CN107881593B

CN107881593B - Double-anisotropic conductive green fluorescent Janus structure film and preparation method thereof

Info

Publication number: CN107881593B
Application number: CN201711112939.7A
Authority: CN
Inventors: 于文生; 李晓冰; 马千里; 田娇; 李丹; 奚雪; 王昕璐; 董相廷; 王进贤; 刘桂霞
Original assignee: Changchun University of Science and Technology
Current assignee: Changchun University of Science and Technology
Priority date: 2017-11-14
Filing date: 2017-11-14
Publication date: 2020-12-22
Anticipated expiration: 2037-11-14
Also published as: CN107881593A

Abstract

The invention relates to a double-anisotropic conductive green fluorescent Janus structure film and a preparation method thereof, belonging to the technical field of nano material preparation. The invention comprises five steps: (1) preparation of Tb (BA) by precipitation method₃(phen) complex; (2) preparing polymethyl methacrylate (PMMA); (3) preparing a spinning solution; (4) preparation [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]The anisotropic conductive green fluorescent Janus nanoribbon array film is prepared by adopting a parallel double-nozzle electrostatic spinning technology; (5) and preparing the bi-anisotropic conductive green fluorescent Janus structure film. The prepared Janus structure film has good bi-anisotropic conductivity and green fluorescence at the same time. The method is simple and easy to implement, can be used for batch production, and the novel nano-structure material has wide application prospect.

Description

Double-anisotropic conductive green fluorescent Janus structure film and preparation method thereof

Technical Field

The invention relates to the technical field of nano material preparation, in particular to a double-anisotropic conductive green fluorescent Janus structure film and a preparation method thereof.

Background

Anisotropic conductive films are a new type of electronic component interconnection materials, have unidirectional conductivity and other directional insulativity, and have been widely used in the fields of electronic packaging, chip attachment, and electrode bonding. Classified according to their conductive directions, they can be classified into the following two categories: type I anisotropic conductive film: such an anisotropic conductive film is conductive in the film thickness direction and insulating in the film plane direction, and the production technology of such an anisotropic conductive film is now well-established and has been widely used in electronic devices; type II anisotropic conductive film: the anisotropic conductive film has different conductive properties along different directions of the film surface, and generally has anisotropic conductive properties along two perpendicular directions of the film surface, wherein one direction is conductive, and the other direction is insulating. The research on the II type anisotropic conductive film is still in the laboratory exploration stage, and the industrial production and application are not realized.

Janus material refers to two chemical compositions or one chemical composition but different structures and has a definite partition structure in the same system, so that the Janus material has dual properties such as hydrophile/hydrophobe, polarity/non-polarity, luminescence/conduction, horizontal conduction/vertical conduction and the like, and is one of leading edges and hot research directions in the field of material science. The Janus nanoribbon refers to two chemical compositions which have definite partition structures in the same nanoribbon and have two or more properties, for example, one side of the nanoribbon has a light-emitting function, the other side of the nanoribbon has a conductive function, if a special receiving device is adopted, the Janus nanoribbons can be directionally arranged to form a Janus nanoribbon array film, and the array film has the light-emitting and conductive functions.

Rare earth metal terbium complex Tb (BA)₃phen，Tb³⁺The europium ion, BA, phen, phenanthroline and terbium ion are adopted as raw materials, and the fluorescent material is a green fluorescent material with unique performance due to the unique electronic configuration of the terbium ion, and has the advantages of high luminous intensity, good stability, high fluorescence quantum yield, good monochromaticity and the like, so that the fluorescent material is widely applied. Polyaniline PANI has become one of the hot spots in the research of the conductive polymer field due to its advantages of easy synthesis, high conductivity, good environmental stability, etc. Polyaniline PANI with one-dimensional nano-structure such as nano-wire, nano-rod, nano-tube and nano-fiber has been synthesized.

Previous studies have demonstrated that conductive polyaniline PAN in dark colorsI and rare earth complex Tb (BA)₃phen direct mixing can significantly reduce the luminous effect, so Tb (BA) is obtained₃The good luminous effect of phen must be Tb (BA)₃phen and PANI realize effective separation. If the conductive polymer polyaniline PANI is mixed with the polymethyl methacrylate PMMA to prepare the nanobelt, the conductive PANI is continuous, the high conductivity of the nanobelt is ensured, one side of the Janus nanobelt is conductive, and Tb (BA)₃phen is dispersed in macromolecular PMMA to prepare a nanobelt, and the other side of the nanobelt, which is taken as the other side of the Janus nanobelt, has the light-emitting characteristic to form [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]The green light-emitting and conductive dual-function Janus nanoribbon can ensure that the conductive polyaniline PANI and Tb (BA)₃phen realizes effective separation and obtains good luminous effect. If a special device is adopted, Janus nanoribbon array films can also be obtained, so that the conductivity is strong along the length direction of the nanoribbons, and the conductivity is strong along the direction vertical to the nanoribbons due to non-conductive Tb (BA)₃A phen/PMMA structural unit, which has an insulating property in the direction and thus has anisotropic conductivity, thus obtaining [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]The method comprises the steps of preparing an anisotropic conductive green fluorescent Janus nano-belt array film, constructing the same Janus nano-belt array film by utilizing a secondary electrospinning technology, firmly combining the two array films to form a left structure and a right structure to obtain the Janus structure film, wherein the length direction of the nano-belt is vertical in the left half side and the right half side of the Janus structure film, namely the conductive direction is vertical, so that the Janus structure film has a double-anisotropic conductive characteristic and a green light emitting function. The special nano-structure film has important application prospect in future nano-structure devices and medical diagnosis and treatment. At present, no relevant literature report is found.

Us patent No. 1975504 discloses a technical solution relating to electrospinning, which is an effective method for preparing continuous micro-nanofibers of macroscopic length, first proposed by Formhals in 1934. The method is mainly used for preparing polymer nano-fiber and is characterized in that charged polymer solution or melt is subjected to static electricityThe micro-nano fiber is drawn by electrostatic force in a field and sprayed out by a nozzle to be projected to an opposite receiving screen, so that wire drawing is realized, and then, a solvent is evaporated at normal temperature, or a melt is cooled to normal temperature and solidified to obtain the micro-nano fiber. Over the last decade, the technical solution of preparing inorganic compounds such as oxide nanofibers by electrospinning method has emerged in the field of inorganic fiber preparation, said oxides including TiO₂、ZrO₂、Y₂O₃、Y₂O₃:RE³⁺(RE³⁺＝Eu³⁺、Tb³⁺、Er³⁺、Yb³⁺/Er³ ⁺)、NiO、Co₃O₄、Mn₂O₃、Mn₃O₄、CuO、SiO₂、Al₂O₃、V₂O₅、ZnO、Nb₂O₅、MoO₃、CeO₂、LaMO₃(M＝Fe、Cr、Mn、Co、Ni、Al)、Y₃Al₅O₁₂、La₂Zr₂O₇And the like metal oxides and metal composite oxides. Q.Z.Yu, et al, polyaniline PANI nanofiber [ mater.Sci.Eng.B,2008,150,70-76 ] was prepared by electrostatic spinning technology]. The prior art successfully prepares a macromolecule nanobelt by utilizing an electrostatic spinning technology [ Materials Letters,2007,61: 2325-; journal of Polymer Science Part B Polymer Physics 2001,39: 2598-]. Some have produced porous SnO from organic compounds of tin using a combination of electrospinning and organometallic compound decomposition techniques₂Nanobelt [ Nanotechnology,2007,18:435704]. Some people firstly prepare PEO/stannic hydroxide composite nanobelts by utilizing an electrostatic spinning technology, and roast the PEO/stannic hydroxide composite nanobelts to obtain porous SnO₂Nanoribbons [ J.Am.Ceram.Soc.,2008,91(1):257 one 262-]. Dongcing et al prepared rare earth trifluoride nanobelts by electrostatic spinning technology [ Chinese patent application No.: 201010108039.7]And titanium dioxide nanobelts [ chinese invention patent, grant no: ZL200810050948.2]And Gd₃Ga₅O₁₂:Eu³⁺Porous nanobelt [ chemical journal of higher school, 2010,31(7),1291-]. Dongcing et al using a single spinneret and using electrospinningPAN/Eu (BA)₃phen composite luminescent nano-fiber [ novel chemical material, 2008,36(9),49-52]. Dong-Ting et al prepared Eu (BA) using an electrospinning technique using a single spinneret₃phen/PANI/PVP photoelectric dual-function composite nano-fiber (proceedings of higher school chemistry, 2012,33(8),1657-]. Dong-Xiang-Ting et al prepared Eu (BA) by electrospinning₃phen/PVP// PANI/PVP photoelectric dual-function two parallel nanometer fiber bundles [ national invention patent, application number: 201210407369.5]. Dongting et al prepared a single anisotropic conductive-magneto-optic tri-functional Janus nanoribbon array using electrospinning (national patent for invention, grant No. 201410795673.0; adv. Funct. Mater. 2015,25,2436-2443). At present, no relevant report of preparing the bi-anisotropic conductive green fluorescent Janus structure film by utilizing the electrospinning technology is found.

When the electrostatic spinning technology is used for preparing the nano material, the types of raw materials, the molecular weight of the high-molecular template agent, the composition of the spinning solution, the parameters of the spinning process and the structure of the spinning nozzle have important influences on the appearance and the size of a final product. The invention adopts the electrostatic spinning technology, a spinneret consists of two 12# truncated syringe needles with the same diameter and arranged in parallel double spinneret heads, Tb (BA)₃phen complex, PMMA, N-dimethylformamide DMF and chloroform CHCl₃The mixed solution is a spinning solution prepared from aniline, camphorsulfonic acid, ammonium persulfate, PMMA, DMF, CHCl₃Mixing, forming another spinning solution after aniline is polymerized into polyaniline, controlling the viscosity of the spinning solution is crucial, and obtaining [ Tb (BA) under the optimal process conditions₃phen/PMMA]//[PANI/PMMA]The method comprises the steps of constructing the same Janus nanobelt array film by utilizing a secondary electrospinning technology, firmly combining two array films to form a left structure and a right structure to obtain the Janus structure film, and enabling the length directions of the nanobelts to be vertical in the left half and the right half of the Janus structure film, namely the conducting directions to be vertical, so that the Janus structure film with the double-anisotropy conducting property and the green light emitting function is obtained.

Disclosure of Invention

In the background art, the electrostatic spinning technology is adoptedPreparing polymer, metal oxide, metal fluoride and metal composite oxide nano-fiber and nano-belt, PAN/Eu (BA)₃phen composite luminescent nanofiber, polyaniline PANI nanofiber, Eu (BA)₃phen/PANI/PVP photoelectric double-function composite nano-fiber, Eu (BA)₃The nano-fiber array comprises a phen/PVP// PANI/PVP photoelectric dual-function two-strand parallel nano-fiber bundle and a single anisotropic conductive-magnetic-optical three-function Janus nano-belt array. The starting materials, templating agent, solvent, and final desired product used are different from the process of the present invention. The invention adopts the electrostatic spinning technology and prepares [ Tb (BA) by using parallel double-nozzle₃phen/PMMA]//[PANI/PMMA]The green fluorescent conductive Janus nanoribbon array film with the anisotropic structure is constructed by utilizing a secondary electrospinning technology, the two array films are firmly combined together to form a left-right structure, the green fluorescent double-anisotropic conductive Janus structure film is obtained, and the conductive film with the novel structure is added to the field of anisotropic conductive film materials.

The invention is realized by firstly adopting a precipitation method to prepare Tb (BA)₃phen complex with Tb (BA)₃phen, PMMA, DMF and CHCl₃The mixed solution of (A) is used as a spinning solution, and aniline, camphorsulfonic acid, ammonium persulfate, PMMA, DMF and CHCl are used as the spinning solution₃Mixing, forming another spinning solution after aniline is polymerized into polyaniline, and controlling the viscosity of the spinning solution is very important. Adopting parallel double-nozzle and applying electrostatic spinning technology to make electrostatic spinning so as to obtain (Tb (BA))₃phen/PMMA]//[PANI/PMMA]The anisotropic conductive green fluorescent Janus nanoribbon array film is constructed by utilizing a secondary electrospinning technology, and the two array films are firmly combined together to form a left-right structure, so that the green fluorescent double-anisotropic conductive Janus structure film is obtained. The method comprises the following steps:

(1) preparation of Tb (BA) by precipitation method₃phen complexes

0.9346g Tb₄O₇Dissolving in 20mL concentrated nitric acid, heating and evaporating to dryness to obtain Tb (NO)₃)₃Adding 40mL of absolute ethyl alcohol into the crystal to prepare Tb (NO)₃)₃The ethanol solution of (a); adding 1.8320g benzoic acid and 0.9910g phenanthroline into 100mL absolute ethyl alcohol to prepare a mixed ligand solution, heating to 50-60 ℃, and adding Tb (NO) under the condition of continuous stirring₃)₃The ethanol solution is added into the mixed ligand solution drop by drop, and concentrated NH is added₃·H₂Adjusting pH to 6-6.5, reacting for 3h, washing the precipitate with water and ethanol for 3 times, and drying in drying oven at 60 deg.C for 12h to obtain Tb (BA)₃A phen complex;

(2) preparation of polymethyl methacrylate PMMA

Weighing 100g of Methyl Methacrylate (MMA) and 0.1g of dibenzoyl peroxide (BPO), adding the weighed Methyl Methacrylate (MMA) and 0.1g of BPO into a 250mL three-necked bottle with a reflux device, uniformly stirring, vigorously stirring the solution at the temperature of 90-95 ℃, refluxing until the solution has certain viscosity, stopping heating while continuously stirring and naturally cooling to room temperature when the viscosity is similar to that of glycerol, then pouring the solution into a test tube with the pouring height of 5-7cm, standing for 2h after pouring until the solution in the test tube has no bubbles, then transferring the test tube into a 50 ℃ drying box, standing for 48h, hardening the liquid in the test tube into a transparent solid, finally increasing the temperature of the drying box to 110 ℃ and preserving the temperature for 2h to finish the polymerization reaction, and naturally cooling to room temperature to obtain the polymethyl methacrylate (PMMA);

(3) preparing spinning solution

18.0000g of chloroform and 1.8000g of DMF were mixed with 1.0000g of PMMA and 0.1000g of Tb (BA)₃The phen complex is stirred for 24 hours to obtain a spinning solution with a green light-emitting function; adding 1.0000g of PMMA (polymethyl methacrylate) into a mixed solvent of 18.0000g of chloroform and 1.8000g of DMF (dimethyl formamide), stirring for 2 hours to obtain a uniform colloidal liquid, adding 0.3000g of aniline and 0.7492g of camphorsulfonic acid into the colloidal liquid, stirring for 2 hours, adding 0.7352g of ammonium persulfate, stirring for 30 minutes, and then putting the solution into a refrigerating chamber of a refrigerator at 5 ℃ for 24 hours to obtain another spinning solution with a conductive function;

(4) preparation [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]Anisotropic conductive green fluorescent Janus nanoribbon array film

Two branches are respectively provided withA truncated 5mL injector with 12# stainless steel needle head, two stainless steel needle heads are respectively bent by 30 degrees to enable the two needle heads to be in close parallel, a 1mL plastic spray gun head is sleeved on the two parallel stainless steel needle heads to enable the tips of the two stainless steel needle heads to be positioned in the middle of the plastic spray gun head, 3mL of two spinning solutions are respectively injected into the two injectors, a vertical spraying mode is adopted, a receiving device is a horizontally placed cylindrical aluminum rotary drum with the length of 20cm and the diameter of 7cm, the rotating speed is 1500r/min, other spinning parameters are that the spinning voltage is 6kV, the distance between the needle heads and the rotary drum is 12cm, the environmental temperature is 20-28 ℃, the relative humidity is 20-30%, and after the spinning solutions are exhausted, a product [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]An anisotropic conductive green fluorescent Janus nanoribbon array film;

(5) preparation of double-anisotropic conductive green fluorescent Janus structure film

Will be described [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]The anisotropic conductive green fluorescent Janus nanoribbon array film is taken down from an aluminum rotary drum, cut into a rectangle with the Janus nanoribbon direction of 2.2cm and the nanoribbon direction perpendicular to the Janus nanoribbon direction of 2cm, rotated by 90 degrees, fixed on the aluminum rotary drum, and covered by aluminum foil with the thickness of 2 multiplied by 2cm²The remaining 2X 0.2cm²The area of the second electro-spinning film is taken as the connecting surface of the second electro-spinning film, the dosage of the spinning solution and the spinning parameters are the same as those of the first electro-spinning process, the second electro-spinning is carried out, after the spinning is finished, the film is taken down from an aluminum rotary drum to be cut, and 2 multiplied by 4cm is obtained²A bi-anisotropic conductive green fluorescent Janus structural film.

The area of the prepared double-anisotropic conductive green fluorescent Janus structure film in the process is 2 multiplied by 4cm²From [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]The anisotropic conductive green fluorescent Janus nanoribbon array film is compounded from the left and the right, and the left and the right halves are directionally arranged [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]Each Janus nano-belt has the width of 9.24 mu m and the thickness of 805nm, the length direction of the nano-belt is vertical in the left half and the right half of the Janus structure film, namely the conducting direction is vertical, the conductivity is strong along the length direction of the nano-belt, and the average conductance is 2.12 multiplied by 10^-6S, alongThe conductivity perpendicular to the length direction of the nanobelt is weak, and the average conductance is 2.59 multiplied by 10^-10S, having bi-anisotropic conductivity; under the excitation of ultraviolet light at 304nm, bright green light with a main peak at 545nm is emitted; the prepared Janus structure film has good green fluorescence and double-anisotropic conductive functions, and the purpose of the invention is achieved.

Drawings

FIG. 1 is an SEM photograph of a dual anisotropic conductive green fluorescent Janus structure film, which is also referred to as the abstract drawing;

FIG. 2 is an SEM photograph of a Janus nanoribbon array film in a bi-anisotropic conductive green fluorescent Janus structure film;

FIG. 3 is a histogram of the width distribution of Janus nanoribbons in a bi-anisotropic conductive green fluorescent Janus structured film;

FIG. 4 is a line analysis energy dispersion spectrum of Janus nanoribbons in a bi-anisotropic conductive green fluorescent Janus structured film;

FIG. 5 is an optical micrograph of a single Janus nanoribbon in a bi-anisotropic conducting green fluorescent Janus structured film;

FIG. 6 is a graph of the excitation spectrum of a bi-anisotropic conducting green fluorescent Janus structural membrane;

FIG. 7 is a graph of the emission spectrum of a bi-anisotropic conductive green fluorescent Janus structural film;

fig. 8 is a color coordinate diagram of a bi-anisotropic conductive green fluorescent Janus structural film.

Detailed Description

Terbium oxide Tb selected by the invention₄O₇The purity of the compound is 99.99%, and the compound is N, N-dimethylformamide, chloroform, nitric acid, benzoic acid, phenanthroline, absolute ethyl alcohol, ammonia water, aniline, camphorsulfonic acid, dibenzoyl peroxide, methyl methacrylate and ammonium persulfate which are all commercially available analytical pure products; self-made in a deionized water laboratory; the glassware and equipment used are those commonly used in the laboratory.

Example (b): 0.9346g Tb₄O₇Dissolving in 20mL concentrated nitric acid, heating and evaporating to dryness to obtain Tb (NO)₃)₃Adding 40mL of absolute ethyl alcohol into the crystals to prepare Tb (b)NO₃)₃The ethanol solution of (a); adding 1.8320g benzoic acid and 0.9910g phenanthroline into 100mL absolute ethyl alcohol to prepare a mixed ligand solution, heating to 50-60 ℃, and adding Tb (NO) under the condition of continuous stirring₃)₃The ethanol solution is added into the mixed ligand solution drop by drop, and concentrated NH is added₃·H₂Adjusting pH to 6-6.5, reacting for 3h, washing the precipitate with water and ethanol for 3 times, and drying in drying oven at 60 deg.C for 12h to obtain Tb (BA)₃A phen complex; weighing 100g of Methyl Methacrylate (MMA) and 0.1g of dibenzoyl peroxide (BPO), adding the weighed Methyl Methacrylate (MMA) and 0.1g of BPO into a 250mL three-necked bottle with a reflux device, uniformly stirring, vigorously stirring the solution at the temperature of 90-95 ℃, refluxing until the solution has certain viscosity, stopping heating while continuously stirring and naturally cooling to room temperature when the viscosity is similar to that of glycerol, then pouring the solution into a test tube with the pouring height of 5-7cm, standing for 2h after pouring until the solution in the test tube has no bubbles, then transferring the test tube into a 50 ℃ drying box, standing for 48h, hardening the liquid in the test tube into a transparent solid, finally increasing the temperature of the drying box to 110 ℃ and preserving the temperature for 2h to finish the polymerization reaction, and naturally cooling to room temperature to obtain the polymethyl methacrylate (PMMA); 18.0000g of chloroform and 1.8000g of DMF were mixed with 1.0000g of PMMA and 0.1000g of Tb (BA)₃The phen complex is stirred for 24 hours to obtain a spinning solution with a green light-emitting function; adding 1.0000g of PMMA (polymethyl methacrylate) into a mixed solvent of 18.0000g of chloroform and 1.8000g of DMF (dimethyl formamide), stirring for 2 hours to obtain a uniform colloidal liquid, adding 0.3000g of aniline and 0.7492g of camphorsulfonic acid into the colloidal liquid, stirring for 2 hours, adding 0.7352g of ammonium persulfate, stirring for 30 minutes, and then putting the solution into a refrigerating chamber of a refrigerator at 5 ℃ for 24 hours to obtain another spinning solution with a conductive function; two 5mL syringes respectively provided with truncated No. 12 stainless steel needles are adopted, the two stainless steel needles are respectively bent by 30 degrees, the two needle points can be tightly parallel, a 1mL plastic spray gun head is sleeved on the two parallel stainless steel needles, the tips of the two stainless steel needles are positioned in the middle part of the plastic spray gun head, 3mL two spinning solutions are respectively injected into the two syringes, and the two syringes are connected in a vertical spraying modeThe collecting device is a cylindrical aluminum rotary drum which is horizontally arranged and has the length of 20cm and the diameter of 7cm, the rotating speed is 1500r/min, other spinning parameters are that the spinning voltage is 6kV, the distance between a needle point and the rotary drum is 12cm, the ambient temperature is 20-28 ℃, the relative humidity is 20-30 percent, and after the spinning solution is exhausted, the Tb (BA) is obtained₃phen/PMMA]//[PANI/PMMA]An anisotropic conductive green fluorescent Janus nanoribbon array film; will be described [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]The anisotropic conductive green fluorescent Janus nanoribbon array film is taken down from an aluminum rotary drum, cut into a rectangle with the Janus nanoribbon direction of 2.2cm and the nanoribbon direction perpendicular to the Janus nanoribbon direction of 2cm, rotated by 90 degrees, fixed on the aluminum rotary drum, and covered by aluminum foil with the thickness of 2 multiplied by 2cm²The remaining 2X 0.2cm²The area of the second electro-spinning film is taken as the connecting surface of the second electro-spinning film, the dosage of the spinning solution and the spinning parameters are the same as those of the first electro-spinning process, the second electro-spinning is carried out, after the spinning is finished, the film is taken down from an aluminum rotary drum to be cut, and 2 multiplied by 4cm is obtained²A bi-anisotropic conductive green fluorescent Janus structural film. The double-anisotropic conductive green fluorescent Janus structure film has a left half structure and a right half structure, wherein the length directions of the nanobelts are vertical, and the nanobelts are arranged in an orientation manner and are shown in figure 1; janus nanoribbons in the prepared double-anisotropic conductive green fluorescent Janus structure film are directionally arranged to form an array film, the thickness of a single Janus nanoribbon is 805nm, and the thickness is shown in figure 2; the width of the Janus nanoribbon in the prepared double-anisotropic conductive green fluorescent Janus structure film is 9.24 mu m, which is shown in figure 3; the distribution of S and Tb can reflect polyaniline and Tb (BA) respectively₃phen distribution, wherein S element is distributed on one side of Janus nanoribbon only, Tb element is distributed on the other side of Janus nanoribbon, which is consistent with the structure of Janus nanoribbon, as shown in FIG. 4; a single Janus nanoribbon comprising dark colored polyaniline on one side and colorless transparent Tb (BA) on the other side₃The phen complex, shown in FIG. 5; with 545nm as the monitoring wavelength, the double anisotropic conductive Janus structure film has a wide excitation band at 200-360nm, the peak value of the excitation band is 304nm, and the excitation band can be classified as the pi → pi transition of the ligand, as shown in FIG. 6; under the excitation of ultraviolet light at 304nm, the bi-anisotropic conductive Janus structure film emitsBright green light with major peak at 545nm, corresponding to Tb ion⁵D₄→⁷F₅Transitions, shown in FIG. 7; under the excitation of ultraviolet light at 304nm, the color coordinate values x and y of the fluorescence color emitted by the bi-anisotropic conductive Janus structure film are 0.2401 and 0.468 respectively, and the emitted fluorescence color is green, which is shown in FIG. 8; in the left half and the right half of the prepared double-anisotropic conductive green fluorescent Janus structure film, the length direction of the nanobelt is vertical, namely the conductive direction is vertical, the conductivity is strong along the length direction of the nanobelt, and the average conductance is 2.12 multiplied by 10^-6S, and weak conductivity along the direction perpendicular to the length of the nanoribbon, with an average conductance of 2.59X 10^-10S, the prepared Janus structure film has good green fluorescence and double-anisotropic conductivity.

The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims

1. The preparation method of the double-anisotropic conductive green fluorescent Janus structure film is characterized in that the double-anisotropic conductive green fluorescent Janus structure film is prepared as a product by adopting a parallel double-spinneret electrostatic spinning technology, and the preparation method comprises the following steps:

(1) preparation of Tb (BA) by precipitation method₃phen complexes

0.9346g Tb₄O₇Dissolving in 20mL concentrated nitric acid, heating and evaporating to dryness to obtain Tb (NO)₃)₃Adding 40mL of absolute ethyl alcohol into the crystal to prepare Tb (NO)₃)₃The ethanol solution of (a); adding 1.8320g benzoic acid and 0.9910g phenanthroline into 100mL absolute ethyl alcohol to prepare a mixed ligand solution, heating to 50-60 ℃, and adding Tb (NO) under the condition of continuous stirring₃)₃The ethanol solution is added into the mixed ligand solution drop by drop, and concentrated NH is added₃·H₂Adjusting pH to 6-6.5 with O, reacting for 3 hr, and sequentially adding water to the obtained precipitateWashing with ethanol for 3 times, and drying in drying oven at 60 deg.C for 12h to obtain Tb (BA)₃A phen complex;

(2) preparation of polymethyl methacrylate PMMA

Weighing 100g of Methyl Methacrylate (MMA) and 0.1g of dibenzoyl peroxide (BPO), adding the weighed Methyl Methacrylate (MMA) and 0.1g of BPO into a 250mL three-necked bottle with a reflux device, uniformly stirring, vigorously stirring the solution at 90-95 ℃ and refluxing until the solution has certain viscosity, stopping heating while continuously stirring and naturally cooling to room temperature when the viscosity is similar to that of glycerol, pouring the solution into a test tube with the pouring height of 5-7cm, standing for 2h after pouring until the solution in the test tube has no bubbles, transferring the test tube into a 50 ℃ drying box, standing for 48h, hardening the liquid in the test tube into a transparent solid, raising the temperature of the drying box to 110 ℃ and preserving the temperature for 2h to finish the polymerization reaction, and naturally cooling to room temperature to obtain the polymethyl methacrylate (PMMA);

(3) preparing spinning solution

Adopting two 5mL syringes respectively provided with a truncated No. 12 stainless steel needle, respectively bending the two stainless steel needles by 30 degrees to enable the two needle points to be closely parallel, sleeving a 1mL plastic spray gun head on the two parallel stainless steel needles to enable the tip ends of the two stainless steel needles to be positioned in the middle part of the plastic spray gun head, respectively injecting 3mL of two spinning solutions into the two syringes, and respectively adopting a mode of adopting two injection syringesThe vertical spraying mode is characterized in that the receiving device is a horizontally placed cylindrical aluminum rotary drum with the length of 20cm and the diameter of 7cm, the rotating speed is 1500r/min, other spinning parameters are that the spinning voltage is 6kV, the distance between a needle point and the rotary drum is 12cm, and the ambient temperature is 20-28^oC, the relative humidity is 20% -30%, and after the spinning solution is exhausted, Tb (BA) is obtained₃phen/PMMA]//[PANI/PMMA]An anisotropic conductive green fluorescent Janus nanoribbon array film;

Will be described [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]The anisotropic conductive green fluorescent Janus nanoribbon array film is taken down from an aluminum rotary drum, cut into a rectangle with the Janus nanoribbon direction of 2.2cm and the nanoribbon direction perpendicular to the Janus nanoribbon direction of 2cm, rotated by 90 degrees, fixed on the aluminum rotary drum, and covered by aluminum foil with the thickness of 2 multiplied by 2cm²The remaining 2X 0.2cm²The area of the second electro-spinning film is taken as the connecting surface of the second electro-spinning film, the dosage of the spinning solution and the spinning parameters are the same as those of the first electro-spinning process, the second electro-spinning is carried out, after the spinning is finished, the film is taken down from an aluminum rotary drum to be cut, and 2 multiplied by 4cm is obtained²A double anisotropic conductive green fluorescent Janus structure film consisting of [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]The anisotropic conductive green fluorescent Janus nanoribbon array film is compounded from the left and the right, and the left and the right halves are directionally arranged [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]Each Janus nano-belt has the width of 9.24 mu m and the thickness of 805nm, the length direction of the nano-belt is vertical in the left half and the right half of the Janus structure film, namely the conducting direction is vertical, the conductivity is strong along the length direction of the nano-belt, and the average conductance is 2.12 multiplied by 10^-6S, and weak conductivity along the direction perpendicular to the length of the nanoribbon, with an average conductance of 2.59X 10^-10S, the prepared Janus structure film has double-anisotropic conductivity, emits bright green light with a main peak at 545nm under the excitation of 304nm ultraviolet light, and has good green fluorescence and double-anisotropic conductivity.

2. The bi-anisotropic conductive green fluorescent material prepared by the preparation method of claim 1Janus structure film, characterized by comprising [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]The anisotropic conductive green fluorescent Janus nanoribbon array film is compounded from the left and the right, and the left and the right halves are directionally arranged [ Tb (BA)₃phen/PMMA]//[PANI/PMMA]The Janus nanoribbon consists of nanoribbons, the length direction of the nanoribbons is vertical, namely the conducting direction is vertical, the conductivity is strong along the length direction of the nanoribbons, the conductivity is weak along the direction vertical to the length direction of the nanoribbons, the nanoribbons have double-anisotropy conductivity, the prepared Janus structural film has good green fluorescence and double-anisotropy conducting functions, the area of the film is 2 multiplied by 4cm²。