CN103193999A - Method and equipment for preparing strip structures on conjugated polymer surfaces through pulse lasers - Google Patents
Method and equipment for preparing strip structures on conjugated polymer surfaces through pulse lasers Download PDFInfo
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- CN103193999A CN103193999A CN2013101225116A CN201310122511A CN103193999A CN 103193999 A CN103193999 A CN 103193999A CN 2013101225116 A CN2013101225116 A CN 2013101225116A CN 201310122511 A CN201310122511 A CN 201310122511A CN 103193999 A CN103193999 A CN 103193999A
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Abstract
The invention discloses a method for preparing strip structures on conjugated polymer surfaces through pulse lasers. The method comprises steps of: selecting a conjugated polymer film which is electrochemically deposited and polymerized on conducting glass as a polymer; putting the polymer film in a sample chamber with an optical transparent window and fixing the polymer film on a three-dimensional precision displacement platform; then expanding a pulse laser beam, focusing the expanded pulse laser beam to form a linear beam through a cylindrical lens, and emitting the linear beam to the surface of the polymer film; controlling the output energy of a laser so that the energy density of a coherent part is less than the energy density threshold required for polymer melting; moving the sample chamber by utilizing the three-dimensional precision displacement platform, thus forming the up-and-down strip structure on the polymer surface which is irradiated by the beam. The resolution ratio of the strip structure formed by the method can reach submicron and even nanoscale, and the strip structure is hopefully applied to liquid crystal display parts and polymer solar cell modules.
Description
Technical field
The present invention relates to the photoelectron material technical field, particularly utilize the pulse laser induced all methods of periodicity striated structure of big area that prepare quickly and efficiently on the conjugated polymers surface.
Background technology
The orderly rice striated surface structure of the spontaneous formation of single bundle of pulsed laser direct irradiation surface of polymer material is the important phenomenon in laser physics field.Because striped has height rule, this phenomenon is called as induced with laser surface periodic structure (LIPSS).The formation of LIPSS is because incident light and surface scattering ripple interfere the periodic distribution to laser energy density, impels polymer molecule to produce formation such as local migration, degraded.In recent years, people have obtained induced with laser periodic surface microstructure at polyethylene terephthalate (PET), polycarbonate (PC) and polyether-ether-ketone surface of polymer material such as (PEEK).The LIPSS structure is in the liquid crystal aligning template, and the surface modification of polymkeric substance etc. is used widely.Conjugated polymers is that a class has the polymkeric substance that the two keys of singly-bound replace conjugation formation, it has unique electronics, electrochemistry and optical property, therefore has important use at aspects such as the energy, information storage, opto-electronic device, sensor, military stealthy techniquies.Technology (Vandyke LS formerly, Brumlik CJ, Martin CR, Yu ZG, Collins GJ, UV laser ablation of electronically conductive polymers, Synth.Met.1992,52 (3): adopt UV laser beam focusing radiation polypyrrole and polyaniline film surface 299-304), utilize the ablation of laser to prepare the conjugated polymers surface micro-structure at film surface, this method is owing to adopt UV-light as light source, since the energy of these wavelength laser photons greater than or close to the bond energy of polymkeric substance, often be accompanied by photolysis or the photodegradation of polymer materials in the preparation process of microstructure, polymer properties is subjected to obvious influence.Patent CN1654516A utilizes two bundle femtosecond lasers to interfere method of focusing, form series of points on the conjugated polymer thin films surface, and in each point, comprise conductive polymer periodic low-light grid structure, form the required energy density of striated structure and melt required energy density threshold greater than conjugated polymers.This method needs two-beam to act on simultaneously, the equipment complexity that needs, and the method for employing spot scan, the gained graphics area is very limited, thereby has limited carrying out of its applied research.Beam energy density height, so the easy oxidized degraded of polymkeric substance simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiency of above-mentioned technology, a kind of periodically method of striated structure of big area conjugated polymers surface preparation for preparing fast and efficiently is provided, method and apparatus of the present invention can directly pass through one-off scanning on large-area conjugated polymers surface, prepare not have and melt the conjugated polymers of degraded, can satisfy the actual requirement of production in enormous quantities, concrete implementation step is:
1. prepare conjugated polymer thin films at conductive glass surface with electrochemical polymer, polymeric film is positioned in the sample chamber;
2. with a bundle of pulsed laser through beam expanding lens, focused on by cylindrical mirror then, form the wire hot spot and accumulate in polymer film surface;
3. control the output energy of laser apparatus, make the energy density of coherent melt required energy density threshold less than conductive polymers;
4. control translation stage and move, form periodically low-light grid structure on the polymeric film surface that the laser coherence field action is crossed.
Wherein, step 1 may further comprise the steps in the aforesaid method: it is indoor that (1) has the conductive glass substrate of polymeric film to be positioned over the sealed sample of band optical lens light window deposition polymerization; (2) be the numerical range that sets in advance to vacuum tightness with the described airtight cavity extracting air that optical transmission window is housed, further, described step 1 comprises that also one or more the mixture with assist gas charges in the sample chamber, described assist gas refers to inscribe in the preparation process at polymeric film, play passivation, prevent that polymkeric substance from melting the gas of Degradation, comprises N
2, among He, Ne, the Ar one or more.
In aforesaid method, described step 2 specifically comprises: with the pulsed laser beam of laser apparatus output after expanding, light beam after utilizing the focusing optical element with shaping pools line spot, focus on sample film surface annex, the pulse width of described laser apparatus output laser from femtosecond to a millisecond scope, the laser apparatus output frequency is from 0.1-100K hertz scope, and the single pulse energy of laser apparatus output is from 1000 joules of scopes of 0.1 millijoule.And described pulsed laser beam shaping and focusing back are linear beam spot, and the width of hot spot is at 10 microns to 1 millimeter.Described focusing optical element is to carry out folk prescription to focusing on or respectively to the asymmetrical single optical element of compression or two and plural optical element combination, can converging the single optical element of formation wire or the combination of a plurality of optical elements to light beam as cylindrical mirror, post lens, grating etc. to laser beam.
In aforesaid method, described step 3 specifically comprises: according to the size of type of polymer and polymeric film, determine required laser energy density, pulse width, optical maser wavelength and sweep velocity.
The present invention also provides a kind of equipment of quick preparation big area conjugated polymer film striated surface structure, it is characterized in that:
The sealed sample chamber of band optical transmission window, its inner placement conjugated polymer film also forms the laser writing environment;
The shaping focus part is to laser beam shaping and be focused to line spot, the described polymer film surface of irradiation;
Controlling System is controlled described laser beam and is carried out raster scanning at polymer surfaces, in polymer film surface striation structure.
Preferably, described vacuum chamber is the airtight cavity that optical window is housed, and described cavity extracting air is the numerical range that sets in advance to vacuum tightness.Further, can in closed chamber, charge into one or more rare gas elementes by substitute mode.
Preferably, described shaping focus part comprises beam shaping, spatial filter, beam expander device and focusing optical element.Wherein, described focusing optical element is to carry out folk prescription to focusing or respectively to the asymmetrical single optical element of compression or two and plural optical element combination to laser beam.
Preferably, described Controlling System is determined required laser energy density, pulse width, optical maser wavelength and sweep velocity according to the size of type of polymer and polymeric film.
The present invention it adopt line focus beam flying method and apparatus to prepare conjugated polymers striated surface structure, the preparation efficiency height, and the polymer film surface microstructure good uniformity of preparing, be particularly suitable for making solar cell and polymer film surface grating.Adopting this method to prepare conjugated polymer film striated surface structure is that polymer molecular chain produces the migration orientation and produces, and can not melt degraded, Stimulated Light device single pulse energy and restriction repetition rate.
Description of drawings
Fig. 1 is the device synoptic diagram of the inventive method with pulse laser induced conjugated polymers surface periodic striped microstructure.
The Photomicrograph of the conjugated polymer film striated surface structure that Fig. 2 makes for the inventive method.
Embodiment
Method below by the pulse laser induced conjugated polymers striated surface of the present invention of embodiment structural membrane is described further, to the understanding of the present invention and advantage thereof.
Fig. 1 is the principle of work synoptic diagram of the pulse laser induced conjugated polymers striated surface of the present invention structure, and the concrete steps of the inventive method comprise:
1. prepare conjugated polymer thin films at conductive glass surface with electrochemical polymer, polymeric film is positioned in the sample chamber;
2. a bundle of pulsed laser is expanded through beam expanding lens, focused on by cylindrical mirror then, form the wire hot spot and accumulate in polymer film surface;
3. control the output energy of laser apparatus, make the energy density of coherent melt required energy density threshold less than conductive polymers;
4. control translation stage and move, form periodically low-light grid structure on the polymeric film surface that the laser coherence field action is crossed.
Embodiment 1:
1. prepare conjugated polymer film at conductive glass surface: adopt the ITO conductive glass as working electrode, Pt sheet conductance electrode is as counter electrode, and saturated calomel electrode is as reference electrode.Measure the 0.8mL thiophene and add in the 50mL boron trifluoride ether solution, insert three electrodes, continue to feed N
2About 10min.Polyase 13 0min generates the Polythiophene film under the 1.1V constant potential; Under the 0.2V constant potential, scan then, the oxidation state film is reduced to eigenstate Polythiophene film, takes out working electrode, this moment, its surface formed thin film, utilize alcohol flushing clean and under nitrogen atmosphere, dry up and make the film glass sample, this sample is placed on the sample table.
2. be 2 * 10 with described airtight cavity extracting air to the vacuum tightness that transparent optical window is housed
-2Pa.
3. selecting pulse width for use is the femtosecond pulse of 45fs, and wavelength is 800nm, and pulse repetition rate is 10Hz, and pulse energy density is 1J/cm
2, light beam is that the condenser lens of 40cm impinges perpendicularly on sample surfaces by focal length, focuses on back irradiation and is about 40 μ m to the live width on the sample, and the about 10mm of length, formation femtosecond laser coherent field is radiated at the film sample surface.
4. by the motion of the described three-dimensional mobile platform of computer control, translational speed is 0.02mm/s, forms the conductive polymer periodic microstructure film.As shown in Figure 2, this film striated structure cycle is 20 μ m.
Embodiment 2:
1. prepare conjugated polymer film at conductive glass surface: adopt the ITO conductive glass as working electrode, Pt sheet conductance electrode is as counter electrode, and saturated calomel electrode is as reference electrode.Measure the 0.8mL thiophene and add in the 50mL boron trifluoride ether solution, insert three electrodes, continue to feed N
2About 10min.Polyase 13 0min generates the Polythiophene film under the 1.1V constant potential; Under the 0.2V constant potential, scan then, the oxidation state film is reduced to eigenstate Polythiophene film, takes out working electrode, this moment, its surface formed thin film, utilize alcohol flushing clean and under nitrogen atmosphere, dry up and make the film glass sample, this sample is placed on the sample table.
2. be 2 * 10 with described airtight cavity extracting air to the vacuum tightness that transparent optical window is housed
-2Pa.
3. selecting laser system for use is the Nd:YAG ps pulsed laser and ns pulsed laser device of harmonic wavelength 532nm, pulsewidth 10ns, high repetition frequency 10Hz.Laser beam is after 200cm condenser lens, focal length are the cylindrical mirror of 40cm, to impinge perpendicularly on the polymeric film sample surfaces at last by focal length successively, and the laser energy density of employing is 30～66J/cm
2, focusing on back irradiation by cylindrical mirror is 60 μ m to the Line of light spot width on the sample, length is 18mm.
4. by the three-dimensional mobile platform of computer control, translational speed is 0.02mm/s, and scanning samples is realized large-area treatment, forms periodically striated structure of conjugated polymers.
Embodiment 3:
1. prepare conjugated polymer film at conductive glass surface: adopt the ITO conductive glass as working electrode, Pt sheet conductance electrode is as counter electrode, and saturated calomel electrode is as reference electrode.Measure the 0.8mL thiophene and add in the 50mL boron trifluoride ether solution, insert three electrodes, continue to feed N
2About 10min.Polyase 13 0min generates the Polythiophene film under the 1.1V constant potential; Under the 0.2V constant potential, scan then, the oxidation state film is reduced to eigenstate Polythiophene film, takes out working electrode, this moment, its surface formed thin film, utilize alcohol flushing clean and under nitrogen atmosphere, dry up and make the film glass sample, this sample is placed on the sample table.
2. be 2 * 10 with described airtight cavity extracting air to the vacuum tightness that transparent optical window is housed
-2Pa is by Ar to 1x10
5Pa repeats above-mentionedly to vacuumize and towards rare gas element action three times, form the Ar Working environment at last.
3. selecting laser system for use is the Nd:YAG ps pulsed laser and ns pulsed laser device of harmonic wavelength 532nm, pulsewidth 10ns, high repetition frequency 10Hz.Laser beam is after 200cm condenser lens, focal length are the cylindrical mirror of 40cm, to impinge perpendicularly on the polymeric film sample surfaces at last by focal length successively, and the laser energy density of employing is 30～66J/cm
2, focusing on back irradiation by cylindrical mirror is 60 μ m to the Line of light spot width on the sample, length is 18mm.
4. by the three-dimensional mobile platform of computer control, translational speed is 0.02mm/s, and scanning samples is realized large-area treatment, forms periodically striated structure of conjugated polymers.
Claims (10)
1. the method and apparatus at conjugated polymers surface preparation striated structure is to utilize pulse laser to cause that at polymer surfaces incident light and catoptrical interference the conjugated polymers surface forms periodically striated structure, and its specific practice is:
1. at conductive glass surface electrochemical production conjugated polymer thin films, polymeric film is positioned in the sample chamber of band optical clear window, the sample chamber is fixed on the accurate automatically controlled three-dimensional mobile platform;
2. with a bundle of pulsed laser after beam expanding lens expands, focused on by cylindrical mirror, form the wire hot spot and accumulate in polymer film surface;
3. control the output energy of laser apparatus, make the energy density of coherent melt required energy density threshold less than polymkeric substance;
4. control platform and move, form periodically low-light grid structure on the polymeric film surface that the laser coherence field action is crossed.
2. the method for preparing conjugated polymers striated surface structure according to claim 1 is characterized in that described conjugated polymer thin films is the derivative of Polythiophene, polypyrrole and polyaniline or polymkeric substance.
3. method according to claim 1 is characterized in that, described step 1 may further comprise the steps: (1) is positioned over polymeric film in the closed chamber that the optical clear window is housed; (2) be the numerical range that sets in advance to vacuum tightness with the described airtight cavity extracting air that optical window is housed; (3) further, also can in the sample chamber, charge into inert protective gas.
4. method according to claim 3 is characterized in that, the described vacuum values scope that sets in advance is 10
-5-10
-2Pa.Described step 1 comprises also and charges into a kind of of rare gas element or its mixture that described assist gas comprises N
2, one or more mixing among He, Ne, the Ar.
5. method according to claim 1, it is characterized in that, to a millisecond scope, the laser apparatus output frequency is from 0.1～100K hertz scope from femtosecond for the pulse width that swashs no light beam from the pulse of laser apparatus output, and the single pulse energy that laser apparatus is exported is from 0.1 millijoule-1000 joule scope.
6. method according to claim 1 is characterized in that, described pulsed laser beam shaping and focusing back are linear beam spot, and the width of hot spot is at 10 microns to 1 millimeter.
7. a pulse laser is characterized in that at the equipment of conjugated polymers surface preparation surface undulation striated structure, comprising:
The sample chamber, band optical clear window, its inner polymeric film of placing can form vacuum and protection of inert gas environment;
The light beam focus part is to laser beam shaping and be focused to line spot, the described polymer film surface of irradiation;
Controlling System is controlled described laser beam polymer film surface is carried out raster scanning, in polymer film surface striation structure.
8. equipment according to claim 7 is characterized in that, described vacuum chamber is the airtight cavity that the optical clear window is housed, and described cavity extracting air to vacuum tightness is the numerical range that sets in advance, and can charge into assist gas in described closed chamber.
9. equipment according to claim 7 is characterized in that, described shaping focus part comprises beam shaping, spatial filter, beam expander device and focusing optical element.
10. equipment according to claim 7 is characterized in that, described Controlling System is determined required laser energy density, pulse width, optical maser wavelength and sweep velocity according to the size of type of polymer and polymeric film.
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Cited By (9)
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| CN104900738A (en) * | 2015-04-30 | 2015-09-09 | 西南科技大学 | Method for converting solar energy into electric energy through electromagnetic induction |
| CN106432780A (en) * | 2016-11-10 | 2017-02-22 | 厦门大学 | Method for growing conjugate ring slice with light transmittance regulated by electric field on indium tin oxide |
| CN106744674A (en) * | 2017-01-11 | 2017-05-31 | 兰州空间技术物理研究所 | A kind of manufacture method of across the yardstick function micro-nano structure in surface |
| CN106832380A (en) * | 2017-02-24 | 2017-06-13 | 天津大学 | A kind of method that utilization Laser Processing prepares picture on surface polymer film |
| WO2018014468A1 (en) * | 2016-07-18 | 2018-01-25 | 北京灵犀微光科技有限公司 | System and method for preparing polymer dispersed liquid crystal holographic grating |
| CN109294233A (en) * | 2018-09-25 | 2019-02-01 | 重庆大学 | A kind of nano-conductive fiber/polymer composite, preparation method and application |
| CN110385530A (en) * | 2019-07-15 | 2019-10-29 | 中国科学院合肥物质科学研究院 | A kind of method that quasi-molecule laser etching calcium fluoride crystal forms periodic stripe |
| CN112008232A (en) * | 2020-08-11 | 2020-12-01 | 华东师范大学 | Method and device for preparing periodic stripe structure on surface of glass coated with ITO film |
| CN114591527A (en) * | 2022-03-07 | 2022-06-07 | 南京理工大学 | Preparation method of polymer film surface periodic structure regulated by laser wavefront |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1654516A (en) * | 2005-01-20 | 2005-08-17 | 中国科学院上海光学精密机械研究所 | Method for preparing conductive polymer periodic microstructure |
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2013
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1654516A (en) * | 2005-01-20 | 2005-08-17 | 中国科学院上海光学精密机械研究所 | Method for preparing conductive polymer periodic microstructure |
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| CN104900738A (en) * | 2015-04-30 | 2015-09-09 | 西南科技大学 | Method for converting solar energy into electric energy through electromagnetic induction |
| WO2018014468A1 (en) * | 2016-07-18 | 2018-01-25 | 北京灵犀微光科技有限公司 | System and method for preparing polymer dispersed liquid crystal holographic grating |
| US11262698B2 (en) | 2016-07-18 | 2022-03-01 | Journey Technology, Ltd. | Preparation system and method for polymer-dispersed liquid crystal holographic grating |
| CN106432780A (en) * | 2016-11-10 | 2017-02-22 | 厦门大学 | Method for growing conjugate ring slice with light transmittance regulated by electric field on indium tin oxide |
| CN106744674A (en) * | 2017-01-11 | 2017-05-31 | 兰州空间技术物理研究所 | A kind of manufacture method of across the yardstick function micro-nano structure in surface |
| CN106832380A (en) * | 2017-02-24 | 2017-06-13 | 天津大学 | A kind of method that utilization Laser Processing prepares picture on surface polymer film |
| CN109294233A (en) * | 2018-09-25 | 2019-02-01 | 重庆大学 | A kind of nano-conductive fiber/polymer composite, preparation method and application |
| CN109294233B (en) * | 2018-09-25 | 2021-03-19 | 重庆大学 | Nano conductive fiber/polymer composite material strain sensor |
| CN110385530A (en) * | 2019-07-15 | 2019-10-29 | 中国科学院合肥物质科学研究院 | A kind of method that quasi-molecule laser etching calcium fluoride crystal forms periodic stripe |
| CN112008232A (en) * | 2020-08-11 | 2020-12-01 | 华东师范大学 | Method and device for preparing periodic stripe structure on surface of glass coated with ITO film |
| CN114591527A (en) * | 2022-03-07 | 2022-06-07 | 南京理工大学 | Preparation method of polymer film surface periodic structure regulated by laser wavefront |
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