CN101320209A - Production method of surface conducting polymer graphic pattern - Google Patents
Production method of surface conducting polymer graphic pattern Download PDFInfo
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- CN101320209A CN101320209A CNA2008100509228A CN200810050922A CN101320209A CN 101320209 A CN101320209 A CN 101320209A CN A2008100509228 A CNA2008100509228 A CN A2008100509228A CN 200810050922 A CN200810050922 A CN 200810050922A CN 101320209 A CN101320209 A CN 101320209A
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Abstract
The invention belongs to the technology of the functional material surface patterning, in particular to a preparation method for surface conducting polymer patterns. The method is that a conducting polymer thin film formed on the base surface by the method of spin coating or oxidation polymerization; then patterns are imprinted on the polymer barrier layer of the conducting polymer thin film through the nano-imprint; isotropic etching is carried out with the patterns as the masks, and thus the surface conducting polymer patterns with controllable structure and size are prepared on the base surface. The problem that the high density and high productivity are not simultaneous is solved by the method. On the basis, the resolution of the surface conducting polymer patterns is several times higher than that of the masks. The invention has the characteristics of low cost, high efficiency and mature technology, is coincidence with the industrialization standards, and can be used for making optical, electronic, magnetic and biological devices as well as producing sensors and dischargeable batteries; the application ability of the functional materials such as the conducting polymer, etc., is greatly improved.
Description
Technical field
The invention belongs to the functional material picture on surface and construct technology, be specifically related to a kind of preparation method of surface conducting polymer graphic pattern, it is to utilize the film of the method for spin coating or oxidative polymerization at substrate surface formation conducting polymer, the polymer barrier layer that will be spin-coated on the conducting polymer thin film by nano impression impresses out pattern then, with the pattern of this impression is that mask carries out all to etching, thereby goes out the controlled surface conducting polymer graphic pattern of physical dimension in substrate surface preparation.
Background technology
Conducting polymer is not only a kind of electricity that had both, the unique material of optics and magnetic property, and possess outstanding machining property, and for example in light weight, processing easily, characteristics such as good bandability, thereby be subjected to people's extensive concern.Yet traditional being used to prepares the method for surface conducting polymer graphic pattern, is difficult to high density and high yield are combined, and therefore, designing and Implementing a kind of method that the two can be combined becomes the difficult problem that a urgent need is captured.
Surface conducting polymer graphic nano/micron pattern has important application aspect a lot, for example, and light emitting diode, organic field effect tube, integrated circuit, polymer electroluminescence material, artificial muscle, sensor, biocompatible materials etc.Because the significance of surface conducting polymer graphic pattern in scientific research and practical application, people have been developed multiple method of constructing surface conducting polymer graphic pattern.People such as Lidzey utilize water miscible photoresist by laser ablation, and having prepared resolution is the light emitting diode matrix of 10 μ m, and does not destroy the electric conductivity (Org.Electron.2005,6,221) of polymkeric substance.People such as Granlund have introduced the method for constructing polymer LED with soft lithographic technique, the author is cast on the seal with aggressiveness before the polysiloxane, heating causes crosslinked turning over and makes flexible polymkeric substance (PDMS) pattern, utilizes the PDMS seal that conducting polymer is transferred in the substrate; Perhaps in substrate, prepare conductive polymer membrane in advance, utilize the PDMS seal that the part film is thrown off; In addition, capillary action also is applicable to the system of this soft etching, the one side in the space that forms when preprepared PDMS seal and substrate combine adds the solution of conducting polymer, make conducting polymer be diffused into (Adv.Mater.2000 in whole spaces by capillary action like this, 12,269).Scanning probe microscopy also is a kind of method that surface conducting polymer graphic pattern is constructed in success, people such as Jahromi prepare earlier adulterant and oxygenant hybrid films in advance on substrate of glass, then at this spin coating one deck polymethylmethacrylate (PMMA) film above tunic, use the atomic-force microscope needle-tip etching, expose adulterant and oxygenant hybrid films, sample is exposed in pyrroles's atmosphere, at the part of exposing polymerization (ChemPhysChem2002 optionally, 3,693).And the method for directly writing with pen of people such as Grinstaff and Liu report is directly write out the pattern of conducting polymer in substrate, the live width of conductive polymer nanometer line can be passed through humidity, voltage that applies and the speed of writing are regulated and control, structure resolution can reach below the 100nm, this method is that a kind of being applicable at laboratory stage prepares complex surface method of patterning (J.Am.Chem.Soc.2002,124,522).
Compare with other nano-scale patterns technology, nanometer embossing (NIL) is the high technology of a kind of cost low yield, and this technology is based on make the barrier polymers mechanically deform on nanoscale.Potpourri with conducting polymer or conducting polymer is the restraining barrier, can use nanometer embossing pattern conductive polymkeric substance (J.Vac.Sci.Technol.B2001,19,487; Synth.Met.2001,121,1309).Yet, own characteristic according to nano impression, directly method for stamping is only applicable to glass transition temperature (Tg) or can ultraviolet causes crosslinked conducting polymer, and directly the shortcoming on the other hand brought of impression is the destruction that can cause the conducting polymer performance as follow-up etching of constructing step.In order to expand nanometer embossing in the application aspect the pattern conductive polymkeric substance, we have developed a kind of method based on nanometer embossing and lift-off technology, yet the thickness of the pattern of the conducting polymer that this method is constructed is subjected to the restriction of stripping process.This be because, realize successful peeling off, the thickness of the conducting polymer of deposition must be littler than the thickness on restraining barrier, this has just limited electric conductivity performance of surface conducting polymer graphic pattern.
In the nano impression process, the pattern that impression obtains all is that the negative sense of die plate pattern duplicates usually, that is to say that the resolution of pattern is controlled by template resolution.High-resolution pattern requires high-resolution template, and this just needs long-time, expensive template preparation process.In order to break through this restriction, a kind of phenomenon that is become " rabbit ears " is applied in the nano impression process, the generation of this phenomenon is owing to barrier polymers in moulding process is not full of and soaks into template surface (Adv.Funct.Mater.2006,16,1555 fully; NanoLett.2007,7,1869), this phenomenon is for constructing high resolving power with the template of simple and inexpensive and complicated patterns provides a kind of simple pathway.
The method that this patent relates to be a kind of novelty in conjunction with the nanometer embossing that utilizes " rabbit ears " phenomenon and all to lithographic technique in conjunction with the method for preparing surface conducting polymer graphic pattern.Here, polymer barrier layers such as PMMA are spin-coated on the preprepared conducting polymer thin film, on polymer films such as PMMA, carry out nano impression then.The pattern of impression is by on equal conductive polymer membranes below lithographic method is transferred to, and improves resolution in this process.Utilize this method, not only can protect the performance of conducting polymer, and can also utilize the template of micron dimension to construct out the structure of micron even nanometer scale.The thickness of the conductive polymer pattern of this method preparation is not limited by stripping process, can be applied to fields such as optics, electricity, magnetics, biology.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of surface conducting polymer graphic pattern, it is by making conducting polymer (polyaniline, polypyrrole, polythiophene etc.) form homogeneous film in the monocrystalline silicon piece of crossing in cleaning, oxidized silicon chip, piezoid, glass sheet, ito glass sheet, sheet metal or the mica sheet substrate, and on this film, carry out the spin coating, impression of polymer barrier layer and all to etching, then remaining restraining barrier is washed off, thereby in substrate, obtained surface conducting polymer graphic pattern.
We find after deliberation, and the surface conducting polymer graphic pattern that utilizes this method to construct can obviously reduce in the process destruction to the conducting polymer thin film performance.The direct method for stamping of bibliographical information, reduction (J.Vac.Sci.Technol.B2001,19,487 that can cause its conductance several magnitude of conducting polymer thin film; Synth.Met.2001,121,1309), and utilize our this construction method, can guarantee being reduced within the order of magnitude of conducting polymer conductance.As shown in Figure 6, still exist through the whole characteristic absorption peak of constructing process conducting polymer polyaniline, the variation of peak shape and peak position is also very little, illustrates that the process of constructing does not do a lot of damage to the performance of conducting polymer.
Utilize the cost of the surface conducting polymer graphic pattern that the method for this patent constructs low, technology is simple, and the productive rate height, has stronger practicality.Owing to guaranteed that conducting polymer still keeps aspect performances such as original electricity, optics, magnetics, therefore have widely at electronics, optics, biology, chemical field and use, particularly have extremely important application at aspects such as sensor, optical device, photoelectric device, electron device, magnetic device, chemistry and biology devices.
The preparation method of the described surface conducting polymer graphic pattern of this patent may further comprise the steps:
(1) method of substrate surface by spin coating or oxidative polymerization in cleaning prepares the thick conducting polymer thin film of 10nm～30nm;
(2) the thick polymer barrier layer of spin coating 200nm～800nm on conducting polymer thin film, and carry out nano impression, forming the polymer barrier layer pattern, this pattern and impression block structure are complete or not exclusively complementary;
(3) the polymer barrier layer pattern is carried out all to oxygen plasma etch, the residual polymer barrier layer of flush away then, thus in substrate, obtain surface conducting polymer graphic pattern.
Surface conducting polymer graphic pattern through above step obtains characterizes by atomic force microscope, ultraviolet-visible spectrophotometer, has proved that this patterning method has kept original performance of conducting polymer substantially.
The method that obtains conducting polymer thin film at substrate surface mainly contains two kinds, and first kind is spin coating conductive polymer solution in substrate, and the rotating speed of spin coating is 500～5000rpm, and the time is 1～3min; Another is the method that adopts oxidative polymerization, N-(3-trimethoxy propyl group) pyrrole monomer with 10 μ L～10mL conducting polymer monomer (aniline, pyrroles or thiophene etc.), 10 μ L～1mL, and 0.02g～5g ferric trichloride oxygenant, be dissolved in water, ethanol or the isopropyl alcohol of 10mL～1000mL, then substrate is put into this oxidative polymerization system, the time of oxidative polymerization is 5min～24h, temperature of reaction is 0～45 ℃, thereby the thickness that obtains in substrate is the conducting polymer thin film of 10nm～30nm.
Spin coating is used for the polymer barrier layer of nano impression on conducting polymer thin film, impresses afterwards, and its key step is as follows:
(1) spin coating polymethylmethacrylate (PMMA), polystyrene, mr-L7030 or mr-L6000 etc. on conducting polymer thin film, spin speed is 1000rpm～5000rpm, time is 1min～5min, after the spin coating with substrate sample at 90 ℃～150 ℃ annealing 5min～60min, and then obtain the polymer barrier layer that thickness is 200～800nm on the conducting polymer surface;
(2) template that impression is used is carried out fluorination treatment, reduces the surface energy of template, and the stripping process of follow-up template and polymer barrier layer can be carried out smoothly.Its process is: at first, with the oxygen plasma system template surface is handled, purpose is to remove the organism of surface adsorption, oxygen gas flow rate 80mL/min～200mL/min, power 100W～300W, processing time 1min～15min; Again with high purity water to template surface ultrasonic cleaning 2～3 times, each time is 2min～5min, makes thoroughly cleaning of surface; Then template is placed dry 30min～3h under 70 ℃～200 ℃ temperature conditions, last on hot platform the method by heating on template self assembly last layer fluoro silylating reagent (as perfluor decyl-1,1,2,2-tetrahydrochysene-trichlorosilane), carry out fluorination treatment 1h～5h at 150 ℃～350 ℃.
(3) template of above-mentioned substrate and fluorination treatment is placed in the nano marking press impresses, the nano impression temperature is 80 ℃～220 ℃, impression pressure is 20bar～55bar, the impression time is 100s～800s, then on polymer barrier layer, obtain and formwork structure fully or not exclusively complementary pattern, after impression finishes with template and sample separation.
Can select the template of different resolution, different structure according to the demand of conductive polymer pattern, and can improve pattern resolution (as shown in Figure 9) by selecting specific template.In this patent, the template that is fit to be quartzy, silicon or metal form, and its surface be regular pattern,, the strip pattern of width gradual change equal as spacing or protruding square pattern etc.
The Hang Zhuo of pattern Jin that impression is obtained is to etching, and the residual polymer barrier layer of flush away: the etching apparatus of selection is common all to the plasma etching instrument, condition is oxygen gas flow rate 80mL/min～200mL/min, power 30W～300W, processing time 5min～30min.By this step etching process, pattern on the polymer barrier layer is transferred on the conducting polymer thin film of lower floor, and, owing to all do not have vertically and the selectivity between the side direction to plasma etching, can realize overetch by prolonging etching time or increasing etching power, test in real time with the sample of atomic force microscope after to etching, guarantee the etching result, guarantee that promptly unnecessary restraining barrier and conducting polymer are thoroughly removed, realized the further raising of conductive polymer pattern resolution.Ultrasonic 5s～30min removes remaining polymer barrier layer on the conducting polymer thin film in acetone afterwards, thereby obtains conductive polymer pattern at substrate surface.
The described method of this patent can constructing micrometre and the surface conducting polymer graphic pattern of nanoscale, and utilization " rabbit ears " phenomenon and the method that excessively all combines have been realized to plasma etching, successfully solved the difficult problem that high density and high yield are difficult to walk abreast, on this basis, the resolution of surface conducting polymer graphic pattern improves several times than the template of using.
In addition, this method of constructing picture on surface also is applicable to the patterning of the metallic film (gold, copper, cobalt, nickel, platinum, silver, cadmium, indium and germanium etc.) that suprabasil individual layer self-assembled film (terminal is alkyl, mercaptan, amino, fluorine etc.) or steaming are crossed.
This method cost is low, efficient height, technology maturation, meet industrialized standard, can be used to make optics, electricity, magnetics, biology device, also can be used for sensor and can discharge and recharge the production etc. of battery, significantly improve the application power of functional materials such as conducting polymer.
Description of drawings
Fig. 1: utilize the method for oxidative polymerization to prepare the experimental provision synoptic diagram of conducting polymer thin film;
Fig. 2: the key step synoptic diagram of constructing the conducting polymer picture on surface;
Fig. 3: embodiment 1 obtains utilizes the atomic force microscope photo of the polyaniline film that oxidative polymerization obtains;
The atomic force microscope photo of the template of using when impressing among Fig. 4: the embodiment 1;
The atomic force microscope photo of the surface aggregate thing barrier layer pattern that Fig. 5: embodiment 1 impression obtains;
The atomic force microscope photo of the surperficial polyaniline pattern after oxygen plasma etching and flush away polymer barrier layer that Fig. 6: embodiment 1 obtains;
The surperficial polyaniline pattern that Fig. 7: embodiment 1 obtains and the uv-visible absorption spectra of film;
The atomic force microscope photo of the template that impression uses among Fig. 8: the embodiment 2;
The atomic force microscope photo of the surface aggregate article pattern that Fig. 9: embodiment 2 impressions obtain;
The atomic force microscope photo of the surperficial polyaniline pattern after oxygen plasma etching and flush away barrier polymers that Figure 10: embodiment 2 obtains.
As shown in Figure 1, the method of oxidative polymerization prepares the experimental provision synoptic diagram of conducting polymer thin film, 11 is temperature control sample table, and 12 is beaker, and 13 for being fixed with the ptfe sheet of experiment with substrate (as the titanium dioxide silicon chip), 14 is test tube clamp, 15 are thermometer (being used for measuring more accurately temperature), and 16 is iron stand, and 17 is thermopair, 18 is magnetic stir bar, and 19 are the experiment substrate.
Heating on the temperature control sample table 11 of thermopair 17 control temperature (error ± 1 ℃), (solution (as aqueous solution) of 0.02g～5g) is contained in the beaker 12 of 300mL with a certain amount of oxygenant such as ferric trichloride, (0 ℃～45 ℃ of control temperature control sample table temperature, shown in the figure be 25 ℃), regulate the speed (100rpm～800rpm) of magnetic stir bar simultaneously, the stable back of system adds polymer monomer in solution, as aniline (10 μ L～10mL) and N-(3-trimethoxy propyl group) pyrrole monomer (10 μ L～1mL).The substrate that will be used to deposit is fixed on ptfe sheet by adhesive tape, and is fixed on beaker 12 inwalls with test tube clamp 14.Under at the uniform velocity stirring, make polyreaction continue 5min～24h.
The copolymerization technique of conducting polymer and other material is considered to a kind of effective ways that improve this base polymer dissolubility and processability.By regulating ratio between monomer, the character of conducting polymer (for example electric conductivity or adhesive force) can both be adjusted.The ability of sticking is the key issue in the micro-processing technology (for example peeling off in the plated metal process), usually, conducting polymer makes it not to be able to take stripping process because its film can not attach to substrate, and the result causes it to be easy to break away from formation self-supporting film from substrate.Utilize copolymerization process to regulate the ability of sticking and electric conductivity thereof between conducting polymer and substrate in the present invention.Because one of comonomer that uses N-(3-trimethoxy propyl group) pyrroles can form covalent bond with substrate in the present invention, like this, has just solved this key issue.Because the universality of copolymerization technique, our this invention is applicable to the polymerization of multiple polymers.In this patent, the thickness that concentration that we can be by telo merization and reaction time are controlled conductive polymer membrane.
As shown in Figure 2, the process synoptic diagram that utilizes nano-imprinting method and all combine and construct the surface conducting polymer graphic pattern method to plasma etching.The A step is for obtaining the film of conducting polymer in substrate, 21 is the substrates of using in the experiment such as silicon dioxide, and 22 is conducting polymer thin film.The B step is a polymer barrier layer such as spin coating PMMA on this layer conducting polymer thin film, and polymer barrier layer is impressed.23 is polymer barrier layer such as PMMA, 24 templates for impression usefulness.Wherein, therefore conducting polymer thin film 22 does not change in moulding process substantially because its stable in properties does not have glass transition temperature.Polymer barrier layer 23 is a kind of polymkeric substance that typically have glass transition temperature, reaches its glass transition temperature in temperature and takes place when above to flow, and exerting pressure in this course makes in its space that is filled into template.The C step to plasma etch process, because etching does not have directional selectivity, so realize side direction and vertical etching simultaneously, had both etched away unnecessary polymer P MMA restraining barrier and layer/polyaniline conductive thin polymer film for all, had improved the lateral resolution of pattern again.The D step is last cleaning process, and through ultrasonic in acetone, remaining restraining barrier PMMA can remove, the surperficial polyaniline pattern that obtains expecting.
As shown in Figure 3, corresponding embodiment 1 utilizes the atomic force microscope photo of the polyaniline film that oxidation copolymerization obtains, and its sweep limit is 4 μ m * 4 μ m.As can be seen from Figure, film surface is very smooth, and polyaniline is spherical in shape in film, and diameter is between 50～70nm.
As shown in Figure 4, corresponding embodiment 1, for impressing the atomic force microscope photo (sweep limit is 30 μ m * 30 μ m) of the template of using, wherein 42 is the template band of projection, 41 is the template groove of template bar interband.Shown in photo, the width gradual change of template groove, by 1 μ m to 2.4 μ m.Strip width is fixed as 2.4 μ m, and the degree of depth is 350nm.
As shown in Figure 5, corresponding embodiment 1, be the atomic force microscope photo (sweep limit is 30 μ m * 30 μ m) of the restraining barrier PMMA picture on surface constructed with nano-imprinting method, wherein 51 is the polymer barrier layer band of projection, and 52 is the polymkeric substance groove of polymer barrier layer bar interband.By the photo of atomic force microscope as can be seen, the surface aggregate article pattern is complementary fully with the used die plate pattern of impression, the width gradual change of polymer barrier layer band, by 1 μ m to 2.4 μ m, the width of polymer barrier layer groove is fixed as 2.4 μ m, and the degree of depth is 350nm.
As shown in Figure 6, corresponding embodiment 1, with oxygen gas plasma etching PMMA and following polyaniline, after the acetone cleaning, the photo (sweep limit is 30 μ m * 30 μ m) that atomic force microscope characterizes, wherein 61 is the conducting polymer thin film band.Shown in the atomic force microscope photo, the resolution of the surperficial polyaniline pattern that obtains is improved, compare with former PMMA pattern, the width of conducting polymer band dwindles to some extent, wherein 61 become 2.1 μ m by 3.2 μ m, 62 become 200nm by 1.2 μ m, change with strip width, and the amplitude of dwindling is slightly different.
As shown in Figure 7, corresponding embodiment 1 is the ultraviolet-visible absorption spectroscopy of surperficial polyaniline linear pattern and film.(curve a) is compared as can be known with the spectrum (curve b) of film, and the performance of etching process p-poly-phenyl amine does not cause too much influence by the spectrum of surperficial linear pattern.We think it mainly is because etching has been removed the polyaniline in the groove the strong reduction in peak.Characteristic absorption peak at the 320nm place is referred to think ∏-∏
*Interact, and n-∏
*Transition brings the absorption at 600nm place.As shown in the figure, the curve of polyaniline picture on surface is compared with the curve of film, n-∏
*The generation red shift of transition peak, we think that this is to have taken place in the process to mix and go doping, recrystallization, crosslinked or other change owing to constructing in structure.
As shown in Figure 8, corresponding embodiment 2 constructs the atomic force microscope photo (sweep limit is 30 μ m * 30 μ m) of the template that pattern uses for utilizing " rabbit ears " phenomenon, and wherein 81 is the square projection of template, and 82 is the template edge between square projection.Shown in photo, the length of side of square projection is 5.2 μ m, highly is 350nm, and the width of template edge 82 is 3.6 μ m.
As shown in Figure 9, corresponding embodiment 2, the atomic force microscope photo of the surperficial PMMA pattern of constructing with nano impression " rabbit ears " phenomenon, its sweep limit is 30 μ m * 30 μ m.By the photo of atomic force microscope as can be seen, polymkeric substance does not form the pattern complementary fully with template, but forms " well " font structure.Bossing 81 complementations of the in-profile 91 of polymer barrier layer " well " and used template, the width at polymer barrier layer edge 92 are 1.8 μ m.
As shown in figure 10, corresponding embodiment 2 utilizes " rabbit ears " phenomenon impression PMMA and following polyaniline with the oxygen gas plasma etching, and after cleaning through acetone, with the photo that atomic force microscope characterizes, its sweep limit is 30 μ m * 30 μ m.Shown in the atomic force microscope photo, the resolution of the polyaniline picture on surface that obtains is compared with " well " word structure that impression obtains and is improved, compare with the PMMA pattern resolution and to double (width at conducting polymer thin film 102 edges is 0.9 μ m), and compare with template edge 82, improved four times.
Embodiment
Further illustrate the inventive method and application below by embodiment, rather than will limit the present invention with these embodiment.The present invention is mainly by forming the conducting polymer homogeneous film in smooth substrate, and carries out the spin coating, impression on restraining barrier and all to etching, then remaining restraining barrier is washed off, thereby obtained surface conducting polymer graphic pattern on this film.
Embodiment 1:
Aniline monomer is done under the oxygenant condition at ferric trichloride, can oxidative polymerization generate polyaniline, and can form uniform films in substrate.We add N-(3-trimethoxy propyl group) pyrrole monomer in polymerization system, with the aniline copolymerization, strengthened the ability of sticking of polyaniline film and substrate.
The preparation condition of polyaniline film:
Aniline 1mL, N-(3-trimethoxy propyl group) pyrrole monomer 40 μ L, ferric trichloride 0.72g, 25 ℃ of temperature, time 10min.
Characterize the polyaniline film pattern with the atomic force microscope pattern of rapping, as shown in Figure 3.As can be seen from the figure, polyaniline can form homogeneous film in the silicon dioxide substrate, and its thickness is 20nm, and surfaceness is about 7.157nm.Spin coating PMMA film (400nm) on this tunic then is through 120 ℃ of annealing 5min.Impression uses the silicon template of strip pattern, as shown in Figure 4.The fluorination treatment process that the silicon template is concrete is: template surface is handled oxygen gas flow rate 120mL/min, power 300W, processing time 3min with the oxygen plasma system; Again with high purity water to template surface ultrasonic cleaning 3 times, each time is 5min, makes thoroughly cleaning of surface; Then template is placed 120 ℃ of dry 1h down, the last method self assembly last layer fluoro silylating reagents (perfluor decyl-1,1,2,2-tetrahydrochysene-trichlorosilane) on template that on hot platform, pass through 250 ℃ of heating 3h.It is 170 ℃ that the impression condition is controlled at temperature, pressure 50bar, time 500s.Impression separates sample after finishing with template, obtain the strip pattern complementary fully with formwork structure, as shown in Figure 5.Carry out etching with oxygen gas plasma afterwards.Etching condition is oxygen gas flow rate 120ml/min, power 30W, processing time 10min.With acetone ultrasonic cleaning 30s, the surperficial polyaniline pattern that obtains has promptly obtained the alternate structure of substrate, electrically conductive polyaniline as shown in Figure 6 in substrate with the sample handled well.Through this etching process, the resolution of pattern has improved 0.7 times～6 times.Its uv-vis spectra characterization result as shown in Figure 7.
Embodiment 2:
The surperficial spin coating of handling well among the embodiment 1 there is the polyaniline sample of PMMA film impress with the silicon template (as shown in Figure 8) that has eurymeric (square pattern of projection) pattern.The fluorination treatment process that the silicon template is concrete is: template surface is handled oxygen gas flow rate 120mL/min, power 300W, processing time 3min with the oxygen plasma system; Again with high purity water to template surface ultrasonic cleaning 3 times, each time is 5min, makes thoroughly cleaning of surface; Then template is placed 120 ℃ of dry 1h down, the last method self assembly last layer fluoro silylating reagents (perfluor decyl-1,1,2,2-tetrahydrochysene-trichlorosilane) on template that on hot platform, pass through 250 ℃ of heating 3h.The impression condition is controlled at temperature at 170 ℃, pressure 50bar, time 500s.As shown in Figure 9, after impression finishes sample is separated with template, obtain no longer " well " word shape pattern with the formwork structure complementation, pattern resolution doubles.Carry out etching with oxygen gas plasma, etching condition is controlled to be oxygen gas flow rate 120ml/min, power 30W, etching time 10min.With the sample of handling well acetone ultrasonic cleaning 30s, by this process, the resolution of pattern doubles once more, as shown in figure 10.
Embodiment 3:
When pyrrole monomer is made oxygenant at ferric trichloride, similar polyreaction also can take place form film.
The preparation condition of polypyrrole film:
Pyrroles 400 μ L, N-(3-trimethoxy propyl group) pyrrole monomer 40 μ L, ferric trichloride 0.72g, 25 ℃ of temperature, time 10min.
(its thickness is 20nm) spin coating PMMA film (400nm) on this tunic then is through 120 ℃ of annealing 5min.The impression condition is controlled at temperature at 170 ℃, pressure 50bar, time 500s.Impression uses the silicon template of strip pattern, its fluorination treatment process such as embodiment 1.Impression separates sample after finishing with template, obtain the strip pattern complementary fully with formwork structure.Carry out etching with oxygen gas plasma afterwards.Etching condition is controlled to be oxygen gas flow rate 120ml/min, power 30W, etching time 10min.With the sample of handling well acetone ultrasonic cleaning 30s, the surperficial polypyrrole pattern that obtains and shown in Figure 6 similar.
Embodiment 4:
Film of poly pyrrole among the embodiment 3 surface spin coating PMMA film (400nm) is impressed its fluorination treatment process such as embodiment 1 with the silicon template that has the eurymeric pattern.The impression condition is controlled at temperature at 170 ℃, pressure 50bar, time 500s.Obtain no longer " well " word shape pattern with the formwork structure complementation.The resolution of structure doubles.Carry out etching with oxygen gas plasma.Etching condition is controlled to be oxygen gas flow rate 120ml/min, power 30W, etching time 10min.With the sample of handling well acetone ultrasonic cleaning 30s, by this process, the resolution of pattern improves once more, with shown in Figure 10 similar.
Embodiment 5:
When thiophene monomer is made oxygenant at ferric trichloride, similar polyreaction also can take place form film.
The preparation condition of polythiophene film:
Thiophene 400 μ L, N-(3-trimethoxy propyl group) pyrrole monomer 40 μ L, ferric trichloride 0.72g,
25 ℃ of temperature, time 10min.
(its thickness is 20nm) spin coating PMMA film (400nm) on this tunic then, through 120 ℃ of annealing 5min, the impression condition is controlled at temperature at 170 ℃, pressure 50bar, time 500s.Impression uses the silicon template of strip pattern, its fluorination treatment process such as embodiment 1.Impression separates sample after finishing with template, obtain the strip pattern complementary fully with formwork structure.Carry out etching with oxygen gas plasma afterwards.Etching condition is controlled to be oxygen gas flow rate 120ml/min, power 30W, etching time 10min.With the sample of handling well acetone ultrasonic cleaning 30s, the surperficial polyaniline pattern that obtains and shown in Figure 6 similar.
Embodiment 6:
Polythiophene film among the embodiment 5 surface spin coating PMMA film (400nm) is impressed its fluorination treatment process such as embodiment 1 with the silicon template that has the eurymeric pattern.The impression condition is controlled at temperature at 170 ℃, pressure 50bar, time 500s.Obtain no longer " well " word shape pattern with the formwork structure complementation, the resolution of structure doubles.Carry out etching with oxygen gas plasma.Etching condition is controlled to be oxygen gas flow rate 120ml/min, power 30W, etching time 10min.With the sample of handling well acetone ultrasonic cleaning 30s, by this process, the resolution of pattern improves once more, with shown in Figure 10 similar.
Claims (10)
1, a kind of preparation method of surface conducting polymer graphic pattern, its step is as follows:
(1) method of substrate surface by spin coating or oxidative polymerization in cleaning prepares the thick conducting polymer thin film of 10nm～30nm;
(2) the thick polymer barrier layer of spin coating 200nm～800nm on conducting polymer thin film, and carry out nano impression, form the polymer barrier layer pattern;
(3) the polymer barrier layer pattern is carried out all to oxygen plasma etch, the residual polymer barrier layer of flush away then, thus in substrate, obtain surface conducting polymer graphic pattern.
2, the preparation method of a kind of surface conducting polymer graphic pattern as claimed in claim 1 is characterized in that: used conducting polymer thin film is the film of polyaniline, polypyrrole or polythiophene.
3, the preparation method of a kind of surface conducting polymer graphic pattern as claimed in claim 1 is characterized in that: the preparation of conducting polymer thin film is a spin coating conductive polymer solution in substrate, and the rotating speed of spin coating is 500～5000rpm, and the time is 1～3min; Or the method for employing oxidative polymerization, with conducting polymer monomer aniline, pyrroles or the thiophene of 10 μ L～10mL, the N-of 10 μ L～1mL (3-trimethoxy propyl group) pyrrole monomer, and 0.02g～5g ferric trichloride oxygenant, be dissolved in water, ethanol or the isopropyl alcohol of 10mL～1000mL, then substrate is put into this oxidative polymerization system, the time of oxidative polymerization is 5min～24h, and temperature of reaction is 0～45 ℃; Thereby the thickness that obtains in substrate is the conducting polymer thin film of 10nm～30nm.
4, the preparation method of a kind of surface conducting polymer graphic pattern as claimed in claim 1, it is characterized in that: polymer barrier layer is polymethylmethacrylate, polystyrene, mr-L7030 or mr-L6000, the spin coating condition is 1000rpm～5000rpm, time is 1min～5min, after the spin coating 90 ℃～150 ℃ annealing 5min～1h.
5, the preparation method of a kind of surface conducting polymer graphic pattern as claimed in claim 1 is characterized in that: the nano impression temperature is 80 ℃～220 ℃, and pressure is 20bar～55bar, and the impression time is 100s～800s.
6, the preparation method of a kind of surface conducting polymer graphic pattern as claimed in claim 1 is characterized in that: template is quartz, silicon or metal form, and template carries out using after the fluorination treatment.
7, the preparation method of a kind of surface conducting polymer graphic pattern as claimed in claim 1 is characterized in that: all the condition to oxygen plasma etch is oxygen gas flow rate 80mL/min～200mL/min, power 30W～300W, processing time 5min～30min.
8, the preparation method of a kind of surface conducting polymer graphic pattern as claimed in claim 1 is characterized in that: ultrasonic 5s in the acetone～residual polymer barrier layer of 30min flush away.
9, the preparation method of a kind of surface conducting polymer graphic pattern as claimed in claim 1 is characterized in that: substrate is monocrystalline silicon piece, oxidized silicon chip, piezoid, glass sheet, ito glass sheet, sheet metal or mica sheet.
10, the prepared application of surface conducting polymer graphic pattern in optical device, photoelectric device, electron device, magnetic device, chemistry or biology device of each method of claim 1-9.
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