CN109256239B - Poly (3-hexylthiophene) conductive network structure and preparation method thereof - Google Patents
Poly (3-hexylthiophene) conductive network structure and preparation method thereof Download PDFInfo
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- CN109256239B CN109256239B CN201810848629.XA CN201810848629A CN109256239B CN 109256239 B CN109256239 B CN 109256239B CN 201810848629 A CN201810848629 A CN 201810848629A CN 109256239 B CN109256239 B CN 109256239B
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- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Abstract
The invention discloses a poly (3-hexylthiophene) conductive network structure and a preparation method thereof. Preparing an ultrahigh molecular weight polyethylene solution, and spin-coating the solution on an oxidized hot silicon wafer by using a spin coater to obtain an ultrahigh molecular weight polyethylene shish-kebab network structure; and then dripping the prepared poly (3-hexylthiophene) solution on the network structure to prepare the poly (3-hexylthiophene) conductive network structure. The method is simple and easy to operate, and has short preparation time and high efficiency; the obtained network structure is arranged in a ring shape and has good conductivity, and the network structure has good application prospect when being used as a polymer conductive network.
Description
Technical Field
The invention belongs to the technical field of conductive polymer processing. In particular to a poly (3-hexylthiophene) conductive network structure and a preparation method thereof.
Technical Field
The discovery of the conductive polymer has extremely important influence on the innovation of manufacturing technology in the microelectronic and photoelectric industries. Conductive polymers not only have unique electrical (optical, magnetic) properties, but are also easy to process, having a unique combination of properties that other materials do not possess.
Poly (3-hexylthiophene) (P3HT for short) has unique structural characteristics (pi electron conjugated system) as an excellent conjugated photoelectric material, and has a great potential application market in the aspects of optical display, field effect transistors, solar cells and the like due to low cost, high field effect mobility and strong solution processability and higher self-organization and charge transmission performance compared with other polythiophene materials. Therefore, since the discovery of conductive polymers, the materials have attracted considerable attention and have been intensively studied. At present, three methods for inducing the poly (3-hexylthiophene) to crystallize are available, wherein one method is that the poly (3-hexylthiophene) is induced to crystallize on a layer of oriented film by a melt film drawing method, and the poly (3-hexylthiophene) is not in direct contact with a silicon wafer in the process, so that the conductive effect is poor; secondly, a solvent evaporation method is adopted, but the process is slow, the efficiency is poor, and the operation difficulty is large; thirdly, other high molecular polymers are adopted to induce the poly (3-hexylthiophene) epitaxial crystallization, but each poly (3-hexylthiophene) crystal is lack of connection, so that the conductivity of the poly (3-hexylthiophene) crystal is poor.
Polyethylene, as a typical semicrystalline polymer, possesses a compact chemical structure. The ultrahigh molecular weight polyethylene is thermoplastic engineering plastic with a linear structure and excellent comprehensive performance, a shish-kebab network structure can be formed by an ultrahigh molecular weight polyethylene solution through an ultrahigh stretching process, a straight chain crystal in the structure is used as shish, and a folded chain crystal is used as kebab, so that the structure has good thermal stability and can be better used as an inductor for preparing a poly (3-hexylthiophene) conductive network structure.
The poly (3-hexylthiophene) conductive network is prepared by combining poly (3-hexylthiophene) and ultra-high molecular weight polyethylene and inducing poly (3-hexylthiophene) epitaxial crystallization by using the ultra-high molecular weight polyethylene by utilizing the property that poly (3-hexylthiophene) is easy to nucleate on the surface of other materials.
Disclosure of Invention
In order to achieve the purpose, the invention provides a poly (3-hexylthiophene) conductive network structure and a preparation method thereof, the method is simple and easy to operate, the time is short, the efficiency is high, and the prepared poly (3-hexylthiophene) conductive network structure has good conductivity;
in addition, the poly (3-hexylthiophene) conductive network structure prepared by the method has the advantages that the P3HT nanofibers (P3HT crystals) are microscopically oriented in edge-on orientation and are uniformly and vertically arranged on the ultrahigh molecular weight polyethylene network structure to form a shish-kebab structure, the structure is macroscopically isotropic, and each P3HT crystal is mutually connected and forms a network structure by virtue of the ultrahigh molecular weight polyethylene network structure; the prepared P3HT nano-fiber (P3HT crystal) is in direct contact with a silicon wafer, and the conductivity of the network structure is enhanced by the structure.
The invention is realized by the following technical scheme
A preparation method of a poly (3-hexylthiophene) conductive network structure comprises the following steps:
(1) preparing an ultrahigh molecular weight polyethylene shish-kebab network structure:
a. dissolving and mixing ultra-high molecular weight polyethylene in a solvent, and then heating the mixture to obtain an ultra-high molecular weight polyethylene solution;
b. taking a silicon wafer, carrying out oxidation treatment on the silicon wafer, placing the oxidized silicon wafer in a spin coater after the oxidation treatment is finished, and then heating and preserving heat on the silicon wafer placed on the spin coater;
c. b, after the silicon wafer on the spin coater is heated and insulated, quickly placing the heated and dissolved ultrahigh molecular weight polyethylene solution in the step a on the silicon wafer of the spin coater for spin coating, and after the spin coating is finished, cooling the ultrahigh molecular weight polyethylene spin-coated on the silicon wafer to room temperature to obtain an ultrahigh molecular weight polyethylene shish-kebab network structure;
(2) preparation of poly (3-hexylthiophene) conductive network structure (preparation of conductive network structure by ultra-high molecular weight polyethylene-induced poly (3-hexylthiophene) epitaxial crystallization):
d. dissolving poly (3-hexylthiophene) in a solvent, heating a mixed solution of the poly (3-hexylthiophene) and the solvent to completely dissolve the poly (3-hexylthiophene), and obtaining a poly (3-hexylthiophene) solution after complete dissolution;
e. d, dripping the poly (3-hexylthiophene) solution obtained in the step d on the ultrahigh molecular weight polyethylene shish-kebab network structure prepared in the step 1; after the dripping coating is finished, naturally volatilizing, and completely volatilizing the solvent to obtain a conductive network structure of poly (3-hexylthiophene);
or firstly heating the ultra-high molecular weight polyethylene shish-kebab network structure cooled to room temperature on the silicon wafer prepared in the step (1) until the temperature is the same as that of the poly (3-hexylthiophene) solution obtained in the step d, and after heating, keeping the temperature at the temperature; after the heat preservation is finished, dripping the poly (3-hexylthiophene) solution obtained in the step d on the ultrahigh molecular weight polyethylene shish-kebab network structure on the silicon chip after the heat preservation; and after the dripping is finished, naturally volatilizing, and completely volatilizing the solvent to obtain the conductive network structure of the poly (3-hexylthiophene).
Further, the solvent for dissolving the ultra-high molecular weight polyethylene in the step a is paraxylene; the step a, heating the mixture for 2-3 hours at 130-135 ℃.
Further, the mass fraction of the ultrahigh molecular weight polyethylene in the ultrahigh molecular weight polyethylene solution obtained in the step a is 0.02-0.04%.
Further, the silicon wafer in the step b is P100; the specific process of oxidizing the silicon wafer comprises the following steps: oxidizing the silicon wafer for 1 hour under the irradiation of an ultraviolet lamp; heating the silicon wafer placed in the spin coater: heating the silicon wafer to 50-80 ℃, and preserving heat for 3-5 min under the condition.
Further, when the high molecular weight polyethylene solution in the step c is spin-coated, the rotation speed of a spin coater is 4000rpm, and the spin-coating time is 30 s.
Further, the solvent for dissolving the poly (3-hexylthiophene) in the step d is p-xylene, chloroform or chlorobenzene; the heating of the mixed solution of the poly (3-hexylthiophene) and the solvent comprises the following steps: heating at 40-70 deg.C for 5 hr (70 deg.C for 5 hr when p-xylene or chlorobenzene is used as solvent; 40 deg.C for 5 hr when chloroform is used as solvent).
Furthermore, the mass fraction of the poly (3-hexylthiophene) in the poly (3-hexylthiophene) solution obtained in the step d is 0.001-0.005%.
Further, the weight average molecular weight of the ultra-high molecular weight polyethylene is 3 × 106g/mol～4×106g/mol。
The poly (3-hexylthiophene) conductive network structure prepared by the method.
Firstly, dissolving a certain amount of ultra-high molecular weight polyethylene by using a solvent, completely dissolving the ultra-high molecular weight polyethylene under a heating condition to obtain an ultra-high molecular weight polyethylene solution, simultaneously carrying out oxidation treatment on a silicon wafer to be used, placing the silicon wafer in a spin coater after oxidation, and heating and preserving heat of the silicon wafer; then placing the obtained ultrahigh molecular weight polyethylene solution on a heated silicon chip in a spin coater, performing spin coating by using the spin coater, and cooling to room temperature after the spin coating is finished to obtain a shish-kebab network structure of the ultrahigh molecular weight polyethylene; then poly (3-hexylthiophene) is dissolved in a solvent and heated to prepare a poly (3-hexylthiophene) solution, the solution is dripped on the surface of the ultrahigh molecular weight polyethylene shish-kebab network structure, because the crystal cell parameters of the polyethylene (110) crystal face and the poly (3-hexylthiophene) (100) crystal face are matched very well, therefore, P3HT can nucleate on the ultra-high molecular weight polyethylene network structure, and the growth of P3HT nano-fiber in the pi-pi stacking direction has advantages due to the stronger pi-pi interaction among molecules, the crystals of P3HT therefore adopt an edge-on orientation, i.e., the a-axis is perpendicular to the substrate, and the b-axis and c-axis are parallel to the substrate (note: the pendant groups of P3HT are oriented along the a-axis, the pi-pi stacking is oriented along the b-axis, and the backbone is oriented along the c-axis), and are otherwise aligned along the pendant groups to form a multi-layered structure.
Compared with the prior art, the invention has the following positive beneficial effects
The conductive network structure is prepared by adopting the ultra-high molecular weight polyethylene with stable structure to induce the poly (3-hexylthiophene) epitaxial crystallization, the method is simple to operate and short in preparation time, and the prepared P3HT conductive network structure has excellent conductive performance;
the edge-on oriented poly (3-hexylthiophene) nano-fiber is obtained by the method, and the poly (3-hexylthiophene) fiber can be intuitively observed to be vertically distributed on the ultrahigh molecular weight polyethylene net structure; the P3HT nano fibers are microscopically oriented in edge-on and vertically arranged on an ultrahigh molecular weight polyethylene network structure to form a shish-kebab structure, macroscopically isotropic, and by means of the ultrahigh molecular weight polyethylene network structure, each P3HT crystal (P3HT nano fiber) is mutually connected to form a network structure, and the P3HT crystal (P3HT nano fiber) is directly contacted with a silicon wafer, so that the structures can obviously enhance the conductivity of the P3HT network structure; by adopting the method, the nucleation and growth of the P3HT can be controlled by controlling the type, temperature, mass fraction and the like of the solvent, and the required conductive network structure is obtained. The P3HT conductive network structure prepared by the method has good conductivity, can be used for preparing conductive devices, and has good application prospect.
Drawings
FIG. 1 is a graph showing the results of testing the conductivity of a product prepared in example 1; the right picture in fig. 1 is a partial enlarged view of the left picture; the pure white area in the figure is the silicon wafer at the bottom, the gray and black networks in the figure are conductive networks formed by the epitaxial crystallization of the P3HT induced by the ultra-high molecular weight polyethylene, and as the deeper the color in the figure is, the more black the part of the conductive network is better (as can be known from a current scale of a picture at the right of the figure 1, the conductivity is gradually enhanced along with the deepening of the color), the conductivity of the formed P3HT network structure is far better than that of the silicon wafer, namely, the P3HT conductive network structure has good conductivity.
The figure is a conductive signal obtained by applying a voltage of 6V to a conductive network structure sample of poly (3-hexylthiophene) prepared in example 1 by scanning in a PeakForce-TUNA mode of an atomic force microscope;
FIG. 2 is a height view showing the structure of an ultra high molecular weight polyethylene shish-kebab network prepared in example 1;
FIG. 3 shows a height diagram of the conductive network structure of poly (3-hexylthiophene) prepared in example 1 (as indicated by the vertical marks on the right side of the diagram, white is a silicon wafer, the height of the conductive network structure is 0 nm; the colored portion is a conductive network structure, and the height of the conductive network structure gradually increases as the color deepens); the right picture in fig. 3 is a partial enlarged view of the left picture;
FIG. 4 is a graph showing the results of testing the conductivity of the product prepared in example 2; in FIG. 4, the right picture is a partial enlarged view of the left picture; the pure white area in the figure is the silicon wafer at the bottom, the gray and black networks in the figure are conductive networks formed by the epitaxial crystallization of the P3HT induced by the ultra-high molecular weight polyethylene, and as the deeper the color in the figure is, the more black the part of the conductive network is better (as can be known from a current scale of a picture at the right of the figure 4, the conductivity is gradually enhanced along with the deepening of the color), the conductivity of the formed P3HT network structure is far better than that of the silicon wafer, namely, the P3HT conductive network structure has good conductivity.
The figure is a conductive signal obtained by applying a voltage of 6V to a conductive network structure sample of poly (3-hexylthiophene) prepared in example 2 by scanning in a PeakForce-TUNA mode of an atomic force microscope;
FIG. 5 is a height view of the ultra high molecular weight polyethylene shish-kebab network structure prepared in example 2;
FIG. 6 is a height view of the conductive network structure of poly (3-hexylthiophene) prepared in example 2; in FIG. 6, the right picture is a partial enlarged view of the left picture;
FIG. 7 is a graph showing the results of conducting property measurements of the product prepared in example 3; in FIG. 7, the right picture is a partial enlarged view of the left picture; the pure white area in the figure is the silicon wafer at the bottom, the gray and black networks in the figure are conductive networks formed by the epitaxial crystallization of the P3HT induced by the ultra-high molecular weight polyethylene, and as the deeper the color in the figure is, the more black the part of the conductive network is better (as can be known from a current scale of a picture at the right of 7 in the figure, the conductivity is gradually enhanced along with the deepening of the color), the conductivity of the formed P3HT network structure is far better than that of the silicon wafer, namely, the P3HT conductive network structure has good conductivity.
The figure is a conductive signal obtained by applying a voltage of 6V to a conductive network structure sample of poly (3-hexylthiophene) prepared in example 3 by scanning in a PeakForce-TUNA mode of an atomic force microscope;
FIG. 8 is a height view of the ultra high molecular weight polyethylene shish-kebab network structure prepared in example 3;
FIG. 9 is a height view of the conductive network structure of poly (3-hexylthiophene) prepared in example 3; in FIG. 9, the right picture is a partial enlarged view of the left picture;
FIG. 10 is a height view of the ultra high molecular weight polyethylene shish-kebab network structure prepared in example 4;
FIG. 11 is a height view of the conductive network structure of poly (3-hexylthiophene) prepared in example 4; the right picture in fig. 11 is a partial enlarged view of the left picture;
FIG. 12 is a height view of the ultra high molecular weight polyethylene shish-kebab network structure prepared in example 5; the right picture in fig. 12 is a partial enlarged view of the left picture;
FIG. 13 is a height view of the conductive network structure of poly (3-hexylthiophene) prepared in example 5; the right picture in fig. 13 is a partial enlargement of the left picture.
Detailed Description
The present invention will be described in more detail with reference to the following embodiments, but the present invention is not limited to the embodiments.
The reagents used in the following examples are analytically pure, spin-on coating apparatus (developed by institute of microelectronics, national academy of sciences, KW-4A type), silicon wafer (Zhejiang crystal opto-electronic technology, Inc.), ultraviolet lamp (aerospace Honda 30W double U type germicidal ultraviolet lamp); the detection was carried out using an atomic force microscope (Dimension Icon, Bruker, USA).
Example 1
The weight average molecular weight of the ultra-high molecular weight polyethylene used in this example was (3.5 × 10)6g/mol), from hoechS AG, (Frankfurt am Main, Germany), the poly (3-hexylthiophene) used having a number average molecular weight of 5.23 × 103g/mol, from Shanghai Sedi Biotech, Inc.
The conductivity detection of the poly (3-hexylthiophene) conductive network structure is shown in figure 1, and the obtained structure is shown in figure 3; as can be seen from FIG. 1, the prepared P3HT network structure has very good conductivity;
the preparation method of the poly (3-hexylthiophene) conductive network structure comprises the following steps:
(1) preparation of ultrahigh molecular weight polyethylene shish-kebab network structure
a. Taking 5mg of ultra-high molecular weight polyethylene, placing the ultra-high molecular weight polyethylene in a p-xylene solvent, mixing and stirring, heating the mixed solution at 130 ℃ for 2 hours, completely dissolving the ultra-high molecular weight polyethylene in the solution after heating, and diluting the completely dissolved solution by using the p-xylene at 130 ℃ to obtain the ultra-high molecular weight polyethylene with the mass fraction of 0.02% in the ultra-high molecular weight polyethylene solution;
b. taking a P100 silicon wafer 1cm multiplied by 1cm, oxidizing for 1 hour under the irradiation of an ultraviolet lamp, placing the silicon wafer on a spin coater after the oxidation is finished, heating the silicon wafer on the spin coater to 70 ℃, and preserving heat for 3min at the temperature;
c. b, after the heat preservation of the silicon wafer on the spin coater in the step a is finished, quickly taking 0.03ml of the ultrahigh molecular weight polyethylene solution with the temperature of 130 ℃ and the mass fraction of 0.02% in the step a, placing the solution on the silicon wafer, starting the spin coater, and spin-coating for 30s at the rotating speed of 4000 rpm; after the spin coating is finished, cooling the ultrahigh molecular weight polyethylene and the silicon wafer which are spin-coated on the silicon wafer to room temperature to obtain an ultrahigh molecular weight polyethylene shish-kebab network structure; then, detecting the obtained ultrahigh molecular weight polyethylene shish-kebab network structure by using an atomic force microscope, wherein the result is shown in figure 2;
(2) preparation of poly (3-hexylthiophene) conductive network structure (preparation of conductive network structure by ultra-high molecular weight polyethylene-induced poly (3-hexylthiophene) epitaxial crystallization):
d. 10mg of poly (3-hexylthiophene) is put into p-xylene for mixing and dissolving, and the poly (3-hexylthiophene) is heated for 5 hours at the temperature of 70 ℃ to completely dissolve the poly (3-hexylthiophene) to obtain a poly (3-hexylthiophene) solution with the mass fraction of 0.5 percent; then, diluting 0.5% of poly (3-hexylthiophene) solution by adopting a p-xylene solvent with the temperature of 70 ℃ to obtain a poly (3-hexylthiophene) solution with the mass fraction of 0.005% of poly (3-hexylthiophene);
e. taking 0.03ml of the poly (3-hexylthiophene) solution with the temperature of 70 ℃ and the mass fraction of 0.005 percent obtained in the step d, dropwise coating the solution on the ultrahigh molecular weight polyethylene shish-kebab network structure prepared in the step 1, naturally cooling to room temperature after the dropwise coating is finished, and completely volatilizing the solvent to obtain the conductive network structure of the poly (3-hexylthiophene); then, the conductive network structure of the poly (3-hexylthiophene) was detected by an atomic force microscope, and the result is shown in fig. 3.
Example 2
The weight average molecular weight of the ultra-high molecular weight polyethylene used in this example was (3.5 × 10)6g/mol), from hoechtAG, (Frankfurt am Main, Germany), the number-average molecular weight of the poly (3-hexylthiophene) used was 5.23 × 103g/mol, from Shanghai Sedi Biotech, Inc.
The conductivity detection of the poly (3-hexylthiophene) conductive network structure is shown in FIG. 4, and the obtained structure is shown in FIG. 6; as can be seen from fig. 4, the prepared P3HT network structure has very good conductivity;
the preparation method of the poly (3-hexylthiophene) conductive network structure comprises the following steps:
(1) preparation of ultrahigh molecular weight polyethylene shish-kebab network structure
a. Taking 5mg of ultra-high molecular weight polyethylene, placing the ultra-high molecular weight polyethylene in a p-xylene solvent, mixing and stirring, heating the mixed solution at 130 ℃ for 2 hours, completely dissolving the ultra-high molecular weight polyethylene in the solution after heating, and diluting the completely dissolved solution by using the p-xylene at 130 ℃ to obtain the ultra-high molecular weight polyethylene with the mass fraction of 0.03 percent in the ultra-high molecular weight polyethylene solution;
b. taking a P100 silicon wafer 1cm multiplied by 1cm, oxidizing for 1 hour under the irradiation of an ultraviolet lamp, placing the silicon wafer on a spin coater after the oxidation is finished, heating the silicon wafer on the spin coater to 70 ℃, and preserving heat for 3min at the temperature;
c. b, after the heat preservation of the silicon wafer on the spin coater in the step a is finished, quickly taking 0.03ml of the ultrahigh molecular weight polyethylene solution with the temperature of 130 ℃ and the mass fraction of 0.03% in the step a, placing the solution on the silicon wafer, starting the spin coater, and spin-coating for 30s at the rotating speed of 4000 rpm; after the spin coating is finished, cooling the ultrahigh molecular weight polyethylene and the silicon wafer which are spin-coated on the silicon wafer to room temperature to obtain an ultrahigh molecular weight polyethylene shish-kebab network structure; then, detecting the obtained ultrahigh molecular weight polyethylene shish-kebab network structure by using an atomic force microscope, wherein the result is shown in fig. 5;
(2) preparation of poly (3-hexylthiophene) conductive network structure (preparation of conductive network structure by ultra-high molecular weight polyethylene-induced poly (3-hexylthiophene) epitaxial crystallization):
d. 10mg of poly (3-hexylthiophene) is put into p-xylene for mixing and dissolving, and the poly (3-hexylthiophene) is heated for 5 hours at the temperature of 70 ℃ to completely dissolve the poly (3-hexylthiophene) to obtain a poly (3-hexylthiophene) solution with the mass fraction of 0.5 percent; then, diluting the 0.5% poly (3-hexylthiophene) solution into a poly (3-hexylthiophene) solution with the mass fraction of 0.005% by adopting a p-xylene solvent with the temperature of 70 ℃;
e. taking 0.03ml of the poly (3-hexylthiophene) solution with the temperature of 70 ℃ and the mass fraction of 0.005 percent obtained in the step d, dropwise coating the solution on the ultrahigh molecular weight polyethylene shish-kebab network structure prepared in the step 1, naturally cooling to room temperature after the dropwise coating is finished, and completely volatilizing the solvent to obtain the conductive network structure of the poly (3-hexylthiophene); then, the conductive network structure of the poly (3-hexylthiophene) was detected by an atomic force microscope, and the result is shown in fig. 6.
Example 3
The ultra-high molecular weight polyethylene used in this example had a molecular weight of (3.5 × 10)6g/mol) as weight average molecular weight, obtained from hoechstAG, (Frankfurt am Main, Germany), the number average molecular weight of the poly (3-hexylthiophene) used was 5.23 × 103g/mol, from Shanghai Sedi Biotech, Inc.
The conductivity detection of the poly (3-hexylthiophene) conductive network structure is shown in FIG. 7, and the obtained structure is shown in FIG. 9; as can be seen from fig. 7, the prepared P3HT network structure has very good conductivity;
the preparation method of the poly (3-hexylthiophene) conductive network structure comprises the following steps:
(1) preparation of ultrahigh molecular weight polyethylene shish-kebab network structure
a. Taking 10mg of ultra-high molecular weight polyethylene, placing the ultra-high molecular weight polyethylene in a p-xylene solvent, mixing and stirring, heating the mixed solution at 130 ℃ for 2 hours, completely dissolving the ultra-high molecular weight polyethylene in the solution after heating, and diluting the completely dissolved solution by using the p-xylene at 130 ℃ to obtain the ultra-high molecular weight polyethylene with the mass fraction of 0.04% in the ultra-high molecular weight polyethylene solution;
b. taking a P100 silicon wafer 1cm multiplied by 1cm, oxidizing for 1 hour under the irradiation of an ultraviolet lamp, placing the silicon wafer on a spin coater after the oxidation is finished, heating the silicon wafer on the spin coater to 70 ℃, and preserving heat for 3min at the temperature;
c. b, after the heat preservation of the silicon wafer on the spin coater in the step a is finished, quickly taking 0.03ml of the ultrahigh molecular weight polyethylene solution with the temperature of 130 ℃ and the mass fraction of 0.04% in the step a, placing the solution on the silicon wafer, starting the spin coater, and spin-coating for 30s at the rotating speed of 4000 rpm; after the spin coating is finished, cooling the ultrahigh molecular weight polyethylene and the silicon wafer which are spin-coated on the silicon wafer to room temperature to obtain an ultrahigh molecular weight polyethylene shish-kebab network structure; then, detecting the obtained ultrahigh molecular weight polyethylene shish-kebab network structure by using an atomic force microscope, wherein the result is shown in fig. 8;
(2) preparation of poly (3-hexylthiophene) conductive network structure (preparation of conductive network structure by ultra-high molecular weight polyethylene-induced poly (3-hexylthiophene) epitaxial crystallization):
d. 10mg of poly (3-hexylthiophene) is put into chloroform to be mixed and dissolved, and the mixture is heated for 5 hours at the temperature of 40 ℃ to completely dissolve the poly (3-hexylthiophene) to obtain a poly (3-hexylthiophene) solution with the mass fraction of 0.5 percent; then, a chloroform solvent with the temperature of 40 ℃ is adopted to dilute the 0.5 percent poly (3-hexylthiophene) solution into a poly (3-hexylthiophene) solution with the mass fraction of 0.005 percent of poly (3-hexylthiophene);
e, heating the ultrahigh molecular weight polyethylene shish-kebab network structure prepared in the step (1) to 40 ℃, taking 0.03ml of the poly (3-hexylthiophene) solution with the temperature of 40 ℃ and the mass fraction of 0.005% obtained in the step d, dropwise coating the solution on the ultrahigh molecular weight polyethylene shish-kebab network structure heated to 40 ℃, naturally cooling to room temperature after the dropwise coating is finished, and completely volatilizing the solvent to obtain the conductive network structure of the poly (3-hexylthiophene); then, the conductive network structure of the obtained poly (3-hexylthiophene) was examined by an atomic force microscope, and the results are shown in fig. 9.
Example 4
The ultra-high molecular weight polyethylene used in this example had a molecular weight of (3.5 × 10)6g/mol), as weight average molecular weight, from hoechtAG, (Frankfurt am Main, Germany) and the number average molecular weight of the poly (3-hexylthiophene) used was 36.6 × 103g/mol, available from (1-Material Inc.).
A poly (3-hexylthiophene) conductive network structure, the resulting structure is shown in fig. 11.
The preparation method of the poly (3-hexylthiophene) conductive network structure comprises the following steps:
(1) preparation of ultrahigh molecular weight polyethylene shish-kebab network structure
a. Taking 5mg of ultra-high molecular weight polyethylene, placing the ultra-high molecular weight polyethylene in a p-xylene solvent, mixing and stirring, heating the multi-mixed solution at 130 ℃ for 2 hours, completely dissolving the ultra-high molecular weight polyethylene in the solution after heating, and diluting the completely dissolved solution by using the p-xylene at the temperature of 130 ℃ to obtain the ultra-high molecular weight polyethylene with the mass fraction of 0.02% in the ultra-high molecular weight polyethylene solution;
b. taking a P100 silicon wafer 1cm multiplied by 1cm, oxidizing for 1 hour under the irradiation of an ultraviolet lamp, placing the silicon wafer on a spin coater after the oxidation is finished, heating the silicon wafer on the spin coater to 70 ℃, and preserving heat for 3min at the temperature;
c. b, after the heat preservation of the silicon wafer on the spin coater in the step a is finished, quickly taking 0.03ml of the ultrahigh molecular weight polyethylene solution with the temperature of 130 ℃ and the mass fraction of 0.02% in the step a, placing the solution on the silicon wafer, starting the spin coater, and spin-coating for 30s at the rotating speed of 4000 rpm; after the spin coating is finished, cooling the ultrahigh molecular weight polyethylene and the silicon wafer which are spin-coated on the silicon wafer to room temperature to obtain an ultrahigh molecular weight polyethylene shish-kebab network structure; then, detecting the obtained ultrahigh molecular weight polyethylene shish-kebab network structure by using an atomic force microscope, wherein the result is shown in fig. 10;
(2) preparation of poly (3-hexylthiophene) conductive network structure (preparation of conductive network structure by ultra-high molecular weight polyethylene-induced poly (3-hexylthiophene) epitaxial crystallization):
d. 10mg of poly (3-hexylthiophene) is put into chlorobenzene to be mixed and dissolved, and the mixture is heated for 5 hours at the temperature of 70 ℃ to completely dissolve the poly (3-hexylthiophene) to obtain a poly (3-hexylthiophene) solution with the mass fraction of 0.5 percent; then, a chlorobenzene solvent with the temperature of 70 ℃ is adopted to dilute the 0.5 percent poly (3-hexylthiophene) solution into a poly (3-hexylthiophene) solution with the mass fraction of 0.005 percent of poly (3-hexylthiophene);
e. heating the ultrahigh molecular weight polyethylene shish-kebab network structure prepared in the step (1) to 70 ℃, taking 0.03ml of the poly (3-hexylthiophene) solution with the temperature of 70 ℃ and the mass fraction of 0.005% obtained in the step d, dropwise coating the solution on the ultrahigh molecular weight polyethylene shish-kebab network structure heated to 70 ℃, naturally cooling to room temperature after the dropwise coating is finished, and completely volatilizing the solvent to obtain the conductive network structure of the poly (3-hexylthiophene); then, the conductive network structure of the obtained poly (3-hexylthiophene) was examined by an atomic force microscope, and the results are shown in fig. 11.
Example 5
In this embodimentThe molecular weight of the ultra-high molecular weight polyethylene is (3.5 × 10)6g/mol) as weight average molecular weight, obtained from hoechstAG, (Frankfurt am Main, Germany), the number average molecular weight of the poly (3-hexylthiophene) used was 5.23 × 103g/mol, from Shanghai Sedi Biotech, Inc.
A poly (3-hexylthiophene) conductive network structure, the resulting structure being shown in fig. 13.
The preparation method of the poly (3-hexylthiophene) conductive network structure comprises the following steps:
(1) preparation of ultrahigh molecular weight polyethylene shish-kebab network structure
a. Taking 5mg of ultra-high molecular weight polyethylene, placing the ultra-high molecular weight polyethylene in a p-xylene solvent, mixing and stirring, heating the multi-mixed solution at 130 ℃ for 2 hours, completely dissolving the ultra-high molecular weight polyethylene in the solution after heating, and diluting the completely dissolved solution by using the p-xylene at the temperature of 130 ℃ to obtain the ultra-high molecular weight polyethylene with the mass fraction of 0.04% in the ultra-high molecular weight polyethylene solution;
b. taking a P100 silicon wafer 1cm multiplied by 1cm, oxidizing for 1 hour under the irradiation of an ultraviolet lamp, placing the silicon wafer on a spin coater after the oxidation is finished, heating the silicon wafer on the spin coater to 70 ℃, and preserving heat for 3min at the temperature;
c. b, after the heat preservation of the silicon wafer on the spin coater in the step b is finished, quickly placing 0.03ml of the ultrahigh molecular weight polyethylene solution with the temperature of 130 ℃ and the mass fraction of 0.04 percent obtained in the step a on the silicon wafer, starting the spin coater, and spin-coating for 30s at the rotating speed of 4000 rpm; after the spin coating is finished, cooling the silicon wafer to room temperature to obtain an ultrahigh molecular weight polyethylene shish-kebab network structure; then, detecting the obtained ultrahigh molecular weight polyethylene shish-kebab network structure by using an atomic force microscope, wherein the result is shown in fig. 12;
(2) preparation of poly (3-hexylthiophene) conductive network structure (preparation of conductive network structure by ultra-high molecular weight polyethylene-induced poly (3-hexylthiophene) epitaxial crystallization):
d. 10mg of poly (3-hexylthiophene) is put into p-xylene for mixing and dissolving, and the poly (3-hexylthiophene) is heated for 5 hours at the temperature of 70 ℃ to completely dissolve the poly (3-hexylthiophene) to obtain a poly (3-hexylthiophene) solution with the mass fraction of 0.5 percent; then, diluting the 0.5% poly (3-hexylthiophene) solution into a poly (3-hexylthiophene) solution with the mass fraction of 0.005% by adopting a p-xylene solvent with the temperature of 70 ℃;
e. heating the ultrahigh molecular weight polyethylene shish-kebab network structure prepared in the step (1) to 70 ℃, then taking 0.03ml of the poly (3-hexylthiophene) solution with the temperature of 70 ℃ and the mass fraction of 0.005% obtained in the step d, dropwise coating the solution on the ultrahigh molecular weight polyethylene shish-kebab network structure heated to 70 ℃, naturally cooling to room temperature after the dropwise coating is finished, and completely volatilizing the solvent to obtain the conductive network structure of the poly (3-hexylthiophene); then, the conductive network structure of the obtained poly (3-hexylthiophene) was examined by an atomic force microscope, and the results are shown in fig. 13.
Claims (6)
1. A preparation method of a poly (3-hexylthiophene) conductive network structure is characterized by comprising the following steps:
(1) preparation of ultrahigh molecular weight polyethylene shish-kebab network structure
a. Dissolving and mixing ultra-high molecular weight polyethylene in a solvent, heating the mixture to completely dissolve the ultra-high molecular weight polyethylene, and obtaining a solution of the ultra-high molecular weight polyethylene after complete dissolution; the mass fraction of the obtained ultrahigh molecular weight polyethylene solution is 0.02-0.04%;
b. taking a silicon wafer, carrying out oxidation treatment on the silicon wafer, placing the oxidized silicon wafer in a spin coater after the oxidation treatment is finished, and then heating and preserving heat on the silicon wafer placed on the spin coater;
the silicon wafer in the step is a P100 silicon wafer; the specific process for carrying out oxidation treatment on the silicon wafer comprises the following steps: oxidizing the silicon wafer for 1 hour under the irradiation of an ultraviolet lamp; heating the silicon wafer placed in the spin coater: heating the silicon wafer to 50-80 ℃, and preserving heat for 3-5 min under the condition;
c. b, after the silicon wafer is heated and insulated, placing the heated and dissolved ultrahigh molecular weight polyethylene solution in the step a on a silicon wafer of a spin coater for spin coating, and after the spin coating is finished, cooling the ultrahigh molecular weight polyethylene spin-coated on the silicon wafer to room temperature to obtain a shish-kebab network structure of the ultrahigh molecular weight polyethylene;
when the ultrahigh molecular weight polyethylene solution is subjected to spin coating, the rotating speed of a spin coating instrument is 4000rpm, and the spin coating time is 30 s;
(2) preparing a poly (3-hexylthiophene) conductive network structure:
d. dissolving poly (3-hexylthiophene) in a solvent, heating a mixed solution of the poly (3-hexylthiophene) and the solvent to completely dissolve the poly (3-hexylthiophene), and obtaining a solution of the poly (3-hexylthiophene) after dissolution;
e. d, dripping the poly (3-hexylthiophene) solution prepared in the step d on the ultrahigh molecular weight polyethylene shish-kebab network structure prepared in the step 1; after the dripping coating is finished, naturally volatilizing, and completely volatilizing the solvent to obtain a conductive network structure of poly (3-hexylthiophene);
or firstly heating the ultra-high molecular weight polyethylene shish-kebab network structure cooled to room temperature on the silicon wafer prepared in the step (1) until the temperature is the same as that of the poly (3-hexylthiophene) solution obtained in the step d, and after heating, keeping the temperature at the temperature; after the heat preservation is finished, dripping the poly (3-hexylthiophene) solution obtained in the step d on the ultrahigh molecular weight polyethylene shish-kebab network structure on the silicon chip after the heat preservation; and after the dripping is finished, naturally volatilizing, and completely volatilizing the solvent to obtain the conductive network structure of the poly (3-hexylthiophene).
2. The method for preparing a poly (3-hexylthiophene) conductive network structure according to claim 1, wherein the solvent for dissolving the ultra-high molecular weight polyethylene in step a is p-xylene; the mixture is heated at 130-135 ℃ for 2-3 hours.
3. The method for preparing the poly (3-hexylthiophene) conductive network structure according to claim 1, wherein the solvent for dissolving the poly (3-hexylthiophene) in step d is p-xylene, chloroform or chlorobenzene; the mixed solution of the poly (3-hexylthiophene) and the solvent is heated for 5 hours at the temperature of 40-70 ℃.
4. The method for preparing the poly (3-hexylthiophene) conductive network structure according to claim 3, wherein the mass fraction of the poly (3-hexylthiophene) in the poly (3-hexylthiophene) solution obtained in step d is 0.001% -0.005%.
5. The method for preparing the poly (3-hexylthiophene) conductive network structure according to any one of claims 1 to 4, wherein the weight average molecular weight of the ultra-high molecular weight polyethylene is 3 × 106g/mol ~ 4×106g/mol。
6. A poly (3-hexylthiophene) conductive network structure prepared by the method of claim 1.
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