CN110116273A - The method that femtosecond laser synergistic oxidation reaction prepares broad band anti-reflection structure - Google Patents

The method that femtosecond laser synergistic oxidation reaction prepares broad band anti-reflection structure Download PDF

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CN110116273A
CN110116273A CN201910484540.4A CN201910484540A CN110116273A CN 110116273 A CN110116273 A CN 110116273A CN 201910484540 A CN201910484540 A CN 201910484540A CN 110116273 A CN110116273 A CN 110116273A
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femtosecond laser
sample
method described
micron
sea urchin
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姜澜
柳海林
胡洁
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Beijing Institute of Technology BIT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/362—Laser etching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/60—Preliminary treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B23K2103/12—Copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Abstract

The present invention relates to the methods that femtosecond laser synergistic oxidation reaction prepares broad band anti-reflection structure, belong to anti-reflection structure processing technique field.Material to be processed (sample) is first placed in femtosecond laser processing light path system by this method, using focusing objective len, the hot spot of femtosecond laser is made to focus on sample surfaces；Then the movement that the switch and translation stage of mechanical shutter in optical path are processed by control femtosecond laser, makes the focal beam spot of femtosecond laser successively carry out the ablation in the direction x and the direction y in sample surfaces, prepares micron order cone structure array in sample surfaces；Finally sample is placed in the mixed solution of the ammonium persulfate and sodium hydroxide that stir evenly, oxidation reaction, which occurs, makes sample surfaces grow sea urchin shape micron and nanometer composite structure.The prior art is compared, implementation process of the present invention is simple, reproducible；Structure is able to maintain stable and excellent antireflective property in over an ultra, has higher application value in fields such as photovoltaic, military affairs.

Description

The method that femtosecond laser synergistic oxidation reaction prepares broad band anti-reflection structure
Technical field
The invention belongs to anti-reflection structure processing technique fields, and in particular to a kind of using femtosecond laser and oxidation reaction The method that collaborative processes preparation has the sea urchin shape micron and nanometer composite structure of the high antireflective property of ultra-wide spectrum band.
Background technique
The antireflective property of material has extremely important application in numerous areas.For example, absorption of the enhancing to sunlight, Can more efficiently, fully solar energy be collected and be utilized, facilitate the implementation and popularization of clean energy resource.Infrared band The reduction of reflectivity can weaken the infra-red detectable of material, be based on the performance, can further develop and be applied to military affairs On stealth technology.For another example, wave-length coverage is 8-15 μm of infrared waves, very due to its vibration frequency with human body cell element It is close, the resonance in human body cell between atom and molecule can be caused, to promote the movement of human body cell, accelerate blood and follow Ring promotes to remove the harmful substance gathered in blood vessel, and promotes the generation of enzyme, prevents aging, enhances the function of immune system, because And it is referred to as " life light "；The enhancing technology absorbed to life light wave band is studied, it is with higher in biomedicine field Application value.
Micro-, the nanostructure for preparing specific morphology on the surface of the material, facilitate the promotion of material antireflective property.Micro-, Usually there are two types of types for the technology of preparing of nanostructure, are process from top to bottom and from bottom to top respectively.It is one from top to bottom The process of kind of removal material, common technology such as etches, nano impression.Usually have by structure prepared by top-down methods There is good pattern, but the efficiency of this mode is lower, it is difficult to realize the preparation of large area, abundant structure.Self-absorption Correction Factor It is to be grown by means such as chemistry or deposit micro-, nanostructure, including thermal oxide, electrostatic precipitation, chemical vapor deposition etc..From The characteristics of lower and upper method is high-efficient, but the pattern of its preparation structure is often not regular enough, uniform, and controllability is poor, it is difficult to The performance for being optimal.
Although the micro- of material surface, nanostructure are capable of the antireflection ability of reinforcing material, particular dimensions it is single Structure often can only generate absorption to the electromagnetic wave of relatively narrow wavelength bands；The anti-reflective performance for realizing wider wave-length coverage, then must Complicated multiple dimensioned three-dimensional structure must be relied on, to meet the absorption characteristics of different-waveband light.Micron and nano combined three-dimensional table Face structure can make material be provided simultaneously with the light absorpting ability on micro-meter scale and nanoscale, and then enable material wider Bands of a spectrum within the scope of show excellent antireflective property.
Realization of the ultra-wide spectrum with antireflective property proposes challenge to the preparation method of structure.With good controllability Complicated micro-nano compound structure is difficult to prepare by single technical process.Therefore, new micro-nano technology technology is developed, efficiently Ideal micro-nano compound structure is prepared, antireflective property of the material in wider wave-length coverage is realized, is increasingly becoming micro-nano system Make the hot spot of research field.
Summary of the invention
The purpose of this method is that solve the above-mentioned problems, providing a kind of preparation of femtosecond laser synergistic oxidation reaction method has The sea urchin shape micron and nanometer composite structure of the high antireflective property of ultra-wide spectrum band, by being acted synergistically using femtosecond laser and chemical oxidation Means, prepare regular appearance, controllable good micron and nanometer composite structure on the surface of the material, and in the wave-length coverage of ultra-wide spectrum band Has stable and excellent antireflective property in (200~16000nm).
This method mainly include femtosecond laser patterning ablation and alkaline environment under over cure acid ion to ablated area Oxidation process.By this method the sea urchin shape array of structures comprising a large amount of nano wires can be prepared on copper sheet surface.
Wherein, ablation of the femtosecond laser to copper sheet can construct the micron cone battle array that surface is covered with abundant nano particle Column；Meanwhile the ablation of femtosecond laser also can generate selective oxidation to finished surface, cause changing for copper surface chemical ingredient Become.The variation in metal surface physical structure and chemical component occurs, the oxidation process of subsequent over cure acid group can be had an impact With the effect of adjusting, the region growing for inducing Femtosecond-Laser Pulse Excitation to cross goes out more nanowire structures.By femtosecond laser and mistake The synergistic effect of sulfate radical oxidation, is finally prepared the micron and nanometer composite structure of sea urchin shape.
The sea urchin shape micron and nanometer composite structure prepared using this method macroscopically remains the micron cone of femtosecond laser building Shape contour feature, thus have the filling light ability on micro-meter scale；It is grown in the dense nano wire on surface simultaneously, can make to fill out It fills and generates the variation of refractive index gradient in air therein, the variation of refractive index gradient then can further cause structure reflectivity Reduction.In summary feature, sea urchin shape micron and nanometer composite structure prepared by this method are 200~16000nm's in wavelength In ultra-wide spectrum band range, excellent, stable antireflective property can be kept, this performance solar battery, photodetector, The stealthy equal numerous areas of military affairs, all have huge application value.
For realization goal of the invention, it is achieved through the following technical solutions:
The sea urchin shape micron and nanometer composite structure side of the femtosecond laser synergistic oxidation reaction preparation high antireflective property of ultra-wide spectrum band Method, comprising the following steps:
Preferably, building femtosecond laser processing light path system before work described in step 1.
1. material to be processed (sample) is placed in femtosecond laser processing light path system, using focusing objective len, swash femtosecond The hot spot of light focuses on material surface to be processed；
Preferably, the sample is metal.
Preferably, the sample is copper sheet.
Preferably, described sample is placed in front of femtosecond laser is processed in light path system first cleans material to be processed To remove the spot and oxidation film on processing object surface.
Preferably, the cleaning is successively to use dehydrated alcohol, the hydrochloric acid of 0.3mol/L, distilled water, respectively in ultrasound It is cleaned 5 minutes in machine.
2. processing the movement of the switch and translation stage of mechanical shutter in optical path by control femtosecond laser, make femtosecond laser Focal beam spot successively carries out the ablation in the direction x and the direction y in sample surfaces, prepares micron order cone cell knot in sample surfaces Structure array；
Preferably, being adjusted by the movement speed of the energy, translation stage that control the femtosecond laser, the spacing in the direction xy Control the pattern of femtosecond laser ablation surface texture.
Preferably, the laser energy of the femtosecond laser is 20mW, the movement speed of translation stage is 200 μm/s, femtosecond Laser is being 30 μm perpendicular to the direction x and perpendicular to the mobile spacing of the single in the direction y.
Preferably, in the mixed solution of the ammonium persulfate and sodium hydroxide for being placed in sample and stirring evenly it Before, sample is first successively used to dehydrated alcohol, distilled water, cleans 5 minutes in ultrasonic machine respectively to remove remained on surface add Work clast.
3. sample is placed in the mixed solution of the ammonium persulfate and sodium hydroxide that stir evenly, oxidation reaction, which occurs, makes sample Product surface grows sea urchin shape micron and nanometer composite structure.
Preferably, the concentration of the ammonium persulfate: 0.13mol/L, the concentration of the sodium hydroxide: 2.5mol/L, instead Between seasonable: 30min, reaction temperature: 25 DEG C of room temperature environments.
Preferably, the sample obtained after step 3 reaction is taken out, it is with the distilled water of flowing that sample surfaces are remaining molten Liquid cleans up, and is placed in a vacuum drying oven, 2 hours dry at a temperature of 30 DEG C.
The utility model has the advantages that
The prior art is compared, the invention has the characteristics that:
1. uniform, regular micron can be constructed in copper metallic face to the ablation of copper sheet using femtosecond laser Grade cone structure array, this micron cone array are the premise and necessary condition that sea urchin shape structure is formed；
2. femtosecond laser has the instantaneous energy density of superelevation, nano particle abundant can be generated in ablated surface；Together Shi Yinqi selective oxidation makes partial ablation surface be oxidized to copper oxide.The presence of nano particle increases copper surface and solution The contact area of middle over cure acid group, hydroxide ion, accelerates the speed of growth of Kocide SD nano wire, and makes part in solution Hydroxide ion is largely consumed in a short time, causes the reduction of local pH, such as reaction equation (1)；And local pH It is quick reduce and the presence of surface oxidation copper material, hindering oxygen copper oxide hydrolysis in solution becomes the reaction of copper oxide, such as Reaction equation (2).It eventually leads to containing less copper oxide nanometer flower-based in product, but there is more Kocide SD nanometer Line, overall structure are similar to sea urchin shape；
Cu(OH)2→CμO+H2O(2)
3. combining femtosecond laser Gauss optical field distribution feature, by certain size design, (ablation depth, adjacent micron are bored Center spacing), obtained array of structures has excellent filling light ability after processing femtosecond laser.It is irradiated to micron cone array On light, can reflect, constantly decrease energy, and be absorbed by structure repeatedly between adjacent surface；Finally prepare Sea urchin shape array of structures remains the ablation pattern of femtosecond laser on micro-meter scale, thus has the filling luminous energy on micro-meter scale Power；
4. by the sea urchin shape structure after the oxidation of over cure acid group, the number of nanowires that surface vertical-growth goes out is considerable, long It spends uniform.From the top to the bottom, density is by dredging close variation for these nano wires, so that being filled in the refractive index n of air thereini Also it changes correspondingly (such as formula (3), fiIt is air fill factor, is reduced with the increase of nanowire density；And variation tendency is smaller and smaller, according to reflectivity (ri) and refractive index between Relational expression (formula (4)) further enhances made it is found that reflectivity values are reduced with the reduction of air refraction increase tendency The antireflection ability of standby structure；
5. the result that comparison is aoxidized under alkaline environment by over cure acid group without the finished copper sheet of femtosecond laser it is found that The ablation for only passing through femtosecond laser, just there is the generation of a large amount of nano wires；The region that do not crossed by femtosecond laser ablation, receives Rice noodles are few, instead a large amount of flower clusters structure；The collaboration aoxidized by femtosecond laser ablation and over cure acid group Effect, can just prepare the sea urchin shape micron and nanometer composite structure for meeting ideal performance demand；
6. by prepared sea urchin shape array of structures be respectively placed in ultraviolet (200-380nm), visible light (380-780nm), Under near-infrared (780-1500nm), far infrared (1500-16000nm) wave band carry out antireflective property test, it is minimum can be real Now compared to the ultra-low reflectance on polishing copper surface 0.7%, 5.3%, 1.7%, 1.3%.
7. the Synergistic method operating process is simple, favorable repeatability, and does not require high temperature and pressure vacuum etc. during realizing Harsh conditions.Prepared structure is able to maintain superelevation and stable antireflective property, in solar energy in ultra-wide spectrum band range Battery, photodetector, there are higher application values for the military numerous areas such as stealthy.
Detailed description of the invention
Fig. 1 is the femtosecond for the sea urchin shape micron and nanometer composite structure that the embodiment of the present invention prepares the high antireflective property of ultra-wide spectrum band Laser-processing system index path.
Fig. 2 is the technique for the sea urchin shape micron and nanometer composite structure that the embodiment of the present invention prepares the high antireflective property of ultra-wide spectrum band Flow chart；Wherein, the copper sheet that (a) was cleaned；(b-c) the micron wimble structure array and partial enlargement that femtosecond laser ablation is formed show It is intended to；(d) sample after femtosecond laser is processed is placed in the mixed solution of ammonium persulfate and sodium hydroxide and oxygen occurs Change the schematic diagram of reaction；(e) the sea urchin shape micron and nanometer composite structure schematic diagram of femtosecond laser synergistic oxidation reaction method preparation.
Micron wimble structure after Fig. 3 femtosecond laser is processed and the sea via the preparation of femtosecond laser synergistic oxidation reaction method Gallbladder shape body structure surface shape appearance figure: wherein (a) is the scanning of the micron wimble structure array formed behind femtosecond laser ablation copper sheet surface Electron microscope (SEM) figure；It (b) is the SEM figure of micron wimble structure surface amplification in (a) figure；(c) for by femtosecond laser and oxygen Change the SEM figure of the sea urchin shape micron and nanometer composite structure array prepared after reaction synergistic effect；It (d) is sea urchin shape single in (c) figure The SEM of structure schemes.
Fig. 4 is transmission electron microscope (TEM) result figure for the nano wire removed from sea urchin shape micro nano structure: wherein (a) the nanowire structure shape appearance figure observed under transmission electron microscope；It (b) is the height in nanowire portion region in (a) figure Resolution Transmission Electron micro-image；It (c) is the diffraction pattern in nanowire portion region in (a) figure.
Fig. 5 is the ablation without femtosecond laser, the copper sheet directly aoxidized under alkaline environment by over cure acid ion Surface texture shape appearance figure: wherein (a) is to aoxidize 30 points by over cure acid ion under alkaline environment through the copper sheet after over cleaning The SEM of clock rear surface pattern schemes；It (b) is the SEM figure of flower clusters single in (a) graph structure.
Fig. 6 is the transmission electron microscope result figure for the nanometer sheet removed from flower clusters structure: wherein (a) is nanometer The shape appearance figure that chip architecture is observed under transmission electron microscope；(b) high-resolution for nanometer sheet partial region in (a) figure is saturating Penetrate electron micrograph image；It (c) is the diffraction pattern of nanometer sheet partial region in (a) figure.
Fig. 7 is the sea urchin shape structure prepared through the reaction of femtosecond laser synergistic oxidation, is directly aoxidized by over cure acid group The reflectance test result of flower clusters structure and the polishing copper surface after over cleaning: wherein (a) is three kinds of structures ultraviolet The reflectance curve of wave band；It (b) is reflectance curve of three kinds of structures in visible light wave range；It (c) is three kinds of structures in near-infrared The reflectance curve of wave band；It (d) is reflectance curve of three kinds of structures in far infrared band；Solid line represents the anti-of sea urchin shape structure Penetrate rate；Dotted line represents the reflectivity of flower clusters；Chain-dotted line represents the reflectivity on polishing copper surface.
Specific embodiment
In order to keep the purpose of the present invention, technical solution and advantage clearer, clear, with reference to the accompanying drawings and examples The present invention will be further described.
Embodiment 1
Select specification for 10 × 10 × 1mm3Copper sheet as material to be processed, femtosecond laser collaboration that the present invention will be described in detail The method that oxidation reaction prepares the sea urchin shape micron and nanometer composite structure of the high antireflective property of ultra-wide spectrum band, comprising the following steps:
(1) build femtosecond laser processing light path system as shown in Figure 1, specifically include that femto-second laser, lighting source, (CCD) system of imaging, computer, power attenuation piece, mechanical shutter, beam splitter, dichroscope, focusing objective len, six degree of freedom are flat Moving stage and copper sheet sample.It is 800nm that femto-second laser, which issues wavelength, and pulse duration 50fs, repetition rate is 1kHz's Laser.Propagation of the laser Jing Guo optical path, is irradiated to power attenuation on piece, by adjusting attenuator, can obtain from exit direction The laser of different-energy.Using the switch of computer controlled machine tool shutter, so make laser by dichroscope back reflection to gather On focus objective lens, by the focussing force of focusing objective len, finally it is focused on the surface of copper sheet.The illumination light that lighting source issues It is irradiated to the surface of copper sheet after beam splitter, dichroscope and focusing objective len, by reflection, the process of processing is being imaged (CCD) it is imaged in system.It can control the movement of translation stage by computer, adjust the switch of mechanical shutter, from imaging (CCD) system observes the process of femtosecond laser in real time.
(2) it is assisted using ultrasonic machine, successively cleans copper sheet sample using dehydrated alcohol, the hydrochloric acid of 0.3mol/L, distilled water, To remove the spot and oxidation film of sample surfaces.The copper sheet sample after cleaning is fixed on high-precision six-freedom degree translation stage later On, femtosecond laser is focused on sample surfaces by the plano-convex focusing objective len for being 100mm by focal length.Later, it is controlled by computer Translation stage is first moved in parallel in the x-direction according to certain speed, after move in parallel in the y-direction, finally will be such as the sample of Fig. 2 (a) Product process the cone cell micrometer structure as shown in Fig. 2 (b), (c).Laser energy, the direction xy spacing, swashs at translation stage movement speed The parameters such as optical wavelength, pulsewidth, frequency and polarization can all have an impact the surface texture of preparation.Wherein, laser energy, translation The movement speed of platform, the spacing in the direction xy are three mostly important parameters.Therefore, under conditions of meeting application, selection control The energy of laser processed, the movement speed of translation stage, the spacing in the direction xy regulate and control the pattern of femtosecond laser ablation surface texture.This It is respectively 10mW, 20mW, 30mW, 40mW that the energy of femtosecond laser is controlled in embodiment, and the movement speed of translation stage is 100 μm/ S, 200 μm/s, 500 μm/s, 1000 μm/s, the spacing in the direction xy are 10 μm, 30 μm, 50 μm.
(3) (the NH of 40ml is prepared4)2S2O8It with the mixed solution of NaOH, stirs evenly, wherein (NH in control solution4)2S2O8Concentration be 0.13mol/L, the concentration of NaOH is 2.5mol/L.Use ultrasonic machine as auxiliary, successively uses dehydrated alcohol Copper sheet print of the femtosecond laser after processed is cleaned up with distilled water, removes machining chips, and add with without femtosecond laser The polishing copper sheet of work together, immerses in configured mixed solution, 30min is reacted in the environment of 25 DEG C of room temperature, such as Fig. 2 (d) It is shown.To keep the homogeneity of nanowire structure grown, the stabilization of solution environmental is kept in reaction process, cannot stir or Person shakes solution.After 30 minutes, sample taking-up in the solution will be impregnated, with the distilled water repeated flushing print table of flowing Face, to wash away the reaction liquid remained on sample.Later, print is placed and is kept for 2 hours for 30 DEG C in a vacuum drying oven, with Drying sample.It takes out sample to obtain: via the structure of femtosecond laser synergistic oxidation reaction preparation in micron poppet surface vertical-growth There is a large amount of nano wire, be sporadicly distributed a small amount of nanometer flower structure, appear similar to the pattern of sea urchin shape, such as Fig. 2 (e) institute Show；And it is processed without femtosecond laser, directly by (NH4)2S2O8The copper sheet sample surfaces aoxidized with the mixed solution of NaOH, nanometer The quantity of line is few, is covered by a large amount of flower clusters structure.
By comparing the structure and morphology feature obtained under different laser energy, translation stage movement speed and the direction xy spacing And structure is carried out known to the test of antireflective property: the laser energy of optimization are as follows: 20mW, translation stage movement speed are as follows: 200 μm/s, the direction xy spacing are as follows: 30 μm.At this point, and performance the most regular in the sea urchin shape structure that copper sheet surface is prepared is most It is good.
(4) Fig. 3 (a-b) is to set laser energy as 20mW, 200 μm of translation stage movement speed/30 μm of the direction s, xy spacing When, the SEM figure for the cone structure pattern that femtosecond laser ablation obtains, it can be seen that femtosecond laser has processed whole on copper sheet surface Neat tapered array, while the surface of tapered array includes nano particle abundant, these nano particle micro-structures are to subsequent The generation of nano wire is played the role of indispensable in oxidation process.Fig. 3 (c-d) is that sample passes through femtosecond laser and oxidation reaction Synergistic effect after, the sea urchin shape array of structures and enlarged drawing that are prepared.It can be seen that in the finished micron of femtosecond laser Poppet surface vertical-growth has gone out dense nano wire, and the average length of these nano wires is about 10 μm, and width is about 100nm, shape Shape and quality are all very uniformly.
(5) Fig. 4 (a) is the TEM shape appearance figure of nanowire structure.Fig. 4 b is the high-resolution TEM image of nano wire in Fig. 4 a, Measuring obtained spacing of lattice isMeet in Kocide SD crystal the crystal face parameter of (002) crystal face.Fig. 4 c is Fig. 4 a Selective electron diffraction (SAED) pattern of middle nano wire, a series of concentric rings in SAED pattern show that the nano wire in Fig. 4 a is Heteromorphs；(002), (021) and (020) crystal face in calculated interplanar distance and Kocide SD crystal is schemed according to SAED Spacing is corresponding.These results show that forming the ingredient of the nano wire of sea urchin shape structure is Kocide SD.
(6) Fig. 5 (a-b) is the processing without femtosecond laser, is directly aoxidized under alkaline environment by ammonium persulfate solution Copper sheet sample surface morphology SEM figure.Within the identical reaction time, there is not more nano wire in sample surfaces, and It is to grow a large amount of flower clusters, flower clusters are stacked together, and are thickly covered on copper sheet surface；These flower-shaped groups The diameter of cluster is about 5 μm, shape characteristic and the nanowire-junction grown after femtosecond laser and oxidation process synergistic effect Structure is entirely different.
(7) Fig. 6 (a) be shown from the nanometer chip architecture removed in flower clusters under transmission electron microscope from The shape appearance figure arrived.It is the high-resolution TEM image of nanometer sheet in Fig. 6 a that Fig. 6 b is corresponding, shows that the nanometer sheet is one by being permitted Mostly along the polycrystalline structure of the crystal grain composition of different crystal orientations growth, the parallel lattice fringe spacing measured is respectivelyWithThe interplanar distance of they and (111) in molybdena crystal and (002) crystal face matches.Fig. 6 c is nanometer sheet in Fig. 6 a Selective electron diffraction figure, it is polycrystalline form that SAED pattern, which equally illustrates the nanometer sheet, is calculated according to SAED figure Interplanar distance meets in molybdena crystal (111) and (002) crystal face parameter.These results show to form the nanometer of flower clusters The ingredient of piece is copper oxide.
(8) Fig. 7 is shown the sea urchin shape structure of femtosecond laser synergistic oxidation reaction preparation, is directly aoxidized by over cure acid group The reflectance test result of the flower clusters structure of generation and the polishing copper surface after over cleaning.Wherein Fig. 7 (a) is shown For three kinds of surface textures in the reflectance curve of ultraviolet band, test equipment is UV, visible light near infrared spectrometer.It tested Sample is placed in sample bin by Cheng Zhong, using the substrate of high reflectance as object of reference, collects the reflectivity letter of different sample surfaces Number, and it is depicted as curve.From in Fig. 7 (a) as can be seen that within the scope of the ultraviolet band of 200-380nm, sea urchin shape structure it is anti- It is minimum to penetrate rate, and fluctuation range is small, is able to maintain the stabilization of performance；Average value of the sea urchin shape structure compared to polishing copper reflectivity It is 3.9%, minimum is up to 0.7%；Flower clusters are 38.6% compared to the average value of polishing copper reflectivity, and minimum is 36.8%.7 (b) are shown three kinds of surface textures in the reflectance curve of visible light wave range, test equipment and test method with Ultraviolet band is identical.From in Fig. 7 (b) as can be seen that in the visible light wave segment limit of 380-780nm, sea urchin shape structure it is anti- It is minimum for penetrating rate equally, and fluctuation range is small, is able to maintain the stabilization of performance；Sea urchin shape structure is compared to polishing copper reflectivity Average value be 6.2%, minimum is up to 5.3%；Flower clusters are 34.0% compared to the average value of polishing copper reflectivity, most Low value is 31.0%.7 (c) are shown three kinds of surface textures in the reflectance curve of near infrared band, test equipment and test Method is identical as ultraviolet light wave band.From in Fig. 7 (c) as can be seen that within the scope of the near infrared band of 780-1500nm, sea urchin shape The reflectivity of structure remains minimum, and fluctuation range is small, is able to maintain the stabilization of performance；Sea urchin shape structure is compared to polishing The average value of copper reflectivity is 4.0%, and minimum is up to 1.7%；Flower clusters compared to polishing copper reflectivity average value be 35.0%, minimum 33.6%.6 (d) are shown reflectance curve of three kinds of surface textures in far infrared band, tester Device is Fourier infrared spectrograph.In test process, the reflectance curve of high reflectance substrate is collected first, as reference；It Sample is collected into the reflectivity signals of sample by detector as region to be measured in microscopic system, is selected afterwards, and is depicted as song Line.It can be seen that in the far infrared wave segment limit of 1500-16000nm from Fig. 6 (d), the reflectivity of sea urchin shape structure is much Lower than flower clusters, and keep stable；Sea urchin shape structure is 1.5% compared to the average value of polishing copper reflectivity, and minimum can Up to 1.3%；Flower clusters are 30.2% compared to the average value of polishing copper reflectivity, minimum 20.2%.
In conclusion the sea urchin shape micron and nanometer composite structure prepared by femtosecond laser synergistic oxidation reaction method is in ultra-wide Bands of a spectrum within the scope of, ultralow reflecting properties can be stably kept, have the anti-reflective ability of superelevation, thus in solar-electricity Pond, photodetector, the military fields such as stealthy, have huge application prospect.Tool has not only been constructed in the ablation of femtosecond laser There is the micron order cone structure of filling light ability, while being also the conditio sune qua non of nanowire growth during subsequent oxidation. Femtosecond laser and oxidation process act synergistically under certain condition, can just prepare the sea urchin shape knot for meeting ideal performance demand Structure.Meanwhile this method, in implementation process, without creating the harsh environments condition such as high temperature, high pressure, vacuum, low energy is efficient, behaviour Make simple.
The above has been further described the purpose of invention, technical scheme and beneficial effects.It should be understood that , the above is only a specific embodiment of the present invention, is not intended to limit the scope of protection of the present invention, all in this hair Within bright spirit and principle, any modification, equivalent substitution, improvement and etc. done should be included in protection scope of the present invention Within.

Claims (10)

1. a kind of sea urchin shape micron and nanometer composite structure of the femtosecond laser synergistic oxidation reaction preparation high antireflective property of ultra-wide spectrum band Method, it is characterised in that:
(1) material to be processed (sample) is placed in femtosecond laser processing light path system, using focusing objective len, makes femtosecond laser Hot spot focuses on sample surfaces；
(2) movement that the switch and translation stage of mechanical shutter in optical path are processed by control femtosecond laser, makes the poly- of femtosecond laser Burnt hot spot successively carries out the ablation in the direction x and the direction y in sample surfaces, prepares micron order cone structure in sample surfaces Array；
(3) sample is placed in the mixed solution of the ammonium persulfate and sodium hydroxide that stir evenly, oxidation reaction, which occurs, makes sample Surface grows sea urchin shape micron and nanometer composite structure.
2. according to the method described in claim 1, it is characterized by: building femtosecond laser processing optical path before carrying out step 1 System.
3. according to the method described in claim 1, it is characterized by: the sample is copper sheet.
4. according to the method described in claim 1, it is characterized by: described be placed in sample in femtosecond laser processing light path system It is preceding first to clean material to be processed to remove the spot on processing object surface and oxidation film.
5. according to the method described in claim 4, it is characterized by: the cleaning is successively to use dehydrated alcohol, 0.3mol/L Hydrochloric acid, distilled water, cleaned 5 minutes in ultrasonic machine respectively.
6. according to the method described in claim 1, it is characterized by: passing through the energy, translation stage for controlling the femtosecond laser Movement speed, the spacing in the direction xy regulate and control the pattern of femtosecond laser ablation surface texture.
7. according to the method described in claim 6, it is characterized by: the laser energy of the femtosecond laser is 20mW, translation stage Movement speed be 200 μm/s, femtosecond laser is being 30 μm perpendicular to the direction x and perpendicular to the mobile spacing of the single in the direction y.
8. according to the method described in claim 1, it is characterized by: it is described sample is placed in the ammonium persulfate that stirs evenly and Before in the mixed solution of sodium hydroxide, sample is first successively used to dehydrated alcohol, distilled water, cleans 5 in ultrasonic machine respectively Minute is to remove machining chips remained on surface.
9. according to the method described in claim 1, it is characterized by: the concentration of the ammonium persulfate: 0.13mol/L, the hydrogen The concentration of sodium oxide molybdena: 2.5mol/L, reaction time: 30min, reaction temperature: 25 DEG C of room temperature environments.
10. -9 any method according to claim 1, it is characterised in that: the sample obtained after step 3 reaction is taken out, The remaining solution of sample surfaces is cleaned up with the distilled water of flowing, is placed in a vacuum drying oven, dry 2 at a temperature of 30 DEG C Hour.
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