CN103304827B - Method for preparing macromolecule ultrathin membrane nano wrinkling patterns - Google Patents
Method for preparing macromolecule ultrathin membrane nano wrinkling patterns Download PDFInfo
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- CN103304827B CN103304827B CN201310201454.0A CN201310201454A CN103304827B CN 103304827 B CN103304827 B CN 103304827B CN 201310201454 A CN201310201454 A CN 201310201454A CN 103304827 B CN103304827 B CN 103304827B
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Abstract
The invention discloses a method for preparing macromolecule ultrathin membrane nano wrinkling patterns. The method comprises the following steps of: step one, adding a corresponding solvent into a polymer to prepare a 1-4wt% solution, then performing ultrasonic treatment to accelerate dissolution, and sealing a reagent bottle for later use after completely dissolving; step two, forming a membrane by using a spin-coating method with the prepared solution, and at last, standing for 24 hours so as to completely volatilize the solvent; step three, processing the spin-coated single-layer polymer membrane by using a hyperthermal-hydrogen technology to induce the upper layer of the polymer to crosslink; step four, performing thermal annealing treatment, and taking out a sample after annealing to freely cool at a room temperature so as to obtain a wrinkling pattern. According to the method, the hyperthermal-hydrogen technology is adopted for inducing crosslinking, the method is effective on most polymer systems, only the polymer systems need to contain C-H keys, so a method for ultrathin membrane wrinkling, which is widely applicable to the polymer systems, is provided, and the method ensures that the surface functional groups of a material are not damaged.
Description
Technical field
The invention belongs to the technical field of preparing micro/nano-scale pattern, be specifically related to a kind of method of preparing the wrinkling pattern of macromolecule hyper-film nanometer.
Background technology
Exist the spontaneous tissue of passing through of many complexity to arrange the pattern forming at occurring in nature, in the micro/nano-scale of very small dimensions, as the straticulate structure in the layering surface tissue of molecular crystal, lotus leaf, shell pearl etc.; In the yardstick of the visible even larger uranology rank of naked eyes, as rule arrangement or the larger galaxy arrangement etc. of the ripples shape structure on dust storm mound, celestial body.Along with science and technology continue to less, thinner, gentlier development, the phenomenon that the spontaneous tissue of micro/nano-scale is arranged has been subject to extensive concern.
Wild effect in ultrathin membrane system, can be easy to utilize spontaneous tissue to arrange and form clear and definite, complicated topology, so caused increasing interest.Surface wrinkling is a kind of with regard to representational wild effect in ultrathin membrane system, it is to lead lower spontaneous tissue in unstable two to arrange the highly regular micro/nano-scale pattern that has forming, can find a lot of examples at occurring in nature, as aging human skin, dry fruit surface etc.Surface wrinkling is widely used in the complicated pattern of preparation, manufacture novel electron device, diffraction grating, microlens array, adjustment surface wettability, adjust surperficial adhesiveproperties, change optical property, measure the aspect such as mechanical property of ultrathin membrane.
Wrinkling system generally has bilayer structure, generally that thin, hard film is attached in soft matrix, under external field or the effect of unrelieved stress, just can obtain easily similar wrinkling pattern, these systems can provide abundant configuration of surface and multiple dimensioned ordered arrangement.In wrinkling, have a characteristic wavelength, it is to reach minimum result at film flexing and matrix distortion China and foreign countries force balance, system total energy.In existing research, producing the method for applied stress has mechanically compress or stretching, extension, thermal expansion, solvent-swollen.
Make duplicature system that wrinkling method occur by mechanically compress or the method for stretching, extension, its deformation range is larger, even reaches percent hundreds of from percentum to percent tens.But owing to will being beneficial to stretching, and there is certain intensity and toughness, matrix be in this way all generally polydimethylsiloxane (PDMS), the film on upper strata can be that polymkeric substance can be also by crosslinked polydimethylsiloxane (PDMS) hard formation obtaining by ultraviolet.The data such as the thickness that this method is two-layer can obtain eaily, are easy to carry out quantitative Analysis, so be commonly used to measure the mechanical property of ultrathin membrane.But the specific demand of its matrix has certain restriction to other application of this method.
The method of thermal expansion produces wrinkling, is that bilayer film is placed to for some time under comparatively high temps, then cooling, because the thermal expansivity of topmost thin film is lower than substrate, in shrinking, will produce stress under compression.This method produces, and wrinkling its deformation is less, generally only has percentum.Its hard formation of this method can be the oxygen plasma for polystyrene, UV-crosslinked or obtain with strong acid oxidation of inorganic metal or lower floor, has no report but whether this method is applicable to other the system of only having a kind of polymkeric substance.And, if itself has functional groups material, such as hydroxyl, hydroxy-acid group, amino etc., at oxygen plasma, UV-crosslinked or with after strong acid oxidation, the part that material surface is processed, these groups will be destroyed fall, and the character of material surface and body is changed, and these are all the restrictions for this method application.The method of solvent-swollen also needs with oxygen plasma, UV-crosslinked or obtain the structure that a upper strata is hard formation with strong acid oxidation, and its surface changes with similar above, has identical shortcoming.And the bad control of the condition of solvent-swollen, and swelling area is less, and not all material all conveniently carries out the processing of solvent-swollen, and the form after solvent treatment is also not easy to keep, and if after solvent evaporates, its form is just easy to destroy.Its these features have all limited the application of this method.
Summary of the invention
The present invention is directed to the shortcoming and the deficiency that in prior art, exist, provide a kind of form stable, method simply to prepare the method for the wrinkling pattern of macromolecule hyper-film nanometer.
The present invention is achieved in that
A method of preparing the wrinkling pattern of macromolecule hyper-film nanometer, comprises the steps:
Step 1, will in polymkeric substance, add corresponding solvent be configured to the solution of 1wt%-4wt%, then supersound process accelerate dissolution, seals reagent bottle after dissolving completely for subsequent use;
Step 2, by the solution configuring spin-coating method film forming, the rotating speed of spin coating is from 1000 turn/min of turn/min-3000, spin coating time 30s, can regulate and control to obtain the polymeric film of different thickness according to different rotating speeds, different strength of solution, thickness 20nm-1 μ m, finally places 24h and allows solvent volatilize completely;
Step 3, by superthermal hydrogen technical finesse for monolayer polymer film good spin coating, induced polymer upper strata occurs crosslinked, the condition of superthermal hydrogen is voltage and treatment time, voltage is 100V to 300V, treatment time 1min-10min, and different voltage and treatment time combination can obtain the polymkeric substance bilayer film of different cross-linking effects.
Step 4, the thermal anneal process of carrying out, the temperature of annealing is 100 DEG C-180 DEG C, remains on this annealing temperature and carry out the anneal of 6h, takes out sample and be allowed to condition under room temperature freely coolingly after annealing, just can obtain wrinkling pattern.
Further scheme is: what in described step 2, spin-coating method obtained is the polymeric film of individual layer, and superthermal hydrogen can arrive upper strata after processing be crosslinked hard formation and lower floor is the ELECTRODE WITH BILAYER POLYMERIC thing thin film system of soft formation.
Further scheme is: the cycle 50nm-500nm that described wrinkling pattern is wrinkling, wrinkling amplitude 10nm-500nm.
Further scheme is: described polymkeric substance is indefiniteness homopolymer, crystalline polymer.
Further scheme is: described indefiniteness homopolymer is polystyrene, polydimethylsiloxane, block polymer polystyrene isoprene triblock copolymer, polystyrene divinyl triblock copolymer and urethane.
Further scheme is: described crystalline polymer is poly(lactic acid), syndiotactic polystyrene.
Further scheme is: described solvent is toluene or trichloromethane.
In the present invention, adopted superthermal hydrogen technology, superthermal hydrogen is a kind ofly to utilize hydrogen molecule or hydrogen proton is irradiated to polymer surfaces under certain energy, causes c h bond fracture, forms C free radical, finally causes crosslinked technology.In superthermal hydrogen mechanism, because what use is hydrogen atom or hydrogen molecule, according to physical two articles collision principle, hydrogen atom or hydrogen molecule can be by the hydrogen atoms (atomic efficiency that transmission ofenergy is greater than hydrogen to other molecular weight is very low) in polymkeric substance that is transferred to of Energy Efficient rate in collision process, because the energy of c h bond is lower than other atom and the energy of key that forms of carbon atom in polymkeric substance, so in the situation that controlling energy, superthermal hydrogen technology can well realize selectivity and interrupt c h bond, realizes crosslinked.
Compared with prior art, there is following advantage in the present invention:
1, the present invention has adopted superthermal hydrogen technological guide crosslinked, effective to most polymers system, only needs to contain in polymeric system c h bond.So provide a kind of wrinkling method of ultrathin membrane that is widely used in polymeric system, and it can not destroy the surface-functional group of material.
2, a kind of method of preparing the wrinkling pattern of macromolecule hyper-film nanometer provided by the invention, its mild condition, the wrinkling Nano grade that is of a size of, by regulating a series of conditions (spin coating condition, the crosslinked condition of superthermal hydrogen, annealing conditions etc.) in Wrinkling can regulate the characteristic dimension of wrinkling pattern, by using special substrate etc. can realize the morphology control of wrinkling pattern.
3, the present invention has adopted simple method to obtain the wrinkling pattern of several polymkeric substance, for additive method, want that other materials is made to wrinkling pattern needs complicated special dies, the present invention has heightened simplicity and the operability of constructing micro/nano-scale pattern greatly, and industrialized possibility is provided.
Brief description of the drawings
Fig. 1 is the wrinkling pattern of polystyrene (PS) prepared by the present invention, characteristic wavelength 209nm.
Fig. 2 is the 3D rendering that has groove silicon chip that the present invention uses.
Fig. 3 is the morphology control of the wrinkling pattern of polystyrene (PS) prepared of the present invention, and we have used fluted silicon chip as substrate, has realized wrinkling along the wrinkling object of a direction.
Fig. 4 is the wrinkling pattern of the block polymer polystyrene isoprene triblock copolymer (SIS) prepared of the present invention.
Fig. 5 is the wrinkling pattern of the crystalline polymer poly(lactic acid) (PLA) prepared of the present invention.
Embodiment
Provide specific embodiment below so that technical scheme of the present invention is further described; but what deserves to be explained is that following examples can not be interpreted as limiting the scope of the invention; the technical field skilled person in this field, according to the content of foregoing invention, does the improvement of some non-intrinsically safes and adjusts still to belong to protection scope of the present invention to the present invention.
Embodiment 1
First select the solvent toluene of polystyrene (PS), but weigh a certain amount of polystyrene, and add the toluene of respective amount to be configured to the solution of 1wt%, then supersound process accelerate dissolution, seals reagent bottle after dissolving completely for subsequent use.By the solution configuring spin-coating method film forming, the turn/min of rotating speed 2000 of spin coating, spin coating time 30s, finally places 24h and allows solvent volatilize completely.By superthermal hydrogen technical finesse for monolayer polymer film good spin coating, induced polymer upper strata occurs crosslinked, voltage 300V, the treatment time 2min of superthermal hydrogen.Then carry out thermal anneal process, 130 DEG C of the temperature of annealing, annealing time is 6h, takes out sample and fast coolingly just can obtain wrinkling pattern by it after annealing.Wrinkling pattern as shown in Figure 1.
Embodiment 2
First select the solvent toluene of polystyrene (PS), but weigh a certain amount of polystyrene, and add the toluene of respective amount to be configured to the solution of 1wt%, then supersound process accelerate dissolution, seals reagent bottle after dissolving completely for subsequent use.By the solution configuring spin-coating method film forming, fluted silicon chip for substrate (seeing accompanying drawing 2), the turn/min of rotating speed 2000 of spin coating, spin coating time 30s, finally places 24h and allows solvent volatilize completely.By superthermal hydrogen technical finesse for monolayer polymer film good spin coating, induced polymer upper strata occurs crosslinked, voltage 300V, the treatment time 2min of superthermal hydrogen.Then carry out thermal anneal process, 130 DEG C of the temperature of annealing, annealing time is 6h, after annealing, take out sample by its quick cooling wrinkling pattern (seeing accompanying drawing 3) that just can obtain, because the wrinkling groove that is subject to limits, so can only shrink along groove direction, realize the object of wrinkling pattern Regularization.
Embodiment 3
First select the solvent toluene of block polymer polystyrene isoprene triblock copolymer (SIS), but weigh a certain amount of block polymer polystyrene isoprene triblock copolymer (SIS), and the toluene that adds respective amount is configured to the solution of 1wt%, then supersound process accelerate dissolution, seals reagent bottle after dissolving completely for subsequent use.By the solution configuring spin-coating method film forming, the turn/min of rotating speed 3000 of spin coating, spin coating time 30s, finally places 24h and allows solvent volatilize completely.By superthermal hydrogen technical finesse for monolayer polymer film good spin coating, induced polymer upper strata occurs crosslinked, voltage 300V, the treatment time 5min of superthermal hydrogen.Then carry out thermal anneal process, 120 DEG C of the temperature of annealing, annealing time is 6h, takes out sample by its quick cooling wrinkling pattern (seeing accompanying drawing 4) that just can obtain after annealing.
Embodiment 4
The solvent trichloromethane of first selective freezing polymer poly lactic acid (PLA), but weigh a certain amount of crystalline polymer poly(lactic acid) (PLA), and the trichloromethane that adds respective amount is configured to the solution of 1wt%, then supersound process accelerate dissolution, seals reagent bottle after dissolving completely for subsequent use.By the solution configuring spin-coating method film forming, the turn/min of rotating speed 2000 of spin coating, spin coating time 30s, finally places 24h and allows solvent volatilize completely.By superthermal hydrogen technical finesse for monolayer polymer film good spin coating, induced polymer upper strata occurs crosslinked, voltage 300V, the treatment time 1min of superthermal hydrogen.Then carry out thermal anneal process, the temperature 70 C of annealing, annealing time is 6h, takes out sample by its quick cooling wrinkling pattern (seeing accompanying drawing 5) that just can obtain after annealing.
In order better to study the impact on wrinkling pattern wavelength under spin coating condition, superthermal hydrogen treatment condition and thermal annealing condition, contriver has also carried out further research.
Select the solvent of toluene as polystyrene (PS), be configured to the solution of 1wt%, utilize method of the present invention, only have the Parameter Conditions in following table to revise, then by controlling different spin coating condition, superthermal hydrogen treatment condition and thermal annealing condition, obtain wrinkling pattern wavelength as shown in the table.
Wrinkling wavelength under table one, different condition
| Spin coating condition | The superthermal hydrogen 300V treatment time | Thermal annealing condition | Wrinkling wavelength |
| 2000r/min | 1min | 130℃6h | 240nm |
| 2000r/min | 1.5min | 130℃6h | 217nm |
| 2000r/min | 2min | 130℃6h | 224nm |
| 2000r/min | 3min | 130℃6h | 223nm |
| 2000r/min | 5min | 130℃6h | 224nm |
| 2000r/min | 10min | 130℃6h | 223nm |
| 1000r/min | 2min | 130℃6h | 283nm |
| 1500r/min | 2min | 130℃6h | 264nm |
| 2000r/min | 2min | 130℃6h | 209nm |
| 2500r/min | 2min | 130℃6h | 198nm |
| 3000r/min | 2min | 130℃6h | 189nm |
| 2000r/min | 2min | 110℃6h | 167nm |
| 2000r/min | 2min | 120℃6h | 196nm |
| 2000r/min | 2min | 130℃6h | 209nm |
| 2000r/min | 2min | 150℃6h | 230nm |
Claims (3)
1. prepare a method for the wrinkling pattern of macromolecule hyper-film nanometer, it is characterized in that comprising the steps:
Step 1, will in polymkeric substance, add corresponding solvent be configured to the solution of 1wt%-4wt%, then supersound process accelerate dissolution, seals reagent bottle after dissolving completely for subsequent use;
Step 2, by the solution configuring spin-coating method film forming, the rotating speed of spin coating is from 1000 turn/min of turn/min-3000, spin coating time 30s, can regulate and control to obtain the polymeric film of different thickness according to different rotating speeds, different strength of solution, thickness 20nm-1 μ m, finally places 24h and allows solvent volatilize completely;
Step 3, by superthermal hydrogen technical finesse for monolayer polymer film good spin coating, induced polymer upper strata occurs crosslinked, the condition of superthermal hydrogen is voltage and treatment time, voltage is 100V to 300V, treatment time 1min-10min, and different voltage and treatment time combination can obtain the polymkeric substance bilayer film of different cross-linking effects;
Step 4, the thermal anneal process of carrying out, the temperature of annealing is 100 DEG C-180 DEG C, remains on this annealing temperature and carry out the anneal of 6h, takes out sample and be allowed to condition under room temperature freely coolingly after annealing, just can obtain wrinkling pattern;
Described polymkeric substance is polystyrene, block polymer polystyrene-isoprene triblock copolymer or poly(lactic acid);
Described solvent is toluene or trichloromethane.
2. prepare according to claim 1 the method for the wrinkling pattern of macromolecule hyper-film nanometer, it is characterized in that: what in described step 2, spin-coating method obtained is the polymeric film of individual layer, superthermal hydrogen can arrive upper strata after processing be crosslinked hard formation and lower floor is the ELECTRODE WITH BILAYER POLYMERIC thing thin film system of soft formation.
3. the method for preparing according to claim 1 the wrinkling pattern of macromolecule hyper-film nanometer, is characterized in that: the cycle 50nm-500nm that described wrinkling pattern is wrinkling, wrinkling amplitude 10nm-500nm.
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| HK1215127A2 (en) | 2015-06-17 | 2016-08-12 | Master Dynamic Ltd | Apparatus, device and process for coating of articles |
| CN105181891A (en) * | 2015-07-31 | 2015-12-23 | 天津大学 | Method for construction of polypyrrole membrane with hierarchical morphology based on in-situ wrinkling and solvent swelling |
| CN105061731A (en) * | 2015-07-31 | 2015-11-18 | 天津大学 | Method for constructing multistage morphology polypyrrole membrane based on in situ wrinkling and thermal expansion |
| CN105001439A (en) * | 2015-08-24 | 2015-10-28 | 中物院成都科学技术发展中心 | Method for improving surface wetting property of thin polymer film through surface grafting |
| CN105699703B (en) * | 2016-01-26 | 2018-08-03 | 天津大学 | The method for measuring the softening of azobenzene film light using surface wrinkling |
| CN107249247A (en) * | 2017-06-08 | 2017-10-13 | 宏基领先科技有限公司 | Overheat the atomic excitation device of hydrogen cross-linking reaction |
| CN109445001B (en) * | 2018-10-10 | 2020-05-26 | 北京航空航天大学 | Method for generating micro-nano lenses in batches |
| CN110734037B (en) * | 2019-10-25 | 2023-01-24 | 哈尔滨工业大学 | Method for constructing surface fold structure of high polymer material |
| CN111333023B (en) * | 2020-03-02 | 2023-09-26 | 北京大学 | Preparation method and application of solvent-induced photoresponsive polymer surface micro-nano structure |
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