CN103862171A - Method for preparing two-dimensional periodic metal particle array structure through dual-wavelength femtosecond lasers - Google Patents
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Abstract
双波长飞秒激光制备二维周期金属颗粒阵列结构的方法。本发明提出利用聚焦双色飞秒激光脉冲在金属表面制备二维周期颗粒阵列结构的方法和实现装置,其特点为金属颗粒结构在两维方向上呈周期性亚微米量级分布。通过采用非线性倍频技术实现不同特征参数的双色飞秒激光,并经共路或分路的时间延迟后由同一光学元件共线聚焦照射在样品上,形成的二维周期结构图案可通过改变倍频晶体的方位角和双色激光的功率配比等进行有效调控。本发明的优点是:利用飞秒激光不同波长和偏振特性的组合设计,方便快捷地实现亚微米量级二维周期金属颗粒阵列结构的制备。本发明提出的双色飞秒激光制备新方法在材料微纳米加工领域有着潜在的重要应用。
A method for preparing a two-dimensional periodic metal particle array structure with a dual-wavelength femtosecond laser. The invention proposes a method and device for preparing a two-dimensional periodic particle array structure on a metal surface by using focused two-color femtosecond laser pulses. Two-color femtosecond lasers with different characteristic parameters are realized by using nonlinear frequency doubling technology, and the same optical element is colinearly focused on the sample after the time delay of the common path or the split path, and the formed two-dimensional periodic structure pattern can be changed by changing The azimuth angle of the frequency doubling crystal and the power ratio of the two-color laser are effectively regulated. The invention has the advantage that the preparation of submicron-scale two-dimensional periodic metal particle array structure is realized conveniently and quickly by using the combined design of different wavelengths and polarization characteristics of the femtosecond laser. The new preparation method of the two-color femtosecond laser proposed by the invention has potential important applications in the field of material micro-nano processing.
Description
技术领域:Technical field:
本发明涉及飞秒激光在金属材料表面制备二维周期亚微米量级颗粒阵列结构的方法和加工装置,应用了飞秒激光脉冲在金属表面诱导周期性亚波长条纹结构随入射激光波长和偏振态发生变化的物理效应,属于超快激光应用与微纳米加工领域,未来可能在与表面等离子体波(Surface plasmon polaritons---SPPs)有关的新型纳米光子器件的设计与制备等方面具有重要潜在应用。The invention relates to a method and a processing device for preparing a two-dimensional periodic submicron-scale particle array structure on the surface of a metal material with a femtosecond laser. The femtosecond laser pulse is used to induce a periodic subwavelength stripe structure on the metal surface that varies with the incident laser wavelength and polarization state. The changing physical effect belongs to the field of ultrafast laser application and micro-nano processing. It may have important potential applications in the design and preparation of new nano-photonic devices related to surface plasmon polaritons---SPPs in the future. .
背景技术:Background technique:
近年来,飞秒激光技术及其商业化器件的快速发展和日趋成熟吸引了诸多学科领域内研究人员的广泛关注,特别是由于飞秒激光脉冲具有的脉冲时间短、峰值功率高和聚焦功率密度大等特点,使其在与超快过程检测、强场物理、非线性显微成像、激光烧蚀推进、材料改性和高精密加工等基础科学研究和先进制造技术开发和应用等方面具有广泛的应用前景。In recent years, the rapid development and maturity of femtosecond laser technology and its commercial devices have attracted extensive attention from researchers in many disciplines, especially due to the short pulse time, high peak power and focused power density of femtosecond laser pulses. Large and other characteristics make it widely used in basic scientific research and advanced manufacturing technology development and application such as ultrafast process detection, strong field physics, nonlinear microscopic imaging, laser ablation propulsion, material modification and high precision processing. application prospects.
特别是在超高精密加工、处理和制备领域,飞秒激光脉冲作为一种能够对材料和器件实现微纳米尺度上组织结构改变及其功能特性调控的新兴手段而受到世界各国科学家的广泛关注。与传统采用光学、电子束和离子束曝光进行掩膜刻蚀的加工工艺相比较,飞秒激光微纳米加工与制备技术具有操作简单、灵活、速度快、成本低和精度高等优点,已逐步发展成为当前激光、光电子和机械工程领域内的前沿研究方向。目前,人们利用飞秒激光已对金属、半导体、聚合物和透明电介质等成功实现了微米、亚微米甚至纳米尺度上的加工、制备与制作。特别是最近大量的实验研究表明:当单束低能量飞秒激光通过光学聚焦后以重复或扫描方式照射样品材料表面或内部时,在光斑覆盖区域内会出现一维周期或准周期性排列的条纹、沟槽或类光栅结构,其空间周期随着入射飞秒激光能量和脉冲数目发生变化,并且可以远小于入射激光波长,而条纹空间排列方向则与入射激光的偏振态紧密相关【Pulse number dependence of laser-induced periodic surface structures for femtosecondlaser irradiation of silicon,Journal of Applied Physics2010,108:034903;Formation ofextraordinarily uniform periodic structures on metals induced by femtosecond laser pulses,Journal of Applied Physics2006,100:023511;Femtosecond-laser-induced nanostructureformed on hard thin films of TiN and DLC,Appl.Phys.A,2003,76:983-985】。同时,针对这种奇特的物理现象,人们也给予了大量系统深入的理论研究,并相继提出了“自组织、二次谐波和表面波干涉”等多种物理模型加以分析和模拟【Self-organized pattern formationupon femtosecond laser ablation by circularly polarized light,2006,252:4702-4706;Formationof nanogratings on the surface of a ZnSe crystal irradiated by femtosecond laser pulses,Physical Review B,2005,72:125429;Surface Electromagnetic waves in optics,OpticalEngineering,31:718-730】。相比较而言,其中入射激光与其在材料表面诱导产生等离子体波(SPPs)之间的干涉理论能够更好合理地解释所观测到的实验现象,因此目前它已被多数人所接受。Especially in the field of ultra-high-precision processing, processing and preparation, femtosecond laser pulses have attracted widespread attention from scientists all over the world as an emerging method that can change the structure of materials and devices at the micro-nano scale and control their functional properties. Compared with the traditional processing technology of optical, electron beam and ion beam exposure for mask etching, femtosecond laser micro-nano processing and preparation technology has the advantages of simple operation, flexibility, high speed, low cost and high precision, and has been gradually developed. Become the frontier research direction in the field of laser, optoelectronics and mechanical engineering. At present, people have successfully realized the processing, preparation and production of metals, semiconductors, polymers and transparent dielectrics on the micron, submicron and even nanometer scales by using femtosecond lasers. In particular, a large number of recent experimental studies have shown that when a single beam of low-energy femtosecond laser is optically focused and irradiates the surface or interior of the sample material in a repetitive or scanning manner, there will be one-dimensional periodic or quasi-periodic arrangements in the area covered by the spot. Stripes, grooves or grating-like structures, whose spatial period changes with the incident femtosecond laser energy and pulse number, and can be much smaller than the incident laser wavelength, while the spatial arrangement direction of the stripes is closely related to the polarization state of the incident laser [Pulse number dependence of laser-induced periodic surface structures for femtosecondlaser irradiation of silicon,Journal of Applied Physics2010,108:034903;Formation ofextraordinarily uniform periodic structures on metals induced by femtosecond laser pulses,Journal of Applied Physics2006,100:023511;Femtosecond-laser-induced nanostructure formed on hard thin films of TiN and DLC, Appl. Phys. A, 2003, 76:983-985]. At the same time, a large number of systematic and in-depth theoretical studies have been given to this peculiar physical phenomenon, and various physical models such as "self-organization, second harmonic and surface wave interference" have been proposed to analyze and simulate [Self- organized pattern formationupon femtosecond laser ablation by circularly polarized light,2006,252:4702-4706;Formationof nanogratings on the surface of a ZnSe crystal irradiated by femtosecond laser pulses,Physical Review B,2005,72:125429;Surface Electromagnetic waves in optics, Optical Engineering, 31:718-730]. In comparison, the interference theory between the incident laser and the plasma waves (SPPs) induced on the material surface can better and reasonably explain the observed experimental phenomena, so it has been accepted by most people at present.
与此同时,人们还通过大量研究发现飞秒激光在金属和半导体表面诱导产生的这些周期或非周期性微纳米结构能够有效增强材料的多种功效和物化性能【陈烽、张东石等,飞秒激光制备金属表面超疏水微结构的方法,发明专利号:200910021923;杨建军、张楠、杨阳等,利用激光制备微结构靶提高激光推进冲量耦合系数的方法,发明专利号:At the same time, a large number of studies have found that these periodic or non-periodic micro-nanostructures induced by femtosecond lasers on the surface of metals and semiconductors can effectively enhance various efficacy and physical and chemical properties of materials [Chen Feng, Zhang Dongshi, etc., femtosecond Method for preparing super-hydrophobic microstructures on metal surfaces by laser, invention patent number: 200910021923; Yang Jianjun, Zhang Nan, Yang Yang, etc., using laser to prepare microstructure targets to improve laser propulsion impulse coupling coefficient, invention patent number:
201110087843;Brighter Light Sources from Black Metal:Significant Increase in EmissionEfficiency of Incandescent Light Sources Physical Review Letters,2009,102:234301】,从而极大地拓展和提升了材料和器件的应用潜能与价值,在太阳能利用、高灵敏度光电探测、固体照明和医疗器件制备等方面具有非常广阔的实际应用空间。201110087843; Brighter Light Sources from Black Metal: Significant Increase in Emission Efficiency of Incandescent Light Sources Physical Review Letters, 2009, 102: 234301], thus greatly expanding and enhancing the application potential and value of materials and devices, in solar energy utilization, high sensitivity Photoelectric detection, solid-state lighting and medical device preparation have very broad practical application space.
然而在此需要强调的是:在以往关于飞秒激光微纳米加工的研究过程中,大多数实验均是选择采用单一中心波长的飞秒激光脉冲作为入射光源,而且在材料表面主要是诱导形成的周期性条纹结构呈一维空间分布。为了进一步拓展飞秒激光制备的表面结构类型,最近人们提出将相同波长的飞秒脉冲分成多光束激光,然后利用它们的空间干涉原理在半导体材料表面制备出二维周期微纳结构【Fabrication of a two-dimensional periodicmicroflower array by three interfered femtosecond laser pulses on Al:ZnO thin films,NewJournal of Physics,2010,12:043025;Enhanced optical absorptance of metals usinginterferometric femtosecond ablation,Optics Express,2007,15:13838-13843;贾鑫、贾天卿,飞秒激光束制备非对称微纳复合周期花样的系统及方法,发明专利号:201310172920;陈建文、高鸿奕、谢红兰等,飞秒激光单脉冲形成二维纳米尺度周期结构的工作装置,发明专利号:03142107】。由于这些实验方法主要涉及到单一波长的多光束干涉情况,因此实际的光路设计和工作装置比较复杂,且制备形成的二维结构空间周期也将受到干涉光路精密调整的影响。However, what needs to be emphasized here is that in the previous research on femtosecond laser micro-nano processing, most of the experiments chose to use femtosecond laser pulses with a single central wavelength as the incident light source, and mainly formed on the surface of the material. The periodic stripe structure is distributed in one-dimensional space. In order to further expand the types of surface structures prepared by femtosecond lasers, it has recently been proposed to divide femtosecond pulses of the same wavelength into multi-beam lasers, and then use their spatial interference principle to prepare two-dimensional periodic micro-nano structures on the surface of semiconductor materials [Fabrication of a two-dimensional periodicmicroflower array by three interfered femtosecond laser pulses on Al:ZnO thin films,NewJournal of Physics,2010,12:043025;Enhanced optical absorptance of metals usinginterferometric femtosecond ablation,Optics Express,2007,15:13838-13843;贾鑫, Jia Tianqing, system and method for preparing asymmetric micro-nano composite periodic pattern with femtosecond laser beam, invention patent number: 201310172920; Chen Jianwen, Gao Hongyi, Xie Honglan, etc., working device for forming two-dimensional nanoscale periodic structure by femtosecond laser beam single pulse , Invention Patent No.: 03142107]. Since these experimental methods mainly involve multi-beam interference of a single wavelength, the actual optical path design and working device are relatively complicated, and the spatial period of the two-dimensional structure formed will also be affected by the precise adjustment of the interference optical path.
发明内容:Invention content:
本发明所要解决的技术问题是:如何利用两种不同波长的飞秒激光脉冲在金属材料表面快速制备二维周期性排布的亚微米颗粒阵列结构,掌握其中的系统设计思路、工艺制作方法、实现装置和关键要素等,从而实现对金属表面亚微米结构阵列的排列方向、尺寸大小和空间周期进行有效调控。The technical problem to be solved by the present invention is: how to use femtosecond laser pulses of two different wavelengths to quickly prepare a two-dimensional periodic arrangement of submicron particle array structures on the surface of metal materials, and master the system design ideas, process manufacturing methods, Realize devices and key elements, etc., so as to effectively control the arrangement direction, size and space period of the submicron structure array on the metal surface.
本发明通过巧妙利用飞秒激光不同波长和偏振特性的组合设计,采用简易实验装置便可以方便快捷地在金属表面制备出排列方向和尺寸大小均可改变的亚微米量级二维周期金属点阵结构。与传统的二维周期结构制作过程相比较,本发明提出的技术方法相对简单、快捷、方便、可操作性高,克服了传统光路设计与制作技术方法所带来的繁杂工序。The present invention cleverly utilizes the combined design of different wavelengths and polarization characteristics of femtosecond lasers, and adopts a simple experimental device to conveniently and quickly prepare sub-micron two-dimensional periodic metal lattices on the metal surface that can be changed in arrangement direction and size structure. Compared with the traditional two-dimensional periodic structure manufacturing process, the technical method proposed by the present invention is relatively simple, fast, convenient and highly operable, and overcomes the complicated procedures brought about by the traditional optical path design and manufacturing technical method.
本发明的技术方案:Technical scheme of the present invention:
双波长飞秒激光制备二维周期金属颗粒阵列结构的方法,本发明应用BBO晶体倍频技术性实现基频和倍频双波长飞秒激光脉冲的混合输出,且两者经共线或分路可变时间延迟传输后,再以共线方式经同一光学元件聚焦照射在金属表面,制备形成具有二维周期分布的亚微米量级颗粒阵列结构。另外,通过改变双波长激光脉冲的功率配比、时间延迟量和倍频晶体的相位匹配角等关键参数,实现对微结构阵列的周期、尺寸和排列方向进行调控,为在固体材料和器件表面快速加工制备二维周期微纳结构提供新方法。本发明方法的具体操作步骤是:A method for preparing a two-dimensional periodic metal particle array structure with a dual-wavelength femtosecond laser. The present invention uses BBO crystal frequency doubling technology to realize the mixed output of fundamental frequency and frequency-doubled dual-wavelength femtosecond laser pulses, and the two can be collinear or split. After transmission with a variable time delay, the same optical element is used to focus and irradiate the metal surface in a collinear manner to prepare and form a submicron-scale particle array structure with a two-dimensional periodic distribution. In addition, by changing the key parameters such as the power ratio of the dual-wavelength laser pulse, the amount of time delay, and the phase matching angle of the frequency-doubling crystal, the period, size, and alignment direction of the microstructure array can be regulated, providing a basis for solid materials and device surfaces. Rapid processing of two-dimensional periodic micro-nanostructures provides a new method. The concrete operating steps of the inventive method are:
第一步,金属靶样品的制作和固定The first step, the fabrication and fixation of the metal target sample
将金属固体靶材料表面进行机械打磨和抛光后,用去离子水超声清洗干净得到金属靶样品,然后在空气环境中将金属靶样品固定在三维精密移动平台上,并通过计算机控制来实现对样品在空间三维(x-y-z)方向上的精密移动;After the surface of the metal solid target material is mechanically ground and polished, it is ultrasonically cleaned with deionized water to obtain a metal target sample, and then the metal target sample is fixed on a three-dimensional precision mobile platform in an air environment, and the sample is controlled by a computer. Precise movement in three dimensions (x-y-z) in space;
所述金属靶样品的材料为钼或钨金属材料。The material of the metal target sample is molybdenum or tungsten metal material.
第二步,双波长飞秒激光的获取和传输The second step, the acquisition and transmission of dual-wavelength femtosecond laser
通过将激光器输出的飞秒激光脉冲垂直照射到BBO非线性晶体上,获得基频和倍频信号混合输出的双波长飞秒激光脉冲,然后将两者经过共线固定光路或者分路时间可变延迟光路的传输后,以共线方式经同一光学聚焦元件后垂直照射在金属靶样品表面;By vertically irradiating the femtosecond laser pulse output by the laser onto the BBO nonlinear crystal, the dual-wavelength femtosecond laser pulse output by mixing the fundamental frequency and frequency-doubled signals is obtained, and then the two pass through a collinear fixed optical path or a variable splitting time After delaying the transmission of the optical path, it passes through the same optical focusing element in a collinear manner and then irradiates vertically on the surface of the metal target sample;
第三步,金属靶样品表面的调整The third step, the adjustment of the surface of the metal target sample
控制三维精密移动平台,使上述金属靶样品能够沿垂直和平行于激光光束的方向进行精密移动,同时调整金属靶样品表面倾斜度使金属靶样品加工表面在整个加工移动过程中始终与激光传播方向保持相互垂直;Control the three-dimensional precision moving platform, so that the above-mentioned metal target sample can be precisely moved along the direction perpendicular and parallel to the laser beam, and at the same time adjust the surface inclination of the metal target sample so that the processing surface of the metal target sample is always in line with the laser propagation direction during the entire processing movement process keep perpendicular to each other;
第四步,聚焦元件焦点位置的确定The fourth step is to determine the focus position of the focusing element
选择入射飞秒激光功率为10毫瓦,然后沿平行于光束传播的方向逐步移动样品,在金属靶样品表面形成系列烧蚀凹坑,并依据烧蚀凹坑尺寸的变化情况确定聚焦飞秒激光束的焦点位置;Select the incident femtosecond laser power as 10 milliwatts, and then gradually move the sample along the direction parallel to the propagation of the beam to form a series of ablation pits on the surface of the metal target sample, and determine the focus of the femtosecond laser according to the change in the size of the ablation pits. The focal position of the beam;
第五步,金属靶样品表面的定位The fifth step, the positioning of the surface of the metal target sample
调节三维精密移动平台使得金属靶样品表面从聚焦元件的焦点位置沿逆光束传播方向移动至焦点前方的300~600微米范围内;Adjust the three-dimensional precision mobile platform so that the surface of the metal target sample moves from the focal position of the focusing element to the range of 300-600 microns in front of the focal point along the reverse beam propagation direction;
第六步,二维周期阵列结构的制备The sixth step, preparation of two-dimensional periodic array structure
在保证双色飞秒激光脉冲均能经过聚焦元件照射到样品表面情况下,控制三维精密移动平台使得金属靶样品在垂直于光束方向的平面内进行二维移动扫描,并通过调节基频和倍频激光功率、偏振态、样品表面与焦点之间的距离,从而在金属靶样品表面制备出不同的二维周期颗粒阵列分布。In the case of ensuring that the two-color femtosecond laser pulse can be irradiated to the sample surface through the focusing element, the three-dimensional precision mobile platform is controlled to make the metal target sample perform two-dimensional mobile scanning in a plane perpendicular to the beam direction, and by adjusting the fundamental frequency and double frequency Laser power, polarization state, and the distance between the sample surface and the focal point are used to prepare different two-dimensional periodic particle array distributions on the surface of the metal target sample.
第二步所述获得双波长飞秒激光产生的具体方法是:基于I类o+o→e相位匹配模式的BBO晶体非线性倍频技术,将激光器产生的飞秒激光脉冲转化为基频和倍频信号同时输出的双波长飞秒激光,并通过旋转BBO晶体的方位角来改变其相位匹配角度。当相位匹配为最佳状态时,获得的双波长飞秒激光均为线偏振态,且两者偏振方向相互垂直,而当相位匹配偏离最佳角度时,获得的倍频激光仍然保持线偏振但基频激光却变为椭圆偏振态。The specific method for obtaining dual-wavelength femtosecond laser generation in the second step is: based on the BBO crystal nonlinear frequency doubling technology of the I type o+o→e phase matching mode, the femtosecond laser pulse generated by the laser is converted into the fundamental frequency and The dual-wavelength femtosecond laser is simultaneously output by the frequency-doubled signal, and the phase matching angle is changed by rotating the azimuth angle of the BBO crystal. When the phase matching is in the best state, the obtained dual-wavelength femtosecond laser is linearly polarized, and the polarization directions of the two are perpendicular to each other. When the phase matching deviates from the optimal angle, the obtained frequency-doubled laser still maintains linear polarization but The fundamental frequency laser becomes elliptically polarized.
第二步所述采用共线固定光路实现双波长飞秒激光传输的具体方法是:将激光器输出的飞秒激光垂直照射到BBO倍频晶体上产生和输出双波长飞秒激光脉冲,然后两者以共线方式传输并由二向色镜反射后,经同一光学元件获得聚焦并垂直照射在金属靶样品表面。The specific method of using the collinear fixed optical path in the second step to realize dual-wavelength femtosecond laser transmission is: vertically irradiate the femtosecond laser output from the laser onto the BBO frequency doubling crystal to generate and output dual-wavelength femtosecond laser pulses, and then both After being transmitted in a collinear manner and reflected by a dichroic mirror, it is focused by the same optical element and irradiated vertically on the surface of the metal target sample.
第二步所述采用分路时间可变延迟光路实现双波长飞秒激光传输的方法是:The method described in the second step to realize dual-wavelength femtosecond laser transmission by using the branching time variable delay optical path is:
(1)首先,将激光器输出的飞秒激光脉冲经分束器后形成两个能量相同的激光脉冲,并将两者分别引入不同的时间延迟光路中,其中一臂光路中采用BBO倍频和滤波技术实现仅有倍频飞秒激光的输出,而另一臂光路保持基频飞秒激光的传输;(1) First, the femtosecond laser pulse output by the laser is passed through the beam splitter to form two laser pulses with the same energy, and the two are respectively introduced into different time-delayed optical paths, and BBO frequency doubling and The filtering technology realizes the output of only the frequency doubled femtosecond laser, while the other arm optical path maintains the transmission of the fundamental frequency femtosecond laser;
(2)经过两臂各自时间可变延迟光路传输后的双波长飞秒激光,经强度衰减后再由二向色镜合束后以共线传输方式到达一个共同的光学聚焦元件,并垂直照射在金属靶样品表面。(2) After the dual-wavelength femtosecond lasers are transmitted through the time-variable delay optical paths of the two arms, after intensity attenuation, the beams are combined by dichroic mirrors, and then reach a common optical focusing element in a collinear transmission mode, and are irradiated vertically on the surface of the metal target sample.
其中,调节两臂光路使得照射到金属靶样品表面的基频激光相对于倍频激光脉冲时间延迟范围为-50皮秒<Δτ<260皮秒。Among them, the optical paths of the two arms are adjusted so that the time delay range of the fundamental-frequency laser irradiated on the surface of the metal target sample relative to the frequency-doubled laser pulse is -50 picoseconds<Δτ<260 picoseconds.
第六步所述的调节基频和倍频飞秒激光功率的方法是:通过利用中性衰减片或者1/2波片与偏振片的组合来实现对双波长激光功率的控制。The method for adjusting the power of the fundamental frequency and frequency-doubled femtosecond laser described in the sixth step is to realize the control of the power of the dual-wavelength laser by using a neutral attenuation plate or a combination of a 1/2 wave plate and a polarizer.
所述金属靶样品扫描速度为0.005毫米/秒至0.4毫米/秒。The scanning speed of the metal target sample is 0.005 mm/s to 0.4 mm/s.
所述光学聚焦元件为显微物镜或光学透镜。The optical focusing element is a microscope objective lens or an optical lens.
所述二向色镜对基频飞秒激光的反射率小于5%,而对倍频飞秒激光的反射率大于60%。The reflectivity of the dichroic mirror to the fundamental frequency femtosecond laser is less than 5%, and the reflectivity to the double frequency femtosecond laser is greater than 60%.
在制备二维周期阵列结构的过程中,当双波长飞秒激光脉冲均为线偏振态时,所需倍频与基频激光的功率比值范围为1<γ<7;当倍频飞秒激光为线偏振而基频飞秒激光为椭圆偏振时,所需倍频与基频激光的功率比值范围约为0.8<γ<3。In the process of preparing a two-dimensional periodic array structure, when the dual-wavelength femtosecond laser pulses are all linearly polarized, the power ratio range of the required frequency-doubling and fundamental-frequency laser is 1<γ<7; when the frequency-doubling femtosecond laser When the femtosecond laser is linearly polarized and the fundamental frequency femtosecond laser is elliptically polarized, the power ratio range of the required frequency doubling to the fundamental frequency laser is about 0.8<γ<3.
当调节倍频晶体的相位匹配角偏离最佳状态时,在他之后输出的基频激光变为椭圆偏振态,而倍频激光保持线偏振但其偏振方向发生改变,从而实现对颗粒阵列结构排列方向在±35°范围内的倾斜调控。When the phase matching angle of the frequency doubling crystal deviates from the optimal state, the fundamental frequency laser output after him becomes elliptical polarization state, while the frequency doubling laser maintains linear polarization but its polarization direction changes, so as to realize the arrangement of the particle array structure Tilt regulation within the range of ±35°.
在金属靶样品表面制备出的二维周期阵列结构实际上是由二个相互垂直方向的周期条纹在空间交叉组成形成,其中长周期变化范围为230~300纳米,短周期变化范围为580~640纳米,交叉形成的金属颗粒的尺寸变化范围为200~550纳米。The two-dimensional periodic array structure prepared on the surface of the metal target sample is actually formed by two mutually perpendicular periodic stripes intersecting in space. Nano, the size of the metal particles formed by the intersection ranges from 200 to 550 nanometers.
上述第六步中所述的样品移动速度范围为0.005~0.4毫米/秒内,最小移动精度为1微米,相邻两条扫描线之间的距离范围为2~100微米。The moving speed of the sample described in the sixth step above ranges from 0.005 to 0.4 mm/s, the minimum movement accuracy is 1 micron, and the distance between two adjacent scanning lines ranges from 2 to 100 microns.
所述的调整BBO晶体方位角是通过在垂直于入射激光平面内旋转倍频晶体o轴与入射基频激光偏振方向之间的夹角θ来实现,晶体方位角选择在最佳相位匹配情况时作为参考零点,其变化范围为θ=-35°~35°。The adjustment of the azimuth angle of the BBO crystal is achieved by rotating the angle θ between the o-axis of the frequency doubling crystal and the polarization direction of the incident fundamental frequency laser in a plane perpendicular to the incident laser. As a reference zero point, its variation range is θ=-35°~35°.
本发明的优点和有益效果:Advantages and beneficial effects of the present invention:
(1)应用线偏振的近红外飞秒激光脉冲经BBO晶体产生的基频和倍频双波长飞秒激光脉冲,以共线方式聚焦后垂直照射在金属样品表面诱导形成二维周期分布的亚微米颗粒阵列结构。本发明工艺简单,成本低,效率高,且可以大面积实现。(1) Apply linearly polarized near-infrared femtosecond laser pulses through BBO crystals to generate dual-wavelength femtosecond laser pulses with fundamental frequency and doubled frequency, focus in a collinear manner, and then vertically irradiate on the surface of the metal sample to induce the formation of two-dimensional periodic distribution of sub Microparticle array structure. The invention has the advantages of simple process, low cost and high efficiency, and can be realized in a large area.
(2)利用BBO倍频晶体产生基频和倍频激光脉冲的不同波长和偏振态组合设计,在样品表面一步式完成亚微米量级的二维周期结构写入,且二维结构的空间周期在两个方向各不相同。(2) Using the BBO frequency doubling crystal to generate different wavelengths and polarization combinations of the fundamental frequency and frequency doubling laser pulses, the two-dimensional periodic structure of the submicron level is written on the sample surface in one step, and the spatial period of the two-dimensional structure differ in both directions.
(3)通过在垂直于入射激光平面内旋转倍频晶体方位角,即可导致其后输出双波长激光的偏振特性和功率配比发生改变,从而方便地实现对材料表面形成二维周期阵列结构的空间排列方向和周期等形貌特征进行有效调控。(3) By rotating the azimuth angle of the frequency doubling crystal in the plane perpendicular to the incident laser, the polarization characteristics and power ratio of the output dual-wavelength laser can be changed, so as to facilitate the formation of a two-dimensional periodic array structure on the surface of the material The shape characteristics such as spatial arrangement direction and period can be effectively controlled.
附图说明Description of drawings
图1为本发明设计的双波长飞秒激光共线传输光路图。Fig. 1 is a diagram of the collinear transmission optical path of the dual-wavelength femtosecond laser designed in the present invention.
图2为本发明设计的双波长飞秒激光分路传输时间可变延迟光路图。Fig. 2 is a diagram of the variable delay optical path of the dual-wavelength femtosecond laser split transmission time designed in the present invention.
图1和图2中的标号说明为:1表示飞秒激光器、2表示中心波长为800纳米的飞秒激光、3表示中心波长为800纳米飞秒激光的全反射镜、4表示中心波长为800纳米的中性衰减片、5表示BBO倍频晶体、6表示双色飞秒激光、7表示二向色镜、8表示光学聚焦元件、9表示金属靶样品、10表示三维精密移动平台、11表示中心波长为800纳米激光分束器、12表示可调时间延迟线,13表示中心波长为400纳米激光的滤光片。The label descriptions in Fig. 1 and Fig. 2 are: 1 represents a femtosecond laser, 2 represents a femtosecond laser with a center wavelength of 800 nanometers, 3 represents a total reflection mirror with a center wavelength of 800 nanometers of a femtosecond laser, and 4 represents a center wavelength of 800 nanometers. Nano neutral attenuator, 5 means BBO frequency doubling crystal, 6 means two-color femtosecond laser, 7 means dichroic mirror, 8 means optical focusing element, 9 means metal target sample, 10 means three-dimensional precision mobile platform, 11 means center The wavelength is a laser beam splitter with a wavelength of 800 nanometers, 12 represents an adjustable time delay line, and 13 represents an optical filter with a center wavelength of 400 nanometers laser.
图3为制备获得的二维周期亚微米颗粒阵列结构,其中A为实施例3在BBO晶体为最佳匹配角度θ=0°,即入射光偏振方向与BBO晶体o轴方向平行时,金属钼表面形成的二维周期亚微米颗粒阵列结构,B为A的放大细节图。Figure 3 is the prepared two-dimensional periodic submicron particle array structure, where A is the best matching angle θ=0° for the BBO crystal in Example 3, that is, when the polarization direction of the incident light is parallel to the o-axis direction of the BBO crystal, the metal molybdenum The two-dimensional periodic submicron particle array structure formed on the surface, B is the enlarged detail of A.
图4为实施例4在BBO晶体方位角偏离最佳相位匹配角度,即θ≠0°时,金属钼表面上形成二维周期阵列结构方向的变化情况,图中左上角标注为倍频晶体o轴与入射基频激光偏振方向之间的夹角θ,其中,A为夹角θ=-25°的情况,B为夹角θ=35°的情况。Fig. 4 is embodiment 4 when the BBO crystal azimuth angle deviates from the optimal phase matching angle, that is, when θ≠0°, the change of the direction of the two-dimensional periodic array structure formed on the surface of metal molybdenum, the upper left corner of the figure is marked as the frequency doubling crystal o The angle θ between the axis and the polarization direction of the incident fundamental frequency laser, where A is the case where the angle θ=-25°, and B is the case where the angle θ=35°.
图5为实施例5在总功率为6毫瓦、400纳米倍频激光延后56皮秒时在金属钼表面上形成的二维亚波长周期结构分布情况。Fig. 5 shows the distribution of two-dimensional sub-wavelength periodic structures formed on the surface of metal molybdenum when the total power is 6 milliwatts and the frequency-doubled laser of 400 nanometers is delayed by 56 picoseconds in Example 5.
具体实施方式:Detailed ways:
以下结合附图对本发明“双波长飞秒激光制备二维周期金属颗粒阵列结构的方法”的具体实施方式作详细说明。The specific implementation of the "method for preparing a two-dimensional periodic metal particle array structure" by a dual-wavelength femtosecond laser of the present invention will be described in detail below in conjunction with the accompanying drawings.
实施例1Example 1
如图1所示光路结构,飞秒激光器1产生的飞秒激光2入射到全反射镜3后,其反射光经中性衰减片4垂直照射到BBO倍频晶体5表面,之后产生的双波长飞秒激光6经过二向色镜7,入射到聚焦元件8,经聚焦后的双色飞秒激光照射到固定在三维精密移动平台10上的金属靶样品9表面,诱导形成二维周期分布的亚微米颗粒阵列结构。As shown in the optical path structure in Figure 1, after the
其中,从飞秒激光器产生输出的激光脉冲具体以下特征参数:重复频率1000赫兹、脉冲宽度为50飞秒、中心波长为800纳米、水平线偏振。它们经过全反射镜和中性衰减片后垂直入射到厚度为1毫米的BBO非线性倍频晶体上,并基于I类o+o→e相位匹配模式产生输出中心波长为400纳米倍频信号和剩余中心波长为800纳米基频信号的混合双波长飞秒激光脉冲。两者共线传输并以45°角入射到二向色镜上,获得不同的反射效率后再经一个4倍显微物镜实现光束聚焦。通过控制三维精密移动平台将样品表面移至激光焦点前300~600微米距离,并以0.01~0.4毫米/秒的扫描速度在沿与光束传播方向垂直的平面内移动样品,最终在样品表面实现二维周期亚微米颗粒阵列结构的快速制备。Among them, the laser pulse output from the femtosecond laser has the following characteristic parameters: a repetition frequency of 1000 Hz, a pulse width of 50 femtoseconds, a center wavelength of 800 nanometers, and horizontal linear polarization. After passing through the total reflection mirror and the neutral attenuator, they are vertically incident on the BBO nonlinear frequency doubling crystal with a thickness of 1 mm, and based on the type I o+o→e phase matching mode, the output center wavelength is 400 nanometers frequency doubling signal and The remaining hybrid dual-wavelength femtosecond laser pulses centered on the 800 nm fundamental frequency signal. The two are transmitted collinearly and are incident on the dichroic mirror at an angle of 45°. After obtaining different reflection efficiencies, the beam is focused by a 4x microscope objective lens. By controlling the three-dimensional precision mobile platform, the sample surface is moved to a distance of 300-600 microns in front of the laser focus, and the sample is moved in a plane perpendicular to the beam propagation direction at a scanning speed of 0.01-0.4 mm/s, and finally two-dimensional laser beam is achieved on the sample surface. Rapid preparation of dimension-periodic submicron particle array structures.
实施例2Example 2
如图2所示光路结构,飞秒激光器1产生的飞秒激光2经分束器11后形成两个激光脉冲,然后分别进入两个不同的光路,其中一臂光路中的飞秒激光只是经过中性衰减片4后到达二向色镜7,另一臂光路的飞秒激光经全反射镜3和中性衰减片4后进入可调时间延迟线12,然后经过时间延迟后垂直照射到BBO倍频晶体5上,之后再经滤光片13到达二向色镜7,两路激光分别经二向色镜7透射和反射后成为共线传输的双波长飞秒激光脉冲,它们经光学元件8聚焦后垂直照射到固定在三维精密移动平台10上的金属靶样品9表面,诱导形成二维周期分布的亚微米颗粒阵列结构。The optical path structure shown in Figure 2, the
其中,从飞秒激光器输出的重复频率1000赫兹、脉冲宽度为50飞秒、中心波长为800纳米的水平线偏振飞秒激光脉冲,经分束器后形成两个能量等同的飞秒激光脉冲并分别进入两个不同方向的光路传播,其中一臂光路中的飞秒激光仅是通过衰减器获得合适的强度调控,而另一臂光路中的飞秒激光则通过可调时间延迟线后垂直照射到厚度为1毫米的BBO非线性倍频晶体上,并基于I类o+o→e相位匹配模式产生输出中心波长为400纳米和中心波长为800纳米的混合双波长飞秒激光,然后采用400纳米滤光片将基频激光滤掉从而实现只有倍频飞秒激光的传输。在两臂光路中传播的不同波长飞秒激光脉冲最终经合束器后实现共线传输,然后经过一个4倍显微物镜聚焦后垂直照射到样品表面。通过控制三维精密移动平台将样品表面移至激光焦点前300~600微米距离,并以0.01~0.4毫米/秒的扫描速度在沿与光束传播方向垂直的平面内移动样品,最终在样品表面实现二维周期亚微米颗粒阵列结构的快速制备。Among them, the horizontal linearly polarized femtosecond laser pulse output from the femtosecond laser has a repetition frequency of 1000 Hz, a pulse width of 50 femtoseconds, and a center wavelength of 800 nanometers. After passing through the beam splitter, two femtosecond laser pulses with equal energy are formed and separated The femtosecond laser in the optical path of one arm only obtains proper intensity regulation through the attenuator, while the femtosecond laser in the optical path of the other arm passes through the adjustable time delay line and irradiates vertically to the On the BBO nonlinear frequency doubling crystal with a thickness of 1 mm, and based on the type I o+o→e phase matching mode, a hybrid dual-wavelength femtosecond laser with an output center wavelength of 400 nm and a center wavelength of 800 nm is generated, and then a 400 nm The optical filter filters out the fundamental frequency laser so as to realize the transmission of only frequency doubled femtosecond laser. The femtosecond laser pulses of different wavelengths propagating in the optical paths of the two arms are finally collinearly transmitted after passing through the beam combiner, and then focused by a 4x microscope objective lens and then irradiated vertically to the sample surface. By controlling the three-dimensional precision mobile platform, the sample surface is moved to a distance of 300-600 microns in front of the laser focus, and the sample is moved in a plane perpendicular to the beam propagation direction at a scanning speed of 0.01-0.4 mm/s, and finally two-dimensional laser beam is achieved on the sample surface. Rapid preparation of dimension-periodic submicron particle array structures.
实施例3Example 3
在实例1中的光路基础上,采用中性衰减片将入射到BBO晶体上的基频飞秒激光功率进行衰减,并旋转BBO晶体的方位角来获得最大倍频效率,即此时实现晶体o轴与入射基频激光偏振方向平行,从而导致其后输出的剩余800纳米激光保持原有的线偏振,而400纳米倍频激光也为线偏振,且两者偏振方向相互垂直。经二向色镜反射后双波长飞秒激光的总功率为2毫瓦,将样品表面放置在激光焦点前400微米位置处。图3所示为样品扫描速度为0.04毫米/秒时获得加工效果的扫描电子显微图像,其中放大倍数分别为2万和6万倍。从该图中可知:形成的椭圆形金属颗粒结构呈现明显的二维周期性阵列分布,即沿横向和纵向排列的空间周期分别为Λ=616纳米和236纳米,椭圆形颗粒在两个方向上的尺寸大约为Φ=(448,230)纳米。On the basis of the optical path in Example 1, a neutral attenuator is used to attenuate the fundamental frequency femtosecond laser power incident on the BBO crystal, and the azimuth angle of the BBO crystal is rotated to obtain the maximum frequency doubling efficiency, that is, the crystal o The axis is parallel to the polarization direction of the incident fundamental-frequency laser, so that the remaining 800-nm laser output afterwards maintains the original linear polarization, while the 400-nm frequency-doubled laser is also linearly polarized, and the polarization directions of the two are perpendicular to each other. The total power of the dual-wavelength femtosecond laser after reflection by the dichroic mirror is 2 milliwatts, and the sample surface is placed at a position 400 microns in front of the laser focus. Figure 3 shows the scanning electron micrographs of the processing effect obtained when the sample scanning speed is 0.04 mm/s, and the magnifications are 20,000 and 60,000 times, respectively. It can be seen from the figure that the formed elliptical metal particle structure presents an obvious two-dimensional periodic array distribution, that is, the spatial periods arranged along the horizontal and vertical directions are Λ=616 nm and 236 nm, respectively, and the elliptical particles are in two directions The size is about Φ = (448,230) nanometers.
实施例4Example 4
在实例1的装置基础上,保持入射到材料表面上的双波长飞秒激光总功率、样品位置和扫描速度等实验参数不变,但此时通过在垂直于入射激光的平面内旋转BBO晶体的方位角,使得其o轴相对于入射基频激光线偏振方向发生倾斜,从而导致输出倍频激光的偏振方向随之转动,且倍频效率也发生相应变化;另外,由于此时倍频晶体o轴与入射基频激光偏振方向的夹角不等于零,则倍频过程中入射基频激光会在晶体内产生偏振方向相互垂直的e光和o光分量,从而影响从晶体出射后的剩余基频激光的偏振特性,即此时它变为椭圆偏光。因此,尽管说在此种情况下从BBO晶体出射的双波长激光总功率没有变化,但是其中基频和倍频激光的功率配比和偏振态等均发生改变。图4所示为当旋转BBO晶体o轴与入射光线偏振方向夹角分别为θ=-25°和35°时,金属钼表面上形成的二维周期性结构分布,其中阵列结构的空间排列方向相对于实例3中的情况发生逆/顺时针方向的倾斜,且二维空间周期分别为Λ=(682,284)纳米和(698,290)纳米。On the basis of the device in Example 1, the experimental parameters such as the total power of the dual-wavelength femtosecond laser incident on the surface of the material, the position of the sample, and the scanning speed are kept constant, but at this time by rotating the BBO crystal in the plane perpendicular to the incident laser The azimuth angle makes its o-axis tilt relative to the linear polarization direction of the incident fundamental-frequency laser, which causes the polarization direction of the output frequency-doubled laser to rotate accordingly, and the frequency-doubling efficiency also changes accordingly; in addition, because the frequency-doubling crystal o The angle between the axis and the polarization direction of the incident fundamental frequency laser is not equal to zero, then the incident fundamental frequency laser will generate e-light and o-light components with polarization directions perpendicular to each other in the crystal during the frequency doubling process, thus affecting the remaining fundamental frequency after exiting the crystal The polarization properties of the laser light, i.e. when it becomes elliptically polarized. Therefore, although the total power of the dual-wavelength laser emitted from the BBO crystal does not change in this case, the power ratio and polarization state of the fundamental-frequency and frequency-doubled lasers change. Figure 4 shows the distribution of two-dimensional periodic structures formed on the surface of metal molybdenum when the angles between the o-axis of the rotating BBO crystal and the polarization direction of the incident light are θ=-25° and 35°, respectively, and the spatial arrangement direction of the array structure is The counter/clockwise tilt occurs relative to the case in Example 3, and the two-dimensional spatial periods are Λ=(682,284) nm and (698,290) nm, respectively.
实施例5Example 5
在实例2中的光路基础上,首先将激光器输出的基频飞秒激光脉冲经分束器后进入两个不同的时间延迟光路,其中一臂光路中放置BBO晶体并采用滤波技术实现仅有倍频飞秒激光的输出和传播,而另一臂光路保持原有基频飞秒激光的传输,两者由合束器转化为共线传输方式,并经共同的光学元件聚焦后垂直照射在金属样品表面。调整两臂双波长飞秒激光均为线偏振态且偏振方向相互垂直,其中倍频与基频激光的功率比值约为2:1,到达样品表面的基频激光相对于倍频激光的时间延迟范围为-10皮秒<Δτ<220皮秒。图5所示为总功率为6毫瓦、400纳米倍频激光延后56皮秒时在金属钼表面上形成的二维亚波长结构分布,周期分别为Λ=654和239纳米。On the basis of the optical path in Example 2, the fundamental frequency femtosecond laser pulse output by the laser first passes through the beam splitter and then enters two different time-delayed optical paths, in which a BBO crystal is placed in the optical path of one arm and filtering technology is used to realize only multiple The output and propagation of the femtosecond laser, while the optical path of the other arm maintains the transmission of the original femtosecond laser of the fundamental frequency. sample surface. Adjust the two-arm dual-wavelength femtosecond lasers to be linearly polarized and the polarization directions are perpendicular to each other. The power ratio of the frequency-doubled and fundamental-frequency laser is about 2:1, and the time delay of the fundamental-frequency laser reaching the surface of the sample relative to the frequency-doubled laser The range is -10 picoseconds < Δτ < 220 picoseconds. Figure 5 shows the distribution of two-dimensional subwavelength structures formed on the surface of metal molybdenum when the total power is 6 milliwatts and the frequency-doubled laser of 400 nanometers is delayed by 56 picoseconds. The periods are Λ=654 and 239 nanometers, respectively.
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员,在不脱离原来发明原理的前提下,还可以做若干改进和和变化。如果设计的基本制备原理与本方法相同,则这些改进和变化也应视为在本发明的保护范围内。The above descriptions are only preferred implementations of the present invention. It should be pointed out that those skilled in the art may make some improvements and changes without departing from the principle of the original invention. If the basic preparation principle of the design is the same as the method, these improvements and changes should also be considered within the protection scope of the present invention.
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