，以及不同加工技术、辅助液体种类以及加工参数等对不同硬脆材料加工质量的影响，介绍了液体辅助激光加工技术目前主要的应用，最后，简要阐述了该技术存在的问题和未来的潜在发展。
Abstract:Due to the stable mechanical and chemical properties, excellent photoelectric properties, and other advantages, hard and brittle materials have been widely used in aerospace, the photoelectric industry, and other fields. Laser fabrication is an ideal technology for hard and brittle materials processing due to its high precision, high energy, and non-contact properties. In order to achieve the removal of hard and brittle materials, high laser energy is usually required, resulting in low structural accuracy and poor surface quality. This review introduces the advances of liquid-assisted laser fabrication technology in the processing of hard and brittle materials, introduces the principles of three liquid-assisted laser fabrication technologies, and compares their advantages and disadvantages. The effects of different processing technologies, types of auxiliary liquids, and processing parameters on the quality of different materials were summarized in detail. The main applications of liquid-assisted laser fabrication technology were summarized, and the existing problems and potential development of this technology were discussed.
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图 1 液体辅助激光加工技术框架简图
Figure 1. Outline of the review about liquid-assisted laser fabrication
图 2 (a) 液相激光加工原理图； (b) 基于液相激光烧蚀产生的空化气泡的产生、膨胀、坍塌以及持久性气泡产生[11]；(c) 基于水下持续气泡辅助飞秒激光烧蚀技术制备尾部同心圆宏观结构[18]；(d) 基于飞秒激光冲击喷丸液体烧蚀技术制备孔状裂纹结构的不同角度形貌展示[19]
Figure 2. (a) Schematic diagram of liquid phase laser processing; (b) Generation, expansion, collapse, and persistent bubble generation based on cavitation bubbles generated by liquid phase laser ablation [11]; (c) Preparation of tail concentric circle macrostructure based on underwater sustained bubble-assisted femtosecond laser ablation technology[18]; (d) Preparation of porous crack structure based on femtosecond laser impact shot peening liquid ablation technology with different angles and morphology display[19]
图 3 (a) 基于飞秒激光的激光诱导背部湿法刻蚀光路系统示意图[24]；(b) 利用激光诱导背部湿法刻蚀技术在不同环境下制备的孔的形貌对比[25]；(c) 激光诱导背部湿法刻蚀产生空化气泡的流体动力学的阴影图[26]
Figure 3. (a) Schematic diagram of laser induced back wet etching optical path system based on femtosecond laser[24] ; (b) Comparison of the morphologies of the holes prepared by laser-induced wet back etching under different environments[25]; (c) Shadow diagram of the hydrodynamics of cavitation bubbles produced by laser-induced wet back etching[26]
图 4 (a) 利用辅助液体与材料本体和改性区域反应速率不同进行选择性刻蚀的流程图[34]；(b) 利用辅助液体只与改性区域反应而进行选择性刻蚀的流程图[35]
Figure 4. (a) Flow chart of selective etching using the reaction rates of the auxiliary liquid and the material body and modified area[34]; (b) Flow chart for selective etching using an auxiliary liquid reacting only with the modified region[35]
图 5 (a) 在硅表面生成了三种不同的微纳米结构[55]； (b) 在光敏玻璃内波制备出微通道结构[88]；(c) 在蓝宝石表面通过各向异性刻蚀制备的三角形凹坑结构[89]
Figure 5. (a) Three different micro-nano structures are generated on the silicon surface[55]; (b) Microchannel structures are prepared by internal waves in photosensitive glass[88]; (c) Triangular pits prepared by anisotropic etching on the sapphire surface[89]
图 6 (a) 在蓝宝石表面制备单个任意形貌微透镜[90]；(b) 金刚石表面制备不同形貌的微光涡旋发生器[91]；(c) 在镀膜蓝宝石表面制备均匀排布的仿生蛾眼增透结构[92]；(d) 在硫化物表面制备的高均匀性的人工复眼结构[35]
Figure 6. (a) A single microlens with arbitrary morphology was prepared on the sapphire surface[90]; (b) Preparation of low-light level vortex generators with different morphologies on the diamond surface[91]; (c) The bionic moth-eye anti-reflection structure was prepared uniformly on the surface of the coated sapphire[92]; (d) Highly homogenous artificial compound eye structures prepared on the surface of sulfide[35]
图 7 (a) 三层多分支的微流控系统[94]；(b) 叶轮可旋转的辅助微通道系统[94]；(c) 能够控制液体流动方向的微腔和微球嵌套系统结构[95]
Figure 7. (a) Three-layer multi-branch microfluidic system[94]; (b) Auxiliary microchannel system with rotating impeller[94]; (c) A nested system structure of microcavities and microspheres that can control the direction of liquid flow[95]
图 8 (a) 激光诱导微射流辅助消融方法制备的通孔阵列[19]；(b) 不同形貌的无锥度微孔[98]；(c) 激光诱导微射流辅助消融方法制备的微通道阵列[19]
Figure 8. (a) Through hole array prepared by laser-induced micro-jet assisted ablation[19]; (b) Non-taper pores with different morphologies[98]; (c) Microchannel array prepared by laser-induced microjet assisted ablation[19]
表 1 三种技术优缺点比较
Table 1. Comparison of advantages and disadvantages of three technologies
液体激光烧蚀 激光诱导背面湿法刻蚀 湿法腐蚀辅助激光改性 优点 1、阻隔加工过程中空气对材料的影响，尤其是避免对金属的氧化；
2、液体起到冷却作用，减少热影响区；
3、液体的流动有效减少碎屑堆积，减少沉积层和重铸层的产生，提高表面质量。1、易于去除产生的碎屑，加工过程不受碎屑影响；
2、流体同样起着冷却的作用，可以提高加工质量；
3、加工质量和精度较高，损伤较小。1、容易进行三维加工；
2、加工能量低，易提高加工精度；
3、分布进行，加工过程不受液体的影响。不足 1、激光穿过辅助液体，增加了激光能量损耗，包括液体中的光吸收和散射等；
2、加工过程中液体的扰动对聚焦光束产生影响，导致光束质量下降，结构表面质量较差。1、吸收液一般是丙酮、甲苯、芘等有毒物质，具有环境和安全问题；
2、难以制备复杂的三维结构。1、对于各向同性腐蚀，难以制备棱角分明的结构；
2、难以对化学稳定性良好或耐腐蚀材料进行刻蚀。
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表 2 不同材料不同辅助液体加工
Table 2. Different materials assist in liquid processing
材料 辅助液体 加工方法 激光器类型
(波长/nm，脉冲宽度)制备结构 时间 引用 光敏玻璃 10%HF 退火+湿法腐蚀 fs激光器(775，150 fs) 三维垂直微流控结构 2004 [44] 光敏玻璃 10%HF 湿法腐蚀 fs激光器(515，260 fs) 微透镜 2022 [45] 光敏玻璃 10%HF 湿法腐蚀 fs激光器 芯片内三维结构 2011 [46] 光敏玻璃 化学电镀液 FS激光直接烧蚀+化学电镀 fs激光器(1045，457 fs) 微电器件 2013 [47] 光敏玻璃和SU-8 10%HF 湿法腐蚀+双光子聚合 fs激光器(1045，360 fs) 三维微流控结构 2014 [48] 二氧化硅 10%HF 湿法腐蚀 罗氏线圈电流换能器 2016 [49] 二氧化硅 高锰酸钾 背部湿法刻蚀 fs激光器(515，500 fs) LIPSS 2018 [50] 二氧化硅 磷酸/硫酸铜 背部湿法刻蚀 掺镱光纤激光器(1064，100 ns） 高纵深比通道 2020 [51] 二氧化硅 HF 湿法腐蚀 fs激光器(800，50 fs) 三维螺线管微线圈 2014 [41] 硅 5%HF 两步湿法腐蚀 fs激光器(800，35 fs) 深纳米光栅 2022 [52] 硅 KOH(20wt%): 异丙醇=4:1 湿法腐蚀 fs激光器(800，35 fs) 纳米间隙结构 2021 [53] 硅 5%HF 湿法腐蚀+聚合物转写 fs激光器(800，30 fs) 微透镜阵列模板 2012 [54] 硅 氢氧化钾(20%):异丙醇(IPA，4%)=4:1 湿法腐蚀 fs激光器(800，35 fs) 大面积微纳米结构 2017 [55] 硅 40%KOH 背部湿法刻蚀 fs激光器(1552.5，900 fs) 深凹槽 2022 [33] 硅 40%KOH 背部湿法刻蚀 fs激光器(1552.5，900 fs) LIPSS 2020 [56] 硅 水 液体辅助激光加工 fs激光器(790，30 fs) LIPSS 2014 [12] -- -- 液体辅助激光加工 -- LIPSS [57-60] 硅 水 UPB-fs-LAL fs激光器(1030，223 fs) 尾部同心圆结构 2020 [21] 硅 水 fs-LSPAL fs激光器(1030，223 fs) 裂纹结构 2020 [22] 硅 水，乙醇 背部湿法刻蚀 fs激光器(800，120 fs) 孔 2019 [25] 硅 饱和芘/丙酮 背部湿法刻蚀 KrF准分子激光器(248，20 ns） 倾斜微沟槽 2010 [61] 硅 水/乙醇 液体辅助激光加工 Yb: KGW飞秒激光器(515，217 fs) 切割硅晶片 2022 [11] 硅 20%HF 湿法腐蚀 fs激光器(800，50 fs) 孔阵列 2015 [39] 熔融石英 10%HF 湿法腐蚀 fs激光器 谐振器 2022 [62] 熔融石英 10 mol/L的KOH 湿法腐蚀 fs激光器 微轴棱锥 2022 [63] 熔融石英 5%HF 湿法腐蚀 fs激光器(800，120 fs) 大面积微透镜阵列 2018 [64] 熔融石英 5%HF 湿法腐蚀 fs激光器(1030，230 fs) 凹槽 2019 [65] 熔融石英 KOH 湿法腐蚀 fs激光器 芯片内三维结构 2011 [46] 熔融石英 0.5 mol的芘/甲苯和甲苯 背部湿法刻蚀 ps激光器(355，10 ps)
ps激光器(266，10 ps)LIPSS 2010 [66] 熔融石英 0.5 mol芘/甲苯 ns背部刻蚀+fs烧蚀 fs激光器(248，500 ps)
Ti:蓝宝石激光器(775，130 fs)LIPSS 2006 [67] 熔融石英 丙酮/芘 背部湿法刻蚀 XeCl准分子激光器(308，30 ns） 微透镜阵列 2004 [26] 蓝宝石 H3PO4: H2SO4=1:3 湿法腐蚀+掩膜 压力传感器 2021 [68] 蓝宝石 H3PO4: H2SO4=1:3 湿法腐蚀 fs激光器(1028，190 fs) 微透镜阵列 2018 [38] 蓝宝石 H3PO4: H2SO4=1:3 湿法腐蚀 fs激光器(800，120 fs) SWS减反结构 2017 [69] 蓝宝石 5%HF 湿法腐蚀 fs激光器 无锥度通孔 2022 [61] 蓝宝石 40%KOH 湿法腐蚀 fs激光器(800，120 fs) 大面积微透镜阵列 2018 [64] 蓝宝石 氯苯 背部湿法刻蚀 ps激光器(266，150 ps) 光栅 2007 [70] 蓝宝石 甲苯 背部湿法刻蚀 ps激光器(355，10 ps) 凹槽 2010 [71] 蓝宝石 硫酸铜 背部湿法刻蚀 Nd:YAG激光器(1064，120 ns) 凹槽 2017 [31] 4H-SiC 正丁醇溶液 背部湿法刻蚀-微射流 fs激光器(520，300 fs) 孔和凹槽 2022 [19] 硒化锌ZnSe H2O2(26%): NH4OH(28%)=1:3 湿法腐蚀 fs激光器(800，130 fs) 脊形波导 2022 [72] 硼硅酸盐玻璃 8.5 mol/L的KOH 湿法腐蚀 三维自由形状 2021 [73] 氟化物 甲苯 背部湿法刻蚀 ps激光器(355，10 ps) 凹槽 2010 [71] 钠钙玻璃 硫酸铜 背部湿法刻蚀+液相沉积 掺镱光纤激光器(1064，100 ps) 微铜图案 2020 [74] 锗晶片 水/乙醇 液体辅助激光加工 Nd: YAG激光器(1064，10 ps) 切割锗晶片 2016 [75] K9玻璃 8%HF 湿法腐蚀+转写硫族玻璃 fs激光器(800，50 fs) 复眼 2022 [35]
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