CN117047283A - Femtosecond laser controllable manufacturing method of angle-sensitive periodic gold nano-bump - Google Patents
Femtosecond laser controllable manufacturing method of angle-sensitive periodic gold nano-bump Download PDFInfo
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- CN117047283A CN117047283A CN202310300002.1A CN202310300002A CN117047283A CN 117047283 A CN117047283 A CN 117047283A CN 202310300002 A CN202310300002 A CN 202310300002A CN 117047283 A CN117047283 A CN 117047283A
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000010931 gold Substances 0.000 title claims abstract description 54
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 54
- 230000000737 periodic effect Effects 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000002086 nanomaterial Substances 0.000 claims abstract description 44
- 238000012545 processing Methods 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000005286 illumination Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000002063 nanoring Substances 0.000 claims description 8
- 238000003384 imaging method Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 6
- 230000010287 polarization Effects 0.000 claims description 4
- 239000002101 nanobubble Substances 0.000 claims description 3
- 238000002366 time-of-flight method Methods 0.000 claims description 3
- 238000002679 ablation Methods 0.000 claims 1
- 238000005259 measurement Methods 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 238000000059 patterning Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001209 resonance light scattering Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- -1 nanocups Substances 0.000 description 1
- 239000002107 nanodisc Substances 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
- 239000002078 nanoshell Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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Abstract
A femtosecond laser controllable manufacturing method of angle-sensitive periodic gold nano-protrusions belongs to the technical field of micro-nano processing. The invention adopts a femtosecond laser direct writing mode to prepare the large-area controllable periodic super surface, on one hand, the selective area, large area, flexibility, high efficiency, patterning and high-precision preparation of the multi-layer film configuration super surface can be realized; on the other hand, the super-surface nano structure can be continuously regulated and controlled based on the ultrafast characteristic of the femtosecond laser, and the transverse-vertical resonance mode can be excited according to different angles of illumination light, so that the structural color with angular anisotropy is formed. The preparation method can realize the angle-sensitive controllable large-area periodic plasmon super surface and has wide application value.
Description
Technical Field
The invention relates to a method for realizing a large-scale periodic gold nanostructure through femtosecond laser induction, and belongs to the technical field of femtosecond laser application.
Background
Plasmonic nanostructures, which have been designed and fabricated in different ways over the last decades, have contributed greatly to the regulation of electromagnetic waves on a sub-wavelength scale, especially structures such as nanogaps, nanocaps, nanoshells, nanocups, nanopillars, nanodiscs, and related composite structures, and thus the fabrication and spectral characteristics of nanostructures have received widespread attention. The plasmon nano structure shows obvious light bending, absorption and scattering characteristics and strong plasmon resonance, and the spectral position of the plasmon nano structure can be effectively regulated and controlled in the ultraviolet, visible light and near infrared range by changing the shape, the size, the arrangement and the like of the single nano structure. Such periodic plasmonic nanostructures can be used as color displays, nanophotonic devices, subharmonic generators, solar cells, and the like as sensing elements for surface enhanced fluorescence and raman spectroscopy (SERS) biosensors. Along with the increasing innovation of nano science and technology, the shape and the size of the nano material can be cut, and the components and the morphology of the nano material can be effectively regulated. Therefore, the preparation method and the process of the novel metal plasmon nanometer structure are more and more, and the rapid development of surface plasmons is greatly promoted. Conventional processing techniques typically employ shorter wavelengths to achieve greater precision, such as electron beams, ion beams, X-rays, and deep ultraviolet laser beams. However, these techniques also have disadvantages such as high cost, severe conditions (vacuum, etc.), complex processing procedures, inefficiency, and poor sample contamination flexibility. Therefore, the research on how to prepare the controllable periodic gold nano structure with high precision and large area to realize the optical characteristics has wide application value.
Laser direct writing has proven to be a reliable method of processing compared to the conventional methods of processing described above. Because of the ultra-fast and ultra-strong characteristic of the femtosecond laser, the femtosecond laser can achieve submicron and even nanoscale processing precision, and is expected to realize large-scale, low-cost and patterned manufacturing of the periodic nanostructure. Aiming at the challenges encountered in the reliable preparation of the surface plasmon metal micro-nano structure facing specific optical application, a simple, efficient, novel and flexible preparation method is provided, and the large-scale periodic gold nano structure is realized through femtosecond laser induction, so that the stable and reliable preparation of the metal structure and the application in the related optical field are realized.
Disclosure of Invention
In the invention, we propose a method for preparing a periodical MIM type gold nano-bump structure array by processing a noble metal film by a femtosecond laser direct writing technology. The method is based on the femtosecond laser super-fast absorption principle and obvious threshold effect, and realizes fine control on the morphology and the size of the gold nano structure by precisely controlling the transient local heat and the subsequent mass translation and redistribution of the molten metal film through the interaction of the femtosecond laser pulse and the MIM configuration gold film. The resonance light scattering excited by the nanostructures is changed by the change of the size and the morphology of the nanostructures, and bright plasmon structure colors such as red, yellow, green, purple and the like can be generated. Compared with a conventional medium-supported plasmon nano structure, plasmon resonance in MIM configuration can greatly narrow the spectrum, and high-saturation structural color is realized.
The aim of the invention is achieved by the following technology:
a metal-medium-metal multilayer structure using silicon as substrate, wherein the top layer is metal nano-particles with surface plasmon property, and the middle layer is 30nm SiO 2 The bottom layer is a 100nm gold film that acts as a reflective layer.
Preferably, the top of the MIM type gold nano-bulge structure can be a hemisphere, bowl or cone-shaped bulge;
preferably, the gold nanoparticles have an average diameter d 1 The value range is 349-400 nm;
preferably, the gold nanoparticles have an average height d 2 The value range is 312-853 nm;
the femtosecond laser manufacturing method of the controllable periodical gold nanometer bulge comprises the following steps:
step one, sample preparation at 10X 10cm 2 Depositing a 100nm gold film on a silicon substrate by adopting a magnetron sputtering coating mode;
preferably, the substrate material is selected to be silicon;
preferably, a plasma enhanced chemical vapor deposition method is used to grow 30nm SiO on 100nm gold film 2 ；
Preferably, the method also adopts the magnetron sputtering mode to make SiO 2 A 50nm gold film was deposited thereon. Identification of SiO by ellipsometer 2 And the thickness of the gold nanofilm.
Step two, laser energy adjustment: the method adopts a mode of combining a half wave plate, a polaroid and a continuous attenuation sheet, adds a neutral density sheet with fixed attenuation proportion before laser enters an objective lens, and selects a long-focus objective lens for processing. The laser energy is accurately regulated and controlled in a high-power high-attenuation mode, so that the laser energy can be continuously regulated;
preferably, the pulse energy is controlled to be 6.9-36.5 nJ.
Preferably, the focusing objective lens is selected to be 50X and the numerical aperture is 0.6;
and thirdly, fixing the processed sample on a nano-scale three-dimensional displacement table driven by a PC (the motion resolution can reach 50 nm), observing through CCD imaging, adjusting a light path, ensuring that the incident direction of laser is vertical to the processed sample surface, and focusing a laser focus on the sample surface. Different scanning speeds are set, and a time-of-flight method is adopted to process nano bubble structures with regular and orderly arranged morphology, nano columnar protrusions and nano rings with regular and orderly arranged morphology. Large area processing of nano-structures is realized;
preferably, the laser wavelength is 800nm &400nm, and the repetition frequency is 1KHz;
preferably, the laser processing stage movement speed is in the range of 1 to 4mm/s.
Advantageous effects
The invention adopts a mode of combining high-power high-attenuation frequency-doubling laser and a long-focus objective lens, and realizes high repeatability of manufacturing the gold nanostructure ordered array. Meanwhile, resonance light scattering supported by the nano structures can be regulated and controlled due to the size and shape changes of the nano structures, and bright plasmon structure colors such as red, yellow, green and purple are generated. The vertical and horizontal plasmon resonance modes excited by the nano-convex structure can be switched along with the change of the incident angle, and the structural color with angular anisotropy can be formed. The method for printing the highly ordered plasmon nano structure by the laser is expected to be applied to the fields of high-resolution imaging, information storage, nano devices, optical super surfaces, biological sensors and the like.
Drawings
FIG. 1 is a schematic diagram of the periodic gold nano-supersurface structure according to an embodiment;
fig. 2 is a schematic view of a processing optical path of a femtosecond laser induced periodic surface plasmon nanostructure in an embodiment. (high power high attenuation)
Description of the reference numerals: 1-a metal film; 2-a dielectric layer; a 3-metal reflective layer; 4-a substrate; a 5-femtosecond laser; a 6-half wave plate; 7-a polarizer; 8-a continuous attenuation sheet; 9-neutral density tablets; a 10-shutter; 11-dichroic mirrors; 12-beam splitters; 13-illuminating a light source; 14-imaging CCD; 15-achromatic double cemented plano-convex lens; 16-samples; 17-three-dimensional mobile platform.
Fig. 3 is a schematic diagram of a method for preparing a periodic surface plasmon-controllable nanostructure. The substrate is a silicon wafer, and the gold nano film on the top layer can form gold nano structures with different morphologies under the induction of pulse lasers with different energies, such as hemispheres, bowls, conical protrusions and the like.
Fig. 4 is a graph showing different darkfield mirrors capturing the angular sensitive structural colors that occur for two typical gold nanostructures.
Fig. 5 is an SEM image and a dark field optical lens image of a time-of-flight processed large area gold nanostructure.
Detailed Description
The invention is further described below with reference to the drawings and examples.
Embodiment one: regulation and control of gold nanostructure morphology based on laser pulse energy
(1) The half wave plate, the polaroid, the continuous attenuation plate and the neutral density plate are added in the light path to continuously adjust the incident energy of laser
(2) Turning on a mechanical switch, focusing laser on the surface of the material by means of an imaging CCD through an achromatic double-glued plano-convex lens;
(3) Setting the incidence frequency of laser to be 1kHz and controlling the starting time of a mechanical switch cutter, wherein laser pulses act on the surface of a sample according to the set pulse number;
(4) Repeating the step (3), adjusting the optical element to change the laser flux, and processing gold nano structures with different morphologies on the sample.
(5) The evolution of two typical gold nanostructures was observed from different monopulse energies: the laser pulse energy is 6.9-12.1 nJ, and the rapid dissipation of the energy enables the molten gold film to rapidly recrystallize to form a round bubble-shaped structure. When the laser pulse energy reaches 39.3nJ, a nano ring structure is formed, the size of the nano ring is about 1400nm, the peripheral height is about 160nm, and the height of the middle protruding nano structure is 110nm. With the continuous change of laser pulse energy, the size of gold nanoparticles steadily increased from 349nm to 656nm. Dark field microscopic images taken with different dark field objectives 5× (na=0.12), 10× (na=0.25), 20× (na=0.4), 50× (na=0.75). As the numerical objective lens magnification increases, the tilt angle of the illumination source increases. The gold nano-protrusion and the circular gold nano-ring structure can support the resonance of the transverse mode and the longitudinal mode under the excitation of incident light with different angles, and the dominant positions of the two resonance modes are changed along with the change of the angle of the incident light.
Embodiment two: laser wavelength selection for gold nanostructure morphology modulation
(1) The femtosecond laser with the original wavelength of 800nm is multiplied by BBO crystal, the wavelength output of 405+/-10 nm can be realized after the BBO crystal passes through a bandpass filter, the steps of (1), (2), (3) and (4) of the embodiment are repeated,
(2) By using a 50× (na=0.45) long focus (12 mm) uv objective, the spot size focused on the sample surface can reach 738nm, reducing the spot diameter by 27%. Observing the evolution of the gold nanostructure after laser wavelength frequency multiplication: with the increase of pulse energy, the gold nano-protrusion size monotonically increases, and the evolution rule of the gold nano-structure remains unchanged. Compared with the processing result of an objective lens with the wavelength of 800nm at the wavelength of 50× (na=0.6), the energy required for forming the minimum protrusion structure under the condition is reduced by about 25%, which is basically equivalent to the reduction ratio of the laser spot. The minimum size of the formed nanostructure was reduced to 318nm by about 8%.
Embodiment III: controllable large area processing
In the invention, strict temperature and humidity control is adopted, the output current of the laser is controlled in the optimal state of the device so as to ensure the stability of laser output, and the laser pulse energy is continuously adjustable in nanojoule magnitude by a multi-stage attenuation mode. By focusing the laser with a tele objective, structural changes due to defocus are avoided to a great extent. The nanometer bubble structure and the nanometer ring which are regularly and orderly arranged are processed in a large area by adopting a flight time method. Thus confirming the feasibility of processing the large-area periodic arrangement structure and the consistency of the appearance of the nano structure under the same process parameters.
As shown in FIG. 3, a periodic surface plasmon gold nanostructure can have three different forms, namely hemispheres, bowls or conical protrusions
Preferably, the average diameter d1 of the gold nanoparticles is in the range of 349-400 nm;
preferably, the average height d2 of the gold nanoparticles is 312-853 nm;
preferably, the gold nano-bump structure uses silicon as a substrate,
the embodiment is used for explaining a femtosecond laser manufacturing method of controllable periodic gold nano-protrusions. The specific processing flow is shown in the following figure 2:
in this embodiment, a method for processing the femtosecond laser induced periodic surface plasmon polariton nanostructure is controlled, and a specific processing light path is shown in fig. 2. The processing light path is that a femtosecond laser 5 generates femtosecond laser pulses, the femtosecond laser pulses pass through a first half-wave plate 6, a polarizing plate 7 and a continuous attenuation sheet 8, then pass through a neutral density sheet 9, pass through a shutter 10, are reflected by a first reflecting mirror 11, pass through an achromatic double-glued plano-convex lens 15, then are focused on the surface of a sample 16, and the sample 16 to be processed is fixed on a PC three-dimensional moving platform 17; the light source 13 irradiates the sample 16 through the beam splitter 12, the dichroic mirror 11, and the achromatic double cemented plano-convex lens 15, and the reflected light is reflected by the achromatic double cemented plano-convex lens 15, the dichroic mirror 11, and then enters the imaging CCD 14.
The parameters of the femtosecond laser used in the experimental process are as follows: a center wavelength of 800nm, a pulse width<35fs, the repetition frequency is 1kHz, linear polarization is carried out, and the light intensity is Gaussian distribution; the sample to be processed in the experiment is a metal-medium-metal multilayer structure with silicon as a substrate, the structure is a gold film with the top layer of 50nm, and the middle layer is SiO with the thickness of 30nm 2 The bottom layer is a 100nm gold film that acts as a reflective layer.
The processing mode of the system is as follows:
the light path is adjusted to ensure that the incidence direction of the laser is vertical to the surface of the processed sample;
first, the regulation and control of gold nano structure morphology based on laser pulse energy
(1) The half wave plate, the polaroid, the continuous attenuation plate and the neutral density plate are added in the light path to continuously adjust the incident energy of laser
(2) Turning on a mechanical switch, focusing laser on the surface of the material by means of an imaging CCD through an achromatic double-glued plano-convex lens;
(3) Setting the incidence frequency of laser to be 1kHz and controlling the starting time of a mechanical switch cutter, wherein laser pulses act on the surface of a sample according to the set pulse number;
(4) Repeating the step (3), adjusting the optical element to change the laser flux, and processing gold nano structures with different morphologies on the sample.
Fig. 4 shows dark-field microscopic images taken by different dark-field objectives 5× (na=0.12), 10× (na=0.25), 20× (na=0.4), 50× (na=0.75). As the numerical objective lens magnification increases, the tilt angle of the illumination source increases. Research shows that gold nano-protrusions and round gold nano-ring structures can support resonance of transverse and longitudinal modes under the excitation of incident light with different angles, and the dominant positions of the two resonance modes are changed along with the change of the angle of the incident light. From this, it is apparent that both the gold nano-protrusions and the circular gold nano-ring structure exhibit sensitivity to the angle of incident light.
Fig. 5 shows a nano bubble structure with regular and orderly arranged morphology and nano columnar protrusions and nano rings with regular and orderly arranged morphology, which are processed in a large area by a time-of-flight method. The feasibility of processing the large-area periodic arrangement structure and the consistency of the appearance of the nano structure under the same technological parameters are verified.
Claims (4)
1. The femtosecond laser controllable manufacturing method of the angle-sensitive periodic gold nano-bump is characterized by comprising the following steps of:
step one, sample preparation, wherein the sample preparation is characterized by consisting of a multi-layer film, wherein the top layer is a gold film with the thickness of 50nm, and the middle layer is 30nmSiO 2 The medium layer, the bottom layer is a metal reflecting layer of 100 nm;
step two, adjusting laser: the polarization direction of the laser is fixed before the laser enters the objective lens, and the pulse energy of the femtosecond laser irradiated to the surface of the sample is used for adjusting the laser: the polarization direction of the laser before entering the objective lens is fixed, the pulse energy of the femtosecond laser irradiated to the surface of the sample is within 6.9-36.5nJ, and the moving speed of the processing table is v within 1-4mm/s, so that the laser pulse energy is continuously adjustable between ablation thresholds of the metal film with the power of 0.1-1.1 times;
step three, gold nanostructure processing: the surface of a sample is irradiated by laser through selecting a 50X long-focus objective lens and a laser wavelength of 800nm and 400nm, so that processing with controllable morphology is realized; the processing light path is that a femtosecond laser generates femtosecond laser pulses, the femtosecond laser pulses pass through a first half-wave plate, a polarizing plate and a continuous attenuation plate, then pass through a neutral density plate, pass through a shutter, are reflected by a first reflecting mirror, pass through an achromatic double-glued plano-convex lens, and then are focused on the surface of a sample, and the sample to be processed is fixed on a PC three-dimensional moving platform; the illumination white light source irradiates the sample after passing through the beam splitter, the dichroic mirror and the achromatic double-glued planoconvex lens, and the reflected light is reflected by the beam splitter and then enters the imaging CCD.
2. The method for manufacturing the angle-sensitive periodical gold nano-bumps by femtosecond laser controllable fabrication according to claim 1, wherein the method comprises the following steps: the laser is femtosecond laser with polarization output, the pulse width is less than 35fs, the repetition frequency is 1KHz, and the light intensity is Gaussian.
3. The method of manufacturing angle-sensitive periodic gold nanobumps according to claim 1, wherein the measurement of the laser power during processing of the sample is achieved by measuring the laser power before passing through the neutral density plate multiplied by a fixed ratio.
4. The femtosecond laser controllable fabrication method of an angle-sensitive periodic gold nano-bump according to claim 1, wherein the large-area processing of the nano-structure, the scanning speed control, the processing of nano-bubble structures with regular and orderly arranged morphology and nano-columnar bumps or nano-rings with regular and orderly arranged morphology by a time-of-flight method.
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