CN103072940B - A kind of metal micro structure processing method write based on blue laser direct - Google Patents
A kind of metal micro structure processing method write based on blue laser direct Download PDFInfo
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- CN103072940B CN103072940B CN201310012614.7A CN201310012614A CN103072940B CN 103072940 B CN103072940 B CN 103072940B CN 201310012614 A CN201310012614 A CN 201310012614A CN 103072940 B CN103072940 B CN 103072940B
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Abstract
The invention discloses a kind of metal micro structure processing method write based on blue laser direct, it is on silver salt photographic film by the laser beam focusing of blue laser output, and two-dimensional scan is carried out to silver salt photographic film directly write exposure and obtain the metal micro structure figure that is made up of silver-colored line, then silver salt photographic film is cleaned.The present invention can get final product a direct step and generate silver-colored line in exposure, greatly reduces processing link.It is simple that the inventive method has technique, and the feature that equipment cost is low and processing cost is low, can change the parameter of processed metal micro structure easily, be applicable to the processing of microwave band and terahertz wave band Meta Materials.
Description
Technical field
The invention belongs to Laser Micro-Machining field, relate to a kind of method of processing metal micro wire or the one dimension be made up of metal micro line or two-dimensional metallic micro-structural in non metallic substrate, can be used for the preparation of such as microwave band and terahertz wave band Meta Materials etc.
Background technology
Metal micro line is generally attached in non metallic substrate, thickness be hundreds of nanometer to tens microns, width be one micron to hundreds of micron, be generally used for forming one dimension or two-dimensional metallic micro-structural.The size of metal live width determines fine degree and the application of metal micro structure.The metal wire that live width is more than 50 μm is generally used for the electrode making senser element or display device, as resistance strain gage metal gate, and the electrod-array etc. of touch-screen and LCDs.The metal wire that live width is less than 50 μm is generally used for the processing of microwave band and terahertz wave band Meta Materials.
Meta Materials is that some have artificial composite structure or the composite of the extraordinary physical property not available for natural material.Its extraordinary character mainly refers to negative index that negative permittivity and negative magnetoconductivity bring, graded index, stealthy, bandpass characteristics etc.Determine that the key of these extraordinary character is not concrete composition material, but the special ordered structure that these materials arrange.The ad hoc structure of size within the scope of electromagnetic wavelength is generally needed to carry out periodic arrangement to form required ordered structure.For terahertz wave band and microwave band, in corresponding Meta Materials, the size of metal microstructure unit all arrives hundreds of micron dimension tens, and its inner live width is then in micron dimension, and difficulty of processing is larger.
The metal micro structure processing method of current comparative maturity has letterpress, static printing, chemical etching and photoetching etc.Wherein letterpress, static printing are relative with method for chemially etching technique simple, and cost is lower and be adapted to large-scale production, are widely used in the production of metal micro wire and electrode.But be limited to technique itself, the metal live width that they are produced is comparatively thick, is generally all greater than 50 μm, cannot carries out the processing of fine structure.Photoetching is a kind of method for processing microstructure of maturation, metal and nonmetally can to process, and processing live width is micro-to nanoscale.Photoetching is actual is by indirectly processing metal to the process of photoresist.Common practices carries out exposing, develop and etching apply photoresist on metallic diaphragm after, and the metal having photoresist to cover is protected, and the metal not having photoresist to cover is etched away, and finally removes residual photoresist and obtains metal micro structure.Centre also will be cleaned accordingly and dry.These steps need accurate control, longer time and higher quality requirement mostly, and relevant device cost is higher.Therefore photoetching technique has that step is lengthy and tedious, the feature of complex process, length consuming time, apparatus expensive.Owing to being indirectly process metal, just can evaluate crudy after etching, cannot repair defect in process, more cannot in process change at any time process the parameter of metal micro structure.Simultaneously due to the restriction of technique, process the thinner thickness of metal micro structure, be more suitable for the processing of optical region metal micro structure.
Usually use ultraviolet laser as exposure light source in photoetching.325nm helium cadmium (HeCd) laser instrument and 248nm KrF (KrF) excimer laser are the most frequently used light sources, and other YAG Q-switched lasers as semiconductor pumped in 266nm or 355nm, 351nm argon ion laser are also shown in use.Ultraviolet laser not only system complex, price is high, and due to conversion efficiency low, need higher energy consumption when laser instrument runs, when causing process time longer, processing cost uprises.
Summary of the invention
The object of this invention is to provide a kind of metal micro structure processing method write based on blue laser direct, thus a direct step can generate silver-colored line in exposure, greatly reduce processing link.
For achieving the above object, the technical solution used in the present invention is:
The present invention is based on the metal micro structure processing method that blue laser direct writes is: the laser beam focusing exported by blue laser is on silver salt photographic film, and two-dimensional scan is carried out to described silver salt photographic film directly write exposure and obtain the metal micro structure figure that is made up of silver-colored line, then silver salt photographic film is cleaned.
Further, silver salt photographic film of the present invention is silver nitrate photosensitive film.
Further, the wavelength of laser that blue laser of the present invention exports is 400nm ~ 450nm.
Further, blue laser of the present invention is semiconductor laser.
Further, laser beam of the present invention is basic mode light beam.
Further, if the width of the described silver-colored line of the present invention is less than predetermined value, then the focusing focal length of laser beam is tuned up until the width of silver-colored line equals predetermined value; If the width of described silver-colored line is greater than predetermined value, then the focusing focal length of laser beam is turned down until the width of silver-colored line equals predetermined value.
Further, if the width of the described silver-colored line of the present invention is less than predetermined value, then the power output of described blue laser is tuned up until the width of silver-colored line equals predetermined value; If the width of described silver-colored line is greater than predetermined value, then the power output of described blue laser is turned down until the width of silver-colored line equals predetermined value.
Further, if the width of the described silver-colored line of the present invention is less than predetermined value, then the sweep speed of described two-dimensional scan is reduced until the width of silver-colored line equals predetermined value; If the width of described silver-colored line is greater than predetermined value, then the sweep speed of described two-dimensional scan is improved until the width of silver-colored line equals predetermined value.
Further, silver nitrate photosensitive film of the present invention is uniformly coated on by silver nitrate and the mixed solution that is catalyzed into film non-metal base carries out drying to form.
Further, the film that is catalyzed into of the present invention is polyvinyl alcohol, PVP, polyvinylpyrrolidone or polyvinyl butyral resin.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention selects silver salt as photosensitive material.In exposure, silver nitrate is shown in that light decomposes, and the silver particles of generation directly forms silver-colored line, and the width of silver is equal to or slightly less than laser focal spot.Be different from photoetching the processing needing just to complete metal structure through all multiple process routes such as overexposure, development, etchings, the present invention a direct step can generate silver-colored line in exposure, greatly reduce processing link, technological process is simple, can significantly reduce equipment cost and processing cost.
(2) silver-colored line is directly generated when the present invention exposes, microscope (use red illumination) can be passed through observe directly processed metallic pattern in process, thus the quality in process is controlled, can repair the figure in processing easily, also can change the parameter of processed metal micro structure at any time and observe amendment effect, so the present invention is flexible relative to Measures compare such as photoetching.
(3) the present invention selects blue semiconductor laser as exposure light source, is different from the ultraviolet laser used in photoetching, blue semiconductor laser low price, and energy conversion efficiency is higher, and energy consumption is low, can significantly reduce equipment cost and processing cost.Laser instrument is safeguarded simple simultaneously, and volume is little, is easy to the system integration.
(4) the present invention can be used in processing 1 ~ 100 μm of width, the silver-colored line of 0.5 ~ 5 μm of thickness, and increases thickness to 20 μm by methods such as chemical platings.Employing is directly write exposure silver salt and is directly generated silver-colored line, the parameter of processed metal micro structure can be changed easily, adopt blue semiconductor laser as light source, equipment cost and processing cost low, have application prospect at the manufacture field of microwave band and terahertz wave band Meta Materials etc.
Accompanying drawing explanation
Fig. 1 is the structural representation of exposure system used in one embodiment of the present of invention;
Fig. 2 is the microphoto of the local processing the metal micro structure obtained in one embodiment of the invention.
Detailed description of the invention
The key of processing method of the present invention in specific implementation process be realize photosensitive film directly write exposure.Exposure process can use translation stage mobile silver salt photographic film in the plane perpendicular to laser direction of illumination with two-dimensional scan function, and the silver salt (as silver nitrate) on motion track obtains exposure and decomposes, and can be processed into a bullion line on film; Make to computerized control translation stage while this plane carries out two-dimensional scan, by controlling the switch of laser instrument at preposition, metal micro structure figure needed for silver-colored line is formed can be obtained.
The light source used in exposure is blue semiconductor laser.Distinguish according to the wavelength of institute's Output of laser, blue semiconductor laser can be divided into the Multiple Types such as 400nm, 405nm, 430nm, 450nm.Wherein Output of laser wavelength is that the semiconductor laser of 405nm and 450nm is the most common.The output mode of general semiconductor laser is export continuously, and can easily by computer by its whether Output of laser of modulator control.Select the basic mode light beam in semiconductor laser Output of laser to expose, less silver-colored live width can be obtained, improve metal micro structure fineness further.
In process, by changing the focal length of focusing system, the sweep speed of the power output of laser instrument or two-dimensional scan realizes to processed silver-colored line width adjustment, until the width of silver-colored line is equal with predetermined value.The predetermined value of silver line width is determined by the designing requirement of processed metal micro structure.When using the inventive method, if be arranged in 1 ~ 100 μm by the predetermined value of silver-colored line width, then the silver-colored line width of the metal micro structure finally obtained can be made to control in 1 ~ 100 μm.
Expose silver salt photographic film used to be uniformly coated on by silver salt and the mixed solution being catalyzed into film and non-metal base carries out drying to form.Silver salt preferably uses silver nitrate.Because the photodissociation speed of silver nitrate is comparatively slow, expose better selective, the photographic fog phenomenon that there will not be anomalous exposure to cause, optimum is used for the making of the photosensitive film in the inventive method.Silver nitrate photodissociation needs catalyst, simultaneously for preventing silver nitrate crystallization from causing film uneven, can add be catalyzed into film when photosensitive film makes in liquor argenti nitratis ophthalmicus.Being catalyzed into film and preferably using polyvinyl alcohol, PVP, polyvinylpyrrolidone or polyvinyl butyral resin, is good with molecular weight person.The solvent preferred water of liquor argenti nitratis ophthalmicus, methyl alcohol or ethanol.
After exposure, cleaning is carried out to substrate and just can obtain processed micro-sized metal figure.Cleaning fluid is that water maybe can dissolve silver nitrate and be catalyzed into the neutral organic solvent of film.
After metal micro structure machines, the methods such as chemical plating can be used further at silver-colored line plated surface one deck copper, to thicken the thickness of metal wire, thus make metal wire resistance decline further, make metal micro structure reach better action effect.
Below the example that has particular application as in the process of the present invention in the processing of THz wave resonator further describes the present invention.
(1) processing request of resonator:
In the present embodiment, need to process a kind of THz wave resonator having comparatively strong absorption near 0.37THz and 0.73THz.See Fig. 2, in the present embodiment, the periodicity metal micro structure of resonator is made up of flat two-dimensional arrays, and the pattern of each array element nests together for alphabetical " T " and " U ".Wherein, long 135 μm of the horizontal line of letter " T " is formed, long 80 μm of vertical line; Form long 135 μm of the horizontal line of letter " U ", each length of two vertical lines 80 μm; The live width forming each line of letter " T " and " U " is all 10 μm, and the vertical and horizontal spacing between unit is all 200 μm.The overall size of resonator is 10 × 10mm.
(2) preparation of exposure light source:
See Fig. 1, in the present embodiment, exposing light source is blue semiconductor laser 1, and its output wavelength is 405nm, and power output is 50 ~ 80mW, and multimode exports continuously and uses TTL signal to control whether have Laser output.Laser instrument output light carries out modeling through spatial filter 2 and goes out basic mode light beam with filtering.The aperture that spatial filter 2 is 50mm lens and one 30 μm by two focal lengths forms.Spot diameter after modeling is 1.2mm, and laser power is about 25% before modeling.According to institute's machined resonators to the processing request of metal wire live width, focusing system is made up of laser beam expanding lens and 10X infinity flat field microcobjective.For convenience of operation, speculum 4 is used to re-use 10X infinity flat field microcobjective 5 after the basic mode laser beam after 10X changes the light beam irradiated straight down into focus on expanding through beam expanding lens 3.
(3) preparation of photosensitive film:
After the silver nitrate alcoholic solution getting 0.5mL in darkroom respectively and polyvinylpyrrolidone alcoholic solution Homogeneous phase mixing, get 3 and drip and be coated onto on polyester (PET) film, after horizontal rest 5 ~ 10min, ethanol volatilizees complete formation silver nitrate photosensitive film 6.Drip the thickness that the solution droplets quantity used in being coated with can affect processed silver-colored line, quantity is more, and silver-colored line is thicker, and quantity is fewer, and silver-colored line is thinner, but simultaneously by the impact of the factors such as base material, the thickness of silver-colored line is generally in the interval of 0.5 ~ 5 μm.Before mixing, the concentration of silver nitrate is 0.3mg/mL, and the concentration of polyvinylpyrrolidone is 0.2mg/mL.But after mixing, no matter in solution state or dried film, all need to keep in Dark Place.Polyvinylpyrrolidone grade is the minimum K30 of molecular weight.The thickness of polyester (PET) film is 50 μm, and long × wide is 20 × 20mm.Because ethanol and polyester contact angle are comparatively large, cannot realize infiltrating, low temperature plasma flame can be used in advance to carry out surface treatment to polyester (PET) film.
(4) process:
See Fig. 1, silver nitrate photosensitive film 6 is fixed on three-D electric translation stage 7.Three-D electric translation stage 7 can carry silver nitrate photosensitive film 6 and carry out two-dimensional scan in horizontal plane, and its translational speed is the sweep speed of two-dimensional scan.Regulate the angle of pitch of translation stage 7 to guarantee that photosensitive film 6 is in level.Open the Laser output of blue semiconductor laser 1, regulate the height of translation stage 7 with the laser beam focusing launched by blue semiconductor laser 1 on silver nitrate photosensitive film 6.Before formal exposure, the power of the Output of laser of blue semiconductor laser 1 is set to 80mW, translation stage 7 is set as 0.5mm/s in the sweep speed of horizontal plane two-dimensional scan, the edge of egative film examination processing one 100 μm long silver-colored line, utilize reflective measuring microscope amplify 400 × after observe that this silver-colored line width is about 15 μm.Subsequently the sweep speed of translation stage 7 is changed to 0.8mm/s, the silver-colored line of the same length of examination processing, observe that silver-colored line width is about 8.5 μm, but edge quality is deteriorated.Again try processing with the sweep speed of 0.7mm/s, obtain the silver-colored line that width is about 10 μm, but now the quality at silver-colored line edge not as the silver-colored line processed when speed is 0.5mm/s.The sweep speed of translation stage 7 is readjusted into 0.5mm/s, the power output of blue laser is set to 50mW, again the silver-colored line of examination processing, observe that gained silver line width is about 8 μm, and edge quality is better.Keep the sweep speed of translation stage 7, the power of slightly upper adjusting laser Output of laser, try process more than repeating, obtaining sweep speed is 0.5mm/s, and when laser power is 58mW, silver-colored line width is 10 μm and edge quality is better.
As from the foregoing, in the present embodiment, the integrated use adjustment power output of blue laser and these two kinds of methods of sweep speed of two-dimensional scan equal predetermined value to make the width of processed silver-colored line.It should be noted that, the present invention can in these three kinds of methods of focusing focal length of the only sweep speed of the power output of Use Adjustment blue laser, adjustment two-dimensional scan, adjustment laser beam any one, any two or three kinds obtain the silver-colored line that width equals predetermined value.
Specifically, about the focusing focal length of laser beam method of adjustment for: if the width of the silver-colored line processed is less than predetermined value, then can the focusing focal length of laser beam be tuned up until the width of silver-colored line equals predetermined value; If the width of the silver-colored line processed is greater than predetermined value, then the focusing focal length of laser beam can be turned down until the width of silver-colored line equals predetermined value.
About the power output of blue laser method of adjustment for: if the width of the silver-colored line processed is less than predetermined value, then the power output of blue laser can be tuned up until the width of silver-colored line equals predetermined value; If the width of the silver-colored line processed is greater than predetermined value, then the power output of blue laser can be turned down until the width of silver-colored line equals predetermined value.
About the sweep speed of two-dimensional scan method of adjustment for: if the width of the silver-colored line processed is less than predetermined value, then can by the sweep speed of two-dimensional scan reduce until the width of silver-colored line equals predetermined value; If the width of the silver-colored line processed is greater than predetermined value, then the sweep speed of two-dimensional scan can be improved until the width of silver-colored line equals predetermined value.
Make to computerized control translation stage and laser modulator by-line completes the processing of " T " word and " U " word figure in a cellular construction.Use microscope to observe it, find that machining obtains metallic pattern and meets design requirement, without the need to adjusting control program and machined parameters.Continue to make to computerized control translation stage and laser controller completes the processing of each cellular construction one by one.After each unit machines, the processing of translation stage one-dimensional movement 200 μm repetitive again, finally respectively processes 500 construction units in length and breadth on photosensitive film.
Immersed in deionized water by the photosensitive film exposed in darkroom and take out after 5min, take out drying after repeating 3 times, process completes.
Use measuring microscope amplify 400 × (eyepiece 10 ×, object lens 40 ×, transillumination) observe the resonator machined, can see that the silver-colored line width that the present embodiment processes the metal micro structure figure obtained is 10 ± 0.5 μm, be evenly distributed in line, demarcate clear straight (see Fig. 2).Probe-type step instrument is used to measure silver-colored line thickness.The average thickness that result shows silver-colored line is about 1 μm.For check between silver-colored line and polyester film in conjunction with firmness, the metal micro structure processed is positioned in 70W supersonic wave cleaning machine and cleans 25min, have no silver-colored line and come off, illustrate that the firmness that silver-colored line and film substrate combine is better.Use terahertz time-domain spectroscopy instrument (TDS) to test gained resonator, resonator all has stronger resonance absorbing at 0.37THz and 0.73THz two place, and corresponding transmissivity is respectively 8% and 9%.To sum up, the metal micro structure device using the inventive method to process meets design requirement completely.
Claims (11)
1. the metal micro structure processing method write based on blue laser direct, it is characterized in that: the laser beam focusing exported by blue laser is on silver salt photographic film, and two-dimensional scan is carried out to described silver salt photographic film directly write exposure and obtain the metal micro structure figure that is made up of silver-colored line, then silver salt photographic film is cleaned; Described silver salt photographic film is uniformly coated on by silver salt and the mixed solution that is catalyzed into film non-metal base carries out drying to form.
2. a kind of metal micro structure processing method write based on blue laser direct according to claim 1, is characterized in that: described silver salt photographic film is silver nitrate photosensitive film.
3. a kind of metal micro structure processing method write based on blue laser direct according to claim 1 and 2, is characterized in that: the wavelength of the laser that described blue laser exports is 400nm ~ 450nm.
4. a kind of metal micro structure processing method write based on blue laser direct according to claim 1 and 2, is characterized in that: described blue laser is semiconductor laser.
5. a kind of metal micro structure processing method write based on blue laser direct according to claim 3, is characterized in that: described blue laser is semiconductor laser.
6. a kind of metal micro structure processing method write based on blue laser direct according to claim 4, is characterized in that: described laser beam is basic mode light beam.
7. a kind of metal micro structure processing method write based on blue laser direct according to claim 5, is characterized in that: described laser beam is basic mode light beam.
8. a kind of metal micro structure processing method write based on blue laser direct according to claim 1 and 2, is characterized in that: if the width of described silver-colored line is less than predetermined value, then tunes up until the width of silver-colored line equals predetermined value by the focusing focal length of laser beam; If the width of described silver-colored line is greater than predetermined value, then the focusing focal length of laser beam is turned down until the width of silver-colored line equals predetermined value.
9. a kind of metal micro structure processing method write based on blue laser direct according to claim 1 and 2, it is characterized in that: if the width of described silver-colored line is less than predetermined value, then the power output of described blue laser is tuned up until the width of silver-colored line equals predetermined value; If the width of described silver-colored line is greater than predetermined value, then the power output of described blue laser is turned down until the width of silver-colored line equals predetermined value.
10. a kind of metal micro structure processing method write based on blue laser direct according to claim 1 and 2, it is characterized in that: if the width of described silver-colored line is less than predetermined value, then the sweep speed of described two-dimensional scan is reduced until the width of silver-colored line equals predetermined value; If the width of described silver-colored line is greater than predetermined value, then the sweep speed of described two-dimensional scan is improved until the width of silver-colored line equals predetermined value.
11. a kind of metal micro structure processing methods write based on blue laser direct according to claim 2, is characterized in that: described in be catalyzed into film be polyvinyl alcohol, PVP, polyvinylpyrrolidone or polyvinyl butyral resin.
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| CN104004210B (en) * | 2014-05-20 | 2016-08-24 | 华南师范大学 | A kind of method preparing micro structure |
| CN105161390B (en) * | 2015-06-18 | 2017-07-11 | 电子科技大学 | New meta-materials high-power microwave source |
| CN107145039A (en) * | 2017-04-26 | 2017-09-08 | 南京理工大学 | A kind of method of simple and quick patterning perovskite quantum dot |
| CN111112643B (en) * | 2020-02-28 | 2021-06-25 | 山东大学 | Nano silver wire preparation method for nanosecond laser-assisted thermal decomposition of silver nitrate, nano silver wire and application |
| CN114942232A (en) * | 2022-05-20 | 2022-08-26 | 江苏大学 | High-sensitivity terahertz sensor and preparation method thereof |
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| CN100406613C (en) * | 2005-11-17 | 2008-07-30 | 上海交通大学 | Laser induced selective chemical plating process |
| CN101121575B (en) * | 2007-07-06 | 2010-11-03 | 中国科学院上海光学精密机械研究所 | Method for realizing selectivity metallization on glass surface by femto-second laser |
| CN101973512B (en) * | 2010-08-30 | 2013-07-10 | 北京工业大学 | Method for directly writing metal micro-nano structure by ultraviolet laser interferometry etching |
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